DE10225116A1 - Automatic dishwashing detergent with improved glass corrosion protection II - Google Patents

Abstract

Automatic dishwashing detergents or dishwashing aids which contain both zinc salts and crystalline layered silicate of the general formula I DOLLAR A NaMSi¶x¶O¶2x + 1¶ È y H¶2¶O DOLLAR A, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y stands for a number from 0 to 33, are distinguished by significantly improved glass corrosion properties.

Description

The present invention is in the field of automatic dishwashing detergents. In particular The present invention relates to machine dishwashing detergents, zinc salts and certain Contain silicates.

With the progressive automation of various washing and cleaning processes in Household and industry have machine washing and cleaning agents for textiles and dishes has become increasingly important in recent decades.

The so-called low-alkaline cleaners required for automatic dishwashing often contain mixtures of sodium disilicate and soda as builders of alkali, builders such as Citric acid, for example in connection with polycarboxylates and preferably low-foaming, non-ionic surfactants. Bleaching agents, bleach activators, Silver and anti-corrosion agents and, to enhance cleaning ability, enzymes be included. In a typical machine cleaning cycle, this is set in baskets Dishes due to intensive contact with the aqueous cleaning solution at around 65 ° C and pH values cleaned between 9 and 11 and then rinsed clear.

An important criterion for evaluating a machine dishwashing detergent is in addition to it Cleaning performance the visual appearance of the dry dishes after they are done Cleaning. Possible calcium carbonate deposits on dishes or in Machine interiors, for example, can affect and have customer satisfaction thus causal influence on the economic success of such a cleaning agent. On Another longstanding problem with automatic dishwashing is corrosion of glassware, which is usually characterized by cloudiness, streaks and scratches can also manifest by iridescence of the glass surface. The observed effects are based on this essentially on two processes, the leakage of alkali and alkaline earth ions from the glass in Connection with hydrolysis of the silicate network, on the other hand in a deposit silicate compounds on the glass surface. To avoid such corrosion processes there are a number of proposals in the prior art, for example with regard to use of zinc salts.

Prevented according to the teaching of US Pat. No. 3,677,820 (Whirlpool Corporation) a zinc strip in the interior of the dishwasher prevents the corrosion of Glass surfaces during the cleaning process.

European patent application EP 0 383 482 (Procter & Gamble Company) describes finally machine dishwashing detergent, containing insoluble zinc salts, which are characterized by a distinguish improved glass corrosion protection. The insoluble zinc salts have to be achieved of such an effect have a particle size below 1.7 millimeters.

But also the use of silicates to prevent glass corrosion in machines Dishwashing has been described.

International patent application WO 96/12783 (Henkel KGaA) discloses phosphate-free bis low-phosphate machine dishwashing detergent with improved decor and glass protection Basis of citrate-containing formulations that contain crystalline layered silicates.

The subject of the international patent application WO 99/57237 (Clariant GmbH, Henkel KGaA) are phosphate-containing automatic dishwashing detergents which contain a powdery to granular additive which contains as essential components a crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, M represents sodium or hydrogen, x is a number from 1.9 to 22 and y is a number from 0 to 33, and have (co) polymeric polycarboxylic acid and, in addition to glass or decorative effects, also have excellent cleaning performance.

The present invention was based on the object of a machine dishwashing detergent To provide that even with repeated use, the surfaces of glass dishes are not changed corrosively, especially no clouding, streaks or scratches but also no iridescence of the glass surfaces. Preferably, an additive for a machine Dishwashing detergents are provided that are found to be part of machine Dishwashing detergent of any form, for example as a component of powder, tablet, Liquid formulations, cleaning foams or depot products are suitable without these recipes limit.

It has now been found that the aforementioned objects are achieved by machine dishwashing agents or machine dishwashing aids which, in addition to at least one zinc salt, also contain at least one crystalline layered silicate. The present application therefore relates to automatic dishwashing detergents or automatic dishwashing aids containing at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

NaMSi _x O _{2x + 1} .yH ₂ O (I),

wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33.

It has been found to be particularly advantageous for the corrosion-inhibiting action of agents according to the invention It has been shown that the zinc salt (s) and the crystalline layer (s) Silicate (s) of the general formula (I) in a ratio of 10: 1 to 1:50, preferably from 5: 1 to 1:30 and in particular from 3: 1 to 1:10 are included in these agents.

The crystalline layered silicates of the formula (I) are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, e.g. B. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, makatite).

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

Preferred machine dishwashing agents or machine dishwashing aids have in Within the scope of the present application, a proportion by weight of the crystalline layered Silicate of formula (I) from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10% by weight, based in each case on the total weight of these agents.

In addition to the crystalline layered silicates mentioned, agents according to the invention contain zinc salts, preference being given to using both inorganic and organic salts. The following table shows a non-exhaustive list of some preferred zinc salts:

In addition to the non-soluble inorganic zinc salts, i.e. salts which are soluble below 100 mg / l (20 ° C), preferably below 10 mg / l (20 ° C), especially none Have solubility (20 ° C) (Example: zinc oxide) are within the scope of the present application soluble inorganic interest salts, i.e. salts that have a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular Have above 5 g / l, preferred component of agents according to the invention. Among the preferred soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide, Zinc nitrate and the zinc sulfate. Another preferred subject of the present application are therefore automatic dishwashing detergents or automatic dishwashing aids, which at least one zinc salt selected from the group of inorganic zinc salts, preferably from the group of soluble inorganic zinc salts, in particular from the group of zinc bromide, Contain zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.

The spectrum of the zinc salts of organic acids preferred according to the invention, preferably organic carboxylic acids, ranges from salts that are insoluble in water, i.e. a solubility below 100 mg / l, preferably below 10 mg / l, in particular have no solubility, up to such salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / L and in particular above 5 g / l (all Solubilities at 20 ° C water temperature). Belong to the first group of zinc salts for example the zinc citrate, the zinc laurate, the zinc oleate, the zinc oxalate, the zinc tartrate and that Zinc stearate, to the group of soluble organic zinc salts include, for example Zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, the Zinc gluconate, the zinc valerate and the zinc salt of p-toluenesulfonic acid.

In a further preferred embodiment, contain machine according to the invention Dishwashing detergents or automatic dishwashing aids therefore have at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, particularly preferably from the group of soluble zinc salts monomeric or polymeric organic acids, especially from the group zinc acetate, Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, Zinc valerate, zinc p-toluenesulfonate.

Of course, preferred agents according to the invention can also be mixtures of organic and inorganic zinc salts, especially mixtures of soluble organic zinc salts with not soluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with non soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with soluble inorganic zinc salts.

Mechanical are preferred in the context of the present application Dishwashing detergents or automatic dishwashing aids, in which the proportion by weight of the Zinc salt based on the total weight of this agent 0.1 to 10 wt .-%, preferably 0.2 to 7 wt .-% and in particular 0.4 to 4 wt .-%, regardless of which Zinc salts are used, in particular regardless of whether organic or inorganic zinc salts, soluble or insoluble zinc salts or mixtures thereof become.

Agents according to the invention are not subject to any restrictions with regard to their packaging and Supply forms. Machine dishwashing detergents or machine dishwashing aids in the The present invention can therefore be used both in solid and in liquid form to be provided.

Fixed supply forms of the automatic dishwashing agents according to the invention or automatic Dishwashing aids are, for example, fine to coarse-grained powders such as those produced by Spray drying or granulation are obtained, compressed mixtures of substances from the Roll compacting, but also solidified melts or by extrusion or tableting moldings obtained. Such molded articles can be used in the context of the present invention have practically all usable configurations, for example in form a board, in the form of bars or bars, a cube, a cuboid and the like Room element with flat side surfaces and, in particular, cylindrical configurations have a circular or oval cross-section. This last embodiment covers the Presentation form from the actual tablet to compact cylinder pieces with one Height to diameter ratio above 1. Preferred tableted or extruded media have two or more phases in the context of the present invention, for example by their composition, their share in the total volume of the molded body and / or it can distinguish visual appearance.

The phases of such multiphase molded articles can additionally be characterized by a distinguish different dissolution behavior in aqueous phase. Such moldings are suitable advocate the controlled release of certain ingredients, for example in certain rinses of the machine wash program. In a preferred one Embodiment has one of the phases of the molded body as a main component or melt softenable substances from the group of waxes, paraffins and / or polyalkylene glycols. Furthermore, it has proven to be advantageous if the substances which can be melted or softened contained molded body or molded body component is at least largely water-insoluble. The Solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and are preferably below 5 mg / l. In such cases, the meltable or softenable Substances, however, the lowest possible solubility in water, even in water at an elevated temperature, have as far as possible a temperature-independent release of the active substances to avoid. The active substance is released in this way when the melting point is reached. or softening point.

Machine dishwashing aids are used in the context of the present application Means referred to in addition to a commercially available cleaning agent, for example in Form of a special glass protection agent can be added. Such a dosage can both before the start of each wash program and in the form of a depot product, the one causes continuous release of the agent according to the invention take place.

Preferred solid agents according to the invention are in the form of those for a cleaning cycle sufficient dosing unit. An example of such confection forms are Dishwashing (helpful) Central tablets.

If the agents according to the invention are in solid particulate form, but not in the form of divided ones Dosing units before, there is the problem of segregation of individual for these agents Ingredients, in particular the segregation of the agents according to the invention zinc salts and silicates contained in it must be avoided. Examples of such particulate Offer forms are powder or granules. In a preferred embodiment of the The present invention lies in the machine dishwashing detergent or machine dishwasher aids contained zinc salt (s) and / or the contained (s) crystalline layered silicate (s) with one or more further active and / or Framework substance (s) assembled, in particulate form, as a compound.

Since the zinc salts and crystalline layered silicates only a small proportion by weight make preferred machine dishwashing detergent simplifies compounding Because of their "dilution effect" the dosage of these salts in the manufacture machine dishwashing detergent according to the invention. But also in the event that a Agent according to the invention in the form of a special product for glass corrosion protection Commercial cleaning agents are only added by the consumer, the dosage facilitated by the compounding. The advantages of compounding are fully apparent regardless of whether the automatic dishwashing detergent to which the corresponding Compounds are metered in, is solid, liquid or gel-like.

Preferred fixed forms of supply of the automatic dishwashing agent according to the invention contain, for example, fine to coarse-grained powders, such as those obtained by spray drying or granulation can be obtained. Such powders can be marketed as a commercial product or as Premix for compacting, for example for tableting, are used and usually have a particle size in the range of 0.1 to 10 mm. For segregation It is to prevent this powder from the added silicate and / or zinc salt compounds preferred that these compounds have a particle size comparable to the powders.

A preferred subject of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates made up of one or more active and / or builders is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, preferred particulate compounds to avoid segregation processes additionally having a density of 0.1 to 2.0 g / cm ³ , preferably 0.2 to 1.6 g / cm ³ and in particular have from 0.4 to 1.2 g / cm ³ .

Machine dishwashing detergents preferred according to the invention are in particular as a result characterized in that the particles with one or more active and / or framework substances made up zinc salts and / or crystalline layered silicates a percentage by weight Zinc salts or crystalline layered silicates of 0.1 to 80% by weight, particularly preferred from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.

According to the invention, the aforementioned particulate compounds are preferred by Spray drying and / or granulation and / or extrusion and / or roller compaction and / or tableting and / or solidification and / or crystallization, but especially by Spray drying and / or granulation.

In spray drying, an aqueous slurry is used in a first step of the process ("Slurry") produced, which in addition to the zinc salts according to the invention further thermally stable May contain active and / or builder substances, which are under the conditions of Do not volatilize or decompose spray drying and then pump it into the Spray tower transported and sprayed through nozzles located in the top of the tower. Ascending Hot air dries the slurry and evaporates the adhering water so that the detergent Components at the outlet of the tower are obtained as fine powders. This can be done if necessary further temperature-labile components, such as. B. bleach or fragrances can be added.

The preparation of agents according to the invention can be carried out in addition to that described above Spray drying is also done by a granulation process, using a fluidized bed process is particularly preferred in which is stored on horizontal, perforated floors fine-grained bulk material which, in addition to the zinc salts according to the invention, further active and / or May contain scaffolding substances, through which gases (e.g. hot air) flow from below. Under Certain flow conditions result in a state that is similar to that of a boiling Resembles liquid; the layer creates bubbles and the particles of the bulk material are located within the layer in a constant, swirling up and down movement and stay that way sort of in limbo. The large surface of the fluidized material then enables For example, the reaction with other substances such as solvents, solutions of active and / or builders, liquid active substances or other ingredients, which in Room temperature as a solid, very much by increasing the temperature and / or addition limited amounts of liquid additives but at least superficially soften and / or form an adhesive and adhesive strength under the influence of temperature. Typical examples of the The aforementioned substances are water and aqueous solutions, for example also aqueous solutions of the zinc salts according to the invention can be used Surfactant compounds which are liquid or solid at room temperature, in particular nonionic surfactants, or else Polymer compounds of synthetic and / or natural origin, for example (co) polymers Carboxylates.

Another preferred procedure for granulation is the use of Mixers / compressors, such as those used for this purpose in addition to other providers are provided by the Lödige company and which are particularly suitable for the production Particles made up according to the invention are suitable, since they are modified by the user various process parameters such as the number of revolutions of the mixer, the residence time of the Individual components, the dosing time of individual components during the mixing process, the geometry of the mixing elements used or the energy input the possibility of offer targeted control of the product properties of the granules obtained. Also the Grain size and / or density of granules can be influenced in this way, and the preparation of zinc salts according to the invention with one or more further active and / or framework substance (s) in the aforementioned mixers / compressors is therefore within the scope of present invention particularly preferred.

Finally, there is the possibility of using the zinc salts and / or silicates according to the invention to mix other individual components that differ only slightly in their bulk densities distinguish those of the salts mentioned. Such mixtures have only minor Separation tendencies of the components during storage, transport and processing on and are therefore also in a special way for the desired safe and reliable dosage of Silicates and / or zinc salts according to the invention are suitable. Preferably within the scope of the present Mixtures of silicates and / or zinc salts with further active and / or Framework substances, characterized in that the bulk weights of the one another mixed individual components by a maximum of 200 g / l, preferably by a maximum of 150 g / l, preferred differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.

The framework and / or active substances which are used in the packaging described above preferred automatic dishwashing detergents according to the invention can be used, include, among other common ingredients of detergents, for example Builders (builders, cobuilders), surfactants, bleaches, bleach activators, enzymes, dyes, Fragrances, anti-corrosion agents or polymers.

While according to the invention as active and / or framework substances for the assembly Zinc salts are generally suitable for all of the substances mentioned are within the scope of the present However, the invention relates to such automatic dishwashing agents or automatic dishwashing aids particularly preferred in which those with one or more active and / or builder substances assembled zinc salt compounds, active and / or framework substances from the group of Phosphates, carbonates, hydrogen carbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts from 20 to 99% by weight, particularly preferably from 30 to 98% by weight and particularly preferably from 40 to 95% by weight, in each case based on the total weight of the Particles.

Other particularly for the packaging of zinc salts in the context of the present invention preferred active and / or builder substances are the surfactants, preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.

For further description of particularly preferred surfactants or polymeric carboxylates and the Polysulfocarboxylate is to avoid repetition on the following Executions referenced.

Also those in the automatic dishwashing agents according to the invention or automatic ones Silicates contained in dishwashing aids are preferably present in these agents with other active ingredients. or scaffold substances pre-assembled, with here in particular active or scaffold substances from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and the phosphonic acids are used.

Another preferred subject of the present application are therefore mechanical Dishwashing detergent or machine dishwashing auxiliary, characterized in that the crystalline (n) layered silicate (s) of the formula (I) with one or more further active and / or framework substance (s), preferably with one or more further active and / or Builders from the group of organic mono- or polycarboxylic acids, the Hydroxypolycarboxylic acids and the phosphonic acids, in particulate form, as Compound is / are present.

The particulate, with one or more active and / or framework substances Assembled zinc salts and / or crystalline layered silicates can be used to protect Environmental influences and thus to improve their storage stability or to influence the Dissolving behavior can be provided with a coating (coating). coating materials and methods for coating particulate agents are widely described in the literature and are only to be explained below with regard to particularly preferred embodiments.

The use of meltable or softenable substances is particularly preferred Coating material. (The term "coating" means in the context of the present Invention in addition to the coating of one or more pages or surfaces of one particulate agent made up according to the invention also a complete coating, thus the wrapping of this particulate object.) Preferred meltable according to the invention Substances have a melting point above 30 ° C. Should the ready-made Zinc salts and / or crystalline layered silicates at different times, for example can be released during the different rinses of a cleaning process, so this can be done, for example, by using various fusible coatings that differ in their melting point, the melting points of these substances are preferably adapted to the temperature profile of this cleaning process and Difference in melting points is sufficient to separate the individual matrices or To ensure coatings. For example, zinc salts and crystalline ones are provided To release layered silicates at different times are such substances for the different coatings preferred, which differ in terms of their melting point at least 5 ° C, preferably around 10 ° C, particularly preferably around 15 ° C and in particular around distinguish at least 20 ° C, it is further preferred that the melting point at least one of the meltable substances that form a coating below 30 ° C. lies, while the melting point of at least one further substance which is a further matrix or Form coating, is above 30 ° C.

Such coatings can, for example, by dipping, spraying or circulating in a drum coater or coating pan. Are particularly preferred as meltable or softenable substances for the coatings waxes, paraffins, Polyalkylene glycols etc. used.

It has proven to be advantageous if the meltable or softenable substances are not sharp shows a defined melting point, which usually occurs with pure, crystalline substances, but may have a melting range that may include several degrees Celsius. The meltable or softenable substances preferably have a melting range that is between about 45 ° C and about 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificially derived substances that usually Melt above 40 ° C without decomposition and a little above the melting point are relatively low viscosity and non-stringy. They exhibit a strongly temperature-dependent Consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or Ozokerite (earth wax), or petrochemical waxes like petrolatum, paraffin waxes or Microcrystalline waxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or polyalkylene glycol waxes Roger that. As meltable or softenable substances for those that harden by cooling Compounds from other classes of substances which are mentioned can also be used in bulk Meet softening point requirements. As suitable synthetic compounds For example, higher esters of phthalic acid, especially dicyclohexyl phthalate, have is commercially available under the name Unimoll® 66 (Bayer AG). Are also suitable synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example Dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Are reversed also synthetic or semi-synthetic esters from lower alcohols with fatty acids from native ones Sources can be used. Tegin® 90 (Goldschmidt), for example, falls into this class of substances Glyceryl palmitate. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used as meltable or softenable substances.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are high molecular weight, water-insoluble Fatty alcohols usually with about 22 to 40 carbon atoms. The wax alcohols are coming for example in the form of wax esters of higher molecular weight fatty acids (wax acids) than The main constituent of many natural waxes before examples of wax alcohols are lignoceryl alcohol (1- Tetracosanol), cetyl alcohol, myristyl alcohol or melis syl alcohol. The wrapping of the ready-made Zinc salts or crystalline layered silicates may also contain wool wax alcohols contain what is understood to mean triterpenoid and steroid alcohols, for example lanolin, that for example, is available under the trade name Argowax® (Pamentier & Co). Likewise can be used at least in part as part of the meltable or softenable substances Within the scope of the present invention, however, fatty acid glycerol esters or fatty acid alkanolamides optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

Particularly preferred meltable or softenable substances are those from the group of Contains polyethylene glycols (PEG) and / or polypropylene glycols (PPG), being polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Corresponding methods, which are characterized in that the plastic deformable mass (es) at least one substance from the group of polyethylene glycols (PEG) and / or contains polypropylene glycols (PPG) are preferred.

Here, coating agents are preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances. Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the following general formula


are sufficient, where n can have values between 10 and 2000. Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula

H- (O-CH ₂ -CH ₂ ) _n -OH

are sufficient, where n can have values between 20 and approx. 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, the coating materials contain Paraffin wax.

Paraffin waxes show the other natural waxes mentioned within the scope of the present invention the advantage that in an alkaline detergent environment none Hydrolysis of the waxes takes place (as can be expected, for example, in the wax esters) because Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially none Ingredients with a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residues result usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided become.

Preferably meltable or softenable substances to be processed contain at least one Paraffin wax with a melting range of 50 ° C to 60 ° C, preferred Coating materials are characterized in that they have a paraffin wax with a Melting range from 50 ° C to 55 ° C included.

The content of the paraffin wax used is preferably at ambient temperature (in which Usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it within the scope of the present invention. With increasing proportion of solid wax components increases the resilience of the process end products to impacts or friction on others Surfaces, which leads to longer-lasting protection. High levels of oils or liquids Wax components can weaken the coating, opening pores and the active substances are exposed to environmental influences.

In addition to paraffin, the meltable or softenable substances can also be one of the main components or contain several of the waxes or wax-like substances mentioned above. In a Another preferred embodiment of the present invention should be the melt or softenable substances forming mixture must be such that the mass and the resulting formed coating are at least largely water-insoluble. The solubility in water should at a temperature of about 30 ° C about 10 mg / l, do not exceed and preferably below 5 mg / l, lie.

In such cases, however, the meltable or softenable substances should be as small as possible Solubility in water, even in water at an elevated temperature, has a Avoid temperature-independent release of the active substances as much as possible.

Preferred coating materials to be processed according to the invention are thereby characterized in that they contain one or more substances as meltable or softenable substances a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably of 7.5 up to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the Coating material included.

In addition to choosing a suitable coating, the dissolution behavior of the zinc salt or Silicate compounds can also be influenced by the compaction processes mentioned above. Here, in addition to the amount of pressure used and the use of aids, such as for example of binders, in particular the choice of the co-assembled active ingredient (s) and / or framework substances of great importance. Compact ones are particularly suitable Silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various Polycarboxylates due to their delayed solution / dispersion or due to occurring Gelling of these substances or substance mixtures in an aqueous liquor as "depot substances" for the zinc salts or crystalline layered silicates.

Another particularly preferred form of the present application Assembly of automatic dishwashing agents according to the invention or automatic Dishwashing aids are polymer matrices. Such polymer matrices are universal in Different program programs can be used, are characterized by a simple and inexpensive to make and can vary amounts of active agent contain.

The preferred subject of the present application is therefore still mechanical Dishwashing detergents or machine dishwashing aids in which the zinc salt (s) and / or the crystalline layered silicate (s) are assembled in a polymer matrix available.

The active ingredient-containing polymer matrices can be manufactured cheaply and in a wide variety of shapes. By selecting water-soluble or water-insoluble polymers, the inventive one Composition even as packaging for automatic dishwashing detergents or as Basket in which the funds are introduced. It is also possible to do both Combine types of insertion with each other, for example by making a carrier basket water-insoluble, active ingredient-containing polymer matrix a polymer body made of water-soluble, Contains active ingredient-containing polymer matrix. Such products can be made from different matrices the active agents release at different times to different degrees, what to an optimal concentration of active substance at all times during the cleaning program leads.

Are both the zinc salt and the silicates in one in agents preferred according to the invention Polymer matrix pre-assembled, so this assembly can be preferred Embodiments of the present invention both in the same polymer matrix as well take place in different matrices, that is to say that the zinc salt, for example in polymer A is made up, while the silicate was made up in a polymer B. Finally zinc salt and silicate can also be produced using the same polymer, but in separate ones Matrices are assembled.

The agents according to the invention can therefore be used both with water-insoluble and with realize water-soluble polymers or mixtures thereof. Preferred machine Dishwashing detergents or machine dishwashing aids are characterized in that the Polymer matrix comprises one or more water-soluble polymer (s).

The polymer matrices according to the invention can be formulated universally. That's the way it is possible, for example, pre-soak, pre-rinse, cleaning agent for the Main wash or rinse aid. In addition, the invention Compositions can also be combination products, the two or more of the aforementioned Unite resources. The formulation of compositions according to the invention as Addition product, which is hung in the dishwasher, for example, is easy possible. The active ingredient-containing polymer matrix can be particulate in the inventive Compositions are incorporated, but it can also be a compact molded body, which is, for example, either a core that fills a well of a detergent tablet, or a shaped body that is an additive like a deodorant hanger in the dishwasher is introduced. Also baskets which are suitable for taking detergent tablets are, can be produced from the active ingredient-containing polymer matrix. Last but not least, the Active ingredient-containing polymer matrix also used as packaging for automatic dishwashing detergents become. This is particularly the case with completely water-soluble active substance-containing polymer matrices attractive, since the consumer does not have to unpack the product, the direct contact with the Avoid product that is perceived as undesirable and also avoid others Packaging materials can be saved.

• a) 5 bis 99,5 Gew.-% eines oder mehrerer Polymere,
• b) mindestens ein Zinksalz sowie mindestens ein kristallines schichtförmiges Silikat der allgemeinen Formel (I)
  
  NaMSi_xO_2x+1.yH₂O (I),
  
  worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, ist und y für eine Zahl von 0 bis 33 steht, enthält, wobei die Summe der Gewichtsanteile des/der Zinksalze(s) und des/der kristallinen Silikate(s) 0,5 bis 95 Gew.-% beträgt,
• c) 0 bis 30 Gew.-% weiterer Wirk- und/oder Hilfsstoffe umfaßt, wobei sich die Gewichtsangaben jeweils auf das Gesamtgewicht der wirkstoffhaltigen Polymermatrix beziehen.

Agents 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) at least one zinc salt and at least one crystalline layered silicate of the general formula (I)
  
  NaMSi _x O _{2x + 1} .yH ₂ O (I),
  
  where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, the sum of the parts by weight of the zinc salt (s) (s ) and the crystalline silicate (s) is 0.5 to 95% by weight,
• c) 0 to 30% by weight of further active substances and / or auxiliary substances, the weight data relating in each case to the total weight of the active substance-containing polymer matrix.

The polymer matrix of the agents preferred according to the invention comprises 5 to 99.5% by weight of one or several polymers. The term "polymers" denotes in the context of the following application in Based on the IUPAC definition of substances that are chemically uniform from a collective more structured, but usually in terms of degree of polymerization, molecular weight and chain length distinguishing macromolecules. After this, the origin of the term disregarding the IUPAC definition, a polymer is "a substance made up of a variety is made up of molecules in which one or more types of atoms or atomic Groupings (so-called constitutive units, basic building blocks or repetition units) are repeatedly strung together ". The different sized macromolecules of a polymer are made up of so many identical or similar low molecular weight building blocks (monomers), that the physical properties of the substance, especially the viscoelasticity, with Slightly increase or decrease the number of blocks no longer noticeably change. The size of the macromolecules means that the end groups relate relatively little to the Properties of the polymers affect, so that their explicit specification in the following specified structural formulas is mostly omitted.

The polymers forming the matrix of the compositions according to the invention can thereby be both natural and synthetic. Preferred agents according to the invention are characterized in that the polymer matrix is 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 comprises 20 to 80% by weight of one or more polymers, the Weight data relate to the active ingredient-containing polymer matrix.

The average molar mass of the polymers contained in the preferred agents according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and especially at least 12,000 g / mol.

As already mentioned, the agents preferred according to the invention can be both water-insoluble and also contain water-soluble polymers and mixtures of these polymers. According to the invention preferred compositions based on water-insoluble polymer matrices are thereby 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.

• a) Polyacrylsäuren und deren Salzen
• b) Polymethacrylsäuren und deren Salzen
• c) Polyvinylpyrrolidon,
• d) Vinylpyrrolidon/Vinylester-Copolymeren,
• e) Celluloseethern
• f) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
• g) Pfropfcopolymeren aus Polyethylenglykolen und Vinylacetat
• h) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
• i) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
• j) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
• k) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• l) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• m) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• n) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat- Copolymeren und deren Salzen
• o) Copolymeren aus
  • 1. xv-i) ungesättigten Carbonsäuren und deren Salzen
  • 2. xv-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
• p) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• q) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• r) Methacroylethylbetain/Methacrylat-Copolymere
• s) Vinylacetat/Crotonsäure-Copolymere
• t) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• u) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen
• v) gepropften Copolymere aus der Copolymerisation von
  • 1. xxii-i) mindesten einem Monomeren vom nichtionischen Typ,
  • 2. xxii-ii) mindestens einem Monomeren vom ionischen Typ,
• w) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
  • 1. xxiii-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
  • 2. xxiii-i) ungesättigte Carbonsäuren,
  • 3. 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 agents 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:

• a) Polyacrylic acids and their salts
• b) polymethacrylic acids and their salts
• c) polyvinylpyrrolidone,
• d) vinyl pyrrolidone / vinyl ester copolymers,
• e) cellulose ethers
• f) polyvinyl acetates, polyvinyl alcohols and their copolymers
• g) graft copolymers of polyethylene glycols and vinyl acetate
• h) alkyl acrylamide / acrylic acid copolymers and their salts
• i) alkyl acrylamide / methacrylic acid copolymers and their salts
• j) alkyl acrylamide / methyl methacrylic acid copolymers and their salts
• k) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• l) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• m) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• n) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and their salts
• o) copolymers
  • 1. xv-i) unsaturated carboxylic acids and their salts
  • 2. xv-ii) cationically derivatized unsaturated carboxylic acids and their salts
• p) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• q) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• r) Methacroylethylbetaine / methacrylate copolymers
• s) vinyl acetate / crotonic acid copolymers
• t) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• u) 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
• v) grafted copolymers from the copolymerization of
  • 1. xxii-i) at least one monomer of the nonionic type,
  • 2. xxii-ii) at least one monomer of the ionic type,
• w) copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
  • 1. xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. xxiii-i) unsaturated carboxylic acids,
  • 3. 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 active substance-containing polymer matrix has a content in addition to the polymer (s) at least one zinc salt and / or at least one crystalline layered silicate general formula (I), which can be released from the matrix. According to the invention preferred agents are characterized in that they contain at least one zinc salt and at least one contain a crystalline layered silicate of the general formula (I), the sum of the The proportions by weight of these components are 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, each based on the total weight of the active ingredient-containing polymer matrix.

The automatic dishwashing agents or automatic dishwashing aids according to the invention can contain the active ingredient-containing polymer matrix in different amounts. It depends on the active ingredient-containing polymer matrix in the compositions, for example, as a fine particle Powder or granules is contained, is formed as part of a shaped body, or whether it is the Contains composition as packaging, the proportions of the active ingredient Polymer matrix on the overall composition vary. Here are inventive Compositions preferred, 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 contain in particular 2.5 to 20% by weight of the active substance-containing polymer matrix.

Particularly preferred polymer matrices contain at least one zinc salt in amounts such that the composition zinc in oxidized form in parts by weight of 0.01 to 1 wt .-%, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight, in each case based on the total weight of the polymer matrix.

As mentioned at the outset, incorporation of active substance-preferred substances according to the invention is necessary Polymer matrices in the compositions of the invention are not limited the dosage forms or the recipes of these compositions. So besides usual machine dishwashing detergents also pre-wash or pre-rinse products, rinse aid, Machine maintenance or additional products provided as a composition according to the invention become. A preferred embodiment of the composition according to the invention provides that the polymer matrix as a molding to be introduced separately into the dishwasher is provided that the agents from the polymer matrix over several rinse cycles releases. This molded part can either be a dosing cup for other products such as for example, the cleaner, but it can also be used as a separate and separate molded part Embody the additional benefit of protecting the glass. Possible shapes are, for example, the based on known dishwasher dodorants. The design of the Plastic part in translucent, opalescent or completely clear form, for example in form of a stylized diamond. Through such product designs, the through Visualize the resulting sheen in a way that is gentle on the glass.

The variety of shapes is none due to the possibilities of plastic processing Set limits. The active ingredient-containing polymer matrices can easily be used with the usual Methods are transformed.

The shaping processing takes place according to the usual in the plastics processing industry Process, in particular film production and processing, blow molding and injection molding are preferred. All processes have in common that a plastic granulate with Melted with the help of an extruder and fed to shaping tools. It can the plastic granules already contain the agents for glass corrosion inhibition, they can but can also be added during melting in the extruder, which is a special Cost-effective production of the polymer matrices containing the active substance preferred according to the invention allows.

In an additional preferred embodiment, the machine according to the invention Dishwashing detergents or machine dishwashing aids packaged in a way that it enables the active substances contained in these agents to be applied and applied in a targeted manner dosing. For the purpose of this application, the following are particularly suitable pencil-shaped offer form, which, similar to a glue stick, its storage and transport Spatial geometric form does not change, but this, the offer form under the influence of a Pressure moves across a surface in its area of contact with the surface due to the shear forces occurring there loses. The mean is a result of the shear forces acting smeared on the surface and remains there after the application of the shear forces in its new spatial-geometric form, is again stable in shape. With the help of a Such preferred formulations can be applied in a targeted manner to agents according to the invention and dose.

Such dimensionally stable machine dishwashing agents or machine dishwashing aids, which due to their material properties can be spread on a surface under the action of a shear force, but remain in their spatial shape without the action of a shear force, can advantageously be characterized by their penetration numbers. In the context of the present invention, the penetration number is the numerical value which results when the hardness of the agents according to the invention is determined using a texture analyzer, model TA-XT2-I from Stable Micro Systems. The following test parameters are set to carry out this measurement:
TA Mode: Force in the printing direction
TA option: simple test
Trigger value 0.2 g
PPS 200

The penetration number is determined by using a specific measuring tool (TA-15 45 ° cone Stainless steel) with a defined feed rate (0.5 mm / s) up to a defined one Penetration depth (5.0 mm) pressed into the test material and then with a defined Speed (0.2 mm / s) is pulled out of this material. The examined Test materials had a temperature of 23 ° C, the measurements were at 20 ° C Room temperature. The measuring device determined on the basis of that described Experimental setup a numerical value in the unit gram [g]. This numerical value is in the frame referred to the present application as the penetration number. The measurements after the The method described now showed that the preferred dimensionally stable machine Dishwashing detergents or machine dishwashing aids penetration numbers from 200 to 1000 g, preferably from 250 to 900 g, particularly preferably from 300 to 800 g and in particular from Have 350 to 700 g.

Another preferred object of the present invention are therefore according to the invention machine dishwashing detergents or machine dishwashing aids that are dimensionally stable and a penetration number of 200 to 1000 g, preferably of 250 to 900 g, particularly preferably have from 300 to 800 g and in particular from 350 to 700 g.

In the context of the present invention, the term “dimensionally stable” denotes machine Dishwashing detergents or automatic dishwashing aids that have inherent dimensional stability have, which enables them, under normal conditions of manufacture, storage, Transport and handling by the consumer a stable against breakage, not to have disintegrating spatial form, which is also possible under the mentioned conditions not changed for a long time, that is under the usual conditions of manufacture, the Storage, transport and handling by the consumer in the through the Production-related spatial-geometric shape remains, that is, for example, not melts.

The penetration number of 200 to 1000 g which characterizes preferred agents according to the invention can not be in its pure form by active substances such as zinc salts or layered silicates realize. A carrier material or matrix material is therefore necessary for this To provide active substances that meet the physical requirements mentioned means according to the invention. Such a matrix should also contain active ones Agents are compatible, that is, in particular, do not react with them, but rather with them stabilize. Furthermore, the carrier materials should also be the cleaning process that is aimed for do not question, so also with all others during the cleaning and / or Substances used in the care process. Finally, the matrix material preferably be water-soluble or water-dispersible to prevent the occurrence of residues to avoid after application of the agent according to the invention. Are particularly preferred Carrier materials which, in addition to the function as a matrix for the active substance, also have a have a cleaning or nourishing function. From the large number of possible carrier materials have a number of groups of substances as special in the context of the present invention proven advantageous. These substances will be discussed in more detail below.

Preferably dimensionally stable, automatic dishwashing agents according to the invention or machine dishwashing agents Dishwashing aids are therefore included in the scope of the present application characterized in that they polyvinylpyrrolidone (s) and / or polyvinyl alcohol (e) and / or Polyvinyl acetate (e) and / or polyacrylate (e) and / or polyalkylene glycol (e) and / or fat (e) and / or Fatty acid (s) and / or fatty acid esters and / or fatty acid amide (s) and / or fatty alcohols and / or Wax (s) and / or paraffin (s) and / or wax alcohols and / or surfactant (s), preferably contain nonionic surfactant (s), and / or dextrin (s) and / or starch ether, the Weight fraction of this component / these components in the total weight of the dimensionally stable automatic dishwashing and / or dishwashing auxiliary, preferably between 30 and 99% by weight, particularly preferably between 40 and 95% by weight and in particular between 50 and 95% by weight is.

Automatic dishwashing agents or automatic dishwashing aids according to the invention can in addition to the solid or dimensionally stable forms described, also in the form of liquid or flowable agents are made up. In a further preferred embodiment of the present invention have the machine dishwashing detergents or machine Dishwashing aids therefore have a viscosity of 500 to 500,000 mPa.s, preferably from 900 to 200,000 mPa.s and in particular from 1300 to 100,000 mPa.s. The viscosity of the agents according to the invention are applied using customary standard methods (for example Brookfield Viscometer LVT-II measured at 20 rpm and 20 ° C, spindle 3). The expression "liquid or flowable agents "is subsequently used for agents which have a viscosity of 500 to 500,000 mPa.s, preferably from 900 to 200,000 mPa.s and in particular from 1300 to 100,000 mPa.s exhibit.

Such a preferred liquid or contain according to the invention as a preferred ingredient flowable one or more non-aqueous solvents. These come, for example from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides. Non-aqueous solvents which are water-soluble are particularly preferred, wherein "Water-soluble" solvents in the context of the present application are solvents which are used in Room temperature with water completely, d. H. without a miscibility gap.

Suitable non-aqueous solvents preferably come from the group one or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are specified Concentration range are miscible with water. The solvents are preferred selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1- Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents.

Nonionic surfactants that are liquid at room temperature are also within the scope of the application preferred non-aqueous solvents.

A particularly preferred liquid or flowable in the context of the present invention automatic dishwashing detergent or automatic dishwashing auxiliary is thereby characterized in that it contains non-aqueous solvent (s), the solvent (s) is preferably selected from the group of polyethylene glycols and polypropylene glycols, Glycerin, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, Hexylene glycol, ethanol and n-propanol and / or iso-propanol.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol which have the general formula (II)

H- (O-CH ₂ -CH ₂ ) _n -OH (II)

are sufficient, where n can have values between 1 (ethylene glycol, see below) and approx. 16. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight after the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

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

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) as well as the corresponding trade name with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula (III)


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

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

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

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

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3- Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet tasting Liquid with a density of 1.0597 that solidifies at -32 ° C and boils at 214 ° C. The production of 1,3- Propanediol is made from acrolein and water with subsequent catalytic hydrogenation.

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

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

In preferred liquid or flowable automatic dishwashing agents according to the invention or machine dishwashing aids is / are the non-aqueous solvent (s) in Amounts from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, particularly preferably from 1 up to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the total composition.

In the context of this invention, “non-aqueous” is understood to mean a state in which the Free water content in the compositions is clearly below 5% by weight, based on the composition. It it is preferred that the content of the automatic dishwashing detergents according to the invention or automatic dishwashing aids on free, d. H. not in the form of water of hydration and / or Constitution water present water below 10 wt .-%, preferably below 8 wt .-% and in particular even less than 6% by weight, based in each case on the agent. Water can accordingly essentially only in chemically and / or physically bound form or as part of the raw materials or compounds present as a solid, but not as Liquid, solution or dispersion can be introduced into the agent.

As a further preferred ingredient, preferred liquid or flowable machine dishwashing detergents or machine dishwashing aids or several non-ionic surfactants, in short non-ionic surfactants. The amounts in which the nonionic surfactants are preferably used according to the invention between 5 and 30 wt .-%, wherein Particularly preferred agents according to the invention which are 1 to 25% by weight, preferably 2 up to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to 17.5% by weight contain nonionic surfactant (s).

For a detailed description of these nonionic surfactants to avoid repetition of these places on the following comments on the preferred washing or cleaning-active ingredients of preferred agents according to the invention.

To regulate the viscosity, the agents according to the invention can contain further ingredients, with their use, for example, specifically the settling behavior or the pourability or flowability can be controlled. In particular, in non-aqueous systems Combinations of structure donors and thickeners have proven their worth.

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

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

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

The structuring agent a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to increase the physical stability of the agent ensure and adjust the viscosity. Although conventional thickeners like The viscosity control succeeds in polyacrylates or polyurethanes failing in non-aqueous media with the substances mentioned in the non-aqueous system.

Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as Swellability, ion exchange capacity and thixotropy. It is possible the properties to modify the bentonite according to the intended use. Bentonites are considered Clay component common in tropical soils and are known as sodium bentonite z. B. in Wyoming / USA reduced. Sodium bentonite has the most favorable application properties (Swellability) so that its use is preferred in the context of the present invention is. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are artificially produced by Exchange of Ca for Na converted into the more swellable Na bentonites.

The main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or

Al ₂ O ₃ .4SiO ₂ .H ₂ O.nH ₂ O or

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °)

can be described.

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

In combination with the bentonites or as a replacement for them if you do not want to use them , at least partially etherified sorbitols can be used as structure donors.

Sorbitol is a hexahydric alcohol (sugar alcohol), the intramolecular removes one or two moles of water relatively easily and forms cyclic ethers (for example Sorbitan and sorbide). The elimination of water is also possible intermolecularly Form noncyclic ethers from sorbitol and the alcohols concerned. Here too is the Formation of monoethers and bisethers possible, with higher degrees of etherification such as 3 and 4 can occur. Those to be used preferably within the scope of the present invention Sorbitols at least partially etherified are double etherified sorbitols, of which the Dibenzylidensorbitol is particularly preferred. Machine dishwashing detergents are preferred here, which contain doubly etherified sorbitols, in particular dibenzylidene sorbitol, as structure donors.

The preferred liquid or flowable agents according to the invention can be provided by the structuring agents Quantities of 0.1 to 1.0 wt .-%, based on the total agent and on the active ingredient Structure donor included. Preferred agents contain the structuring agent in amounts of 0.2 to 0.9% by weight, preferably in amounts of 0.25 to 0.75% by weight and in particular in amounts of 0.3 up to 0.5% by weight, each based on the total agent.

The preferred liquid or flowable agents according to the invention can be used as thickeners inorganic salts from the group of carbonates, sulfates and amorphous or crystalline Disilicates included. In principle, the salts of all metals mentioned can be used here, the alkali metal salts are preferred. Within the framework of the present invention as a thickener alkali carbonate (s), alkali sulfate (s) and / or amorphous (s) and / or crystalline alkali disilicate (s), preferably sodium carbonate, sodium sulfate and / or amorphous or crystalline sodium disilicate used.

The preferred liquid or flowable agents according to the invention contain the thickeners in Amounts of 5 to 30 wt .-%, based on the total agent. Particularly preferred agents contain the thickener or thickeners in amounts of 7.5 to 28 wt .-%, preferably in amounts of 10 to 26 wt .-% and in particular in amounts of 12.5 to 25 wt .-%, each based on the total funds.

In view of increased settling stability, it is preferred that the in the invention Solids contained agents are used as fine as possible. This is particularly the case with the inorganic thickeners and an advantage for bleaching agents. Here are inventive machine dishwashing detergents preferred, in which the average particle size of the bleaching agents and thickener and the optional builder less than 75 microns, preferably is less than 50 microns and in particular less than 25 microns.

The liquid dishwasher detergents according to the invention can be used to adjust a any desired higher viscosity also other viscosity regulators or thickeners contain. Here, all known thickeners can be used, ie those on the Based on natural or synthetic polymers.

Natural polymers that are used as thickeners for example agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, Guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products mainly come from the group of modified starches and Celluloses, examples include carboxymethyl cellulose and other cellulose ethers, Hydroxyethyl and propyl cellulose and core meal ether called.

Preferred liquid or flowable mechanical in the context of the present invention Dishwashing detergents or machine dishwashing aids contain as thickeners Hydroxyethyl cellulose and / or hydroxypropyl cellulose, preferably in amounts of 0.01 to 4.0% by weight, particularly preferably in amounts of 0.01 to 3.0% by weight and in particular in amounts from 0.01 to 2.0% by weight, based in each case on the total agent.

A large group of thickeners, widely used in a wide variety Find application areas are the fully synthetic polymers such as polyacrylic and Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

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

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

In the context of the present invention, thickeners are also to be used with preference Polyurethanes or modified polyacrylates, based on the total agent, for example can be used in amounts of 0.1 to 5 wt .-%.

Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula IV


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

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

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

Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula V.


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

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

Modified polyacrylates to be used preferably in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Va


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

Products of the formula Va are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% by weight dispersions in water. In the case of the commercial product mentioned, R ⁴ stands for a stearyl radical, R ⁵ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20. The statements made above regarding the water content of the compositions also apply to this dispersion.

Liquid or flowable machine dishwashing agents or machine dishwashing aids preferred in the context of the present invention are characterized in that they additionally contain 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight .-% and in particular 0.1 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference for thickeners of the formula VI


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

The solid or dimensionally stable and liquid or flowable machine according to the invention Dishwashing detergents or dishwashing aids can be used by consumers in conventional Containers, for example bottles, screw jars, canisters, balloons, cups or Spraying vessels are offered, from which he doses them for use. higher viscosity Products can also be found in tubes or dispensers such as those made by toothpaste or Sealants are known to be offered. Such containers are common today Made from water-insoluble polymers and can, for example, from all usual water-insoluble packaging materials exist, the expert in this field are well known. In particular, plastics are preferred polymers To name hydrocarbon base. The particularly preferred polymers include Polyethylene, polypropylene (more preferably oriented polypropylene) and polymer blends such as mixtures of the polymers mentioned with polyethylene terephthalate. Further one or more polymers also come from the group polyvinyl chloride, polysulfones, Polyacetal, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, Cellulose acetobutyrate and mixtures of the polymers mentioned or the polymers mentioned comprehensive copolymers in question.

However, a particularly preferred embodiment of the present invention aims to To provide consumers with pre-portioned agents according to the invention so that he can get them from use the dosage form known tablet advantages and with the quick dissolving and Release rate and the performance advantages of the agents according to the invention can combine. Such pre-portioned agents according to the invention can also be used in water-insoluble packaging is present so that the consumer can use it in must open appropriately. But it is also possible and preferred, portioned to package means according to the invention so that the consumer can easily Handling steps directly, d. H. Put in the dishwasher together with the packaging can. Such packaging includes water-soluble or decomposable packaging such as bags made of water-soluble film (so-called pouches), bags or other packaging water-soluble or decomposable nonwovens or flexible or rigid bodies water-soluble polymers, preferably in the form of filled hollow bodies, which, for example by deep drawing, injection molding, blow molding, calendering, etc.

A preferred subject of the present invention are therefore according to the invention automatic dishwashing detergents or automatic dishwashing aids that are portioned in one water-soluble wrapping are packaged.

Machine dishwashing agents or dishwashing aids according to the invention preferably comprise a completely or partially water-soluble coating. The shape of the wrapper is not on certain forms limited. Basically all Archimedean and Platonic come Bodies, i.e. three-dimensional shaped bodies, as forms of the envelope in question. Examples of that Capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods are the form of the coating or pouch. Hollow bodies with one or more compartments are also used as a covering for the dishwashing detergent is suitable. In preferred embodiments of the invention, the Envelopes in the form of capsules, such as those used in pharmacy Administration of drugs can be used, from bullets or from sachets. The latter are preferably welded or glued to at least one side, in particular as an adhesive preferred embodiments of the invention, an adhesive is used which is water-soluble.

According to a preferred embodiment of the invention, this is the automatic dishwashing detergent or dishwashing aids partially or completely surrounding water-soluble polymer material a water-soluble packaging. This is understood to mean a flat formed part that the Dishwasher detergent partially or completely surrounds. The exact form of such Packaging is not critical and can be largely adapted to the conditions of use become. For example, there are different shapes (such as hoses, pillows, cylinders, Bottles, disks or similar) processed processed plastic foils or plates, capsules and other conceivable forms in question. According to the invention, particular preference is given to films which For example, glued and / or sealed to packaging such as hoses, pillows or the like can, after with partial portions of the cleaning agents according to the invention or with cleaning agents according to the invention were filled themselves.

More preferred according to the invention because of the excellent desired Properties adaptable to physical conditions from plastic film packaging water-soluble polymer materials. Such films are basically from the prior art Technology known.

In summary, both hollow bodies of any shape that are produced by injection molding, Bottle blowing, deep drawing etc. can be produced, as well as hollow bodies made of foils, in particular bags (so-called pouches) as packaging for portioned portions according to the invention Means preferred. Preferred automatic dishwashing agents according to the invention or automatic Dishwashing aids are thus characterized in that the water-soluble coating a bag made of water-soluble film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part.

According to the invention, it is preferred that the one or more enclosures are completed is / are. This has the advantage that the dish detergent is optimal against influences the environment, especially against moisture. You can also use these completed enclosures develop the invention in such a way that the Detergent to protect the contents of the enclosure (s) from moisture at least one gas included, see below.

In principle, all come as materials for the completely or partially water-soluble coating Materials in question, which under the given conditions of a washing process, Rinsing or cleaning process (temperature, pH value, concentration of detergent active Components) can completely or partially dissolve in the aqueous phase. The polymer Materials can particularly preferably belong to the groups (optionally partially acetalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, Starch and its derivatives, especially modified starches, and mixtures (polymer blends, Associations, co-extrudates, etc.) of the materials mentioned. Are particularly preferred Gelatin and polyvinyl alcohols as well as the two materials mentioned, each in combination with Starch or modified starch. There are also inorganic salts and mixtures thereof Materials for the at least partially water-soluble coating in question.

Preferred automatic dishwashing agents according to the invention or automatic Dishwashing aids are characterized in that the covering has one or more Materials from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, Polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

Particularly preferred automatic dishwashing detergents or automatic dishwashing agents according to the invention Dishwashing aids are characterized in that the covering has one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and their mixtures, more preferably (optionally acetalized) Polyvinyl alcohol (PVAL).

"Polyvinyl alcohols" (abbreviation PVAL, sometimes also PVOH) is the name for polymers of the general structure


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


contain.

Commercially available polyvinyl alcohols with white-yellowish powder or granules Degree of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 or 87-89 mol%, contain a residual content of acetyl groups. They are characterized Manufacturers polyvinyl alcohols by specifying the degree of polymerization of the Starting polymers, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few 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 biological degradable. The water solubility can be checked by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. The polyvinyl alcohol coatings are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leave Pass water vapor through.

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

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the coating, it being preferred according to the invention that the coating comprises 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 , is particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, particularly preferred 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 trademark Mowiol® (Clariant). Particularly within the scope of the present invention Suitable polyvinyl alcohols are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.

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

Other polyvinyl alcohols suitable as material for the hollow mold 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 K.K.).

The water solubility of PVAL can be increased by post-treatment with aldehydes (acetalization) or Ketones (ketalization) can be changed. As particularly preferred and because of their Extremely good cold water solubility has been particularly advantageous here Highlighted polyvinyl alcohols with the aldehyde or keto groups of saccharides or Polysaccharides or mixtures thereof can be acetalized or ketalized. As extreme The reaction products of PVAL and starch can be used advantageously.

Furthermore, water solubility can be achieved by complexing with Ni or Cu salts or by Change treatment with dichromates, boric acid, borax and thus target the desired values to adjust. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, Helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are those called "SOLUBLON®" by PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. their Solubility in water can be adjusted to the degree, and they are films of this product range available in all relevant temperature ranges in the aqueous phase are soluble.

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

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. commercial PVP have molar masses in the range from approx. 2500 to 750 000 g / mol and are hygroscopic powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is predominantly by Hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline conditions is obtained. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on of its provenance. The use of gelatin as a water-soluble shell material is extremely wide, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules common. Gelatin is found in the form of foils because of its compared to the above Low cost polymers of low use.

Dishwashing detergents are also preferred within the scope of the present invention Packaging from at least partially water-soluble film from at least one polymer from the Starch and starch derivatives group, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures of these.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Strength is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched-chain Amylopectin (MW. Approx. 300,000 to 2,000,000). There are also small amounts of lipids, Contain phosphoric acid and cations. During the amylose due to the binding in the 1,4-position forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules, With amylopectin, the chain branches after an average of 25 glucose units through 1.6 Binding to a knot-like structure with about 1500 to 12,000 molecules of glucose. Next Pure starch is used to produce water-soluble coatings for detergents, detergents and Detergent portions also suitable for starch derivatives in the context of the present invention, which can be obtained from starch by polymer-analogous reactions. Such chemically modified Starches include, for example, products from esterifications or etherifications, in which have substituted hydroxy hydrogen atoms. But also strengths in which the hydroxy Groups replaced by functional groups that are not bound via an oxygen atom were used as starch derivatives. Fall into the group of starch derivatives for example alkali starches, carboxymethyl starch (CMS), starch esters and starches and Aminostarches.

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

Preferred casings made of at least partially water-soluble film contain at least one Polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. The wrapping shows according to the manufacturing process different material thicknesses, according to the invention automatic dishwashing agents or automatic dishwashing aids are preferred, in which the wall thickness of the casing 10 to 5000 microns, preferably 20 to 3000 microns, particularly is preferably 25 to 2000 microns and in particular 100 to 1500 microns.

If foil bags (so-called pouches) are chosen as packaging, the water-soluble one shows Film that forms the wrapper, preferably a thickness of 1 to 300 microns, preferably 2 to 200 microns, particularly preferably from 5 to 150 microns and in particular from 10 to 100 microns.

These water-soluble films can be produced by various manufacturing processes. In principle, blowing, calendering and casting processes should be mentioned here. With a preferred one The process is based on a melt with air through a blow mandrel blown a hose. In the calendering process, which is also preferred among the used manufacturing processes are plasticized by suitable additives Raw materials for forming the films are atomized. Here it may be necessary to contact the Spray to connect drying. In the casting process, which also belongs to the preferred manufacturing process is an aqueous polymer preparation on a heatable Drying roller given, after evaporation of the water is optionally cooled and the film printed as a film. This film may become additional before or during the peeling powdered.

An embodiment is preferred according to the invention, according to which the covering as a whole is water soluble, d. H. when used as intended for mechanical cleaning, completely dissolves when the conditions for releasing are met. Especially preferred as completely water-soluble coatings are, for. B. capsules made of gelatin, with advantage Soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls made of Gelatin or (optionally partially acetalized) PVAL or one or more organic and / or inorganic salts, preferably balls of soft gelatin. A major advantage of this embodiment is that the wrapper is practical within a relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the cleaning liquor at least partially dissolves and thus the wrapped content according to the requirements, d. H. the cleaning active material or several materials into which fleet brings.

In another embodiment, which is also preferred due to advantageous properties Invention encompasses the water-soluble coating less or not water-soluble or at all only at higher temperatures water-soluble areas and well water-soluble areas or at lower ones Temperature water soluble areas. In other words, the wrapper does not consist of one uniform material that has the same water solubility in all areas, but from Materials of different water solubility. Here are areas of good water solubility on the one hand to be distinguished from areas with less good water solubility, with poor or even lack of water solubility or in areas where water solubility is only at higher levels Temperature or only at a different pH value or only at a changed one Electrolyte concentration reaches the desired value, on the other hand. This can lead to Intended use under adjustable conditions certain areas of the Loosen the wrap while other areas remain intact. So one forms with pores or Holed casing into which water and / or liquor penetrate, wash-active, rinse-active or detach active ingredients and can discharge them from the casing. In the same Wrapping systems in the form of multi-chamber bags or in the form of hollow bodies arranged one inside the other (e.g. balls: "onion system") are provided. So can be systems with controlled release of the wash-active, rinse-active or Manufacture cleaning-active ingredients.

The invention is not subject to any restrictions on the formation of such systems. So can Envelopes are provided in which a single polymer material covers small areas incorporated compounds (for example salts) which are more water soluble than the polymer material. On the other hand, several polymer materials can also be used different water solubility are mixed (polymer blend), so that the faster soluble polymer material under defined conditions by water or the liquor faster is disintegrated than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less well water-soluble areas or areas that are not water-soluble at all or only in higher areas Temperature water-soluble areas of the envelope are areas made of a material that chemically essentially that of the readily water-soluble areas or at lower Temperature corresponds to water-soluble areas, but has a higher layer thickness and / or has a changed degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or a higher Degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer. Even taking into account the fact that Detergent portions can be removed in accordance with the Invention are provided which have advantageous properties in releasing the Have dish detergent in the respective fleet.

The water-soluble covering material is preferably transparent. Under transparency is in mind this invention to understand that the permeability within the visible spectrum of the Light (410 to 800 nm) greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible Spectrum of light has a transmittance greater than 20%, it is in the sense of the invention to be regarded as transparent.

Dishwashing detergent according to the invention, which in transparent envelopes or containers are packed, can contain a stabilizing agent as an essential component. Stabilizing agents in the sense of the invention are materials which Detergent components in their water-soluble, transparent coatings before decomposition protect or deactivate by exposure to light. Have been particularly suitable here Antioxidants, UV absorbers and fluorescent dyes have been proven.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are capable of metal ions which catalyze the autooxidation, e.g. As copper, to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV- Absorbers can improve the lightfastness of the recipe components. Below are understand organic substances (light protection filters) that are able to transmit ultraviolet rays to absorb and the absorbed energy in the form of longer-wave radiation, for. B. heat to deliver again. Compounds that have these desired properties for example the compounds and derivatives of the effective by radiationless deactivation Benzophenones with substituents in the 2- and / or 4-position. There are also substituted ones Benzotriazoles, such as the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast® H), phenyl substituted in the 3-position Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid suitable. Biphenyl and especially stilbene derivatives, which are commercially available, are of particular importance are available as Tinosorb® FD or Tinosorb® FR ex Ciba. Examples of UV-B absorbers are 3- Benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2- ethylhexyl ester, 4- (dimethylamino) 2-octyl benzoate and 4- (dimethylamino) benzoesäureamylester; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4- Propyl methoxycinnamate, isoamyl 4-methoxycinnamate, 2- 2-cyano-3,3-phenylcinnamate ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylic acid, Salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxybenzmalonate-2-ethylhexyl ester; Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'- hexyloxy) -1,3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as e.g. B. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4- methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3- Benzylidencamphers, such as. B. 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2- oxo-3-bornylidene) sulfonic acid and its salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as for example 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and Enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures be used. In addition to the soluble substances mentioned come for this purpose too insoluble light protection pigments, namely finely dispersed, preferably nanoised metal oxides or Salts in question. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and their Mixtures. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The Oxides and salts are already used in the form of pigments for skin care and skin protection Emulsions and decorative cosmetics are used. The particles should be medium Diameter less than 100 nm, preferably between 5 and 50 nm and in particular have between 15 and 30 nm. They can have a spherical shape, but they can Also such particles are used which are ellipsoidal or otherwise spherical shape have a different shape. The pigments can too surface treated, d. H. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as e.g. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). As Hydrophobic coating agents come mainly from silicones and especially trialkoxyoctylsilanes or Simethicone in question. Micronized zinc oxide is preferably used.

UV absorbers can be used in the dishwashing detergent in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight be included.

Another class of stabilizers to be used preferably are Fluorescent dyes. These include the 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, Naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems and by Heterocyclic substituted pyrene derivatives. The are of particular importance Sulphonic acid salts of the diaminostilbene derivatives, as well as polymeric fluorescent substances, as described in US 5,082,578 be disclosed.

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

In a preferred embodiment, the aforementioned stabilizing agents are used in any Mixtures used. The stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5 wt .-% used.

Preferred machine dishwashing detergents or machine dishwashing aids contain regardless of the type of their assembly, at least one active washing or cleaning Substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, Enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents. These substances will be described in more detail below.

Builder

According to the present invention, machine dishwashing detergents or automatic dishwashing aids, all usually in detergents and cleaning agents builders used, in particular silicates, carbonates, organic Cobuilder 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 represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

Both the monoalkali metal salts and the dialkali metal salts of the Carbonic acid as well as sesquicarbonates can be included in the funds. preferred Alkali metal ions represent sodium and / or potassium ions. In one embodiment, it may be preferred be, the carbonate and / or bicarbonate at least partially separately as a further component or to mix in later. Also compounds made of carbonate, silicate and optionally other auxiliaries such as anionic surfactants or others, Organic builders in particular can be used as separate components in the finished product Funds.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. The alkali metal phosphates are among the many commercially available phosphates particular preference for pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate) in the detergent and cleaning agent industry.

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

Suitable phosphates are sodium dihydrogen phosphate, NaH ₂ PO ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , by condensation the NaH ₂ PO ₄ and the KH ₂ PO ₄ result in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates, and the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate).

In addition to the sodium phosphates mentioned, the corresponding potassium salts or Mixtures of these two are used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Machine dishwashing detergents or preferred in the context of the present inventions automatic dishwashing aids do not contain sodium and / or potassium hydroxide.

Other preferred water-soluble builders are, for example, tripotassium citrate and Potassium water glasses.

Preferred automatic dishwashing detergents or automatic dishwashing aids contain 20 up to 60% by weight of one or more water-soluble builders, preferably citrates and / or Phosphates, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

In preferred embodiments of the present invention, the content of the agents is present water-soluble builders within narrow limits. Here are machine dishwashing detergents or machine dishwashing agents preferred which contain the water-soluble builder (s) in amounts from 22.5 to 55% by weight, preferably from 25 to 50% by weight and in particular from 27.5 to 45 wt .-%, each based on the total agent.

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

The term "metaphosphate" was originally the general term for condensed phosphates with the composition M _n [P _n O _3n ] (M = monovalent metal), but today it is mostly limited to salts with ring-shaped cyclo (poly) phosphate anions. When n = 3, 4, 5, 6, etc., one speaks of tri, tetra, penta-, hexa-metaphosphates. etc. According to the systematic nomenclature of the isopoly anions z. B. called the anion with n = 3 as cyclo-triphosphate.

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

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

As particularly preferred water-softening substances from the above classes of the condensed phosphates are the "Hexametaphosphate" Budit® H6 or H8 from Budenheim proved.

Mechanical are particularly preferred in the context of the present application Dishwashing detergents or automatic dishwashing aids, which additionally have one or more Substances from the group of acidifiers, chelating agents or coating inhibiting polymers contain.

Both inorganic acids and organic acids are suitable as acidifiers, if they are compatible with the other ingredients. For consumer protection reasons and the handling safety are in particular the solid mono-, oligo- and polycarboxylic acids used. From this group citric acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents be, in particular maleic anhydride and succinic anhydride commercially Are available. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of Succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions single ligand occupies more than one coordination site on a central atom, d. H. min. is "bidentate". In this case, stretched connections are normally used Complex formation closed by an ion to form rings. The number of ligands bound depends depends on the coordination number of the central ion.

Common chelate complex images which are preferred in the context of the present invention are for example polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or pendant to this functional groups, which act as ligands can act and with suitable metal atoms usually with the formation of chelated Reacting complexes can be used according to the invention. The polymer-bound ligands of the The resulting metal complexes can originate from only one macromolecule or else belong to different polymer chains. The latter leads to the networking of the material, provided that complex-forming polymers were not previously cross-linked via covalent bonds.

Complexing groups (ligands) are common complex-forming polymers Iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, Amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, Polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Also natural polymers such as cellulose, starch or chitin are complex-forming polymers. About that in addition, these can be achieved through polymer-analogous conversions with additional ligand functionalities be provided.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• b) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• c) geminalen Diphosphonsäuren,
• d) Aminophosphonsäuren,
• e) Phosphonopolycarbonsäuren,
• f) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten. In the context of the present invention, particular preference is given to machine dishwashing detergents or machine dishwashing aids which comprise one or more chelate complexing agents from the groups of

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• b) nitrogen-containing mono- or polycarboxylic acids,
• c) geminal diphosphonic acids,
• d) aminophosphonic acids,
• e) phosphonopolycarboxylic acids,
• f) cyclodextrins

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

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

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

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

As polycarboxylic acids a), carboxylic acids are included in this patent application Monocarboxylic acids - understood, in which the sum of carboxylic and those in the molecule contained hydroxyl groups is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred. Both The alkaline pH values of the treatment solutions required according to the invention are these Complex bilens at least partially as anions. It is immaterial whether it is in the form of acids or introduced in the form of salts. When used as salts, alkali, Ammonium or alkylammonium salts, especially sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from Groups of low molecular weight polyacrylates with molar masses between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also have cobuilder properties. As organic Cobuilders can be used in particular in the dishwasher detergents according to the invention Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

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

As organic cobuilders in the cleaning agents in the context of the present invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. The Acids own next to theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

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

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molecular weights from 1000 to 10,000 g / mol, and particularly preferably from 1200 to 4000 g / mol, may be preferred.

Both polyacrylates and also are particularly preferred in the agents according to the invention Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers are used. The Copolymers containing sulfonic acid groups are described in detail below.

However, it is also possible to use products according to the invention which are known as “3in1” products Combine conventional detergent, rinse aid and a salt replacement function.

• a) ungesättigten Carbonsäuren
• b) Sulfonsäuregruppen-haltigen Monomeren
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise 0.1 to 70% by weight of copolymers

• a) unsaturated carboxylic acids
• b) monomers containing sulfonic acid groups
• c) optionally further ionic or nonionic monomers

contain.

These copolymers cause the dishes treated with such agents subsequent cleaning processes become significantly cleaner than dishes that are washed with conventional agents were rinsed.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes on d. H. after the expiry of the Cleaning programs take the dishes out of the machine earlier and reuse them.

In the context of the present invention, unsaturated carboxylic acids of the formula VII are preferred as the monomer

R ¹ (R ² ) C = C (R ³ ) COOH (VII),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by formula VII 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 VIII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIII),

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 VIIIa, VIIIb and / or VIIIc,

H ₂ C = CH-X-SO ₃ H (VIIIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIIc),

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

Other ionic or nonionic monomers in particular are ethylenic unsaturated compounds. The content of the invention is preferably polymers used on monomers of group iii) less than 20 wt .-%, based on the Polymer. Polymers to be used with particular preference consist only of monomers of Groups i) and ii).

• a) ungesättigten Carbonsäuren der Formel VII
  
  R¹(R²)C=C(R³)COOH (VII),
  
  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,
• b) Sulfonsäuregruppen-haltigen Monomeren der Formel VIII
  
  R⁵(R⁶)C=C(R⁷)-X-SO₃H (VIII),
  
  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)
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt. In summary, copolymers are made of

• a) unsaturated carboxylic acids of formula VII
  
  R ¹ (R ² ) C = C (R ³ ) COOH (VII),
  
  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,
• b) sulfonic acid group-containing monomers of the formula VIII
  
  R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIII),
  
  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 )
• c) optionally further ionic or nonionic monomers

particularly preferred.

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

Particularly preferred copolymers consist of

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

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

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula IX

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IX),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula X.

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _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. Agents according to the invention which contain one or more copolymers are structural units of the formula XI

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are also preferred, a preferred embodiment of the present invention, just like agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of formula XII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (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.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XIV

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-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 preferred.

In summary, automatic dishwashing agents or automatic dishwashing aids according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IX),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XI),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XIV),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _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.

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form are present, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all Sulphonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be exchanged. Corresponding means, which are characterized by that the sulfonic acid groups are partially or fully neutralized in the copolymer preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is preferred for copolymers containing only monomers from groups i) and ii) each 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90 wt .-% monomer from the Group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from the Group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer group iii) included.

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

The content of one or more copolymers in the agents according to the invention may vary Application and desired product performance vary, with preferred automatic dishwashing agents according to the invention are characterized in that they the copolymer (s) in amounts of 0.25 to 50% by weight, preferably 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their 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 either be as a powder or as an aqueous solution be used. 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, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

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

Further preferred copolymers preferably have acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives.

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

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. It is preferably hydrolysis products with medium Molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used 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 30,000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Farther glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts are 3 in zeolite and / or silicate formulations up to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. As Builder from the phosphonate class is preferably HEDP. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.

Agents according to the invention are characterized in the context of the present application in that that they builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably 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 agent.

surfactants

Preferred cleaning agents contain one or more in the context of the present application Surfactant (s) from 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 sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

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

As 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 fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of 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 analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). 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.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. 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 radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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, are preferably used.

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 nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (XV)


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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI)


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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N- Alkoxy or N-aryloxy substituted compounds can then be reacted 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 by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense 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. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, automatic dishwashing agents according to the invention which contain surfactants of the general formula XVII as nonionic surfactant (s) are preferred


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 XVII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula XVII 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 of alcohols of native origin having 12 to 18 carbon atoms, e.g. B. from coconut, palm, tallow or oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula XVII for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and especially 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.

Low-foaming nonionic surfactants are used as preferred additional surfactants. The automatic dishwashing detergents according to the invention contain with particular preference nonionic surfactant that has a melting point above room temperature. As a result, Preferred agents are characterized in that they contain nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, particularly preferred between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, included.

Suitable nonionic additives in addition to the nonionic surfactants contained in the agents according to the invention Surfactants that have melting or softening points in the temperature range mentioned For example, low-foaming nonionic surfactants that are solid at room temperature or can be highly viscous. If highly viscous nonionic surfactants are used at room temperature, this is the case preferred that this has a viscosity above 20 Pa.s, preferably above 35 Pa.s and have above 40 Pa.s in particular. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) - Nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant is included a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.

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

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

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends containing 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 Copolymers of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Examples of nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred automatic dishwashing agent according to the invention contains nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. 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, dishwasher detergents according to the invention are preferred, the end group-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 combination with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants are used, which because of their foaming behavior in machine dishwashing detergents are only of minor importance and mostly only in Amounts below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5 wt .-%, each based on the agent, are used. The invention Agents can thus also anionic, cationic and / or amphoteric as a surfactant component Contain surfactants.

In the context of the present invention, it is preferred that the automatic dishwashing detergents or automatic dishwashing detergent surfactant (s), preferably nonionic surfactant (s), in Amounts from 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight and in particular from 1.0 up to 5 wt .-%, each based on the total agent.

bleach

Bleaching agents and bleach activators are important constituents of detergents and cleaning agents and a preferred automatic dishwashing agent or automatic dishwashing auxiliary 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 2Na ₂ CO ₃ .3H 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.

Detergents for automatic dishwashing can also be bleaches from the group of contain organic bleach. Typical organic bleaching agents used as ingredients in the Can be used in the present invention, the diacyl peroxides such. B. Dibenzoyl. Other typical organic bleaching agents are the peroxy acids, where as Examples include the alkyl peroxy acids and the aryl peroxy acids. preferred Representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as Alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) die aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N- Terephthaloyl-di (6-aminopercapronic acid) can be used.

According to the present invention, bleaching agents for automatic dishwashing can also be used Chlorine or bromine releasing substances are used. Among the appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaches, in particular the Chlorine bleach, with particular preference for sodium percarbonate and / or Sodium perborate monohydrate, in amounts of 0.5 to 40% by weight, preferably 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total mean.

Bleach activators

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below can achieve cleaning agents in the context of the present invention bleach activators contain. As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or are suitable optionally substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso- NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, according to the In 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 and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

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, especially N- Nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10% by weight, based in each case on the total composition.

The bleach activators preferred in the context of the present invention also include the "nitrile quats", cationic nitriles of the formula (XVIII)


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.

The general formula (XVIII) 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 nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.

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 is selected.

Machine dishwashing detergents or preferred in the context of the present invention Dishwashing aids are characterized in that they are the cationic nitrile of the formula (XVIII) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the total weight of the composition.

enzymes

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can use it by removing pilling and microfibrils to preserve color and increase Contribute to the softness of the textile. To bleach or to inhibit the transfer of color can also Oxidoreductases are used. Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and those obtained from its genetically modified variants enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic Enzymes or protease and cellulase or from cellulase and lipase or lipolytic Enzymes or from protease, amylase and lipase or lipolytically active enzymes or Protease, lipase or lipolytic enzymes and cellulase, but especially Protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of special interest. Examples of such lipolytically active enzymes are the known ones Cutinases.

Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases. Cellobiohydrolases, endoglucanases and are preferably used as cellulases -Glucosidases, which are also called cellobiases, or mixtures of these are used. There different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect 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, in each case based on the total mean.

dyes

To the aesthetic impression of machine dishwashing detergent or machine To improve dishwashing aids, they can be colored with suitable dyes. in the Preferred dyes within the scope of the present invention, their selection to the person skilled in the art no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agent and against light and no pronounced Substantivity towards the wash ware so as not to stain it.

Preferred for use in the automatic dishwashing detergent according to the invention or Machine dishwashing aids are all colorants that are oxidatively destroyed in the cleaning process and mixtures of these with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants in or in water Room temperature are soluble in liquid organic substances. For example, are suitable anionic colorants, e.g. B. anionic nitroso dyes. A possible colorant is for example naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as Commercial product available for example as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes. Coming as additional colorants 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® Blue 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).

fragrances

Fragrances are added to the agents in the context of the present invention in order to to improve the aesthetic impression of the products and the consumer in addition to the performance of the Product a visually and sensory "typical and distinctive" product available put.

Individual perfume oils or fragrances can be used in the context of the present invention Fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the type Esters are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear alkanals with 8- 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and Pinene.

However, preference is given to using mixtures of different fragrances which together have one generate an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

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 of the 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-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, machine dishwashing detergents or machine Dishwashing aids preferred, which additionally selected from at least one silver protection agent the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the Alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts from 0.001 to 1% by weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.

Another object of the present application is the use of a automatic dishwashing agents according to the invention or automatic dishwashing aids for Reduction of glass corrosion in automatic dishwashing.

Examples

Glasses that were not soiled were washed in a continuously operated dishwasher a standard dishwasher detergent with a water hardness of 0-1 ° dH.

In comparative example V1, only 24.5 g of a commercially available dishwasher detergent were metered in for each cleaning cycle. In comparative examples V2 and V3, 250 mg of zinc acetate and 400 mg of the crystalline layered silicate Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) were metered in simultaneously with the 24.5 g of the commercially available dishwasher detergent. In Example E1 according to the invention, 250 mg of zinc acetate and 400 mg of Na-SKS-6 were finally metered in, in addition to the dishwasher detergent. The rinsing process was repeated 50 times under the conditions described above. The overall appearance of the wash ware was assessed using the rating scale below.

The results are shown in the table below


Evaluation scale: T0 = no turbidity until T4 = severe turbidity.

The table shows that the automatic dishwashing detergent according to the invention, which the Combination of a zinc salt and a crystalline layered silicate contains, among which mentioned conditions has significantly better glass corrosion properties than Dishwashing detergents that contain only zinc salt or only silicate. The corrosion-inhibiting effect The active ingredient combination of zinc salt and silicate is well above the sum of those for the individual substances observed effects.

Claims (13)

1. Machine dishwashing detergent or machine dishwashing aid containing at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

NaMSi _x O _{2x + 1} .yH ₂ O (I),

wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33. 2. Machine dishwashing detergent or machine dishwashing aid according to claim 1, characterized in that it contains the zinc salt (s) and the crystalline (s) layered silicate (s) of the general formula (I) in a ratio of 10: 1 to 1:50, preferably from 5: 1 to 1:30 and in particular from 3: 1 to 1:10. 3. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 or 2, characterized in that it selected at least one zinc salt from the group of inorganic zinc salts, preferably from the group of soluble inorganic zinc salts, especially from the group zinc bromide, zinc chloride, zinc iodide, Contains zinc nitrate and zinc sulfate. 4. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 or 2, characterized in that it selected at least one zinc salt from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, particularly preferably from the group of soluble zinc salts monomeric or polymeric organic acids, especially from the group zinc acetate, Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, Contains zinc abietate, zinc valerate, zinc p-toluenesulfonate. 5. Automatic dishwashing detergent according to one of claims 1 to 4, characterized in that that the weight fraction of the zinc salt based on the total weight of this agent 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0.4 to 4% by weight. 6. Automatic dishwashing detergent according to one of claims 1 to 5, characterized in that that the proportion by weight of the crystalline layered silicate of the formula (I) based on the total weight of this agent 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-% and is in particular 0.4 to 10% by weight. 7. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 6, characterized in that the zinc salt (s) and / or contained the crystalline layered silicate (s) contained, with one or more further active and / or framework substance (s) assembled, in particulate form, as Compound is / are present. 8. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 7, characterized in that the crystalline (s) layer (s) Silicate (s) of the formula (I) with one or more further active and / or structural substance (s), preferably with one or more further active and / or framework substances from the Group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and of the phosphonic acids, is / are present in particulate form as a compound. 9. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 6, characterized in that the zinc salt (s) and / or the / crystalline (n) layered (n) silicate (s) are assembled in a polymer matrix. 10. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 6, characterized in that it is dimensionally stable and a penetration number from 200 to 1000 g, preferably from 250 to 900 g, particularly preferably from 300 to 800 g and in particular from 350 to 700 g. 11. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 6, characterized in that it has a viscosity of 500 to 500,000 mPa.s, preferably from 900 to 200,000 mPa.s and in particular from 1300 to 100,000 mPa.s having. 12. Machine dishwashing detergent or machine dishwashing aid according to one of the Claims 1 to 11, characterized in that it is portioned in a water-soluble Wrapping is packaged. 13. Use of a machine dishwashing detergent or machine dishwashing aid according to one of claims 1 to 12 for reducing glass corrosion in mechanical Wash the dishes.