DE10313453A1 - Portioned liquid detergent or cleaning composition in water-soluble or -dispersible container, containing water-soluble liquid binder, e.g. polyethylene glycol or glycerol, to improve storage stability - Google Patents

Abstract

In a portioned aqueous liquid detergent or cleaning composition (A) in a water-soluble or water-dispersible container, including a liquid phase and phosphate and/or citrate binder, the liquid phase contains non-surfactant, water-soluble liquid binder (I).

Description

The The present invention relates to portioned detergent and cleaning agent compositions, the consumer the dosage of detergents and cleaning agents facilitate. In particular, the invention relates to portioned washing and detergent compositions in a water soluble or water-dispersible container are packed.

washing and cleaning agents and processes for their production are well known and therefore broadly described in the prior art. Usually they are spray-dried or granulated to the consumer Powder products or as liquid Goods available posed. Following the consumer's desire for simple dosing, have in addition to these two classic variants products in pre-portioned form established in the market and are state of the art also extensively described, in particular pressed molded bodies, ie Tablets, blocks, Briquettes and the like, as well as portions packed in bags or more fluid Detergents and cleaning agents are described.

in the In the case of single-dose amounts of detergents and cleaning agents, the packaged in bags, there are bags from water soluble Foil enforced, the tearing of the packaging by the Consumers unnecessary do. This makes it easy to dose a single one Portion by inserting the bag directly into the washing machine or dishwasher or in their induction bowl, or by throwing it into a predetermined amount of water, for example in a bucket or in the hand wash basin or sink. In bags made of water-soluble As a result, washing and cleaning agents packed in foil are on stand of technology in large Number described.

So discloses the German Ausleschrift 11 30 547 (Procter & Gamble) packs from water soluble Polyvinyl alcohol films made with non-liquid synthetic detergents filled are. To the particle sizes of the packaged detergent is expressed this font is not.

A single dose of a detergent or bleach in a bag that has one or more seams made of water-sensitive material is described in the European patent application EP 143 476 (Akzo NV). In this publication, a mixture of anionic and / or nonionic water-binding polymer and cationic polymer adhesive material is proposed as the water-sensitive suture material.

It has been shown that in the water-soluble or water-dispersible containers packaged detergent and cleaning agent compositions of the stand of technology in many cases an insufficient one storage stability exhibit. In particular, if stored for several weeks occur these products often embrittlement the water-soluble or water-dispersible outer packaging. Continue with these Storage attempts one with considerable Weight loss associated "sweating" of the water-soluble or water dispersible packaging observed in some make with a solidification of the means contained in this packaging accompanied.

The Avoid these problems and provide a portioned portion liquid, i.e. pourable washing or detergent composition, which has a long shelf life is, in particular, no embrittlement the packaging materials and has no weight loss, is the task of the present application

It it has now been found that phosphate-containing portioned, liquid Detergent or cleaning agent with a high water content then one increased storage stability if they contain certain non-surfactant binders.

On The first subject of the present application is therefore a portioned portion liquid, aqueous washing or detergent composition in a water soluble or water-dispersible container, comprising a liquid Phase and phosphate and / or citrate builder, characterized in that the liquid phase contains one or more non-surfactant, water-soluble, liquid binders.

The agents according to the invention contain a liquid matrix, which besides the water also others may contain non-aqueous solvents. These non-aqueous solvents originate, for example, from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides. Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents for the purposes of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Non-aqueous solvents, those 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, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl 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 particularly preferred in the context of the present invention Detergent or cleaning agent composition is characterized in that that the Content of liquid Phase on the non-surfactant, water-soluble, liquid binder (s) 0.1 to 50% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 is up to 40 wt .-% and in particular 2 to 35 wt .-%. As part of In the present application, however, portions are particularly preferred Detergent or cleaning agent compositions which have a content the liquid Phase on the non-surfactant, water-soluble, liquid binder (s) above 8% by weight, preferably between 10 to 50% by weight, preferably between 15 to 45 wt .-%, particularly preferably between 20 to 40 wt .-% and have in particular between 25 to 35 wt .-%.

In a further preferred embodiment of the present invention the portioned detergent or cleaning agent composition at least a non-surfactant, water-soluble, liquid binder from the group polyethylene glycol, polypropylene glycol, glycerin, Glycerine carbonate, ethylene glycol, propylene glycol and propylene carbonate.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol which have the general formula (I) H- (O-CH ₂ -CH ₂ ) _n -OH (I) are sufficient, where n values can be between 1 (ethylene glycol, see below) and approx. 16. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the above formula. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

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, siehe unten) und ca. 12 annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n = 2, 3 und 4 in der vorstehenden Formel.Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula (II)

are sufficient, where n values can be between 1 (propylene glycol, see below) and approx. 12. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in the above formula.

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage. The glycerol content of preferred agents according to the invention, based on the total weight of these agents, is between 2 and 50% by weight, preferably between 4 and 45% by weight, preferably between 8 and 40% by weight and in particular between 11 and 35% by weight. -%.

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

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

from Propylene glycol exist in two isomers, 1,3-propanediol and that 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet tasting liquid density 1.0597, which solidifies at -32 ° C and at 214 ° C boils. 1,3-Propanediol can be produced from acrolein and Water under subsequent catalytic hydrogenation.

Technically 1,2-Propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, represents the density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water. According to the invention particularly preferred agents have a content based on their total weight of propanediol between 0.1 and 20 wt .-%, preferably from 0.2 to 15% by weight, particularly preferably from 0.3 to 10% by weight and in particular from 0.4 to 5% by weight on.

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

The liquid washing agents according to the invention or detergent compositions made up in the containers water or water-dispersible film can be thinned up be highly viscous. "Liquid" indicates in the context of the present invention, flowable agents at room temperature, which can leak out of containers under the influence of gravity. Especially portioned washing or inventive are preferred Detergent compositions in which the liquid phase 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.

to viscosity control can the agents according to the invention contain other ingredients, with their use, for example the settling behavior or the pourability or flowability can be controlled in a targeted manner. In non-aqueous systems in particular combinations of structure donors and thickeners proven.

• a) 0,1 bis 1,0 Gew.-% eines oder mehrerer Strukturgeber aus der Gruppe der Bentonite und/oder mindestens teilweise veretherten Sorbitole sowie
• b) 5,0 bis 30 Gew.-% eines oder mehrerer Verdicker aus der Gruppe der Carbonate, Sulfate und amorphen oder kristallinen Disilikate.

Machine dishwashing detergents preferred in the context of the present invention further contain

• a) 0.1 to 1.0 wt .-% of one or more structurants from the group of bentonites and / or at least partially etherified sorbitols and
• b) 5.0 to 30% by weight of one or more thickeners from the group of the carbonates, sulfates and amorphous or crystalline disilicates.

The Structure donor a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used about physical stability to ensure the means and the viscosity adjust. Although conventional Thickeners such as polyacrylates or polyurethanes in non-aqueous media fail, the viscosity control succeeds with the substances mentioned in the non-aqueous system.

bentonite are contaminated clays caused by weathering of volcanic tuffs have arisen. Because of their high montmorillonite content Bentonites have valuable properties such as swelling ability, Ion exchange capacity and thixotropy. It is possible the properties of the bentonites according to the intended use to modify. Bentonites are found in tropical clay Soils frequently and become as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite shows the cheapest application properties (swellability), so that its Use in the context of the present invention is preferred. Naturally occurring Calcium bentonites come from Mississippi / USA or Texas / USA or from Landshut / D. Of course Ca bentonites obtained become artificial by exchanging Ca for Na into the swellable Na bentonites.

The main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites are clay minerals belonging to the phyllosilicates and here to the dioctahedral smectites, which crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas
Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or
Al ₂ O ₃ · 4SiO ₂ · H ₂ O · nH ₂ O or
Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °)
can be described.

Preferred machine dishwashing detergents are characterized in that montmorillonites are used as structuring agents. Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ⎕⎕picolin, ammonium compounds, hydroxy-aluminosilicate ions, etc. The above. Formulas are only approximate formulas because montmorillonites have a large ion exchange capacity. Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

In Combine with the bentonites or as a substitute for them when using them is not desired can at least partially etherified sorbitols are used as structure donors become.

sorbitol is one of the hexites 6-valent alcohol (sugar alcohol), the intramolecular relatively light splits off one or two moles of water and forms cyclic ethers (for example Sorbitan and sorbide). The elimination of water is also intermolecular possible, where noncyclic ethers from sorbitol and the concerned Form alcohols. Here too is the formation of monoethers and Bis-ether possible being also higher Degrees of etherification such as 3 and 4 can occur. As part of the present The invention is preferably used at least partially etherified Sorbitols are double etherified sorbitols, of which the dibenzylidene sorbitol is particularly preferred. Here are machine dishwashing detergents preferably the sorbitols which are etherified twice as structure donors, especially dibenzylidene sorbitol.

The agents according to the invention can the structuring agents in amounts of 0.1 to 1.0 wt .-%, based on contain the entire agent and on the active substance of the structuring agent. Preferred agents contain the structuring agent in amounts of 0.2 to 0.9% by weight, preferably in amounts of 0.25 to 0.75% by weight and in particular in amounts of 0.3 to 0.5% by weight, in each case based on the entire mean.

The preferred agents according to the invention can be inorganic salts from the group as thickeners which contain carbonates, sulfates and amorphous or crystalline disilicates. In principle, the salts of all metals mentioned can be used, the alkali metal salts being preferred. Alkali carbonate (s), alkali sulfate (s) and / or amorphous (s) and / or crystalline (s) alkali disilicate (s), preferably sodium carbonate, sodium sulfate and / or amorphous or crystalline sodium disilicate, are particularly preferably used as thickeners in the context of the present invention ,

The preferred agents according to the invention contain the thickener in amounts of 5 to 30 wt .-%, based on the entire mean. Particularly preferred agents contain the or the thickeners in amounts of 7.5 to 28 wt .-%, preferably in amounts from 10 to 26% by weight and in particular in amounts from 12.5 to 25 % By weight, based in each case on the total composition.

in the With regard to an increased sedimentation it is preferred that the in the agents according to the invention contained solids if possible finely divided. This is particularly the case with inorganic Thickeners and an advantage for bleaches. Here are machine according to the invention Dishwashing liquid preferred, in which the average particle size of the bleaching agent and thickener and the optional builder less than 75 μm, preferably less than 50 μm and in particular less than 25 μm is.

The liquid machine according to the invention Dishwashing liquid can others to set a possibly higher viscosity viscosity regulators or contain thickeners. Here are all known thickeners usable, i.e. those based on natural or synthetic Polymers.

Out natural polymers used as thickeners find, for example, agar-agar, carrageenan, tragacanth, rubber arabicum, alginates, pectins, polyoses, guar flour, locust bean gum, Strength, Dextrins, gelatin and casein. Modified natural products come from especially from the group of modified starches and celluloses, exemplary here are carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and -propyl cellulose and core meal ether called.

in the Preferred dishwasher detergents within the scope of the present invention contain hydroxyethyl cellulose and / or hydroxypropyl cellulose as thickeners, preferably in amounts of 0.01 to 4.0% by weight, particularly preferably in quantities of 0.01 to 3.0% by weight and in particular in amounts of 0.01 to 2.0 wt .-%, each based on the entire mean.

A size Group of thickeners, widely used in a wide variety Find application areas are the fully synthetic polymers like Polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides and polyurethanes.

Thickeners from the classes of substances mentioned are widely available commercially and are sold, for example, under the trade names Acusol ^® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT- 282-S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH ), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® -thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride -Copolymen, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19–21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high mol Eccular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell) are available.

On The preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide made by Xanthomonas campestris and some other species under aerobic conditions is produced and a molecular weight of 2 to 15 million Daltons having. Xanthan is made from a chain with β-1,4-bound glucose (cellulose) formed with side chains. The structure of the subgroups consists of Glucose, mannose, glucuronic acid, Acetate and pyruvate, the number of pyruvate units being the viscosity of the xanthan certainly.

in the Within the scope of the present invention also preferably to be used Thickeners are polyurethanes or modified polyacrylates, based on the total agent, for example in amounts of 0.1 up to 5 wt .-% can be used.

in der R¹ für einen niedermolekularen oder polymeren Diol-Rest, R² für eine aliphatische oder aromatische Gruppe und n für eine natürliche Zahl steht. R¹ ist dabei vorzugsweise eine lineare oder verzweigte C_2–12-Alk(en)ylgruppe, kann aber auch ein Rest eines höherwertigen Alkohols sein, wodurch quervernetzte Polyurethane gebildet werden, die sich von der oben angegebenen Formel XVI dadurch unterscheiden, daß an den Rest R¹ weitere -O-CO-NH-Gruppen gebunden sind.Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula XVI

in which R ^{1 is} a low molecular weight or polymeric diol radical, R ^{2 is} an aliphatic or aromatic group and n is a natural number. R ¹ is preferably a linear or branched C _2-12 alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the formula XVI given above in that the R ¹ further -O-CO-NH groups are bound.

Technically important PUR are made from polyester and / or polyether diols and, for example, from 2,4- or 2,6-toluenediisocyanate (TDI, R ² = C ₆ H ₃ -CH ₃ ), 4,4'-methylene di (phenyl isocyanate) (MDI, R ² = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

Commercial polyurethane-based thickeners are, for example, under the names Acrysol ^® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ^® L75-N (non-ionic PU dispersion, 50% in water, Borchers), Coatex ^® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ^® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ^® VPW-3116 (PUR dispersion, 43% in water, Henkel) available. For the purposes of the present invention, care must be taken when using aqueous dispersions that the water content of the agents according to the invention remains within the limits specified above. If the use of aqueous dispersions is not possible for these reasons, dispersions in other solvents or the solids can be used.

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 H oder R⁴ und n für eine natürliche Zahl steht. Allgemein sind solche modifizierten Polyacrylate Ester oder Amide von Acrylsäure bzw. einer α-substituierten Acrylsäure. Unter diesen Polymeren bevorzugt sind solche, bei denen R³ für H oder eine Methylgruppe steht. Bei den Polyacrylamiden (X = N-R⁵) sind sowohl einfach (R⁵ = H) als auch zweifach (R⁵ = R⁴) N-substituierte Amidstrukturen möglich, wobei die beiden Kohlenwasserstoffreste, die an das N-Atom gebunden sind, unabhängig voneinander aus gegebenenfalls alkoxylierten verzweigten oder unverzweigten C_8–22-Alk(en)ylresten ausgewählt werden können. Unter den Polyacrylestern (X = 0) sind solche bevorzugt, in denen der Alkohol aus natürlichen oder synthetischen Fetten bzw. Ölen gewonnen wurde und zusätzlich alkoxyliert, vorzugsweise ethoxyliert ist. Bevorzugte Alkoxlierungsgrade liegen zwischen 2 und 30, wobei Alkoxylierungsgrade zwischen 10 und 15 besonders bevorzugt sind.Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula XVII

in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ⁵ ), both single (R ⁵ = H) and double (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another can be selected from optionally alkoxylated branched or unbranched C _8-22 alk (en) yl radicals. Among the polyacrylic esters (X = 0), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers that can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation. Formula XVII only gives formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula XVII is at least 30% by weight can also be used in the context of the present invention. For example copolymers of modified polyacrylates and acrylic acid or their salts can also be used which still have acidic H atoms or basic --COO ^- groups.

in der R⁴ für einen vorzugsweise unverzweigten, gesättigten oder ungesättigten C_8–22-Alk(en)ylrest, R⁶ und R⁷ unabhängig voneinander für H oder CH₃ stehen, der Polymerisationsgrad n eine natürliche Zahl und der Alkoxylierungsgrad a eine natürliche Zahl zwischen 2 und 30, vorzugsweise zwischen 10 und 20 ist. R⁴ ist dabei vorzugsweise ein Fettalkoholrest, der aus natürlichen oder synthetischen Quellen gewonnen wurde, wobei der Fettalkohol wiederum bevorzugt ethoxyliert (R⁶ = H) ist.Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula XVIIa

in which R ^{4 is} a preferably unbranched, saturated or unsaturated C _8-22 alk (en) yl radical, R ⁶ and R ⁷ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number is between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ⁶ = H).

Products of formula XVIIa strength are commercially for example under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available. In the case of the commercial product mentioned, R ⁴ stands for a stearyl radical, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20. Also in this dispersion, what has been said above about the water content of the compositions applies.

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 H oder R⁴ und n für eine natürliche Zahl steht, bevorzugt sind.Portioned detergent or cleaning agent compositions preferred in the context of the present invention contain in their liquid phase 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, with hydroxyethyl cellulose and / or hydroxypropyl cellulose and / or thickeners from the group of the polysaccharides, preferably xanthan, the polyurethanes or the modified polyacrylates being particularly preferred as the thickener of thickeners of the formula XVII

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

Particularly preferred portioned detergent or cleaning agent compositions according to the invention are distinguished by a higher density than conventional detergent or cleaning agent powders, with particular preference being given to those agents in the context of the present application whose liquid phase at 20 ° C. has a density between 1.040 and 1, 70 g / cm ³ , preferably between 1,080 and 1.65 g / cm ³ , particularly preferably between 1.12 and 1.60 g / cm ³ and in particular between 1.24 and 1.55 g / cm ³ .

The inventive washing or cleaning agents contain phosphates and / or citrates. As phosphates are preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) used.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which a distinction can be made between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid HP ₃ O _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits 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, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, 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), NaH ₂ PO 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 the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), KH ₂ PO 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 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 390% P ₂ O ₅ ) a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), KP ₃ O ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more easily 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 _Z O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with 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 reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O 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 of which is 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. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 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 natri umdiphosphate dissolves pentasodium triphosphate 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.

preferred automatic dishwashing detergents contain 10 to 70 wt .-%, preferably 20 to 65 wt .-%, preferred 25 to 60% by weight and in particular 30 to 60% by weight of one or more Phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

The agents according to the invention can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melting or glow phosphates due to their production - which can be derived from acid salts of orthophosphoric acid (phosphoric acids) by condensation. The condensed phosphates can be divided into the metaphosphates [MIn (PO ₃ ) _n ] and polyphosphates (M ^I _{n + 2} P _n O _{3n + 1} or M ^I _n H ₂ P _n O _{3n + 1} ).

The term "metaphosphate" was originally the general term for condensed phosphates with the composition M _n [P _n O _3a ] (M = monovalent metal), but today is mostly limited to salts with ring-shaped cyclo (poly) phosphate anions. With n = 3, 4, 5, 6 etc. are referred to as tri-, tetra-, penta-, hexa-metaphosphates etc. etc. According to the systematic nomenclature of the isopolyanions, the anion with n = 3 is called cyclo-triphosphate.

Metaphosphates are obtained as accompanying substances of Graham's salt, which is falsely referred to as sodium hexametaphosphate, by melting NaH ₂ PO ₄ at temperatures above 620 ° C, with what is known as Maddrell's salt being formed as an intermediate. This and Kurrol's salt are linear polyphosphates, which today are usually not counted among the metaphosphates, but which can also be used with preference as water-softening substances in the context of the present invention.

The crystalline, water-insoluble Maddrell salt, (NaPO ₃ ) _x with x> 1000, which can be obtained at 200–300 ° C from NaH ₂ PO ₄ , goes into the cyclic metaphosphate [Na ₃ (PO ₃ ) ₃ ], which melts at 620 ° C. Depending on the reaction conditions, the quenched, glassy melt is the water-soluble Graham's salt, (NaPO ₃ ) _40-50 , or a glassy condensed phosphate of the composition (NaPO ₃ ) _15-20 , known as Calgon. The misleading name hexametaphosphate is still used for both products. The so-called Kurrol's salt, (NaPO ₃ ) _n with n »5000, also arises from the melt of the Maddrell salt, which is hot at 600 ° C, if it is left at 500 ° C for a short time. It forms highly polymeric water-soluble fibers.

Particularly preferred water-softening substances from the above classes of condensed phosphates, the "hexametaphosphates" Budit ^® H6 and H8 from. Budenheim have proven.

In summary especially contain according to the invention preferred portioned washing or Detergent compositions phosphate builders from the group the polyphosphates, preferably from the group of the tripolyphosphates, particularly preferably from the group of potassium tripolyphosphate and / or Sodium tripolyphosphate, the molar ratio of potassium tripolyphosphate to sodium tripolyphosphate, preferably above 10: 1, especially is preferably above 20: 1 and in particular above 40: 1.

Next the phosphates can the agents according to the invention still contain Citrate. Citrates are preferred sodium citrate and potassium citrate, but especially that Potassium citrate used. The weight percentage of the citrate, in particular of sodium and / or potassium citrate on the total weight of the agents according to the invention is preferably between 2 and 60% by weight, preferably between 4 and 50% by weight, particularly preferably between 6 and 40% by weight and in particular between 8 and 30% by weight.

Especially preferred agents according to the invention contain pentapotassium triphosphate in combination with sodium and / or Potassium citrate, especially pentapotassium triphosphate in combination with potassium citrate, being in a further preferred embodiment the weight ratio of the pentapotassium triphosphate contained in these agents to the also contain citrate, preferably the sodium and / or potassium citrate between 5: 1 and 1: 2, preferably between 4: 1 and 1: 1 and in particular between 3.5: 1 and 1.5: 1.

Independent of the nature of the anions used are within the scope of the previous Invention such portioned detergent or cleaning agent compositions particularly preferred in which the molar ratio of the potassium ions contained to the sodium ions contained above 1: 1, preferably above 10: 1, particularly preferably above 20: 1 and in particular above 40: 1 lies.

The agents according to the invention can in addition to the aforementioned components of the liquid phase and the phosphate builder contain further ingredients, in particular ingredients from the group of active washing or cleaning substances, preferably from the group of bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous Solvent, fabric softener, Protein hydrolyzate, as well as UV absorbers are preferred. Another preferred subject of the present application is therefore a portioned washing according to the invention or detergent composition, characterized in that the washing or detergent composition at least one active substance from the group of from the group of bleaching agents, bleach activators, Polymers, builders, Surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial Active substances, germicides, fungicides, antioxidants, corrosion inhibitors, Antistatic, phobing and impregnating agents, Swelling and sliding solid, non-aqueous solvents, fabric softener, protein hydrolyzate, and contains UV absorbers.

builders are in the compositions of the invention mainly used to bind calcium and magnesium. To the builders counting in the context of the present application in addition to those described above Phosphates in particular the zeolites, silicates, carbonates, and organic cobuilder.

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. 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 Preferred detergents and cleaning agents within the scope of the present invention 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 from 15 to 50% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the detergent or cleaning agent.

If the agents according to the invention are used as automatic dishwashing agents, these agents preferably contain at least one crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline layered silicates of the formula (I) are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, e.g. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyait), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, makatite).

Agents which contain crystalline phyllosilicates of the formula (I) in which x is 2 are particularly suitable for the purposes of the present invention. Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na2Si205). An overview of crystalline layered silicates can be found, for example, in the article published in "Seifen-Öle-Fette-Wwachs, 116 vol., No. 20/1990" on pages 805–808.

In the context of the present application, preferred automatic dishwashing agents or automatic dishwashing aids have a weight fraction of the crystalline layered silicate of the formula (I) from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0, 4 to 10 wt .-%, based in each case on the total weight of these agents. Particularly preferred are dishwasher detergents which have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight. -% and in particular below 2.5 wt .-%, with this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90 wt .-% is silicate of the general formula NaMSi _x O _{2x + 1} · yH ₂ O.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O can be described. The zeolite can be used 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.

Further builders are the alkali carriers. As an alkali carrier apply, for example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali silicates, alkali metasilicates, and mixtures of the aforementioned Substances, in the sense of this invention preferably the alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate used become.

Especially preferred detergents and cleaning agents contain carbonate (s) and / or Bicarbonate (s), preferably alkali carbonates, particularly preferred Sodium carbonate, in amounts of 2 to 50 wt .-%, preferably of 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the detergent or cleaning agent. Especially cleaning agents, in particular cleaning agents, are preferred for the machine dishwashing, which sodium carbonate and / or sodium hydrogen carbonate in quantities from 0.1 to 15% by weight, preferably from 0.2 to 12% by weight, is preferred from 0.4 to 10% by weight, particularly preferably from 0.8 to 8% by weight and in particular from 1.0 to 6% by weight, in each case based on the total weight contain the detergent or cleaning agent.

As organic cobuilders can in the washing machine according to the invention and cleaning agents, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

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

Also the acids can in itself be used. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

As Polymeric polycarboxylates are also suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. 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.

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

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

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

In particular 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 copolymers are those which are preferred as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are further preferred builder substances are polymeric aminodicarboxylic acids Salts or their precursors to call. Polyaspartic acids or their salts and.

Further Suitable builder substances are polyacetals, which are produced by implementation of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups can be obtained. 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.

Other suitable organic builder substances are dextrins, for example oligomers or poly mers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins 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 can be used.

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

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylene diamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-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.

Further Organic cobuilders that can be used are, for example, acetylated ones hydroxy or their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A phosphonates represent another class of substances with cobuilder properties It is particularly hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferred used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylene phosphonate (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 the Octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. 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.

Furthermore can all compounds capable of complexes with alkaline earth ions train as cobuilders.

In preferred embodiments In the present invention, the content of the compositions is water-soluble builders without consideration the phosphates in the range of 0.1 to 20 wt .-%, preferably from 0.2 to 16% by weight, preferably from 0.4 to 14% by weight, particularly preferably from 0.8 to 12% by weight and in particular from 1.0 to 10% by weight, each based on the total mean.

Next the builders can the agents according to the invention further contain surfactants, preferably nonionic surfactants.

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 radical is branched linearly or preferably in the 2-position methyl may 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. at Games for this are 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.

A another class of preferred nonionic surfactants used, the either as the sole nonionic surfactant or in combination used 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 nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid 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 (V),

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 Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1–4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

[Z] is preferably by reductive amination of a reduced sugar obtained, 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 transferred.

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. In particular, however, alcohol ethoxylates with linear residues from 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 Alcohol 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 particular agents according to the invention are preferred, which contain a nonionic surfactant that has a melting point above room temperature. Accordingly, preferred dishwashing detergents characterized in that they nonionic surfactant (s) 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 non-ionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic Surfactants that 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.

Prefers nonionic surfactants to be used as solid at room temperature originate from the groups of alkoxylated nonionic surfactants, especially ethoxylated ones primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

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 detergents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _16-20 monohydroxyalkanols or C _16-20 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 to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably 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 such non-ionic surfactants. Preferred dishwashing detergents are characterized in that that she 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 make up 15% by weight of the total molecular weight of the nonionic surfactant, contain.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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 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 (VI) R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], (VI) 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. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 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, particularly are 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. Machine dishwashing detergents according to the invention which contain surfactants of the general formula VII as nonionic surfactants are preferred here

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 VII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R 'in formula X above 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. Regardless 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 VII 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.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (VIII) R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (VIII) in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which is preferably between 1 and 5 have hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} 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 40.

In the case of particularly preferred nonionic surfactants of the above formula (XIII), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (IX) R ¹ O [CH ₂ CH ₂ O] _x R ² (IX) those nonionic surfactants are particularly preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end group-capped poly (oxyalkylated) nonionic surfactants which are of the formula (X) R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (X) in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 have up to 30 carbon atoms R ² , which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) -. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH obtained.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned Nonionic surfactants represent statistical mean values that are required for a specific Product can be an integer or a fractional number. by virtue of The manufacturing process consists of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, whereby both for the C chain lengths for as well the degrees of ethoxylation or degrees of alkoxylation mean values and resulting in fractional numbers.

Especially preferred washing machine according to the invention or cleaning agents contain at least one nonionic surfactant, preferably at least one end-capped poly (oxyalkylated) Nonionic surfactant, the weight fraction of the nonionic surfactant based on the total weight of the detergent or cleaning agent between 0.5 and 40% by weight, preferably between 1 and 30% by weight, particularly preferably between 2 and 25 and in particular between 2.5 and 23 wt .-%.

at the particularly preferred automatic dishwashing detergents can be regarding their weight fraction of nonionic surfactants two product groups differ. On the one hand there are the dishwashing detergents with a surfactant content below 6 wt .-%, which preferably nonionic surfactants in Amounts from 0.1 to 6 wt .-%, preferably from 0.2 to 5.8 wt .-%, particularly preferably from 0.4 to 5.6% by weight and in particular from 0.8 to 5.4 % By weight, based in each case on the total weight of the washing or cleaning agent. On the other hand, you can but also automatic dishwashing detergents with a high non-ionic surfactant content, which, based on their total weight, between 4.5 and 15% by weight, preferably between 5 and 14% by weight, particularly preferably between 5.5 and 13% by weight and in particular between 6 and 12% by weight, Particularly advantageous with regard to their rinse aid performance his.

In Compound with the surfactants mentioned can - especially in textile detergents - also anionic, cationic and / or amphoteric surfactants are used, wherein these because of their foaming behavior in automatic dishwashing detergents are of minor importance and mostly only in quantities below of 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, based in each case on the agent become. The agents according to the invention can thus also anionic, cationic and / or as a surfactant component contain amphoteric surfactants.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are 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 terminal or internal double bonds by sulfonating 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.

Further 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 especially the sodium salts of the sulfuric acid half esters of the C _12-18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _10-20 oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C _12-16 alkyl sulfates and C _12-15 alkyl sulfates and C _14-15 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 ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol 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). 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.

As other anionic surfactants are particularly suitable for 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 fatty acids, derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or Ammonium salts as well as soluble Salts of 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.

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 V, VI or VII 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.

Next the surfactants and builders can in particular bleaches, bleach activators, enzymes, silver protection agents, Dyes and fragrances, silver protection agents and glass corrosion protection agents preferred ingredients of washing or cleaning agents, in particular of automatic dishwashing detergents, his. Next to it further ingredients may be present, with machine according to the invention Dishwashing liquid are preferred that additionally one or more substances from the group of acidifying agents, Chelating agents or the washing or cleaning active polymers contain.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. 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-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxy-carboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyl acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleaching agent in the cleaning agents according to the invention for machine dishwashing Chlorine or bromine-releasing substances can also be used. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators, which support the effect of the bleaching agents have already been continued above as possible Ingredient of the rinse aid particles mentioned. Known bleach activators are compounds that have one or more Contain N or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or Oximes. Examples are tetraacetylethylene diamine TAED, tetraacetyl methylene diamine TAMD and tetraacetylhexylenediamine TAND, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As Bleach activators can 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 Carbon atom number and / or optionally substituted benzoyl groups. Are preferred multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol esters as well as acetylated sorbitol and mannitol respectively their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl. Hydrophilically substituted acyl acetate and acyl lactams are also preferred. Combinations of conventional ones Bleach activators can be used.

in der R¹ für -H, -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, -OH, -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 -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.Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula

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 _1-24 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.

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 = R⁵ = 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, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CN₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.A particularly preferred agent according to the invention is a cationic nitrile of the formula

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 also 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 applies 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, the cationic nitrile of the formula (CN ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , in which X ^{- stands} for an anion, which is selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate, is particularly preferred.

In addition to the conventional bleach activators or in their place can also so-called bleaching catalysts are incorporated into the rinse aid particles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also with Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable. Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight based on the total agent used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably 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 are used 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 composition, used. But in special cases more bleach activator can also be used.

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. Agents ^according to the invention 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 (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) 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 Proeerase ^® 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, and in the trade name Proleather ^® and Protease P ^® by the company 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. Further development products of this α-amylase are from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar ^® OxAm and from Daiwa Sei ko Inc., Tokyo, Japan, available as Keistase ^® . The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from 8 stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); are as well Fusion products of the molecules mentioned can be used.

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. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. 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, especially if they are for the treatment of textiles are intended, contain cellulases, Depending on the purpose, as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components are advantageously complement in terms of their various performance aspects. To count these performance aspects especially contributions for primary washing performance, for secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® , can also be used. Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Another suitable cellulase from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ^® . Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

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 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing or cleaning agents 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 which interact with the enzymes are additionally preferably added in order to increase the activity of the oxidoreductases in question (enhancers) or to reduce the redox potential between the oxidizing agents Enzymes and soiling to ensure the flow of electrons (mediators).

The in agents according to the invention the enzymes used are either originally from microorganisms, such as the genera Bacillus, Strepfomyces, 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.

The Purification of the enzymes in question is conveniently done per se 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 the enzymes are added in any form established in 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.

alternative can the enzymes for both the fixed as well for the liquid Dosage form are encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes as in enclosed in a solidified or in the core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer covered is. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or Dyes are applied.

such Capsules are made by methods known per se, for example by Shake or roll granulation or applied in fluid-bed processes. Are advantageous granules of this type, for example by applying polymeric film formers, low dust and storage stable due to the coating.

Farther Is it possible, to assemble two or more enzymes so that a single Granulate multiple enzyme activities having.

On 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. Become frequent Benzamidine hydrochloride, borax, boric acids, boronic acids or whose salts or esters are used, including mainly derivatives with aromatic groups, such as ortho, meta or para substituted phenylboronic, or their salts or esters. Furthermore, peptide aldehydes, this means Suitable oligopeptides with reduced C-terminus. As a peptide Protease inhibitors include ovomucoid and leupeptin mention; 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 group-capped fatty acid amide alkoxylates can also be used as stabilizers.

low aliphatic alcohols, but especially polyols, such as Glycerin, ethylene glycol, propylene glycol or sorbitol are further frequently Enzyme stabilizers used. Di-glycerol phosphate also protects against denaturation by physical influences. Calcium salts are also used used, such as calcium acetate or calcium formate as well as magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also according to the enzymati stabilize the components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

reducing agent and antioxidants such as sodium sulfite or reducing sugars increase that stability of the enzymes oxidative decay.

Prefers combinations of stabilizers are 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 can by the combination with boric acid and / or boric acid derivatives and polyols increased and according to the additional use of divalent cations, such as calcium ions reinforced become.

Especially In the context of the present invention, preference is given to using liquid enzyme formulations. Here are agents according to the invention preferred that in addition 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 all detergents or cleaning agents.

color and fragrances can the agents according to the invention be added to the aesthetic impression to improve the emerging products and consumer in addition the performance a visually and sensory "typical and distinctive" product available put. As perfume oils or Fragrances can individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds are of the ester type e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to aldehydes e.g. the linear alkanals with 8–18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together have an appealing fragrance produce. Such perfume oils can also natural Contain fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise 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 directly into the washing or cleaning agents can be incorporated, but it can also be advantageous be the fragrances on carriers to apply, which increase the adhesion of the perfume to the laundry and due to a slower fragrance release for a long-lasting fragrance Take care of textiles. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

Around 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 Difficulties have a 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 textiles, glass, Ceramic or plastic dishes so as not to stain them.

If the agents according to the invention are used as dishwashing agents, these cleaning agents can contain corrosion inhibitors as dispersed substances to protect the items to be washed or the machine, silver protection agents in particular being of particular importance in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. The following may be mentioned as examples of the 3-amino-5-alkyl-1,2,4-triazoles which are preferably to be used according to the invention: 5, -propyl, butyl, pentyl, heptyl, octyl, nonyl -, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2- furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3-amino-1,2,4-triazole. In dishwashing detergents, the alkylamino-1,2,4-triazoles or their physiologically tolerable salts are used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles and mixtures are very particularly effective of these substances.

you often finds active chlorine in cleaner formulations Means that can significantly reduce the corroding of the silver surface. In chlorine-free cleaners are especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are common Use. The transition metal salts which are selected are preferred here 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. Zinc compounds can also be used for prevention corrosion on the wash ware be used.

Instead of of or in addition to the silver protection agents described above, for example the Benzotriazoles in the dispersions according to the invention redox-active substances are used. These substances are preferably inorganic redox-active substances from the group the manganese, titanium, zirconium, hafnium, vanadium, cobalt and Contains cerium salts and / or complexes, the metals preferably are in one of the oxidation states II, III, IV, V or VI.

The Metal salts or metal complexes used should at least partially soluble in water his. The counterions suitable for salt formation include all the usual 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 For the purposes of the invention, compounds are those which have a central atom and one or more ligands and optionally additionally one or more of the above Anions exist. The central atom is one the above Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are monodentate or multidentate; 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, e.g. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition 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. Preferred dishwasher detergents 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, ie completely with a waterproof, but light at the cleaning temperatures soluble material coated to prevent their premature decomposition or oxidation during storage. Preferred coating materials which are applied by known processes, for example melt coating processes according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in a molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a spray zone of the molten coating material which is also continuously generated. The melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The mentioned metal salts and / or metal complexes are in the dispersions according to the invention, in particular automatic dishwashing detergents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5 wt .-%, based on the total weight of the dispersion contain.

On Another important criterion for assessing a machine 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 Leakage of alkali and alkaline earth ions from the glass in combination with hydrolysis of the silicate network, on the other hand in one Deposition of silicate compounds on the glass surface.

The problems mentioned with the agents according to the invention solved if in addition to the above-mentioned 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 more magnesium and / or zinc salts and / or magnesium and / or Zinc complexes.

A preferred class of compounds used to prevent glass corrosion the agents according to the invention can be added are insoluble Zinc salts. these can yourself during the dishwashing process on the glass surface accumulate and prevent metal ions from dissolving there from the glass network as well as the hydrolysis of the silicates. Prevent additionally these insoluble Zinc salts also the deposit of silicate on the glass surface, so that this 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 agents 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. The exact content of the agents in the zinc salt or zinc salts is naturally 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.

There the insoluble Zinc salts during of the dishes cleaning 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 of the insoluble zinc salts is below 1.7 mm, there is no fear of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 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 falling particles size. In the case of very poorly soluble zinc salts, the average particle size is preferably below 100 μm. For even more poorly soluble salts it can be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

A further preferred class of compounds are magnesium and / or Zinc salts) of at least one monomeric and / or polymeric organic Acid. These also cause with repeated use, the surfaces of the glassware do not change corrosively, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Even though 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).

Out 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-undecyladadecanoic acid, 2-undecyladadecanoic acid Tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid contains.

Out 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 (Azelaic acid), decanedioic (Sebacic acid), 2c-butenedioic (Maleic acid), 2t-butenedioic (Fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

Out 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 ( Trimesionsäure).

Out the group of sugar acids: galactonic, Manno acid, Fructonsäure, arabinonic, xylonic, ribonic, 2-deoxy-ribonic, Alginic acid.

Out the group of hydroxy acids: hydroxyphenylacetic (Mandelic acid), 2-hydroxypropanoic (Lactic acid), malic (Malic acid), 2,3-dihydroxybutanedioic 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).

Out the group of oxo acids: 2-oxopropionic (Pyruvic acid), 4-oxopentanoic acid (Levulinic acid).

Out 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 acrylate mid / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / 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 agents according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / 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 dishwasher detergent.

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. 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).

A other possible The chelating agents form a group of ingredients. Chelating agents are substances that are cyclic with metal ions Form connections, where a single ligand has more than one coordination site occupied at a central atom, 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 chelate complex images preferred within the scope of the present invention are for example polyoxycarboxylic acids, 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 from only one macromolecule originate 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, enthalten.In the context of the present invention, machine dishwashing detergents which are particularly preferred are one or more chelating 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 included.

• 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, Diethylentriaminpentaessig-säure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-gly-cin, 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 Aminogruppenhaltige 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-n-hydroxyethyl) 2-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 homologs with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

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

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

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

useful 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), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

As Builders or scale inhibitors are also polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. 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.

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

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

In particular 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. Other preferred copolymers are those that preferably contain acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.

As well are further preferred builder substances are polymeric aminodicarboxylic acids Salts or their precursors to call. Polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

Further Suitable builder substances are polyacetals, which are produced by implementation of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups can be obtained. 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.

Further Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of at least one alcohol function of the saccharide ring to form carbon to oxidize acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylene diamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-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.

Further Organic cobuilders that can be used are, for example, acetylated ones hydroxy or their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A phosphonates represent another class of substances with cobuilder properties It is particularly hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferred used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates come preferably 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 the Octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. 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.

The portioned according to the invention Means can about that copolymers of unsaturated carboxylic acids, sulfonic acid group-containing Monomers and optionally other ionic or nonionic Contain monomers. These copolymers cause the Such items treated dishes in subsequent cleaning operations clearly become cleaner than dishes that have been washed using conventional means. As an additional positive effect occurs a shortening the drying time of the dishes treated with the detergent on, i.e. the consumer can after the cleaning program the dishes earlier Take out of the machine and use again.

The Invention is characterized by an improved "cleanability" of the treated Substrates in later cleaning operations and by a significant shortening compared to the drying time comparable agents without the use of polymers containing sulfonic acid groups out. Drying time is within the framework of the teaching according to the invention in general the literal meaning understood, that is, the time that passes until one in a dishwasher treated dish surface has dried, but especially the time that passes until 90% one with a detergent or rinse aid in concentrated or diluted Form treated surface is dried.

Advantageous is that the mentioned polymers act in suitable amounts as a salt substitute. at the use of such means, the consumer must replenish the salt his dishwasher do not fill up and receives nonetheless streaked, stain-free and deposit-free dishes.

In the context of the present invention, unsaturated carboxylic acids of the formula VIII are preferred as the monomer, R ¹ (R ² ) C = C (R ³ ) COOH (VIII), 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 which can be described by formula I 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 IX R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IX), 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 IXa, IXb and / or IXc, H ₂ C = CH-X-SO ₃ H (IXa), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (IXb), HO ₃ SX- (R ⁶ ) C = C (R ') - X-SO ₃ H (IXc), in which R ⁶ and R ^{1 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 IXa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IXa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IXa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IXb), 3-meth-acrylamido-2-hydroxy-propanesulfonic acid (X = -C ( O) NH-CH ₂ CH (OH) CH ₂ - in formula IXb), allylsulfonic acid (X = CH ₂ in formula IXa), methallylsulfonic acid (X = CH ₂ in formula IXb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IXa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IXb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula IXb), styrene sulfonic acid (X = C ₆ H ₄ in formula IXa), vinyl sulfonic acid (X not present in formula IXa), 3-sulfopropylacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula IXa), 3-Su Isopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IXb), sulfomethacrylamide (X = -C (O) NH- in formula IXb), sulfomethyl methacrylamide (X = -C (O) NH- CH ₂ - in formula IXb) and water-soluble salts of the acids mentioned.

As other ionic or nonionic monomers come in particular ethylenically unsaturated compounds into consideration. 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).

• i) ungesättigten Carbonsäuren der Formel VIII. R¹(R²)C=C(R³)COOH (VIII),in der R¹ bis R³ unabhängig voneinander für -H-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel IX R⁵(R⁶)C=C(R⁷)-X-SO₃H (IX), in der R⁵ bis R⁷ unabhängig voneinander für -N-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

• i) unsaturated carboxylic acids of formula VIII. R ¹ (R ² ) C = C (R ³ ) COOH (VIII), 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,
• ii) Monomers of the formula IX containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IX), in which R ⁵ to R ⁷ 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 un saturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally available 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

particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IIa, IIb und/oder IXc: H₂C=CH-X-SO₃H (IXa), H₂C=C(CH₃)-X-SO₃H (IXb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (IXc),in der R⁶ und R¹ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CN₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

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 IIa, IIb and / or IXc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (IXa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IXb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IXc), in which R ⁶ and R ^{1 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 (CN ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The according to the invention in the Copolymers contained agents can the monomers from groups i) and ii) and, if appropriate, iii) contained in varying amounts, with all representatives from group i) with all Representatives from group ii) and all representatives from the Group iii) can be combined. Particularly preferred polymers have certain structural units which are described below.

For example, agents according to the invention which are characterized in that they contain one or more copolymers which have structural units of the formula X are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X), 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 ) - 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 a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula XI - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XI), 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 ) - 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. Agents according to the invention which contain one or more copolymers which have structural units of the formula XII - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII), contain, in which m and p each for an integer between 1 and 2000 as well as Y for, a space r 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 is -O- (CH ₂ ) - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, likewise a preferred embodiment of the present invention, just as agents are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula XIII - (CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIII), 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 ) - 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, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers which have structural units of the formula XIV - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] p- (XIV), 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 ) 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 and to agents which are characterized in that they contain one or more copolymers which have structural units of the formula XV - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] p- (XV), 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 ) - 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.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-S0 ₃ H] _p - (XI), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII), - (CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIII), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIV), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XV), contain, in which m and p each represent an integer between 1 and 2000 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, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding agents, which are characterized in that the sulfonic acid groups in the copolymer partially or fully neutralized are preferred according to the invention.

The Monomer distribution of the copolymers used in the agents according to the invention is at Copolymers containing only 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 of monomer from group ii), each based on the polymer.

at Terpolymers are particularly preferred those that 20 to 85 wt .-% Monomer from group i), 10 to 60% by weight monomer from the group ii) and 5 to 30% by weight of monomer from group iii).

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

preferred agents according to the invention, which are used as automatic dishwashing detergents can be used for Improving the rinse aid result as wash- or cleaning-active polymers further amphoteric or contain cationic polymers. These particularly preferred polymers are characterized in that they have at least one positive charge. Such polymers are preferably water soluble or water dispersible, that is, they exhibit in water 25 ° C one solubility above 10 mg / ml.

Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula R ¹ (R ² ) C = C (R ³ ) R ⁴ in which R ¹ to R ⁴ 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, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ , where R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X ^⎕ ), methacrylamidopropyl (trimethyl) ammonium ^salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) s X ^⎕ ).

Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers R ¹ (R ² ) C = C (R ³ ) COOH used, 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.

Especially preferred amphoteric polymers contain derivatives as monomer units of diallylamine, especially dimethyldiallylammonium salt and / or Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, Ethyl sulffasts, methyl sulfates, mesylates, tosylates, formates or Acetates in combination with monomer units from the group of the ethylenic unsaturated Carboxylic acids.

The Content of one or more of the washing or cleaning active Polymers in the agents according to the invention may vary depending on the application and the desired product performance.

Preferred according to the invention portioned detergent or cleaning agent composition characterized that the Detergent or cleaning agent composition at least one polymer, preferably a polymer from the group of homo- or copolymers carboxylic acids and / or the homo- or copolymeric polycarboxylic acids and / or the homo- or copolymeric sulfonic acids, in amounts from 0.001 to 70% by weight, preferably from 0.002 to 50 % By weight and in particular from 0.005 to 30% by weight, in each case based on the total weight of the detergent or cleaning agent composition, contains.

The Weight fraction of the described polymers containing sulfonic acid groups based on the total weight of preferred detergents or cleaning agents preferably between 0.1 and 70% by weight, preferably between 1 and 50% by weight, particularly preferably between 2 and 30% by weight and in particular between 3 and 20% by weight.

washing or cleaning-active polymers which have at least one positive Have charge, that is, cationic or amphoteric polymers are in the agents according to the invention, based on their total weight, preferably in amounts of 0.001 to 12 wt .-%, preferred from 0.002 to 10% by weight, particularly preferably from 0.005 to 8% by weight and in particular contain from 0.01 to 6% by weight.

The portioned according to the invention Detergent and cleaning agent compositions are water dispersible or more water soluble containers packed up. The corresponding packaging materials are from the Known in the art and originate, for example, from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, Gelatin and mixtures thereof.

Especially preferred portioned according to the invention Detergent or cleaning agent compositions are characterized in that that the water-soluble or water-dispersible containers one or more water-soluble Polymer (s), preferably one or more polymers from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, Polyethylene oxide, gelatin, cellulose, and their derivatives, preferably Hydroxypropylmethylcellulose, and mixtures thereof.

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

enthalten."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 have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively, so they still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized on the part of the manufacturer by specifying the degree of polymerization the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis 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. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

in the In the context of the present invention, it is preferred that the water-soluble or water-dispersible containers comprises a polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

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 that are particularly suitable as material for the container can be found in the table below:

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

The Water PVAL can be treated with aldehydes (acetalization) or ketones (ketalization) changed become. As particularly preferred and pronounced on the basis of it good solubility in cold water Polyvinyl alcohols have been found to be particularly advantageous, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof can be acetalized or ketalized. As extremely beneficial The reaction products made of PVAL and starch are to be used.

Farther let yourself the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impenetrable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide however water vapor will pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are produced by radical polymerization of 1-vinylpyrrolidone. commercial PVP have molar masses in the range from approx. 2,500 to 750,000 g / mol and are called white, hygroscopic powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molar mass: approx. 15,000 to> 250,000 g / mol), which is mainly due to Hydrolysis of collagen contained in animal skin and bones is obtained under acidic or alkaline conditions. 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 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. Gelatin is found in the form of foils because of their comparison only low for the above-mentioned high-cost polymers Use.

Prefers are also agents according to the invention within the scope of the present invention, the packaging of at least partially water-soluble film of at least a polymer from the group starch and Starch derivatives, Cellulose and cellulose derivatives, in particular methyl cellulose and Mixtures of this consists.

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 to 30% straight-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW approx. 300,000 to 2,000,000). There are also small amounts of lipids, phosphoric acid and Cations included. While the amylose due to the binding in the 1,4-position long, helical, intertwined Forms chains with about 300 to 1,200 glucose molecules the chain for amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch to make water soluble wrappings the detergent, detergent and detergent portions within the scope of the present invention also starch derivatives suitable, which can be obtained by polymer-analogous reactions from starch. 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. The starch derivatives group, for example Alkali strengths, carboxymethyl (CMS), starch ester and ether and amino starches.

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 approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. 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 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 falls under for example alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The water-soluble or water-dispersible container, which are the agents according to the invention can contain produced by any of the methods described in the prior art become.

In preferred embodiments In the present invention, these containers are Foil bags (so-called pouches) or around injection molding or Thermoformings.

Become according to the invention as packaging selected container formed in the form of foil bags, it is preferred that the water-soluble foil, which forms the bag, a thickness of 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 85 μm and in particular from 10 to 70 μm.

Become as water soluble or water-dispersible containers injection molding or deep drawing or blow-molded used, the wall of this preferred water-soluble or water-dispersible container preferably a wall thickness of 50 to 300 μm, preferably of 70 to 200 μm and in particular of 80 to 150 μm on.

On for the Production of water-soluble according to the invention or water-dispersible container Injection molding is a particularly suitable method. 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 closed Flows into the tool. The procedure is mainly for 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 Behälters aus einem wasserlöslichen oder wasserdispergierbaren Material,
• b) Befüllen des Basisformkörpers mit einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung umfassend eine flüssige Phase und Phosphatbuilder,
• c) Verschließen des befüllten Behälters mit einer wasserlöslichen oder wasserdispergierbaren Verschlußeinheit,

dadurch gekennzeichnet, die flüssige Phase ein oder mehrere nichttensidische, wasserlösliche, flüssige Bindemittel enthält.The subject of the present application is therefore also a method for producing a filled water-soluble container comprising the steps:

• a) injection molding a container from a water-soluble or water-dispersible material,
• b) filling the base molding with a liquid detergent or cleaning composition comprising a liquid phase and phosphate builder,
• c) closing the filled container with a water-soluble or water-dispersible closure unit,

characterized in that the liquid phase contains one or more non-surfactant, water-soluble, liquid binders.

at the water-soluble or water-dispersible closure unit, which in step c) for closing of the filled container is used, it is preferably an injection molded body, wherein this body preferably has the same spatial shape as the base molding. Is preferred in the context of the present invention consequently in particular a method in which the closure unit has the same spatial shape as that produced in step a) Container.

In a further preferred embodiment of the described method according to the invention as a locking unit a film is used, this film, for example, by Thermoforming process can be processed shaping. Another preferred subject of the present application is accordingly a The aforementioned method, characterized in that it is in the water-soluble introduced in step c) shutter unit to be a water soluble or water-dispersible film.

It follows from the previous information that the thickness of the water-soluble outer wall of containers according to the invention is not necessarily homogeneous, but can vary depending on the manufacturing process chosen. In the context of the present application, it is preferred that this Fluctuations are within the above-mentioned preferred ranges for the wall thickness of containers according to the invention.

Also the closing of basic molded body and locking unit can be done in different ways. Preferred within the present invention will use closure methods which are based on partial Solvation of the surface of the container and / or the locking unit and / or on heating the container and / or the closure unit to a temperature at which they are plastically deformable, based. Both partial solvation and warming will preferably not on the entire surface of the container and / or the entire surface surface the locking unit take place, but only in the areas in which the following Sealing should take place with the formation of a sealed seam. The warming the surface of the container and / or the closure unit is preferably done through the use of hot air, hot plates, heated Rolling or heat radiation, preferably laser radiation or other IR sources such as glass fiber (optical fiber). Preferred subject of the present application is therefore a previously described method in which the sealing in step c) is carried out by means of fusion bonding.

Next the injection molding process described is the rotary die process for manufacturing in a special way water-soluble according to the invention or water-dispersible container suitable, with the term of the rotary die process in the context the present application also process variants such as the Accogel process, the Reciprocating-Die process using a Norton encapsulation machine, the Colton as well as that Upjohn procedure summarized. The concept of the rotary die process is therefore not restrictive understand, but embraces all process variants known to the person skilled in the art, which are used of form rollers are suitable for the production of filled containers.

• a) Zuführen zweier unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbarer wasserlösllicher oder wasserdispergbierbar Folien auf zwei sich gegensinnig drehende Formwalzen, wobei mindestens eine dieser Formwalzen in ihrer Oberfläche Vertiefungen zur Aufnahme des herzustellenden Behälters aufweist, welche durch Stege begrenzt sind,
• b) Auftragen eines Lösungsmittels auf mindestens eine dieser Folien unter mindestens anteilsweiser Solvatisierung der Oberfläche dieser Folie und/oder Erwärmen mindestens einer dieser Folien auf eine Temperatur bei welcher diese Folie plastisch deformierbar ist,
• c) optionales Tiefziehen und/oder Eindrücken und/oder Einsinken lassen mindestens einer dieser Folien in die Vertiefungen der Formwalze,
• d) Befüllen des Basisformkörpers mit einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung umfassend eine flüssige Phase und Phosphatbuilder,
• d) optionales Auftragen eines Klebemittels,
• e) Zusammenführen der zwei unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbarer wasserlösllicher Folien im Zwischenraum der zwei sich gegensinnig drehenden Formwalzen,
• e) Verkleben und/oder Abquetschen der Folien durch Krafteinwirkung der Stege auf die Folien unter Heraustrennung des Behälters,

dadurch gekennzeichnet, die flüssige Phase ein oder mehrere nichttensidische, wasserlösliche, flüssige Bindemittel enthält.In the context of the present application, however, an automatic rotary die process using two rotating shaping rollers is particularly preferred, comprising the steps:

• a) supplying two plastically deformable, water-soluble or water-dispersible foils which are plastically deformable under the influence of solvent and / or temperature, onto two mold rolls rotating in opposite directions, at least one of these mold rolls having depressions in their surface for receiving the container to be produced, which are delimited by webs,
• b) applying a solvent to at least one of these films with at least partial solvation of the surface of this film and / or heating at least one of these films to a temperature at which this film is plastically deformable,
• c) optional deep drawing and / or pressing in and / or sinking in at least one of these foils into the depressions of the forming roll,
• d) filling the base molding with a liquid detergent or cleaning agent composition comprising a liquid phase and phosphate builder,
• d) optional application of an adhesive,
• e) bringing together the two water-soluble foils which are plastically deformable under the influence of solvent and / or temperature in the space between the two shaping rollers which rotate in opposite directions,
• e) the foils are glued and / or squeezed off by the force of the webs on the foils while the container is removed,

characterized in that the liquid phase contains one or more non-surfactant, water-soluble, liquid binders.

at the implementation This method should be noted that the temperatures for plastic deformation in step b) and the heat seal clearly differentiate can. The general rule is that the temperature selected in steps b) and c) below that for The fusion bonding described above as part of the injection molding process necessary temperatures. For example, HPMC films used, is the temperature for the plastic deformation preferably 85 to 90 ° C, while the fusion bonding in the temperature range from 150 to 170 ° C. For PVA films, the temperatures are for plastic Deformation at about 150 ° C, while the fusion bonding takes place in the range from 160 to 200 ° C. As in the aforementioned make can the warming of the container materials by hot air, thermal radiation or direct contact with suitable heating plates or heated ones Rolling done.

• a) Zuführen einer unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbaren wasserlösllichen oder wasserdispergierbaren Folie auf eine Matrize, welche Vertiefungen zur Aufnahme des herzustellenden Behälters aufweist,
• b) Auftragen eines Lösungsmittels auf diese Folie unter mindestens anteilsweiser Solvatisierung der Oberfläche dieser Folie und/oder Erwärmen dieser Folie bis zu einer Temperatur, bei welche diese plastisch deformierbar ist,
• c) Tiefziehen und/oder Eindrücken und/oder Einsinken lassen dieser Folie in die Vertiefungen der Matrize,
• d) Beaufschlagen der Folie mit einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung, umfassend eine flüssige Matrix und darin dispergierte Feststoffteilchen,
• e) Zuführen einer weiteren wasserlöslichen oder wasserdispergierbaren Folie und Verschließen der tiefgezogenen Form mit dieser Folie,

dadurch gekennzeichnet, die flüssige Phase ein oder mehrere nichttensidische, wasserlösliche, flüssige Bindemittel enthält.Another process suitable for the production of water-soluble or water-dispersible containers is the so-called deep-drawing process, in particular the thermoforming process, the heating used in typical thermoforming processes optionally supplementing / replacing the at least partial solvation of these films in the context of the present application become can. The present application therefore also relates to a method for producing a water-soluble container, comprising the steps:

• a) supplying a water-soluble or water-dispersible film which is plastically deformable under the influence of solvent and / or temperature, to a die which has depressions for receiving the container to be produced,
• b) applying a solvent to this film while at least partially solvating the surface of this film and / or heating this film to a temperature at which it is plastically deformable,
• c) deep drawing and / or indenting and / or sinking this film into the recesses of the die,
• d) applying a liquid detergent or cleaning agent composition to the film, comprising a liquid matrix and solid particles dispersed therein,
• e) supplying a further water-soluble or water-dispersible film and sealing the deep-drawn mold with this film,

characterized in that the liquid phase contains one or more non-surfactant, water-soluble, liquid binders.

During that Let it sink in or impress the plastically deformable film in step c) of the claimed Appropriate procedures for the deformation of these foils represent, is nevertheless within the scope of the present application A particularly preferred method in which the film in step c) under the action of a vacuum on the plastically deformable film is deep-drawn, which is preferably until after the completion of the process remains in step e) and the film is retained in the recess.

The close of a container according to the invention in Step e) of the aforementioned deep-drawing process, as in the rest described methods by gluing or melt gluing take place, both methods optionally in combination with one additional Pressure can. Depending on the composition, suitable adhesives are suitable the films, in addition to the adhesives known to the person skilled in the art, also solvents, such as water. The application of the adhesive to the Foil is made in a preferred process variant of the latter Method preferably after step b) and / or step c) and / or Step d).

The However, sealing can also be done by fusion sealing or pressure respectively. In order to avoid repetitions, be with regard to the sealing at this point on the detailed descriptions as part of the injection molding and rotary die processes directed. In a preferred process variant of the thermoforming process accordingly, the closure takes place in step e) by temperature and / or due to pressure.

In a particularly preferred embodiment points the water-soluble container one or more embossings) and / or one or more imprints). They can also in the container enclosed solids have such embossments or imprints. The embossing or de print can include patterns, shapes, etc. in addition to lettering. That way you can for example universal detergent with a T-shirt symbol, color detergent with a wool symbol, detergent for machine dishwashing Symbols like glasses, Plates, pots, Pans etc. to be identified. The creativity of product managers there are no limits. For example, are suitable as lettering still the name of the product or the manufacturer.

This water-soluble Slides can can be manufactured according to different manufacturing processes. Here are to name principally blowing, calendering and casting processes. At a preferred processes, the films are based on a Melt with air over blown a blow mandrel into a tube. In the calendering process, which is also one of the preferred manufacturing processes used through suitable additives plasticized raw materials atomized to form the foils. Here it may be necessary, in particular, to inject a Connect drying. In the casting process, which is also one of the preferred manufacturing processes an aqueous polymer preparation placed on a heatable drying roller, after evaporation of the Water is optionally cooled and peeled off the film as a film. If necessary, this film before or during of peeling additionally powdered.

However, the casing materials of the water-soluble or water-dispersible container can also be cast into hollow molds. The hollow form of the resulting water-soluble or water-dispersible portioned agents preferred according to the invention comprises at least one solidified melt. This Melt can be a melted pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts which are then combined. Melting from mixtures of substances can be of advantage, for example, when eutectic mixtures are formed which melt significantly lower and thus lower the process costs.

preferred portioned according to the invention Means are characterized in that the hollow shape consists of at least consists of a material or mixture of materials whose melting point in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C. and in particular from 50 to 160 ° C.

Preferably the material of the melt exhibits high water solubility on, for example, above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. is particularly preferred are.

Such Substances come from a wide variety of substance groups. As part of Such melts have been found in particular in the present invention as material for the hollow form has been found to be suitable, consisting of the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic Hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols Sodium acetate trihydrate and / or urea. Here are portioned according to the invention Means particularly preferred in which the material of the hollow mold one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic Hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols Sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 80 wt .-%, based in each case on the weight of the hollow mold.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials for the production of the open hollow form. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as material for the open hollow form. Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, linadic acid, 9tecadienoic acid, 9tecadienoic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) It is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _C18 ', 1 wt .-% C _18' '), Palrnkernölfettsäure (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _C18 ', 1 wt .-% C _18' '), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C ₁₆ ', 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C ₁₈ ', 3 wt% C ₁₈ '', 1 wt% C ₁₈ '''), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C ₁₈ '), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6 wt% C ₁₆ ', 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C ₁₈ ', 10 wt% C ₁₈ ', 0.5 wt% % C ₁₈ '''), technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt. % C ₁₈ , 1% by weight C ₁₈ ') and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight of C ₁₆ , 5% by weight of C ₁₈ , 25% by weight of C ₁₈ ', 45% by weight of C ₁₈ '', 7% by weight of C ₁₈ ''').

The the aforementioned carboxylic acids are technically mostly from native fats and oils Hydrolysis won. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps) is now used on an industrial scale only water is used for cleavage, which the fats in glycerol and the free fatty acids splits. Industrially processes used are, for example, cleavage in the autoclave or continuous high pressure fission. Also the alkali metal salt of the above carboxylic acids or carboxylic acid mixtures can - if necessary in a mixture with other materials - for the production of the open Use hollow form. Salicylic acid and / or, for example, can also be used acetylsalicylic acid or their salts, preferably their alkali metal salts.

Other suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ .

Particularly suitable further melt materials can be found in the table below:

As can be seen in the table, sugars are also suitable materials for the melt. Also preferred are agents which are characterized in that the material of the hollow form contains one or more substances from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of oligosaccharides, Oligosaccharide derivatives, monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or Isomalt ^® .

As Particularly suitable materials for the melt have been found in the Within the scope of the present invention the sugar, sugar acids and Sugar alcohols proven. These substances are generally not only sufficiently soluble but are also characterized by low costs and good processability out. This is how sugar and sugar derivatives, especially those Mono- and disaccharides and their derivatives, for example in the form process their melts, these melts having good solvent power both for dyes as also for have many washing and cleaning-active substances. From solidification resulting from the solidification of the sugar melts is also characterized by a smooth surface and an advantageous look, like high surface brilliance or transparent appearance.

The group of preferred as the material for the melt in the context of the present application include sugar from the group of mono- and disaccharides, and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin, and isomalt, and mixtures ^® of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides. Mixtures of Isomalt ^® and glucose, Isomalt ^® and lactose, Isomalt ^® and fructose, Isomalt ^® and ribose, Isomalt ^® and maltose, glucose and sucrose, Isomalt ^® and maltodextrin or Isomalt ^® and sucrose are particularly preferred as materials for the melt. The weight fraction of ^{Isomalt® in} the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

Farther as material for the melt is particularly preferably mixtures of maltodextrin and glucose, maltodextrin and lactose, maltodextrin and fructose, Maltodextrin and ribose, maltodextrin and maltose or maltodextrin and sucrose. The weight fraction of maltodextrin in the total weight of the aforementioned mixtures preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

As Maltodextrin are used in the context of the present application by enzymatic Breakdown of starch won water soluble Carbohydrates (dextrose equivalents, DE 3-20) with a chain length from 5-10 Anhydroglucose units and a high proportion of maltose. Maltodextrin are used to improve rheological foods u. added caloric properties, taste little sweet u. tend not for retrogradation. Commercial products, for example the company Cerestar are usually spray-dried as free-flowing powders offered and have a water content of 3 to 5 wt .-%.

As isomalt ^® in the context of the present application, a mixture of 6-0-⎕-D-glucopyranosyl-D-sorbitol (1,6-GPS) and 1-0-⎕-D-glucopyranosyl-D-mannitol (1,1 -GPM). In a preferred embodiment, the weight proportion of the 1,6-GPS in the total weight of the mixture is less than 57% by weight. Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid.

object The present invention is in a further preferred embodiment a detergent or cleaning agent in the form of a liquid detergent according to the invention or detergent composition, which at least partially is comprised of a hollow mold from at least one solidified melt. Those hollow shapes which have at least one are particularly preferred another solid comprise, the at least one further solid body at least partly cast into the wall of the hollow mold.

in the In the context of the present invention, the term “hollow shape” denotes at least one enclosing a room Form, whereby the enclosed space can be filled or can be. In addition to the at least one enclosed space, the hollow shape further enclosed spaces and / or not completely enclosed spaces exhibit. The hollow shape must be in Within the scope of the present invention not from a uniform Wall material exist, but can also be several different Materials.

The Inclusion at least of a solid in the wall of the hollow mold is possible, for example, by using a hollow shell is produced from a solidified melt, which at least a solid at least partially encloses. This hollow shell can then filled and - for example by a differently composed melt - be closed. The the two solidified melts together form the hollow form of the preferred ones according to the invention Agent.

Analogous can be at least one solid are also at least partially incorporated into the melt, which closes the hollow shell from solidified melt. In turn form the hollow shell from solidified melt and the solidified Melt that forms the "lid" together the hollow form of the agent according to the invention. In this embodiment can the hollow shell at least partially a solid enclose (then contains the hollow form at least two solids), but it can also be completely free of a solid be because of the sealing melt at least partially enclosed solid bodies is at least according to the invention partly cast into the wall of the hollow mold.

The preferred according to the invention portioned agents comprise a hollow form. For example be a hollow shell which is used to hold the dispersion according to the invention is suitable and can be closed if necessary. It is but also possible (see above) to produce a hollow shell without inclusion of solid and at least one solid into a cavity that closes the mold at least partially embed the solidifying melt. In the Wall of this hollow form is at least one other solid at least partially cast in. "Solid" means in Within the scope of the present invention that the body or bodies at the melting temperature of the melt itself does not melt and also do not dissolve in the melt. When processing into the portioned compositions according to the invention therefore before cooling the melt as a flowable mass as well as solids. Place after cooling the melt the solids are still discrete areas of the cavity wall, the entire cavity but is naturally firm.

in the Preferred portioned washing detergents within the scope of the present application or detergent composition are characterized that the water-soluble or water-dispersible containers is a casting.

Preferred according to the invention is an embodiment according to the container as a whole water soluble is, d. H. if used as intended when washing or machine cleaning, completely dissolves when the for the loosening provided conditions are met. Major advantage of this embodiment is that itself the container within a practically relevant short time - as a non-limiting example can be a few seconds to 5 minutes - under precisely defined conditions solve at least partially in the cleaning liquor and thus accordingly the requirements the enveloped Content, d. H. the cleaning active material or several materials, into the fleet.

In another, also preferred due to advantageous properties embodiment of the invention the water soluble container less water-soluble or not water-soluble or only at a higher temperature water-soluble Areas and well water soluble or areas soluble in water at low temperature. With others Words: the container does not consist of a uniform water solubility in all areas showing material, but from materials of different Water solubility. Areas of good water solubility must be distinguished on the one hand from areas with less good water solubility, with poor or lack of water solubility or from areas where water solubility is only at a higher temperature or only at a different pH value or only at a changed one Electrolyte concentration the desired Value reached, on the other hand. This can lead to improper use under adjustable conditions release certain areas of the container while others Areas remain intact. This creates a pore or hole Container, penetrate into the water and / or liquor, wash-active, rinse-active or detach active ingredients and discharge them from the container can. In the same way you can also systems in the form of multi-chamber containers or in the form of one another arranged containers ("Onion system") can be provided. Systems with controlled release of the washing-active, dishwashing- or cleaning active ingredients.

to The invention is not subject to any restrictions on the formation of such systems. So can container be provided in which a single polymer material small Areas of incorporated compounds (e.g. salts) comprises the more water soluble are as the polymer material. On the other hand, several polymer materials with different ones can also be used Water be mixed (polymer blend), so that the faster soluble polymer material under defined conditions by water or the fleet faster is disintegrated than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the container are areas made of a material which chemically essentially corresponds to that of the corresponds to water-soluble areas or to water-soluble areas at a lower temperature, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the containers do not completely detach, portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties when releasing the detergent or cleaning agent composition into the respective liquor.

The water-soluble container material is preferably transparent. Under transparency is in the sense of this Invention to understand that the permeability within the visible spectrum of light (410 to 800 nm) larger than 20%, preferably greater than 30%, extremely preferred larger than 40% and especially larger than Is 50%. As soon as a wavelength of the visible spectrum of light is greater than 20%, it is to be regarded as transparent in the sense of the invention.

Portioned according to the invention Detergent or cleaning agent compositions that are in transparent containers can be packed contain a stabilizing agent as an essential component. Stabilizing agents in the sense of the invention are materials that the detergent components in their water-soluble, transparent containers Protect against decomposition or deactivation by light. As special Antioxidants, UV absorbers and fluorescent dyes are suitable here proved.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3 '' thiodipropionic acid with C _1-18 alkanols, in particular C _1-18 alkanols, metal ion deactivators which are capable of metal ions, such as copper, which catalyze the autooxidation to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also phenyl-substituted acrylates in the 3-position ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene noncamphene and its derivatives, for example 3- (4-methylbenzylidene) camphor, are to be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2-ethylhexyl ester; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones, such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) pro pan-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can in the detergent or cleaning agent compositions in amounts up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 up to 2.0 and in particular from 0.03 to 1% by weight.

A further preferred class of stabilizers are the fluorescent dyes. These include the 4.4 '' diamino-2.2 '' stilbene disulfonic acids (flavonic acids), 4.4 '' distyryl biphenyls, methyl umbelliferones, Coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, Benzoxazole, Benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives. The sulfonic acid salts are of particular importance of the diaminostilbene derivatives, as well as polymeric fluorescent substances.

fluorescent substances can in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1 wt .-% be included.

In a preferred embodiment the aforementioned stabilizers in any mixtures used. The stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20 % By weight, in particular from 0.02 to 5% by weight.

As already mentioned further above, portioned detergent or cleaning agent compositions according to the invention can be provided in such a way that the packaging is water-soluble on the one hand and tightly closing on the other hand, ie sealed off from the environment. Two embodiments can be implemented according to the invention:
Thus, it corresponds to a preferred embodiment of the invention that the container (s) is / are and contain at least one gas which does not react with the detergent or cleaning agent composition, more preferably in an amount that the total pressure within the or the closed container) is above the external pressure, more preferably is at least 1 mbar above the external pressure. Very particularly preferred embodiments of these portions according to the invention contain at least one gas which does not react with the detergent or cleaning agent composition in such an amount that the total pressure inside the closed containers is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably in Range from 90 mbar to 50 mbar above the external pressure. Particularly in the case of the preferred embodiments with a total pressure inside the container which is significantly above the external pressure, the visual appearance, in particular of film bags, can be significantly improved. The correspondingly packaged compositions have an increased inherent stability and give the impression of a bulging, “powerful” agent. In connection with the present invention, “external pressure” is understood to mean the pressure that prevails on the surrounding side of the containers and on the exterior of the containers works, namely for Time of filling the container with the respective at least one gas.

According to the invention, the containers can contain either one or more gases. In practice, it is preferred to apply a gas to the containers due to the associated lower costs. Preferred detergent or cleaning agent portions according to the invention comprise as gases) at least one gas which is selected from the group N ₂ , noble gas (s), CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons, especially N ₂ , which is cheaply available everywhere. The gases mentioned are advantageously inert to the components of the wash-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention.

According to one another, likewise preferred embodiment is / are container completed and contain at least one substance that reacts with water, one that does not react with the wash-active preparations) Gas releases in an amount that the total pressure is within the closed container increases. Portions in which are particularly advantageous the contained in the container (s) at least one substance when reacting with water at least releases a gas in an amount that the total pressure is within the closed container by at least 1 mbar the external pressure increases, preferably by at least 5 mbar, particularly preferably by a value in the range of 5 to 50 mbar higher than the external pressure. This embodiment is particularly advantageous in that its manufacture over that embodiment, in which the gas is contained in the closed container, greatly simplified is because only the at least one substance has to be added, which at At least contact with moisture / water in the closed container generates a gas. Any moisture that has penetrated into the container continues immediately absorbed by the substance capable of reacting with water and implemented and therefore stands for a deterioration in quality the components of the detergent or cleaning agent composition no longer available. Mixed forms of portions are also conceivable, from the beginning There is at least one gas in the container and one with Water enabled reaction Substance is included.

According to one preferred embodiment In the invention, the substance which releases a gas with water is a component the detergent or cleaning agent composition and is - even more preferred - one hygroscopic substance with the components of washing or Detergent composition is compatible. Preferably such a substance separately from the liquid laundry detergent according to the invention or detergent composition in the water-soluble or water-dispersible containers, being this container preferably within a few seconds, especially within 10 seconds after the contact of the gas-releasing substance with the Detergent composition is sealed. The release of the gas increased then the internal pressure inside the container to a value above of atmospheric pressure and thus achieves the advantages mentioned above.

Examples of such substances are, without being to be understood as limiting, substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} an alkali metal (particularly preferably Li or Na) (for example LiAlH ₄ , NaBH ₄ , NaAlH ₄ ) and M _{B is} B or Al, or M ^I ₂ C ₂ or M ^II C ₂ , where M ^{I is} a monovalent metal and M ^{II is} a divalent metal (for example CaC ₂ ).

The agents according to the invention are in water soluble or water-dispersible containers packed up. However, the use of such containers excludes the packaging water-containing compositions basically not. compositions with a water content below 6 wt .-% grab water-dispersible or water soluble Packaging materials such as polyvinyl alcohol films (PVA films) generally not. In a preferred embodiment, the portions according to the invention are portioned Detergent or cleaning agent compositions characterized in that the liquid Phase is low in water and has a water content of between 0.1 and 6% by weight, preferably between 0.5 and 5% by weight and particularly preferably between 1 and 4% by weight, each based on the total weight of the washing or detergent composition.

Despite the use of water-soluble or water-dispersible container materials, there are also possibilities for the packaging of water-containing compositions with water contents above 6% by weight to prevent the unwanted dissolution of the packaging-forming substances by the agents contained. This is how the European patent describes EP 518 689 B1 (Rhone-Poulenc Agrochimie) the addition of organic or inorganic salts to water-containing compositions, which in a Increasing the electrolyte concentration and reducing the water solubility of the packaging materials, such as polyethylene oxide, methyl cellulose or polyvinyl alcohol results. The coating of water-soluble films with water-insoluble films (laminate films) or particles made of PVdC (polyvinylidene dichloride) or PTFE (polytetrafluoroethylene) are also described in the prior art. Of the aforementioned methods for reducing solubility, the increase in the electrolyte concentration has proven to be particularly advantageous in the context of the present invention. This method enables preferred detergent or cleaning agent compositions contained in the containers to have a water content above 6% by weight without dissolving the water-soluble or water-dispersible container surrounding them. In a further preferred embodiment of the present invention, the portioned detergent or cleaning agent composition contains water and has a water content above 6% by weight, preferably between 10 to 70% by weight, particularly preferably between 20 and 60% by weight and in particular between 30 and 50 wt .-%, each based on the total weight of the liquid detergent or cleaning composition.

such contain water-containing detergent or cleaning agent compositions in the liquid matrix dissolved Salts, the proportion by weight of these salts in the total weight of the Detergent or cleaning composition preferably at least 5% by weight, particularly preferably at least 7% by weight and in particular is at least 12% by weight.

How previously executed are the agents of the invention in water soluble or water-dispersible packaging. This packaging can have one, two, three, four or more receiving chambers. As Ingredients for the receiving chambers are suitable in addition to the washing or cleaning agents also other liquids and solids such as Powders, granules, extrudates, compactates, castings or dimensionally stable gels. As liquids are in addition to low-viscosity, flowable liquids or flowable gels or flowable dispersions, For example, emulsions or suspensions can be used. Considered flowable Active substances or combinations of active substances if they have no inherent dimensional stability, which enables them under usual Conditions of manufacture, storage, transportation and Handling by the consumer a non-disintegrating spatial form to take, this spatial form under the conditions mentioned also about longer Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, unchanged, this means under the usual conditions the manufacture, storage, transport and handling by the consumer in the spatial-geometric due to the production Form persists, that is, does not melt. The determination of fluidity refers in particular to those customary for storage and transportation Conditions, in particular at temperatures below 50 ° C., are preferred below 40 ° C. As liquids therefore, in particular, active ingredients or combinations of active ingredients apply with a melting point below 25 ° C, preferably below 20 ° C, particularly preferably below 15 ° C.

For the combination the above-mentioned forms of solid and liquid detergents or cleaning agents with the agents according to the invention there are now a number of options. The following tables show some preferred embodiments described. The one with liquid, Fill powder or granules Receiving chambers preferably have a seal. For those with compactates, extrudates, castings or dimensionally stable gels filled Sealing chambers are optional, but are preferred.

Water-soluble or water-dispersible packaging with two receiving chambers:

Water-soluble or water-dispersible packaging with three receiving chambers:

I. By stirring various washing or cleaning-active substances into a 50% aqueous pentapotassium triphosphate solution, two aqueous cleaning agents according to the invention of the composition E1, E2, which contain glycerol as a binder, and a comparative formulation V1, which contains no binder, were prepared: Table 1 : Composition of cleaning agents E1, E2 and V1 [parts by weight]:

II. For the storage test, the cleaning agents obtained were filled into PVA tubular bags. PVA films from ChrisCraft (film thickness 76 μm) were used as packaging material. The amount of detergent weighed was 20 g each. The resulting packaged detergents were weighed and exposed to different storage conditions. After four weeks, the weight loss of the packaged agents was determined. The result of this storage test is shown in Table 2: Table 2: Weight loss of cleaning agents E1, E2 and V1 [% by weight]:

The Table 2 shows that the Binder-containing agents E1 and E2 according to the invention after four Weeks of storage show a significantly lower weight loss, than the comparison recipe V1.

Claims (18)

Portioned liquid, aqueous detergent or cleaning agent composition in a water-soluble or water-dispersible container, comprising a liquid phase and phosphate and / or citrate builder, characterized in that the liquid phase contains one or more non-surfactant, water-soluble, liquid binders. Portioned detergent or cleaning agent composition according to claim 1, characterized in that the content of the liquid phase on the non-surfactant, water-soluble, liquid binder (s) 0.1 to 50% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 is up to 40 wt .-% and in particular 2 to 35 wt .-%. Portioned detergent or cleaning agent composition according to one of the claims 1 or 2, characterized in that at least one non-surfactant, water-soluble, liquid Binder selected is from the group polyethylene glycol, polypropylene glycol, glycerin, Glycerine carbonate, ethylene glycol, propylene glycol and propylene carbonate. Portioned detergent or cleaning agent composition according to one of the claims 1 to 3, characterized in that the liquid phase contains water and a water content above 6% by weight, preferably between 10 up to 70% by weight, particularly preferably between 20 and 60% by weight and in particular between 30 and 50 wt .-%, each based on the Total weight of liquid Detergent or cleaning composition. Portioned detergent or cleaning agent composition according to one of the claims 1 to 3, characterized in that the liquid phase is low in water and a water content between 0.1 and 6% by weight, preferably between 0.5 and 5% by weight, particularly preferably between 1 and 4% by weight, in each case based on the total weight of the detergent or cleaning agent composition, having. Portioned detergent or cleaning agent composition according to one of the claims 1 to 5, characterized in that the liquid phase has 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. Portioned detergent or cleaning agent composition according to one of claims 1 to 6, characterized in that the liquid phase at 20 ° C has a density between 1.040 and 1.70 g / cm ³ , preferably between 1.080 and 1.65 g / cm ³ , particularly preferably between 1.12 and 1.60 g / cm ³ and in particular between 1.24 and 1.55 g / cm ³ . Portioned detergent or cleaning agent composition according to one of claims 1 to 7, characterized in that the liquid phase 0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-%, particularly preferably 0.05 to 3 wt. -% and in particular 0.1 to 1.5 wt .-%, of a thickener, preferably a polymeric thickener, with the thickener being hydroxyethyl cellulose and / or hydroxypropyl cellulose and / or thickener from the group of the polysaccharides, preferably xanthan, the polyurethane or the modified polyacrylates with particular preference for thickeners of the formula XVII

in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number, are preferred. Portioned detergent or cleaning agent composition according to one of the claims 1 to 8, characterized in that the phosphate builder is selected from the group of polyphosphates, preferably from the group of tripolyphosphates, particularly preferably from the group of potassium tripolyphosphate and / or sodium tripolyphosphate, being the molar ratio from potassium tripolyphosphate to sodium tripolyphosphate preferably above 10: 1, particularly preferably above 20: 1 and in particular is above 40: 1. Portioned detergent or cleaning agent composition according to one of the claims 1 to 9, characterized in that the molar ratio of contained potassium ions to the sodium ions contained above 1: 1, preferably above 10: 1, particularly preferably above 20: 1 and in particular above 40: 1 lies. 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 active substance from the group or from the group bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, Swelling and sliding solid, non-aqueous solvents, fabric softener, protein hydrolyzate, and contains UV absorbers. Portioned detergent or cleaning agent composition according to one of the claims 1 to 11, characterized in that the detergent or cleaning composition at least one polymer, preferably a polymer from the group the homo- or copolymeric carboxylic acids and / or the homo- or copolymer polycarboxylic and / or the homo- or copolymeric sulfonic acids in amounts of 0.001 to 70 % By weight, preferably from 0.002 to 50% by weight and in particular from 0.005 to 30% by weight, each based on the total weight of the washing or detergent composition. Portioned detergent or cleaning agent composition according to one of the claims 1 to 12, characterized in that the water-soluble or water-dispersible containers one or more water-soluble Polymer (s), preferably one or more polymers from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, Polyethylene oxide, gelatin, cellulose, and their derivatives, preferably Hydroxypropylmethylcellulose, and mixtures thereof. Portioned detergent or cleaning agent composition according to one of the claims 1 to 13, characterized in that the water-soluble or water-dispersible containers comprises a polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is. Portioned detergent or cleaning agent composition according to one of Claims 1 to 14, characterized in that the water-soluble or water-dispersible container comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably of 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 . Portioned detergent or cleaning agent composition according to one of the claims 1 to 15, characterized in that the water-soluble or water-dispersible containers is a film bag and the film has a thickness of 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 85 μm and in particular from 10 to 70 μm, having. Portioned detergent or cleaning agent composition according to one of the claims 1 to 15, characterized in that the water-soluble or water-dispersible containers an injection molding or deep-drawn or blow molded articles comprises the wall of which has a thickness of 50 to 300 μm, preferably 70 to 200 μm and in particular from 80 to 150 μm having. Portioned detergent or cleaning agent composition according to one of the claims 1 to 15, characterized in that the water-soluble or water-dispersible containers is a casting.