DE10258869A1 - Silver protection for automatic dishwashing - Google Patents

Abstract

The invention relates to the use of an active substance-containing matrix containing at least one agent which is able to provide silver corrosion protection during cleaning and / or rinsing processes in a dishwasher, for releasing the agent (s) effective for silver corrosion protection the matrix in the cleaning and / or rinsing processes of the dishwasher.

Description

The present invention relates to the novel use of an active substance-containing matrix (for example a glass, preferably water-soluble glass or a polymer or polymer mixture, preferably a water-soluble Polymers / polymer mixture) for the corrosion protection of silver during cleaning and / or rinsing processes Dishwasher, Compositions for use in a dishwasher for the stated purpose and method of inhibiting corrosion of silver in cleaning and / or rinsing processes in a dishwasher.

It's a well known fact that silver even when not in use, "tarnishes". It is only one Matter of time until there are dark, brownish, bluish to bluish black spots gets or discolored overall and in the usual way Language usage "started".

Even with machine cleaning In practice, problems often arise with silverware of tarnishing and discoloration of the silver surfaces on. Silver can be found here on sulfur-containing substances in the rinse water solved or are dispersed, because when cleaning dishes in household dishwashers are leftovers and thus u. a. also mustard, peas, egg and others sulfur-containing compounds such as mercaptoamino acid in the washing liquor brought in. Even during of machine rinsing much higher Temperatures and the longer ones Favor contact riding with the sulfur-containing food residues compared to manual rinsing tarnishing silver. Due to the intensive cleaning process in the dishwasher becomes the silver surface Moreover Completely degreased and therefore more sensitive to chemical influences.

When using active chlorine The start-up can largely be cleaned by sulfur-containing compounds can be prevented because these compounds by oxidation of the sulfidic Secondary response functions to be converted into sulfones or sulfates.

The problem of tarnishing silver was however again up to date, as an alternative to the active chlorine compounds Active oxygen compounds such as sodium perborate or sodium percarbonate were used, which are used for elimination bleachable soiling, such as tea stains / tea deposits, coffee residues, dyes from vegetables, Lipstick remnants and the like are used.

These active oxygen compounds are used together with bleach activators in modern machine dishwashing detergents used. These means generally consist of the following Function blocks: Builder component (complexing agent / dispersant), Alkali carriers, Bleaching system (bleach + bleach activator), enzymes and wetting agents (Surfactants).

On the changed recipe parameters of the new generation of active chlorine-free detergents with reduced pH values and activated oxygen bleaching, the silver surfaces are generally more sensitive. During the machine rinsing these agents actually set the bleaching agent in the cleaning cycle Agent hydrogen peroxide or active oxygen free. The bleaching Effect of the active oxygen-containing cleaners is through bleach activators strengthened so yes a good bleaching effect is achieved at low temperatures. In the presence of these bleach activators, a reactive intermediate is formed Peracetic acid. Among these changed flushing not only form sulfidic but also in the presence of silver by the oxidizing attack of the intermediate peroxides or of active oxygen prefers oxidic deposits on the silver surfaces. Under high levels of salt additionally chloride deposits arise. reinforced the tarnishing of the silver is also caused by higher residual water hardness during the Cleaning cycle.

Avoiding the silver corrosion, i.e. the formation of sulfidic, oxidic or chloride deposits on silver is the subject of numerous publications. The corrosion of silver is mainly in these descriptions prevented by so-called silver protection agents.

From the British patent GB 1 131 738, alkaline dishwashing detergents are known which contain benzotriazoles as a corrosion inhibitor for silver. In the American patent US 3,549,539 Strongly alkaline machine cleaning agents are described which may contain perborate with an organic bleach activator as an oxidizing agent. Additions of benzotriazole and iron (III) chloride, among others, are recommended as anti-tarnish agents. PH values of preferably 7-11.5 are mentioned. In the European patent specifications EP 135 226 A1 and EP 135 227 A1 weakly alkaline, machine dishwashing detergents containing peroxy compounds and activators are described, which may contain benzotriazoles and fatty acids, among others, as silver preservatives. Finally, is from the German patent application DE 41 28 672 A1 It is known that peroxy compounds, which are activated by the addition of known organic bleach activators, prevent tarnishing of silver parts in strongly alkaline cleaning agents.

The compositions known from the prior art are effective only on egg A specific step in the cleaning cycle is defined, ie when added to a granular detergent composition on the cleaning cycle or when mixed with a liquid rinse aid composition on the rinse cycle. None of the known compositions is able to develop their effect in the pre-wash cycle or in one of the intermediate rinse cycles. In addition, the previously known means do not allow use to be tailored to requirements. The cleaners contain silver protection agents even when no silver is being rinsed and the silver protection agent is therefore not required. Since the consumer usually does not want to keep two different cleaners in stock, there is no dosage form that can also be used as needed.

The present invention lies based on the task of overcoming the aforementioned disadvantages.

Object of the present invention is in a first embodiment the use of an active substance-containing matrix, with a content on at least one agent capable of silver corrosion protection during cleaning and / or rinsing processes dishwasher to provide for the release of (s) for silver corrosion protection effective agent (agents) from the matrix in the cleaning and / or Flushing the Dishwasher.

According to the silver corrosion protection effected by providing an active substance-containing matrix, which comprises a matrix material, that includes at least one agent that exits the matrix can and is able to provide silver corrosion protection during cleaning and / or washing operations of a dishwasher provide.

The word "corrosion" is at its broadest in chemistry common Interpret meaning, especially "corrosion" for every visually just noticeable change in a metal surface, here Silver, be it z. B. a selective discoloration it z. B. a large start-up.

By using an active ingredient Matrix as "carrier" of one or more Agents for the corrosion protection of silver in a dishwasher the disadvantages described above are avoided because the Matrix releases defined amounts of silver corrosion protection agent, You can use the Type of matrix, the type of silver corrosion inhibitor as well the composition of the active ingredient-containing matrix for everyone Tailored application Product made to only ever such a concentration to release active agents that the corrosion protection agents of silverware are effective.

In preferred embodiments In the present invention, the matrix is designed to have several rinse cycles in a normal household Dishwasher survives and in every rinse cycle the agent releases. Preferred embodiments of the present Invention are uses which are characterized in that the matrix a water soluble Glass covers.

Corresponding matrices are in terms of their Glass ingredients, the active substances, physical properties etc. described below.

An alternative way consists in the agent being released from the matrix can and is able to provide silver corrosion protection for cleaning and / or rinsing one dishwasher provide to release from a polymer matrix. It can the polymer matrix from water-insoluble and / or from water-soluble Polymers exist. Another preferred use according to the invention is therefore characterized in that the matrix is a polymer matrix comprising one or more, preferably water-soluble (m / n), polymer (s).

Corresponding matrices are also used here in terms of their ingredients, the active substances, physical properties etc. described below.

The active ingredients used include those according to the invention drug-containing polymer matrices at least one agent that the matrix can be released and is capable of silver corrosion protection during cleaning and / or rinsing processes dishwasher provide. This agent can vary depending on the matrix his; so can in polymer matrices also thermally sensitive compounds, for example organic silver preservatives to be incorporated while at Glass matrices only "more robust" connections in because of the manufacturing conditions Question come. Of course can Here, too, compounds are used that differ under the production conditions convert into suitable compounds, for example carbonates, which form the corresponding oxides when heated, or acetates, which releasing acetic acid or their decomposition products react to the oxides, or sulfates, which pass into the oxides with the release of sulfur trioxide.

Those contained in the matrix according to the invention Agents can as described above from the group of organic or inorganic silver protective agents.

"Organic Silver protection "are those organic substances that are easily reversible Oxidation and / or reduction are accessible. "Inorganic silver protection agents" are therefore all inorganic Substances that simultaneously undergo easy oxidation and / or reduction are accessible.

Examples of organic agents that can be released from the matrix and that are able to provide silver corrosion protection during cleaning and / or rinsing processes of a dishwasher, are ascorbic acid (vitamin C), indole, methionine ( _α- aminomethyl mercaptobutyric acid), N-mono- (C ₁ -C ₄ -alkyl) -glycine, for example N-mono-methylglycine and N, N-di- (C ₁ -C _4- alkyl) -glycines, for example N, N-dimethylglycine and 2-phenylglycine. Also suitable are, for example, substances from the group of the diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, diaminodihydroxypyrimidines, dihydroxynaphtalines, naphthols, pyrazolines, aminohydroquinones, hydroxynolines, hydroxynophenins, hydroxyls, aromatic, aminochinone, aminochloro, aminochloro, diaminophenimines, aminochinone, aromatics, aminochinone, aromatics, aminochinone, aromatics or para position have a further free or substituted by C ₁ -C ₄ alkyl or C ₂ -C ₄ hydroxyalkyl groups, hydroxy or amino group, and the di- or trihydroxybenzenes. The substances from the group p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridinediol, 1- (p-aminophenyl) morpholine, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol are particularly suitable.

bevorzugt, in der in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen steht und ihre Salze mit Mineralsäure, Kohlensäure oder organischen Carbonsäuren.Particularly preferred organic silver protectants come from the group of 3-amino-5-alkyl-1,2,4-triazoles. Here are 3-amino-5-alkyl-1,2,4-triazoles or their salts of the general formula

preferred, in which R represents a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl alkyl radical having 1 to 15 carbon atoms and their salts with mineral acid, carbonic acid or organic carboxylic acids.

As examples of those to be used according to the invention 3-Amino-5-alkyl-1,2,4-triazoles can e.g. 5-propyl, 5-butyl, 5-pentyl, 5-heptyl, 5-octyl, 5-nonyl, 5-decyl, 5-undecyl, 5-dodecyl, 5-isononyl (3-amino-1,2,4-triazole). Preferred acids for the Salt formation is hydrochloric acid, Sulfuric acid, phosphoric acid, carbonic acid, sulphurous Acid, organic carboxylic acids like vinegar, glycolic, citric, succinic acid.

As mentioned earlier, the use of organic Silver protection agents limited to matrices, in which they work without destruction to let.

According to the invention, preference is given to the use of matrices which contain inorganic agents which can be released from the matrix and are able to provide silver corrosion protection during cleaning and / or rinsing processes in a dishwasher. Such inorganic agents originate, for example, from the group of substances Na ₂ S ₂ O ₃ (sodium thiosulfate), Na ₂ S ₂ O ₄ (sodium dithionite) or Na ₂ S ₂ O ₅ (sodium disulfite) based on various oxidation levels of the sulfur.

However, the are particularly suitable Salts or complex compounds of certain metals. In preferred according to the invention Uses that are effective for the protection against silver corrosion Agents (agents) from the group of manganese, titanium, zirconium, Hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.

The metal salts used or Metal complexes should preferably be at least partially soluble in water. 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 in the sense of the invention are compounds consisting of a central atom and one or more Ligands and optionally one or more the above Anions exist. The central atom is one of the above metals in one of the above Oxidation states. The ligands are neutral molecules or Anions that are monodentate or multidentate are. Complete the charge of the central atom and the Charge of the ligand (s) not to zero, depending on whether there is a cationic or an anionic excess of 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.

Particularly preferred metal salts and / or metal complexes are selected from the group MnCO ₃ , Mn (CH ₃ COO) ₂ , 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 their mixtures.

These metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection 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 .

In summary, preferred uses according to the invention are characterized in that the agent (s) from the group MnCO ₃ , Mn (CH ₃ COO) ₂ , MnSO ₄ , Mn (II) citrate, Mn ( II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1-diphos phonat], 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 . ,

details Information on the physical properties and amounts used of the agents, that can be released from the matrix and are able to Silver corrosion protection during cleaning and / or rinsing processes dishwasher can be found below.

Another subject of the present Invention is a composition for use in a dishwasher, containing an active ingredient-containing matrix, containing at least an agent that is able to protect silver and / or rinsing one dishwasher provide.

Compositions according to the invention contain at least one matrix of at least one matrix material and at least one agent that can be released from the matrix and is able to provide silver corrosion protection when cleaning and / or Flushing one dishwasher provide. The agents, individually or in a mixture with each other can be released from the matrix have already been above in the use according to the invention in detail described.

The compositions of the invention can be formulated universally. For example, it is possible to use pre-softeners according to the invention, pre-cleaner, Detergent for the main wash cycle or rinse aid provide. Next to it compositions according to the invention also be combination products, the two or more of the aforementioned Unite resources. Also the formulation of compositions according to the invention as an addition product, for example in the dishwasher hooked is easily possible. This form of offer enables it to the consumer to use detergents that are not silver protection agents included and then always adducts into the machine give if silver protection is needed becomes.

The matrix containing the active ingredient can particulate in the compositions of the invention can be incorporated, but it can also be a compact molded body, which, for example, is either a core, which is a trough Detergent tablet fills, or a molded body, that as an add-on product like a deodorant hanger in the dishwasher is introduced. Cups made from active ingredient-containing polymer matrices can be which for the inclusion of detergent tablets are suitable. Last but not least, an active ingredient-containing polymer matrix can also be used as Packing for automatic dishwashing detergents be used. This is especially true with completely water soluble Active ingredient-containing polymer matrices attractive because of the consumer does not have to unpack the product, direct contact with the product, which is perceived as undesirable is avoided and other packaging materials are also saved become.

As mentioned above, are glasses in particular as matrices or polymers, both glasses and polymers being preferred water soluble or are water dispersible.

A matrix according to the invention can be formed from a glass. The properties of a glass type vary widely with chemical composition. You can have glass by varying the substances and their relative amounts for almost everyone desired Purpose (such as mechanical or thermal stability or water solubility) to construct.

• – Quarzsand (SiO₂; Glassand),
• – Soda Na₂CO₃,
• – Pottasche K₂CO₃,
• – Kalkstein oder besser reiner Marmor CaCO₃,
• – Kreide (eine Mischung aus Kalkstein, Silicaten und Feuerstein (feinverteilter Quarz)),
• – Quarz (Quarzsand oder Feuerstein) SiO₂,
• – Mennige Pb₃O₄,
• – Borax (Natriumtetraborat) Na₂B₄O₇ · 10 H₂O bzw. Na₂O · 2 B₂O₃ · 10 H₂O,
• – Kaolin Al₂(OH)₄Si₂O₅ bzw. Al₂O₃ · 2 SiO₂ · 2 H₂O,
• – Feldspat K[AlSi₃O₈] bzw. K₂O · Al₂O₃ · 6 SiO₂.

The main raw materials are:

• - quartz sand (SiO ₂ ; glass sand),
• - soda Na ₂ CO ₃ ,
• - potash K ₂ CO ₃ ,
• - limestone or better pure marble CaCO ₃ ,
• - chalk (a mixture of limestone, silicates and flint (finely divided quartz)),
• - quartz (quartz sand or flint) SiO ₂ ,
• - Red lead Pb ₃ O ₄ ,
• Borax (sodium tetraborate) Na ₂ B ₄ O ₇ .10 H ₂ O or Na ₂ O. 2 B ₂ O ₃ .10 H ₂ O,
• Kaolin Al ₂ (OH) ₄ Si ₂ O ₅ or Al ₂ O ₃ .2 SiO ₂ .2 H ₂ O,
• - Feldspar K [AlSi ₃ O ₈ ] or K ₂ O · Al ₂ O ₃ · 6 SiO ₂ .

These can be divided into three groups according to their chemical properties: network formers (acidic constituents, for example SiO ₂ , P ₂ O ₅ , As ₂ O ₅ ) network disruptors (basic constituents, for example oxides or carbonates of Ca, according to Claim K and Pb ) and disconnector (e.g. B ₂ O ₃ , Al ₂ O ₃ ).

Glass is a melting product, ie the components are melted during manufacture. A typical glass melt is composed
approx. 70% glass former (quartz),
approx. 20% flux (potash and soda) and
approx. 10% glass hardener (oxides).

By adding (1%) various metal oxides and fluorides, the optical properties and the color of the glass can be specifically changed. The additives lead, titanium and lanthanum oxide, for example, increase the refractive index. Barium oxide and fluoride reduce the dispersion, while the glass melt can be colored with iron, cobalt, vanadium and manganese for sun protection glasses. To achieve phototropy, metal compounds with fluorine, chlorine and bromine (halides) are added to the glass melt.

The following overview shows the composition by some selected Glass types (figures in percent by mass):

• Soda-lime glasses (normal glass) 75.5 SiO ₂ , 12.9 Na ₂ O, 11.6 CaO.
• Potash-lime glasses 76 SiO ₂ , 14.1 K ₂ O, 6.7 CaO, 2.3 Na ₂ O, 0.5 As ₂ O ₅ , 0.1 Al ₂ O ₃ , 0.3 SO ₃ .
• Boron-alumina glasses (Jena glass) 74.5 SiO ₂ , 8.5 Al ₂ O ₃ , 4.6 B ₂ O ₃ , 7.7 Na ₂ O, 3.9 BaO, 0.8 CaO, 0, 1 MgO.
• Supremax glass 56.4 SiO ₂ , 20.1 Al ₂ O ₃ , 8.9 B ₂ O ₃ , 8.7 MgO, 4.8 CaO, 0.6 Na ₂ O, 0.6 K ₂ O.
• Potash-lead glasses (lead crystal glass) 56 SiO ₂ , 32 PbO, 11.4 K ₂ O, 0.1 Al ₂ O ₃ , 0.5 As ₂ O ₅ .

Preferred compositions according to the invention are characterized in that the Matrix as glass-forming component (s) one or more substances from the group phosphorus pentoxide, sodium oxide, potassium oxide, silicon oxide and boron oxide.

All to produce the one you want Glases needed Ingredients are melted in an oven at 1400 to 1500 ° C, for example. The one in the viscous melt contained gas bubbles can be added by adding so-called refining agents remove. multi-hour stir after the purification avoids streaks, inclusions and color casts. There are five basic processing methods for glass in plastic state (Temperature range approx. 900 ° C up to 1200 ° C): To water, Blowing, drawing, pressing and rolling. That way they can composition according to the invention, which comprise a glass matrix are produced by melting of mixtures of the oxide components, or precursors thereof, for such a way sufficient period that a homogeneous melt is obtained, which is subsequently so chilled far until it solidifies. The formation into a shaped body can done in the ways described above, for example by to water (e.g. into a graphite mold), drawing, pressing, rolling or blowing.

By choosing the ingredients the glass matrix can be designed so that it has a defined water solubility has. This can be achieved that the matrix in the rinse after and after solves and thereby releases the agent or agents for silver protection. Depending on water solubility the life of the composition can be several rinse cycles, for example, ten to one hundred cycles.

Compositions according to the invention in which the matrix is a water soluble Covers glass, are preferred.

As already mentioned, can be in glass matrices incorporate only those agents that meet the conditions of glass manufacturing survive undamaged. Usually are therefore the corresponding oxides of the above metals directly or as a "preliminary stage" (for example as carbonate, acetate or sulfate or as another compound which forms the corresponding oxides with decomposition). Especially Mn (II) compounds which give MnO are preferred. Therefore preferred compositions are characterized in that the or the for the silver corrosion protection agent (s) from which Group of oxides of manganese, titanium, zirconium, hafnium, vanadium, Cobalt and cerium originate, the metals preferred are in one of the oxidation states II, III, IV, V or VI.

The glass matrix contains that or the for agents / agents effective against silver corrosion in amounts of 0.1 to 30% by weight, based on the metal oxide or in amounts of 0.1 to 25 wt .-%, based on the metal. Especially preferred glass matrices contain one or more metals from the Group Mn, Co, Ti, Co, Ce or their oxides, with Mn or MnO particularly are preferred. Particularly preferred compositions according to the invention glass-based contain 1 to 25, preferably 2.5 to 20, particularly preferably 3.5 to 15 and in particular 5 to 10% by weight of manganese as MnO or 0.5 to 20, preferably 1.5 to 18, particularly preferred 2.5 to 15 and in particular 4 to 9% by weight of manganese, calculated as Mn.

The advantages of a composition according to the invention, which is based on a glass matrix lies in the high aesthetic The attraction of these compositions and a high level of consumer acceptance. adversely are opposite other matrices higher Production costs.

In contrast to (water-soluble) glasses, active ingredient-containing polymer matrices offer the advantage that they can be manufactured much more cheaply and in a greater variety of shapes. By selecting water-soluble or water-insoluble polymers, the composition according to the invention can even be formulated as packaging for automatic dishwashing detergents or as a basket into which the detergents are introduced. It is also possible to combine the two types of introduction with one another, for example by using a carrier basket made of water-insoluble, active substance-containing polymer matrix and a polymer body made of water-soluble contains active ingredient-containing polymer matrix. Products of this type can release the active agents to different extents from the different matrices at different times, which leads to an optimal concentration of active substance at any time during the cleaning program.

Compositions likewise preferred according to the invention are therefore characterized in that the matrix is a polymer matrix comprising one or more polymer (s).

Such compositions according to the invention can be combined with water-insoluble as well as with water soluble Realize polymers or mixtures thereof. Preferred compositions are characterized in that the Polymer matrix comprises one or more water-soluble polymer (s). Regarding the chemical composition, proportions and other details reference is made to the explanations below. The polymers, which form the polymer matrix individually or in a mixture with one another can, are described below.

• a) 5 bis 99,5 Gew.-% eines oder mehrerer Polymere,
• b) 0,5 bis 95 Gew.-% eines oder mehrerer Agentien, die in der Lage sind, Silberkorrosionsschutz bei Reinigungs- und/oder Spülvorgängen einer Geschirrspülmaschine bereitzustellen,
• c) 0 bis 30 Gew.-% weiterer Wirk- und/oder Hilfsstoffe

umfaßt.Compositions according to the invention are particularly preferably characterized in that the polymer matrix

• a) 5 to 99.5% by weight of one or more polymers,
• b) 0.5 to 95% by weight of one or more agents which are able to provide silver corrosion protection during cleaning and / or washing operations of a dishwasher,
• c) 0 to 30% by weight of further active ingredients and / or auxiliaries

includes.

The polymer matrix of the compositions according to the invention comprises 5 to 99.5% by weight of one or more polymers. The term "polymers" characterizes in The following registration based on the IUPAC definition Substances that are made up of a collective of chemically uniform but usually in terms of degree of polymerization, molecular weight and chain length distinctive macromolecules composed. According to this, the origin of the term is not considered IUPAC definition is a polymer "a substance made up of a variety of molecules is built in which one kind or several kinds of atoms or Atom groups (so-called constitutive units, basic building blocks or repeat units) are repeatedly strung together ". The different huge macromolecules of a polymer are made up of so many of the same or similar low molecular weight Building blocks (monomers) built that the physical properties the substance, especially the viscoelasticity, with a slight increase or No longer noticeably change the reduction in the number of blocks. The Size of the macromolecules, that itself the end groups relatively little on the properties of the polymers impact so that on their explicit specification in the structural formulas given below is mostly dispensed with.

The polymers forming the matrix of the compositions according to the invention can doing both natural as well as being of synthetic origin. Preferred compositions according to the invention are characterized in that the Polymer matrix 7.5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 12.5 to 85% by weight, further preferably 15 to 82.5% by weight and in particular 20 to 80% by weight of one or more Comprises polymers, where the weight information relates to the active ingredient-containing polymer matrix Respectively.

The average molecular weight in the compositions according to the invention contained polymers is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.

As already mentioned, the compositions according to the invention can both water insoluble as also water soluble Contain polymers and mixtures of these polymers. Preferred according to the invention Compositions are based on water-insoluble polymer matrices characterized in that the Polymer matrix one or more water-insoluble polymers from the group polyethylene, Polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, Polycarbonate, polyvinyl chloride, polyurethanes, polyamides and mixtures thereof.

As a polymer matrix are in the frame In the present invention, silicones are also preferably suitable. Under Against the silicones, the silicone rubbers are particularly preferred: These are masses which can be converted into the rubber-elastic state, which are used as base polymers Contain polydiorganosiloxanes that make crosslinking reactions accessible Have groups. As such come mainly H atoms, OH and Vinyl groups in question, which are at the chain ends, however can also be built into the chain.

In addition to this system the agent that can be released from the matrix and that in the Is able to protect against corrosion Glassware during cleaning and / or rinsing processes in a dishwasher to provide, also fillers as an amplifier are incorporated, the type and amount of which are mechanical and chemical Influence the behavior of the vulcanizates significantly. As fillers finely divided silicas, diatomaceous earth (diatomaceous earth), Titanium dioxide, calcium carbonate or iron oxide are used. The matrix can about it can also be colored by inorganic pigments.

Both hot and cold vulcanizing silicone chewing are within the scope of the present invention schuke (high / room temperature vulcanizing = HTV / RTV) can be used. The HTV silicone rubbers are usually plastically deformable, just yet flowable materials, which contain highly disperse silica and as crosslinking catalysts organic peroxides [benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, t-butyl peroxybenzoate, dicumyl peroxide, organometallic salts such as dibutyltin) and after vulcanization at temperatures> 100 ° C heat-resistant, between -100 ° C and +250 ° C elastic silicone elastomers ,. Another crosslinking mechanism consists in an addition of SiH groups to Si-bonded vinyl groups, which is usually catalyzed by noble metal compounds, both of which are incorporated into the polymer chains or at the end thereof. A liquid rubber technology (LSR = Liquid Silicone Rubber) has been established since 1980, in which two liquid silicone rubber components are vulcanized by addition addition in injection molding machines. A distinction can be made between one-component and two-component systems for cold-curing or RTV silicone rubber compounds. The first group (RTV-1) polymerizes slowly at 20 ° C. under the influence of atmospheric humidity, the crosslinking taking place by condensation of SiOH groups with the formation of Si, O bonds. The SiOH groups are by hydrolysis of SiX groups and an intermediate from a polymer with terminal OH groups u. a so-called crosslinker R-SiX ₃ (X = -O-CO-CH ₃ , -NHR) resulting species. In the case of two-component rubbers (RTV-2), z. B. mixtures of silicic acid esters (z. B. ethyl silicate) and organotin compounds are used, with the formation of a Si-O-Si bridge from ° Si-OR and ° Si-OH as a crosslinking reaction by alcohol elimination.

One within the scope of the present invention preferred silicone is, for example, Dow Corning 3110 RTV, which is at room temperature with the Dow Corning RTV catalyst No. 4 can be networked.

Polyethylenes (PE) are polymers belonging to the polyolefins with groupings of the type - [CH ₂ -CH ₂ ] as a characteristic basic unit of the polymer chain. Polyethylenes are produced by polymerizing ethylene using two fundamentally different methods, the high-pressure and the low-pressure process. The resulting products are accordingly often referred to as still pressure polyethylene or low pressure polyethylene; they differ mainly in their degree of branching and, related to this, in their degree of crystallinity and density. Both processes can be carried out as solution polymerization, emulsion polymerization or gas phase polymerization.

The high-pressure process produces branched polyethylenes with low density (approx. 0.915-0.935 g / cm ³ ) and degrees of crystallinity of approx. 40-50%, which are referred to as LDPE types. Products with a higher molecular weight and thus improved strength and stretchability are called NMW-LDPE (HMW = high molecular weight). The pronounced degree of branching of the polyethylenes produced by the high-pressure process can be reduced by copolymerization of the ethylene with longer-chain olefins, in particular with butene and octene; the copolymers have the code LLD-PE (linear low density polyethylene).

The macromolecules of the polyethylenes from low-pressure processes are largely linear and unbranched. These polyethylenes (HDPE) have degrees of crystallinity of 60-80% and a density of approx. 0.94-0.965 g / cm ³ .

Polypropylenes (PP) are thermoplastic polymers of propylene with basic units of the type - [CH (CH ₃ ) -CH ₂ ] -

Polypropylenes can be stereospecific Polymerization of propylene in the gas phase or in suspension highly crystalline isotactic or less crystalline syndiotactic or to produce amorphous atactic polypropylenes. Technically important isotactic polypropylene, where all the methyl groups are located on one side of the polymer chain are. Polypropylene is characterized by high hardness, resilience, rigidity and heat resistance.

An improvement in mechanical Properties of the polypropylenes are achieved by reinforcement with Talc, chalk, wood flour or glass fibers, and also applying metallic coatings is possible what the possibilities more aesthetic Design of the compositions according to the invention extended.

Polytetrafluorethylene (PTFE, Teflon ^® ) are polymers of tetrafluoroethylene with the general formula: - [CF ₂ -CF ₂ ] _n -

Technical products have degrees of polymerization of approximately 5000-100,000, which corresponds to molecular weights of approximately 500,000-10,000,000 g / mol. The polymerization of the monomers is initiated by free radicals and carried out under pressure by means of emulsion or suspension polymerization in order to remove the high heat of polymerization to lead. In the polymerization in suspension, the PTFE is obtained as granules, which are ground to the desired particle size. Fine powder PTFE products, on the other hand, are only obtained by emulsion polymerization. Under suitable conditions, when using ionic surfactants as stabilizers, finely divided stable dispersions with solids contents of 605% can also be produced.

PTFE are thermoelastic polymers with high linearity, relatively high (up to 70%) degree of crystallinity and a melting point of approx. 327 ° C. Polytetrafluorethylene have an extremely high chemical resistance and are in all solvents below 300 ° C insoluble. PTFE can used in a very wide temperature range (–200 ° C to 250 ° C).

Polystyrene (polyphenylethylene, polyvinylbenzene), abbreviation PS, are thermoplastic polymers of the structure - [CH ₂ -CH (C ₆ H ₅ ) _n -

Technically, PS is almost exclusively through radical polymerization of styrene. Most frequently the processes of suspension or bead polymerization, emulsion, bulk and solution polymerization.

Depending on the polymerization conditions the polystyrenes have molecular weights of 170,000 to 1,000,000 g / mol on. Depending on the type of polymerization, a powdery product is obtained (by emulsion, solution and Bead polymerization) or a melt (bulk polymerization). Amorphous PS is crystal clear, stiff and quite brittle; it is against acids, bases, Alcohol and mineral oil resistant, against most solvents however, inconsistent (Stress crack formation) or soluble in them. Also the light resistance is low due to easy photooxidation, as is water absorption.

Polyethylene terephthalates (PET, PETE) are polyesters from the group of polyalkylene terephthalates and have the structure - [C (O) -C ₆ H ₄ -C (O) -O- (CH ₂ ) ₂ -O] _n - on. They are produced industrially either by transesterification of dimethyl terephthalate with ethylene glycol with elimination of methanol to give bis (2-hydroxyethyl) terephthalate and its polycondensation with liberation of ethylene glycol or by direct polycondensation of ethylene glycol and terephthalic acid:
PET have a density of approx. 1.38 g / cm ³ , a melting point of approx. 260 ° C and are semi-crystalline products with high strength, rigidity and dimensional stability, good sliding and wear properties as well as high chemical resistance. The degree of crystallinity (30-40%) is reduced by incorporating foreign building blocks (isophthalic acid and / or 1,4-cyclohexanedimethanol). The resulting copolyesters have high transparency, toughness, dimensional stability and favorable creep, sliding, wear and stress cracking properties.

Polycarbonates (abbreviation PC) are mostly thermoplastic polymers with the general structural formula - [ROC (O) -O] _n - which can be considered formally as polyesters from carbonic acid and aliphatic or aromatic dihydroxy compounds. They are easily accessible by reacting aliphatic diols or bisphenols with phosgene or carbonic acid diesters in polycondensation or transesterification reactions.

about the choice of bisphenols the properties of the polycarbonates can be varied widely. At the same time Different bisphenols can be used in multi-stage polycondensation also build block polymers. Polyester polycarbonates are u. a. by reacting bisphenols with phosgene and aromatic dicarboxylic acid dichlorides accessible.

Aromatic. Polycarbonates have molar masses in the range of approx. 10,000-200,000 g / mol, which can be adjusted using regulators during the polycondensation process. They have a low density (approx. 1.2 g / cm ³ ), relatively high glass transition temperatures (-150 ° C) and melting points (150-300 ° C) and are in a wide temperature range (-150 ° C to 150 ° C) can be used. They are resistant to water, neutral salt solutions, mineral acids, aqueous solutions of oxidizing agents, hydrocarbons, oils and fats, but are dissolved by certain chlorinated hydrocarbons, especially methylene chloride. They are not resistant to aqueous alkalis, amines and ammonia, which can be used as a release mechanism for the active substances in the context of the present invention, since the detergent formulations are mostly alkaline.

Polyvinylchloride (abbreviation PVC) are the polymers of the structure that arise during the radical homopolymerization of vinyl chloride (VC) - [CH 2 -CH (Cl)] n -

The macromolecules are not strictly linear: depending on the monomer conversion and the polymerization temperature, they have about 3-20 short side chains per 1000 C atoms. Technical polyvinylchloride ha ben molecular weights of approx. 30,000-130,000 g / mol.

Polyamides are high-molecular compounds that consist of building blocks linked by peptide bonds. The synthetic polyamides (PA) are, with a few exceptions, thermoplastic, chain-like polymers with recurring acid amide groups in the main chain. According to the chemical structure, the so-called homopolyamides can be divided into two groups: the aminocarboxylic acid types (AS) and the diamine dicarboxylic acid types (AA-SS); A denotes amino groups and S carboxy groups. The former are formed from one building block by polycondensation (amino acid) or polymerization ( _ω- lactam), the latter from two building blocks by polycondensation (diamine and dicarboxylic acid).

The polyamides are encoded from unbranched aliphatic building blocks according to the number of carbon atoms. The designation PA 6 is, for example, the polyamide and _ε- aminocaproic acid or _ε- caprolactam. PA 12 is a poly ( _ε -laurinlactam) made of _ε -laurinlactam. In the AA-SS type, the number of carbon in diamine is mentioned first, followed by that of dicarboxylic acid: PA 66 (polyhexamethylene adipamide) is made from hexamethylene diamine (1,6-hexane diamine) and adipic acid, PA 610 (polyhexamethylene sebacinamide) from 1,6-hexane diamine and Sebacic acid, PA 612 (polyhexamethylene dodecanamide) from 1,6-hexanediamine and dodecanedioic acid.

Polyurethanes (PUR) are polymers (polyadducts) with groupings of the type that are accessible through polyaddition from dihydric and higher alcohols and isocyanates - [CO-NH-R ² -NH-CO-OR ¹ -O] as characteristic basic units of the basic macromolecules, in which R 'represents a low-molecular or polymeric diol residue and R ^{2 represents} an aliphatic or aromatic group. Technically important PURs 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 ].

• i) Polyacrylsäuren und deren Salzen
• ii) Polymethacrylsäuren und deren Salzen
• iii) Polyvinylpyrrolidon,
• iv) Vinylpyrrolidon/Vinylester-Copolymeren,
• v) Celluloseethern
• vi) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
• vii) Pfropfcopolymeren aus Polyethylenglykolen und Vinylacetat
• viii) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
• ix) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
• x) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
• xi) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• xii) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• xiii) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• xiv) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymeren und deren Salzen
• xv) Copolymeren aus xv-i) ungesättigten Carbonsäuren und deren Salzen xv-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
• xvi) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• xvii) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• xviii) Methacroylethylbetain/Methacrylat-Copolymere
• xix) Vinylacetat/Crotonsäure-Copolymere
• xx) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• xxi) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen
• xxii) gepropften Copolymere aus der Copolymerisation von xxii-i) mindesten einem Monomeren vom nicht-ionischen Typ, xxii-ii) mindestens einem Monomeren vom ionischen Typ,
• xxiii) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: xxiii-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, xxiii-ii) ungesättigte Carbonsäuren, xxiii-iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols.

Instead of water-insoluble polymers or in a mixture with them, water-soluble polymers of natural or synthetic origin can also form the polymer matrix. Further preferred compositions according to the invention are characterized in that the polymer matrix comprises one or more water-soluble polymers, the water-soluble polymer (s) preferably being selected from:

• i) polyacrylic acids and their salts
• ii) polymethacrylic acids and their salts
• iii) polyvinyl pyrrolidone,
• iv) vinyl pyrrolidone / vinyl ester copolymers,
• v) cellulose ethers
• vi) polyvinyl acetates, polyvinyl alcohols and their copolymers
• vii) graft copolymers of polyethylene glycols and vinyl acetate
• viii) alkyl acrylamide / acrylic acid copolymers and their salts
• ix) alkyl acrylamide / methacrylic acid copolymers and their salts
• x) alkyl acrylamide / methyl methacrylic acid copolymers and their salts
• xi) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xii) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xiii) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xiv) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and their salts
• xv) copolymers of xv-i) unsaturated carboxylic acids and their salts xv-ii) cationically derivatized unsaturated carboxylic acids and their salts
• xvi) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• xvii) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• xviii) methacroylethylbetaine / methacrylate copolymers
• xix) vinyl acetate / crotonic acid copolymers
• xx) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• xxi) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polykalkylene glycols
• xxii) grafted copolymers from the copolymerization of xxii-i) at least one monomer of the non-ionic type, xxii-ii) at least one monomer of the ionic type,
• xxiii) copolymers obtained by copolymerization of at least one monomer of each of the following three groups: xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, xxiii-ii) unsaturated carboxylic acids, xxiii-iii) esters of long-chain Carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol.

The individual polymers mentioned above are described in more detail below:
Poly (meth) acrylic acids and their salts are described in detail below with the cobuilders.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und – K-Wert-abhängig – Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).Polyvinylpyrrolidones iii) are for example sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred polymers in the context of the present invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

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

Vinylester-vinylpyrrolidone copolymers IV) are for example sold under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred polymers.

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

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

Polymerization of vinyl esters takes place radically according to different processes (solution polymerization, Suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

As cellulose ethers v) are particularly hydroxypropyl cellulose, hydroxyethyl cellulose and methyl as, for example, sold under the trademark Culminal.RTM ^® and Benecel ^® (Aqualon), into consideration.

in R für N oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH_Z-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Ver-etherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxy-ethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.Cellulose ethers can be described by the general formula (III)

R represents N or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. It says in preferred products at least one R in formula (III) for -CH ₂ CH ₂ CH _Z -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups in an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been added to an anhydroglucose unit on average , Hydroxy-ethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Other particularly preferred water-soluble polymers that can be used are polyvinyl acetals, polyvinyl alcohols and their copolymers. Among these, homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers are preferred, so that compositions according to the invention in which the water-soluble polymer (s) is selected / are composed of homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers, are preferred embodiments of the present invention. Homopolymers or copolymers of vinyl alcohol cannot be obtained by polymerizing vinyl alcohol (H ₂ C = CH-OH) since its concentration in tautomer equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore primarily prepared from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure [-CH ₂ CH (OH) -] _n - which in small proportions also structural units of the type [-CH ₂ -CH (OH) -CH (OH) -CH ₂ ] contain.

Commercial polyvinyl alcohols, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered are, have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively so there is still a residual content of acetyl groups. Be characterized the polyvinyl alcohols from the manufacturer by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility 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. Polyvinyl alcohol is largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor through.

Within the scope of the present invention preferred compositions are characterized in that the water-soluble polymer is a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, compositions according to the invention are preferred in which the water-soluble polymer is a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 .

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

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Erkol ^® (Fa. Erkol). Particularly suitable in the present extension polyvinyl alcohols are for example Erkol ^® 3-83, 4-88 Erkol ^®, Erkol ^® 5-88 and 8-88 Erkol ^®.

Further polyvinyl alcohols which are particularly suitable as material for the polymer matrix can be found in the table below:

Other polyvinyl alcohols suitable as material for the polymer matrix 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 ).

Also suitable as water-soluble polymers a) are graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polykalkylene glycols. Such grafted Polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture with other copolymerizable compounds Polyalkylene glycols are polymerized by heat in homogeneous phase obtained in that the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers. As a suitable vinyl ester have for example vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and as an ester of acrylic acid or methacrylic acid those who with low molecular weight aliphatic alcohols, so in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, available are proven.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polyethylene glycols are polymers of ethylene glycol which have the general formula IV H- (O-CH ₂ -CH ₂ ) _n -OH (IV) are sufficient, where n can have values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is technically customary, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

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

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula VI.

• i) mindesten einem Monomeren vom nicht-ionischen Typ,
• ii) mindestens einem Monomeren vom ionischen Typ,
• iii) von Polyethylenglykol und
• iv) einem Vernetzter

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

• i) at least one monomer of the non-ionic type,
• ii) at least one monomer of the ionic type,
• iii) of polyethylene glycol and
• iv) a networked person

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

The monomers can vary widely Be of type and among these the following are preferred: vinyl acetate, Vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, Diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, Stearyl vinyl ether and 1-hexene. The second group monomers can equally be of very different types, among them especially preferably crotonic acid, allyloxyacetic, Vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

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

• i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglykol und
• iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.

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

• i) 5 to 85% by weight of at least one monomer of the nonionic type,
• ii) 3 to 80% by weight of at least one monomer of the ionic type,
• iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).

Other suitable water-soluble polymers are copolymers of alkyl acrylamide with acrylic acid, alkyl acrylamide with methacrylic acid, alkyl acrylamide with methyl methacrylic acid as well as alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, Alkylacrylamide / methacrylic acid / Al-kylaminoalkyl (meth) acrylic acid copolymers, Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, Alkylacryl amide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers as well as copolymers of unsaturated Carboxylic acids, cationically derivatized unsaturated carboxylic acids optionally further ionic or nonionic monomers.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO or -SO ₃ groups, and summarize those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (eg acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (eg acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or nonionic monomers. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are methacroyl ethyl betaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (VI) auf: [-CH(CH₃)-CH(COOH)-]_n (VI)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen

Anionic polymers suitable according to the invention include:

• - vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (VI): [-CH (CH ₃ ) -CH (COOH) -] _n (VI)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, Esters of acrylic acid or methacrylic acid alone or in a mixture with other copolymerizable compounds on polyalkylene glycols by heat polymerization obtained in a homogeneous phase by the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers.

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

• i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglykol und
• iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.

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

• i) 5 to 85% by weight of at least one monomer of the nonionic type,
• ii) 3 to 80% by weight of at least one monomer of the ionic type,
• iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).

• i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
• ii) ungesättigte Carbonsäuren,
• iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols

Copolymers obtained by copolymerization of at least one monomer from each of the following three groups are also suitable according to the invention as ingredient a):

• i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
• ii) unsaturated carboxylic acids,
• iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol

Under short chain carboxylic acids or Alcohols are to be understood as those with 1 to 8 carbon atoms, the carbon chains of these compounds, if necessary, by double-bonded hetero groups such as -O-, -NH-, -S- can be interrupted.

Another particularly preferred Class of polymers used in the compositions according to the invention as a polymer matrix may be included are polyurethanes. Polyurethanes are water-soluble in the sense of the invention, if they are more than 2.5% by weight soluble in water at room temperature.

The polyurethanes consist of at least two different types of monomers,

• - one Compound (A) with at least 2 active hydrogen atoms per molecule and
• - one Di- or polyisocyanate (B).

Compounds (A) can are for example diols, triols, diamines, triamines, polyetherols and polyesterols. The connections with more as 2 active hydrogen atoms usually only in small amounts in combination with a large excess of compounds used with 2 active hydrogen atoms.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and -propylene glycols, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and _{α, ω-} diamines based on long-chain alkanes or polyalkylene oxides.

Polyurethanes, in which the compounds (A) are diols, triols and polyetherols, can be preferred according to the invention his. In particular with polyethylene glycols and polypropylene glycols Molar masses between 200 and 3000, in particular between 1600 and 2500, have in individual cases proven to be particularly suitable. Polyesterols are commonly used by modifying compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid receive.

The compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the general formula VII: O = C = NR ¹ -N = C = O (VII), in which R ^{1 represents} a linking group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ⁴ stands for C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) and in isophorone diisocyanate R ^{4 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) ,

Furthermore, the used according to the invention Polyurethanes or building blocks such as diamines as chain extenders and hydroxy contain. Dialkylolcarboxylic acids such as dimethylol propionic acid are particularly suitable Hydroxy carboxylic acids. With regard to the other building blocks, there is no fundamental one restriction whether it is nonionic, anionic or cationic Building blocks.

For more information on the Structure and manufacture of the polyurethanes is expressly based on the articles in the relevant reviews like Rompps Chemical encyclopedia and Ullmann's encyclopedia of technical chemistry Referred.

• – ausschließlich aliphatische Gruppen im Molekül
• – keine freien Isocyanatgruppen im Molekül
• – Polyether- und Polyesterpolyurethane
• – anionische Gruppen im Molekül.

Polyurethanes, which can be characterized as follows, have proven particularly suitable according to the invention in many cases:

• - only aliphatic groups in the molecule
• - No free isocyanate groups in the molecule
• - Polyether and polyester polyurethanes
• - anionic groups in the molecule.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlstenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.Particularly preferred polyurethanes as the polymer matrix of the compositions according to the invention contain at least partially polyalkylene glycol units in the molecule. Compositions according to the invention are particularly preferred here in which the water-soluble polymer (s) is / are selected from polyurethanes from diisocyanates (VII) and diols (VIII). O = C = NR ¹ -N = C = O (VII), HOR ² -OH (VIII), the diols being selected at least in part from polyethylene glycols (IV) and / or polypropylene glycols (V) H- (O-CH ₂ -CH ₂ ) _n -OH (IV),

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each represent numbers from 5 to 2000.

The reaction mixtures can additionally contain further polyisocyanates. It is also possible for the reaction mixtures - and therefore the polyurethanes - to contain other diols, triols, diamines, triamines, polyetherols and polyesterols. The compounds with more than 2 active hydrogen atoms Usually only used in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.

If additional diols etc. are added certain proportions to the polyethylene and / or polypropylene glycol units present in the polyurethane to consider. Polyurethanes are preferred here, in which at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of the in the polyurethane reacted diols are selected from polyethylene glycols (In and / or polypropylene glycols (V).

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

Examples of compounds optionally further contained in the reaction mixtures for the preparation of the polyurethanes are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and _{α, ω-} diamines based on long-chain Alkanes or polyalkylene oxides. Compositions in which the polyurethanes contain additional diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.

To summarize these statements, particularly preferred compositions in the context of the present invention are characterized in that the water-soluble polymer is a polyurethane composed of diisocyanates (VII) and diols (VIII) O = C = NR ¹ -N = C = O (VII), HOR ² -OH (VIII), where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ N ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or isophorone (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Here are compositions according to the invention in which the water-soluble polymer is a polyurethane which has structural units of the formula (IX) - (OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (IX), in which R ^{1 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ² is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a Number from 5 to 199 and k is a number from 1 to 2000.

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

As already mentioned above, the Reaction mixtures in addition to diisocyanates (VII) and diols (VIII) also other compounds from the group of polyisocyanates (in particular Triisocyanates and tetraisocyanates) and from the group of polyols and / or di or polymaine included. In particular triplets, tetrols, Pentols and hexols as well as di- and triamines can be used in the reaction mixtures be included. A content of compounds with more than two "active" H atoms (all above with the exception of diamines) leads to a partial crosslinking of the polyurethane reaction products and can be beneficial Properties such as control of the dissolution behavior, abrasion stability or flexibility the polymer matrices according to the invention, Process advantages in manufacturing, etc. cause. Usually is the content of such compounds with more than two "active" H atoms on the Reaction mixture less than 20 wt .-% of the total used Reaction partner for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight.

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

A particularly preferred polymer for the Active ingredient-containing polymer matrix is a polymer containing sulfonic acid groups contains. Preferred compositions according to the invention are therefore characterized in that the polymer matrix at least a copolymer of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic Includes monomers. out.

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

Among the unsaturated carboxylic acids that can be described by formula X 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 XI R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XI), in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _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 XIa, XIb and / or XIc, H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XIa), 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2 -methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid 2-methyl-2-propenl-sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide (X = -C (O) NH- in formula XIb), sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.

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

• i) ungesättigten Carbonsäuren der Formel X. R¹(R²)C=C(R³)COOH (X),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 XI R⁵(R⁶)C=C(R⁷)-X-SO₃H (XI), in der R⁵ bis R⁷ 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, 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 bevorzugte Materialien für die PolymermatrixIn summary, copolymers are made of

• i) unsaturated carboxylic acids of formula X. R ¹ (R ² ) C = C (R ³ ) COOH (X), 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 XI containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XI), in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ⁴ ° is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group stands, 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 materials for the polymer matrix

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln XIa, XIb und/oder XIc: H₂C=CH-X-SO₃H (XIa), H₂C=C(CH₃)-X-SO₃H (XIb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (XIc),in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -N, -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(CH₃)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 XIa, XIb and / or XIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ^{7 are} independently selected from -N, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) iii) optionally further ionic or nonionic monomers.

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

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

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the compositions according to the invention is also preferred and is characterized in that the compositions contain one or more copolymers as the polymer matrix, the structural units of the formula XII - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

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. Compositions according to the invention which contain one or more copolymers as the polymer matrix, which structural units of the formula XIV - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (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 ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) stands, are also preferred, a preferred embodiment of the present invention, just as compositions are preferred, which are characterized in that they contain as polymer matrix one or more copolymers which have structural units of the formula XV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-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 ) _n 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.

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

In summary, compositions according to the invention are preferred which contain, as polymer matrix, 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 - (XII), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XV), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI), - [HOOCCH-CHCOOH] _m - [CH ₂ C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVII), contain, in which m and p each represent an integer natural number between 1 and 2000 and Y for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred.

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

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

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

The molar mass of the sulfo copolymers described above used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred compositions 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 .

The active substance-containing polymer matrix can consist exclusively of polymer (s) and those described above There exist agents to achieve glass corrosion inhibition, but it can also contain other ingredients. Additives to be mentioned here in particular, as are customary in polymer production, for example plasticizers, antioxidants, rheology improvers or other processing aids. However, other ingredients from the field of detergents or cleaning agents, for example colors and fragrances, can also be part of the polymer matrix.

As a plasticizer, the compositions according to the invention especially use hydrophilic, high-boiling liquids, whereby if necessary also solids at room temperature as a solution, dispersion or melt can be used. Particularly preferred compositions according to the invention are characterized in that as Plasticizer of one or more materials from the group glycol, Di-, Tn-, Tetra-, Penta-, Hexa-, Hepta-, Octa-, Nona-, Deca-, Undeca-, Dodecaethylene glycol, glycerin, neopentyl glycol, trimethylol propane, Pentaerythritol, mono-, di-, triglycerides, surfactants, in particular nonionic surfactants, as well as their mixtures.

The active ingredient-containing polymer matrix, according to the invention in the Compositions is included, in addition to the polymer (s) contains at least one agent released from the matrix can and that is able to provide corrosion protection for silver for cleaning and / or Flushing one dishwasher provide. Preferred according to the invention Compositions are characterized in that the polymer matrix 1 to 90% by weight, preferably 1.5 to 80% by weight, particularly preferably 2 to 70% by weight, more preferably 2.5 to 60% by weight and in particular 3 to 50% by weight of one or more agents which are able to Silver corrosion protection during cleaning and / or rinsing processes dishwasher to provide includes where the weight information relates to the active ingredient-containing polymer matrix Respectively.

Regardless of whether as a matrix material Glass or polymers or other materials can be used compositions according to the invention contain the active substance-containing matrix in different amounts. So can For example, articles are made that are 100% by weight the matrix containing the active ingredient. Such products can then into the machine as a separate article using suitable dosing devices be introduced. The matrix containing the active ingredient can also be used other ingredients made up into a cleaning agent become. Depending on whether the active ingredient-containing matrix in the compositions is contained as a fine powder, granules, etc., or as a part of a shaped body, or whether it encloses the composition as packaging, the Quantities of the active ingredient matrix in the total composition vary. Compositions according to the invention are preferred here, which, based on the total mass of the composition, 1 to 40% by weight, preferably 1.5 to 35% by weight, particularly preferably 2 to 30% by weight and in particular 2.5 to 20% by weight of the active substance-containing matrix contain.

Depending on the active substance content of the active substance-containing matrix and on the amount of matrix that is contained in the compositions according to the invention, the contents of the compositions according to the invention on the agent that can be released from the matrix and that is able to protect against corrosion during cleaning and / or to provide dishwashing operations for a dishwasher vary. Compositions according to the invention, which are characterized in that, based on the total mass of the composition, they contain at least one from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes in amounts of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, the metals preferably in one of the oxidation stages II, III , IV, V or VI are present and particularly preferred agents 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 . come).

As mentioned at the beginning, the training is necessary active ingredient according to the invention Matrices in the compositions of the invention no restriction in terms of the dosage forms or the recipes of these compositions. So can besides usual automatic dishwashing detergents also pre-wash or pre-wash products, rinse aid, Machine maintenance or additional products as a composition according to the invention to be provided. A preferred embodiment of the composition according to the invention stipulates that the Matrix as a molded part to be placed separately in the dishwasher is provided that about several rinses releases the agents from the matrix. This molding can either a dosing basket for others Products such as the cleaner, but it can also as a separate and independent Embody molded part the additional benefit of silver protection. Possible shapes are based, for example, on the well-known dishwasher dodorants. The design of the glass or plastic part is visually appealing in translucent, opalescent or completely clear form, for example in the form of a stylized diamond or silver bar. By such product designs can be visualize the shine resulting from the silver protection close to the consumer.

The variety of shapes are because of the possibilities there are no limits to glass or plastic processing. The active substance-containing matrices can easily with the usual Methods are transformed.

The shaping processing of plastic-based matrices is carried out according to that in plastics processing working industry usual methods, in particular the film production and processing, blow molding and injection molding are preferred. All processes have in common that a plastic granulate is melted with the help of an extruder and fed to shaping tools. The plastic granules can already contain the agents for inhibiting glass corrosion, but these can also be added during melting in the extruder, which enables the active ingredient-containing matrices according to the invention to be produced particularly cost-effectively.

A melted one is then on the extruder head Polymer blend before, depending on the desired molded part according to common processes the thermoforming of polymers is further processed, whereby deep drawing, so-called rotary die processes, blow molding (Blow extrusion) and injection molding are of particular importance. For example, shaping can be carried out to form foils, which can be processed further below. Depending on what you want The purpose of the molded part can be the material thickness of the Slide vary. For Foil bags, so-called pouches, are less thick choose as for Slides that later for deep-drawing or rotary die processes can be used. Shall the molded parts the active ingredient-containing matrix later used as a kind of packaging, they must of course be water-soluble, to release the contents of the packaging and no residues in the dishwasher to leave.

For foil bags (so-called pouches), it is preferred that the water-soluble Foil that forms the bag, a thickness of 1 to 150 microns, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm, having. Foils for Thermoforming processes preferably have thicknesses that are 1.5 times preferably 2 times and especially 2.5 times that for pouches mentioned values.

In a preferred method the films starting from the melt leaving the extruder with air over blown a blow mandrel into a tube. This can follow cut, filled and be sealed. In the calendering process, that too belongs to the preferred manufacturing processes used through suitable additives plasticized raw materials atomized to form the foils. Here it may be necessary to connect drying to the atomizers. The Films obtained by this process can then also be used as bags shaped and filled be closed.

In a further preferred embodiment In the present invention, the melt leaving the extruder from water soluble Blown polymer blend. Blow molding processes suitable according to the invention include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and diving bubbles.

Leave the wall thickness of the moldings produce different areas by blow molding, by looking at the wall thicknesses the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material, preferably by means of a Adjusting spindle forms when the preform is removed from the extruder nozzle.

The molded body can be made with areas different outer circumference and constant wall thickness Blow molding by changing the wall thickness the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by regulation the amount of thermoplastic material using an adjusting spindle when the preform is removed from the extruder nozzle.

In this way, different geometric configurations of the molded body with and without compartments blow molding. In a single cycle, bottles can be Balls, Santa Clauses, Easter bunnies or other figures blow molds that are filled with funds can, subsequently sealed and then demolded.

It is particularly advantageous that the moldings emboss and / or decorate in the blow mold during blow molding. By appropriate design of the blow mold, a motif can be mirrored transferred to the molded body. That way the surface of the shaped body design practically any. For example, the molded body Information such as calibration marks, application notes, hazard symbols, Brands, weight, filling quantity, Apply expiry date, pictures, etc.

The preform, the molded body and / or the liquid-tight closed molded body can be tubular, spherical or bubble-shaped. Has a spherical shaped body preferably a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferred from> 0.95.

The shape factor in the sense of the present invention can be precisely determined using modern particle measurement techniques with digital image processing. A common method is, for example, the Camsizer ^® system from Retsch Technology or the KeSizer ^® from Kemira. These methods are based on the fact that the bodies are irradiated with a light source and the shaped bodies are recorded, digitized and processed by computer technology as projection surfaces. The surface curvature is determined by an optical measuring method in which the “shadow cast” of the body to be examined is determined and converted into a corresponding form factor. The basic principle for determining the form factor was described, for example, by Gordon Rittenhouse in “A visual method of estimating two -dimensional sphericity "in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81 This optical analysis method is 15 μm to 90 mm. Methods for determining the shape factor for larger particles are known to the person skilled in the art. These are usually based on the principles of the aforementioned procedures.

The walls of the by means of blow molding manufactured molded body have a wall thickness from between 0.05 - 5 mm, preferably from between 0.06-2 mm, preferably from between 0.07-1.5 mm, more preferably from between 0.08-1.2 mm, more preferably from between 0.09 - 1 mm and most preferably between 0.1-0.6 mm.

The filling opening of the hollow body after filling let yourself liquid-tight, preferably by material closure, preferably by means of thermal Treatment, particularly preferably by applying a melt blob, close. The filling opening or openings of the hollow body can also be advantageously by thermal treatment, preferably by fusing the walls adjacent to the opening, in particular by means of clamping jaws, liquid-tight close.

It is particularly preferred according to the invention to use the blow molding process as a BFS (blow-fall-seal) process, so that the manufactured moldings still filled in the blow mold and be locked. With this blow mold / filler closure technique, the desired shape becomes first blown, then filled with the content and then in closed to an operation.

Here, a tube is plasticized water-soluble Plastic material in an open Extruded blow mold, closed the blow mold and by creating an effective pressure gradient on the hose is widened and to form the container applied to the shaping wall of the blow mold.

In a further preferred embodiment The present extension is the melt leaving the extruder from water soluble Polymer blend processed using a injection molding process. The injection molding takes place according to known procedures at high pressures and Temperatures with the steps of closing the to the extruder Spritrgießen connected mold, injection of the polymer at high temperature and high pressure, cooling of the injection molded molding, opening the Shape and remove the molded blank. Other optional steps such as the application of release agents, demolding etc. Known in the art and can be carried out according to technology known per se.

The advantages of the procedure the production by injection molding lie in the mature technology of this procedure, the high flexibility in terms of the materials that can be used, the ability to have exactly the desired wall thickness s To obtain shaped or dimensionally stable hollow body and the possibility of a dimensionally stable in one step with high reproducibility hollow body with one or more integral compartmentalization device (s) manufacture.

In preferred methods according to the invention is at a pressure between 100 and 5000 bar, preferably between 500 and 2500 bar, particularly preferably between 750 and 1500 bar and especially between 1000 and 1250 bar, injection molded.

The temperature of the material that should be injection molded, is preferably above the melting or softening point of the material and thus also depends on the type and composition of the polymer blend. In preferred methods according to the invention is at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and especially injection molded between 140 and 180 ° C.

The tools, the materials record, are preferably preheated and have temperatures above room temperature, with temperatures between 25 and 60 ° C and especially from 35 to 50 ° C are preferred.

Regardless of the material used for the Moldings, but dependent of the ones you want dissolution properties the thickness of the wall can be varied. The wall should be chosen so thin on the one hand that a speedy resolution or disintegration is achieved and the ingredients quickly into the application fleet released, but a certain minimum thickness is also required, the desired shape around the hollow shape Stability, especially dimensional stability, to rent.

Preferred methods according to the invention are therefore characterized in that the wall thickness of the injection molded body 100 to 5000 μm, preferably 200 to 3000 μm, particularly preferably 300 to 2000 μm and in particular 500 to 1500 μm is.

The one produced by injection molding regularly moldings not closed walls on all sides and is on at least one of its sides - at a spherical one or elliptical body in the area of part of its shell - open due to manufacturing. Through the remaining opening is / are in the compartment (s) formed inside the molded body (s) one or preparations). This also happens in a way known per se, for example within the confectionery industry known manufacturing processes; in several steps are also conceivable current procedures. A one step process is particularly preferred if in addition to solid preparations liquid components comprehensive preparations (dispersions or emulsions, suspensions) or even gaseous Formulations comprising components (foams) introduced should be.

Methods according to the invention are summarized preferred, where the molding processing by extrusion in an injection mold (by injection molding) he follows.

In addition to providing compositions, in which the matrix containing the active ingredient either takes on the packaging function or designed as a single part, the can composition according to the invention also as normal "products be realized that the active ingredient-containing matrix as one of contain several substances. Compositions according to the invention can therefore also as automatic dishwashing detergent, rinse aid or machine maintainers are provided in both solid and liquid form become.

Liquid detergent, in Within the scope of the present invention are aqueous and non-aqueous agents based on liquid Components with dynamic viscosities in the range between 0.2 and 1000 mPas, but also more viscous Medium with viscosities above 1000 mPas through to cut-resistant and dimensionally stable gels are possible offer forms. Preferred non-aqueous liquid Detergents contain solvents from the group ethanol, n-propanol, i-piopanol, 1-butanol, 2-butanol, Glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, 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 Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether or their mixtures.

To adjust the viscosity of liquid supply forms the cleaning agent according to the invention these typically also contain one or more thickeners. Preferred thickeners are agar agar, carrageenan, tragacanth, Gum arabic, alginates, pectins, polyoses, guar flour, carob flour, Strength, Dextrins, gelatin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose, hydroxypropyl methyl cellulose, powdered meal ether, Polyacrylic u. Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonite, Zeolites and silicas.

Another typical ingredient liquid aqueous Cleaning agents are hydrotropes. The addition of such substances causes that a slightly soluble Substance in the presence of the hydrotrope, which itself is not a solvent is water soluble becomes. Substances that bring about such an improvement in solubility, are called hydrotropes or hydrotropes. Typical hydrotropes, e.g. in the assembly of liquid detergents or cleaning agents, are xylene and cumene sulfonate. Other substances, e.g. urea or N-methylacetamide, increase the solubility through a structure-breaking Effect where the water structure around the hydrophobic Group of a sparingly soluble Substance is broken down.

Fixed offer forms of the machine according to the invention dishwashing detergent are, for example, fine to coarse-grained powders, such as, for example by spray drying or granulation are obtained from compressed mixtures of substances roller compacting, but also solidified melting or through Moldings obtained by extrusion or tableting. Such moldings can in Within the scope of the present invention practically all usable Have configurations, for example in the form of a table, in the form of bars or bars, a cube, a cuboid and the like Room element with flat side surfaces as well as in particular cylindrical Circular designs or have an oval cross-section. This last embodiment covers the presentation form from the actual tablet to compact cylinder sections with a relationship of height to diameter above 1. Preferred tableted or extruded In the context of the present invention, agents have two or more Phases that are characterized, for example, by their composition, their share in the total volume of the shaped body and / or their optical Can distinguish appearance.

The phases of such multi-phase moldings can yourself in addition through a different dissolution behavior in watery Award phase. Such moldings are suitable for the time controlled release of certain ingredients (controlled release), for example in certain rinses of the machine wash program. In a preferred embodiment exhibits one of the phases of the shaped body as the main component meltable or softenable substances from the Group of waxes, paraffins and / or polyalkylene glycols. Farther it has proven to be advantageous if the melting or softenable substances contained molded body or molded body component at least insoluble in water is. The solubility in water at a temperature of about 30 ° C about 10 do not exceed mg / l and are preferably below 5 mg / l. In such cases the meltable or softenable substances, however, one if possible low water solubility, even in water with increased Temperature, have a temperature-independent release of the active substances preferably largely avoided. The active substance is released this way when the melting or softening point is reached.

In a special embodiment of the present invention, it is finally preferred to add an agent containing the active substance-containing matrix to the rinsing process in addition to a commercially available cleaning agent, for example in the form of a special glass protective agent. Such a dosage can be either before the start of each washing program or in the form of a depot product that is continuous Release of the zinc and / or magnesium salts of organic acid according to the invention effected over several rinse cycles.

Preferred machine according to the invention Dishwashing liquid contain in addition to the builders (builder, Cobuilder) and the active ingredient-containing polymer matrix or several substances from the group of surfactants, bleaching agents, bleach activators, Enzymes, dyes, fragrances, anti-corrosion agents, polymers, or another common one Part of detergents and cleaning agents. These ingredients are described below.

Builder

According to the present invention can in the detergents and cleaning agents all usually in detergents and Builders used in cleaning agents, especially silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 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 the sharp X-ray reflections that are typical of crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Both the monoalkali metal salts can be used as carbonates as well as the dialkali metal salts of carbonic acid as well as sesquicarbonates to be included in the funds. Preferred alkali metal ions Sodium and / or potassium ions. In one embodiment, it may be preferred be, the carbonate and / or bicarbonate at least partially as further Component separately or afterwards admix. Also compounds made of carbonate, silicate, for example and optionally other auxiliaries such as anionic surfactants or other, especially organic builder substances, can be used as separate component in the finished funds.

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

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with a Naronauge and the mash is sprayed. Potassium hydrogen phosphate (primary or monobasic potassium phosphate, potassium biphoshate, 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), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also 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 a distinction can be made between cyclic representatives, the sodium and potassium metaphoshates, and chain-like types, the sodium and 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 sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

In the context of the present inventions preferred automatic dishwashing detergents do not contain sodium and / or potassium hydroxide. A waiver of sodium and / or potassium hydroxide as an alkali source has proven to be particularly advantageous when used as zinc salts zinc gluconate, zinc formate and zinc acetate become.

builders

Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetates, dextrins, other organic cobuilders (see below) and phosphonates. The polymers can also be part of the active substance-containing matrix, but they can also be contained in the agents according to the invention completely independently of this. The substance classes mentioned are described below wrote.

Usable organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), 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, methylglycine, sugar acids and mixtures of these.

The acids themselves can also be used become. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents.

In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any are To call mixtures of these.

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

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

Suitable polymers are in particular Polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol exhibit. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, have, be preferred.

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

Of course you can also the sulfonic acid group-containing polymers described above in the agents according to the invention be included without a mandatory component of the active ingredient To be a matrix.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

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

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

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

Show other preferred copolymers as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and Vinyl acetate.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts are particularly preferred and derivatives.

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

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

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

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

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

Another class of substances with cobuilder properties represent the phosphonates. These are in particular around hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and 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.

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

Agents according to the invention are within the present application characterized in that it contains builders, preferably from the group of silicates, carbonates, organic Cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably from 1 to 95% by weight, particularly preferably from 5 to 90 % By weight and in particular from 10 to 80% by weight, in each case based on the means included.

surfactants

Preferred cleaning agents included in the context of the present application one or more surfactants) the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of _α- sulfo fatty acids (ester sulfonates), for example the _α- sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of 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 -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

Other anionic surfactants especially soaps. Saturated fatty acid soaps are suitable, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

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

Another group of washing-active substances are the non-ionic 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 residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain.

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

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

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

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 (XIX)

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 Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or Propxylated derivatives of this residue.

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-anloxy-substituted Connections can then 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.

In the case of detergents and cleaning agents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. Highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates are very particularly preferred in the sense of the present ending.

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. Automatic dishwashing agents according to the invention which contain surfactants of the general formula XX 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 XX can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula I 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, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. 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 1 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.

As a preferred additional Surfactants become low-foaming non-ionic surfactants used. Contained with special preference the machine according to the invention Dishwashing liquid a nonionic surfactant that has a melting point above room temperature having. Accordingly, preferred agents are characterized in that that she nonionic surfactants) with a melting point above 20 ° C., preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

Suitable in addition to the invention in the Nonionic surfactants contained in non-ionic surfactants or have softening points in the temperature range mentioned, are low-foaming, for example non-ionic surfactants that are solid or highly viscous at room temperature could be. Become highly viscous nonionic surfactants used at room temperature, it is preferred that these a viscosity above of 20 Pas, preferably above 35 Pas and especially above Have 40 Pas. Also nonionic surfactants, which are waxy at room temperature Having consistency is preferred.

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

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

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

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has 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 molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the make up nonionic surfactant.

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

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

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

Other 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 ^{1 2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} N or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl - or 2-methyl-2-butyl radical, x stand 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 latter 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 represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

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

Within the scope of the present invention it is preferred that the Automatic dishwashing liquid Surfactant (s), preferably nonionic surfactant (s), in amounts of 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight and in particular from 1.0 to 5% by weight, based in each case on the total composition.

bleach

Bleaching agents and bleach activators are important components of detergents and cleaning agents, and a detergent and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^–3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first by precipitation in 1899 with ethanol from a solution obtained from sodium carbonate in hydrogen peroxide, but mistakenly as Peroxycarbonate viewed. It was not until 1909 that the compound was used as a hydrogen peroxide addition compound recognized, but the historical term "sodium percarbonate" has been used in practice enforced.

The industrial production of sodium percarbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Cleaning agents for mechanical Wash the dishes can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents used as ingredients in the frame of the present invention are the diacyl peroxides, such as.

Dibenzoyl. 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- phthaloxyhexanoic acid [phthaloxyhexanoic acid] )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutanoic acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

According to the present invention, bleaching agents for automatic dishwashing can also be used Chlorine or bromine releasing substances are 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.

Advantageous funds under the present invention contain one or more bleaches, preferably from the group of oxygen or halogen bleaches, especially chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40 % By weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total mean.

Bleach activators

To when cleaning at temperatures of 60 ° C and below that to achieve an improved bleaching effect, detergents contain bleach activators in the context of the present invention. Can be used as bleach activators Compounds which are preferred under perhydrolysis conditions with aliphatic peroxocarboxylic acids 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic result, are used. Substances that are O- and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carbonsäureanhydnde, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

According to the invention, agents are preferred one or more substances from the group of bleach activators, especially from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts from 0.1 to 20% by weight, preferably from 0.5 to 15 % By weight and in particular from 1 to 10% by weight, in each case based on all the means included.

in denen 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, -CH₂CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂CH(OH)-CH₃, -CH(OH)-CH₂CH₃, -(CH₂CH₂O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.The bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitrites of the formula (XXI),

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.

General formula (XXI) includes a large number of cationic nitriles which can be used in the context of the present invention. The detergent tablets according to the invention particularly advantageously contain cationic nitrites in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.

For reasons of easier synthesis, compounds are preferred in which the radicals R ¹ to R ^{3 are} identical, for example (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 ^- , where X ^- preferably represents an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.

Within the scope of the present invention preferred detergents and cleaning agents are characterized in that that she the cationic nitrile of the formula (XXI) in amounts of 0.1 to 20 % By weight, preferably from 0.25 to 15% by weight and in particular from 0.5 to 10 wt .-%, each based on the weight of the molded body.

enzymes

In particular, there are enzymes from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these hydrolases wear in the wash for removing stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can about that by removing pilling and microfibrils for color retention and increase contribute to the softness of the textile. For bleaching or for inhibition the color transfer can oxidoreductases can also be used. Are particularly well suited from bacterial strains or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humi cola insolens and from their genetically modified variants of enzymatic substances obtained. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or Protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of of special interest. Examples of such lipolytically active Enzymes are the well-known cutinases.

Also have peroxidases or oxidases themselves in some cases proven suitable. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. As cellulases cellobiohydrolases, endoglucanases and glucosidases, which are also called cello bias, or mixtures of these used. Since different types of cellulase differ by their CMCase and avicelase activities can distinguish the desired activities are set by targeted mixtures of the cellulases become.

The enzymes can be adsorbed on carriers or in coating substances embedded to protect them against premature decomposition. preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight, each based on the total mean.

dyes

To give the aesthetic impression of the washing and to improve cleaning agents, they can be mixed with suitable dyes colored become. Preferred dyes in the context of the present invention, the selection of which is of no difficulty for the person skilled in the art high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity towards textile fibers, so as not to stain them.

Preferred for use in the washing and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process, and also mixtures thereof with suitable blue dyes, so-called blue tans. It has proven to be advantageous to use colorants which are soluble in water or in liquid organic substances at room temperature. For example, anionic colorants, for example anionic nitroso dyes, are suitable. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes. Other colorants are Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit Patent blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol Blau GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) are used.

When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity compared to the textile surfaces and here in particular to synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In contrast, in the case of the pigment dyes which are particularly preferred because of their brilliance, but less readily water-soluble, for example the above-mentioned pigmosol dyes, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^-3 to 10 ^-4 % by weight.

fragrances

Fragrances are used in the products The scope of the present invention added to the aesthetic impression of products to improve and consumer in addition to performance of the product a visually and sensorially "typical and distinctive" product put.

In the context of the present invention, individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropylate, stylate propionate, stylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, _∝ -isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.

However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. 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.

Corrosion inhibitors

Detergents for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important 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. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-McTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-McTACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-McTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

The agents according to the invention can be provided, for example, as powders, granules or tablets. Such agents preferably contain the active ingredient-containing matrix in particulate form, which is admixed with the agent or the premixes to be pressed. Compositions preferred according to the invention are characterized in that they contain the active substance-containing matrix in particulate form, where the active substance-containing matrix preferably has an average particle size of at most 500 μm.

In addition, tablets with additional optical characteristics are produced, for example, tray tablets, that contain a separate core. Here are compositions according to the invention preferred which contain the active substance-containing matrix as shaped bodies, preferably by extrusion, casting, injection molding, blow molding or pulling the matrix containing the active ingredient.

As mentioned above, can the matrix containing the active ingredient also as packaging for mechanical Dishwashing liquid or part of it can be used. Compositions are preferred here, which contain the active substance-containing matrix as a covering, which preferably by injection molding, Blow molding, deep drawing, calendering, cold rolling or coating the composition is produced by means of the coating process.

Other objects of the present invention are a method of inhibiting silver corrosion in cleaning and / or rinsing one Dishwasher, characterized by bringing silverware into contact with Washing and / or rinsing water, which contains an effective amount of a composition according to the invention, and a method for inhibiting silver corrosion in cleaning and / or Flushing one Dishwasher, which is characterized in that inside the dishwasher on one for the washing and / or rinsing water accessible Make a composition according to the invention provided.

1) Production of a Manganese Phosphate Glass:

Phosphorus pentoxide, Potassium carbonate, sodium carbonate and calcium carbonate are used. As a forerunner for manganese served e.g. Manganese sulfate or manganese carbonate. Manganese salt and glass former are mixed intensively and heated to 900 ° C in an oven. The resulting melt is kept at this temperature for 3 hours and subsequently gradually cooled to room temperature.

A composition of a manganese-phosphate glass to be used according to the invention is shown here:
68.0% P ₂ O ₅
6.8% MnO
4.8% CaO
18.7% K ₂ O
1.7% Na ₂ O

2) Rinse attempt

A glass with the composition described above was placed in a water-rinsable container and in a household dishwasher used. A formulation free of silver protection is used as a cleaner used that over a conventional one TAED / perborate bleaching system features. The used silver ware will before rinsing cleaned with a cloth and placed in the cutlery basket of the machine.

After 10 rinsing cycles in a 65 ° C program without intermediate cleaning, the silver is removed and evaluated. Rating silver tarnishing:
0 no start-up;
1 easy start;
2 stronger start;
3 strong all-over tarnishing with gold to brown coloring;
4 very strong all-over tarnishing with violet to black coloring)
Machine: Miele 698 SC
Program: 65 ° C universal
Rinse cycles: 10
Water hardness: 16 ° d

The usual black tarnishing when using a silver protection-free cleaner could also after 10 rinse cycles cannot be determined. The silver washware appeared completely corrosion-free, Grade 0.

10 rinse cycles were used for comparison with the above Cleaner performed, the silver protection composition not in the dishwasher was given. After 10 rinse cycles the silver was discolored black, Grade 4.

To reduce the mass loss of the glass the glass was weighed before and after the experiment. On the Test results in an average mass loss of 0.47g per wash.

3) Packaging

The glass can be described as Block poured into a suitable container in the dishwasher and there depending on the amount of glass for more than one rinse cycle remain. Furthermore, the glass according to the invention can be used with conventional Methods are crushed and as a semolina or powder a cleaner be added in appropriate concentration.

Claims (22)

Use of an active ingredient-containing matrix with containing at least one agent capable of protecting against silver corrosion during cleaning and / or rinsing processes dishwasher to provide for the release of (s) for silver corrosion protection effective agent (agents) from the matrix in the cleaning and / or Flushing the Dishwasher. Use according to claim 1, characterized in that that the Matrix a water soluble Glass covers. Use according to claim 1, characterized in that that the Matrix a polymer matrix of one or more, preferably water-soluble (m / n), Polymer (s) comprises. Use according to one of claims 1 to 3, characterized in that that this or those for the silver corrosion protection agent (s) from which Group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes is derived from the metals preferably in one of the oxidation states II, III, IV, V or VI available. Use according to one of claims 1 to 4, characterized in that the agent (s) active for silver corrosion protection from the group MnCO ₃ , Mn (CH ₃ COO) ₂ , 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 . Composition for use in a dishwasher, containing an active ingredient-containing matrix, containing at least an agent that is capable of silver corrosion protection in cleaning and / or Flushing one dishwasher provide. Composition according to claim 6, characterized in that the Matrix a water soluble Glass covers. Composition according to claim 6, characterized in that the Matrix comprises a polymer matrix of one or more polymer (s). Composition according to claim 7, characterized in that the Matrix as glass-forming component (s) one or more substances from the group phosphorus pentoxide, sodium oxide, potassium oxide, silicon oxide and Boron oxide comprises. Composition according to one of claims 7 or 8, characterized in that the or those for the silver corrosion protection agent (s) from which Group of oxides of manganese, titanium, zirconium, hafnium, vanadium, Cobalt and cerium originate, the metals preferred are in one of the oxidation states II, III, IV, V or VI. Composition according to claim 8, characterized in that the polymer matrix a) 5 to 99.5% by weight of one or more polymers, b) 0.5 to 95% by weight of one or more agents capable of are silver corrosion protection during cleaning and / or rinsing processes dishwasher provide, c) 0 to 30% by weight of further active and / or Excipients includes. Composition according to claim 11, characterized in that the Polymer matrix 7.5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 12.5 to 85% by weight, further preferably 15 to 82.5 % By weight and in particular 20 to 80% by weight of one or more polymers comprises where the weight information relates to the active ingredient-containing polymer matrix Respectively. Composition according to one of claims 11 or 12, characterized in that the Polymer matrix 1 to 90 wt .-%, preferably 1.5 to 80 wt .-%, particularly preferably 2 to 70% by weight, more preferably 2.5 to 60% by weight and in particular 3 to 50 wt .-% of one or more agents that in are able to provide silver corrosion protection during cleaning and / or rinsing processes Geschinspülmaschine to provide includes where the weight information relates to the active ingredient-containing polymer matrix Respectively. A composition according to any one of claims 11 to 13, characterized in that the Polymer matrix one or more water-insoluble polymers from the group Polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, Polycarbonate, polyvinyl chloride, the polyurethanes, the polyamides as well their mixtures includes. Composition according to one of Claims 11 to 13, characterized in that the polymer matrix comprises one or more water-soluble polymers, the water-soluble polymer (s) preferably being selected from: i) polyacrylic acids and their salts ii) Polymethacrylic acids and their salts iii) polyvinylpyrrolidone, iv) vinylpyrrolidone / vinyl ester copolymers, v) cellulose ethers vi) polyvinyl acetates, polyvinyl alcohols and their copolymers vii) graft copolymers from polyethylene glycols and vinyl acetate viii) alkylacrylamide / acrylic acid copolymers, methacrylates and acrylic acid copolymers, Copolymers and their salts x) alkyl acrylamide / methyl methacrylic acid copolymers and their salts xi) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts xii) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts xiii) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid-co polymers and their salts xiv) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and their salts xv) copolymers of xv-i) unsaturated carboxylic acids and their salts xv-ii) cationically derivatized unsaturated carboxylic acids and their salts xvi) acrylamidoalkyltrialkylammonol chloride whose alkali and ammonium salts xvii) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts xviii) methacroylethylbetaine / methacrylate copolymers xix) vinyl acetate / crotonic acid copolymers xx) acrylic acid / ethyl acrylate / N-tert-butyl polypropylene acrylamide , Esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols xxii) copolymers grafted from the copolymerization of xxii-i) at least one monomer of the non-ionic type, x xii-ii) at least one monomer of the ionic type, xxiii) copolymers obtained by copolymerizing at least one monomer of each of the three following groups: xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, xxiii- i) unsaturated carboxylic acids, xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol. A composition according to any one of claims 11 to 15, characterized in that it based on the total mass of the composition, 1 to 40% by weight, preferably 1.5 to 35% by weight, particularly preferably 2 to 30% by weight and in particular 2.5 to 20% by weight of the active substance-containing matrix contains. Composition according to one of Claims 11 to 16, characterized in that, based on the total mass of the composition, it comprises at least one from the group consisting of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes in amounts of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, the Me talle preferably in one of the oxidation states II, III, IV, V or VI and particularly preferred agents 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 . A composition according to any one of claims 10 to 17, characterized in that it contains the active substance-containing matrix in particulate form, where the active substance-containing matrix preferably has an average particle size of at most 500 μm. A composition according to any one of claims 10 to 17, characterized in that it contains the active substance-containing matrix as a shaped body, preferably by Extrusion, casting, Spritrgießen, Blow molding or drawing the matrix containing the active ingredient is. A composition according to any one of claims 11 to 17, characterized in that it contains the active substance-containing polymer matrix as a sheath, preferably by Spritrgießen, Blow molding, deep drawing, calendering, cold rolling or coating the composition is produced by means of the coating process. Process for inhibiting silver corrosion in cleaning and / or rinsing one Dishwasher, characterized by bringing silverware into contact with Washing and / or rinse water, an effective amount of a composition according to claims 6 to 20 contains. Process for inhibiting silver corrosion in cleaning and / or rinsing one Dishwasher, characterized in that in Inside the dishwasher on one for the washing and / or rinsing water accessible Make a composition according to claims 6 to 20 is provided.