DE2539531A1 - Dishwashing compsn. - contains a divalent or trivalent cation additive to reduce corrosion - Google Patents

Abstract

Parent patent describes a dishwashing compsn. based on alkali silicates and/or carbonates and/or hydroxides (I) and finely-divided, water-insoluble cpds. of formula (Alk2O)x. Me2O3. (SiO2)y (II) (where Alk is an alkali ion exchangeable with Ca; x = 0.7-1.5; Me is B or Al and y is 0.8-6, pref. 1-3-4) to bond the water-hardening components of the water and which had a Ca-bonding capacity of 100-200 mg CaO/g anhydrous active substance as well as the usual other additives. In this addn. the compsn. contains 0.5-5 wt. % (1-3) of cpds. having di-/tri-valent cations (as their oxides) which are either sparingly water-soluble themselves or form sparingly water-soluble cpds. with the compsn's components without, however, using >20% of the Al silicate's original Ca-bonding capacity. Corrosion of the articles to be cleaned is reduced without significantly increasing the water's hardness.

Description

Addendum to the patent ............. (German Offenlegungsschrift 2 412 836 (D 4666/4750/4767/4816) "Means for machine washing of dishes" The patent (German Offenlegungsschrift 2 412 836) relates to means for machine washing of dishes, which are characterized in that their composition is within the framework the following formulation is: 10 - 60 wt .-% alkali silicates and / or carbonates and / or hydroxides, 10-65% by weight, capable of binding the hardness constituents of the water finely divided water-insoluble, optionally containing bound water Calcium binding capacity of 100 - 200 mg CaO / g anhydrous active substance (= AS) having Compounds of the formula (Alk2O) x. Me2O3. (SiO2) y, in the alk one that is exchangeable with calcium Alkali ion, x a number from 0.7 - 1.5, Me boron or aluminum and y a number from 0.8-6, preferably 1.3-4, and 0-40% by weight of other common constituents of machine dishwashing detergents.

These agents can also contain organic and / or inorganic, optionally contain phosphorus-containing complexing agents, but the total P content should of the agents do not exceed 6% by weight and preferably 3% by weight in order to be environmentally friendly to ensure the means.

For the general usability of cleaning agents for the machine Sinking in the household and commercial is crucial on the one hand by the given Wash program a satisfactory cleaning of the wash items is achieved, on the other hand However, no surface damage (corrosion) even after a large number of rinsing cycles on the items to be washed. Glasses or glasses are particularly susceptible to corrosion. Porcelain on-glaze decorations or glazes of ceramic materials. Express corrosion z. B. in a matting of the glasses, formation of iridescent surfaces, appearance punctiform damage or micro-cracks or fading of on-glass decorations with porcelain.

With the technical development of dishwasher for Household and trade were replaced by the dishwasher and detergent manufacturers Increased corrosion tests carried out on glasses and decorated porcelain. This made the dependence of the glass damage on numerous factors such as z. B. Number and duration of the wash cycles, wash temperature, glass and water types, the entire history of the glass, aging processes between rinsing treatments, Composition and dosage of the detergent, alkalinity of the washing liquor and the like. are shown. The detergent manufacturer can primarily only focus on the composition influence the detergent (see Fette-Seifen-Anstrichmittel, 69, (1967), 182 - 188; 1971, 71: 613-622; 74, (1972), 36-48).

Glass is much less resistant to chemical attack than is commonly believed. Just by water alone, reinforced by its influence by water vapor or alkalis, glass surfaces are attacked and degraded.

Since the rinsing process is necessarily more alkaline with water Solution above room temperature is connected, accordingly, will be a certain The degree of corrosion on less resistant wash ware can hardly be completely avoided.

It has now been found that detergents and cleaning agents based on alkali aluminum silicate by adding compounds of bivalent or trivalent cations an advantageous one Corrosion reduction of the items to be washed, especially those that are generally used softened water, can be achieved. These connections can either be from be sparingly soluble in water from the outset or in the rinsing liquor with other detergent ingredients, especially the cation-exchanging alkali aluminum silicates, poorly soluble compounds result. The agents according to the invention therefore do not lead to a significant one Hardening of the rinsing gel.

The invention therefore relates to a further embodiment of the means for machine washing of dishes according to the patent ................ (German Offenlegungsschrift 2 412 836) and is characterized in that the means 0.5 to 5, preferably 1 to 3% by weight of compounds of divalent or trivalent cations, calculated as oxides, which are either sparingly soluble in water themselves or with cleaning agents ttelbe constituents result in poorly soluble compounds, but by their Addition of a maximum of only 20% of the original calcium binding capacity of the aluminum silicates may be consumed.

The composition of the agents according to the invention is in general as part of the following recipe: 10 - 60 wt .- / a alkali silicates and / or carbonates and / or hydroxides, 10 - 80 wt. aluminum silicates (as active substance) 0.5-5% by weight, preferably 1-3% by weight, of divalent or trivalent compounds Cations, calculated as oxides, but with a maximum total due to their addition only 20% of the original calcium binding capacity of the aluminum silicates is consumed may be, 0 - 40 wt .- other common ingredients of dishwasher detergents.

The alkali silicates, carbonates and hydroxides are to known substances commonly used for this purpose. These connections can optionally also partly through inorganic phosphates and / or organic Phosphorus compounds are replaced, however, their share in the total mixture should not be greater than a total P content of 6% by weight, preferably of 3 wt .-% corresponds.

"Aluminum silicates" have a calcium binding capacity of 100 to 200 mg CaO / g anhydrous active substance (= AS) containing, finely divided, water-insoluble, Compounds of the general formula (Alk2O) x containing mostly bound water . Mm 203 (SiO2) y, in the alk one that is exchangeable with hardness constituents such as Ca2 + or Mg2 + Alkali ion, x a number from 0.7 to 1.5, Me boron or aluminum and y a number from 0.8 - 6, preferably 1.3 -4, according to patent ............... (German Offenlegungsschrift 2 412 836).

One method of making these cation-exchanging aluminum silicates as well as for the determination of the calcium binding capacity is inter alia. in the German Offenlegungsschrift 2 412 837 stated. Depending on the drying conditions, the products contain more or less bound water.

If you want to drive out the water completely, this is done for an hour Heating to 800 OC possible; in this way the AS values of the aluminum silicates are also determined certainly.

The finished sodium aluminum silicates, which are X-ray amorphous or can be crystalline are used for the purposes of the invention. Preferred use crystalline products. Also mixtures of different aluminum silicates as well as crystalline and X-ray amorphous products can be reduced - sometimes with an increase the cleaning effect.

The calcium binding capacity of 100 - 200 mg CaO / g As is found especially for compounds with the composition: 0.7 - 1.1 Na2O. Al203. 1.3 - SiO2.

This molecular formula includes two types of different crystal structures (or their non-crystalline precursors), which are also characterized by their molecular formula differentiate. These are: a) 0.7 - 1.1 Na2O. Al203. 1.3 - 2.4 SiO2 b) 0.7 - 1> 1 Na20. Al203. 2.4-3.3 SiO2.

The different crystal structures are shown in the X-ray diffraction diagram; Details on this can be found in German Offenlegungsschrift No. 2,412,837.

It is particularly advantageous to use aluminum silicates, which are at least 80% by weight of particles with a size of 10 to 0.01 μ, preferably 8 to 0.1 , exist. These aluminum silicates advantageously do not contain any primary or secondary particles above 4o y. Aluminum silicates of this particle size are referred to here as "microcrystalline" designated.

The aluminum silicates are preferred in a concentration of 0.5 - 3 g / l used. In particular, they are combined with alkaline substances Substances which are used in such an amount that the pH of the treatment liquor ranges from 8 to 13. Such alkaline reacting substances are preferred Alkali silicates and alkali carbonates, and, if higher pH values are desired, Caustic alkalis.

A large number of different amounts can be used as corrosion inhibitors Compounds of bivalent or trivalent cations such as Ca2 + Mg2 + zn2 +, Fe2 +, 3+ Zn, Fe, Fe and the like can be used.

These cations are preferred to the detergent in the form of their sparingly soluble Phosphates, carbonates, oxides or hydroxides, silicates, aluminum silicates and the like. added; Calcium ions optionally also in the form of their sulfates. For the production of the aluminum silicates, the same compounds can preferably be used, which serve as a structural substance, d. H. some of those previously in sodium form According to the invention, compounds are loaded with the inhibiting cations, these replacing the sodium ions. Also organic exchange resins of the next The types described below are suitable as carriers of the inhibiting cations. at Use of soluble salts such as B. Ca12, Mg12, FeCl3 or FeSO4 or their hydrates form the cations in the wash liquor with the anions present such as. B. carbonate, Silicate and especially the cation-exchanging aluminum silicate components in Compounds that are sparingly soluble in water, so that the washing liquor does not harden.

The effect of these agents according to the invention is surprising because in order to inhibit the corrosion of the items to be washed, such compounds can be used Cations are used, which act in dissolved form as hardness and usually should be removed from the rinse water by detergent components.

Since the corrosion inhibitors according to the invention do not themselves have any cleaning power have, they should be used in the smallest possible amount. As an advantage A dosage of 0.5 to a maximum of 5% by weight, preferably 1 to 3, has proven successful % By weight, calculated as oxide and based on the total solvent.

Depending on the molecular weight of the corrosion inhibitors used can potentially produce hardness in very different amounts despite the same weight Cations are introduced into the detergent. With a usual dosage of Total detergent of 3 g / l would be calculated using 5% by weight CaCO3 assuming a complete 0 solution, an additional hardness of 8.4 d has been achieved, when using Ca (OH) 2 with the same dosage by weight, on the other hand, of 11.2 d.

In reality, however, as a result of the poor solubility of the corrosion inhibitors in the alkaline rinsing solution and the presence of hardness-binding detergent components even when using city water with 16 od and inhibitors according to 8.4 ° d additional hardness (e.g. 5 wt. CaCO3) in the total detergent of the described Type (compare Example 3) the resulting hardness in the washing liquor does not increased to over 1 d.

It is advisable to use corrosion inhibitors in the detergent to restrict so that by the addition not more than 20 ffi of the original Calcium binding capacity of aluminum silicates is bound. At least $ 80 of exchange capacity should therefore be retained so that the cleaning effect of the detergent is not undesirable to reduce.

The residual hardness binding capacity of the aluminum silicates can be determined by slurring the inhibitor-containing detergent in softened water (e. B. at 3 g / l, 30 minutes at 65 ° C), then filtered, and the calcium binding capacity the remaining aluminum silicates (together with other insoluble ingredients in the formulation) determined in accordance with German Offenlegungsschrift 2,412,837.

The effect of cleaning agents containing aluminum silicate can be reduced by adding small amounts of surfactants, especially nonionic surfactants, to enhance. In addition, there has been an addition of oxidizing substances, in particular of active chlorine compounds, possibly also of peroxo compounds, as advantageous proven.

To the other common ingredients of machine dishwashing detergents thus include the following substances, which are mostly present in the specified amounts are: 0-10% by weight of active chlorine or substances containing active oxygen, 0-10 % By weight surfactants, in particular nonionic surfactants 0-20% by weight sodium sulfate and / or Water.

The cleaning effect of the aluminum silicates continues water-soluble polymers capable of complexing with calcium and magnesium Carboxylic acids or their water-soluble salts or other phosphorus-free frameworks to enhance; the aluminum silicates can be partially replaced by the additives mentioned be replaced.

The complexing agents to be used in combination with the aluminum silicates of the water-soluble polyearboxylic acid type, preferably in the form of their water-soluble Salts are used, for example, carboxymethyl ether, the sugar, the Starch and cellulose. This also includes the polymers of acrylic acid, Hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid, Citraconic acid and the like., The copolymers of above-mentioned carboxylic acid with one another or with ethylenically unsaturated compounds such as ethylene, propylene, Isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, Acrylonitrile, methacrylic acid, crotonic acid, etc., such as. B. the 1: 1 copolymers from maleic anhydride and ethylene or propylene or furan. Finally belong to this group of compounds consisting essentially of acrylic acid and acrolein units or polyhydroxypolycarboxylic acids composed of acrylic acid and vinyl alcohol units or polyaldehydopolycarboxylic acids obtained by copolymerization of acrylic acid and Acrolein or by polymerization of acrolein and subsequent Cannizzaro reaction are optionally obtainable in the presence of formaldehyde.

Combinations of aluminum silicates and polymeric carbon acids or their salts are preferably used in concentrations of 0.5-3 g / l. Included the ratio of luminescent silicate: polymeric carboxylic acids is in the range of 10: 1 up to 1:10, preferably from 4: 1 to 1: 4.

The aluminum silicates can also be used in detergents and cleaning agents partly through finely divided, granular, water-insoluble ones, for binding calcium capable ion exchangers of organic nature are replaced. These are to ion exchangers based on synthetic resin, which preferably have a calcium binding capacity of 20-220, in particular 50-150 mg CaO / g active substance.

The particle size of the organic ion exchanger can be in the range of the commercially available ion exchangers (0.1 - 1 mm). Appropriately used one products with 0.3-0.8 mm particle size.

Ion-exchanging groups capable of binding calcium are e.g. sulfonic acid, phosphonic acid, carboxyl, carboxymethyl, sulfonamide, disulfimide, Carbonamide, dicarbimide and Sulfocarbimide groups. These groups are cross-linked and therefore insoluble in water, but possibly in water The swellable framework of an organic macromolecule, which, depending on its production, is bound may be a polycondensation or a polymerization resin.

The polycondensation resins are obtained, for example, by reaction of phenols or of acidic group-containing phenol derivatives with aldehydes or Ketones, especially with formaldehyde. The acidic groups also subside introduce condensation.

Polymerization resins are preferably obtained by copolymerization of styrene or of styrene derivatives containing acidic groups with crosslinking agents, such as B. divinylbenzene, and optionally subsequent introduction of acidic Groups. The styrene can be replaced by polymerizable carboxylic acids.

These organic cation exchangers are preferred in the form of their Salts used; the cations capable of exchanging with calcium can be the same be like the aluminum silicates.

Combinations of aluminum silicates and organic ion exchangers or their salts are also preferred in concentrations of 0.5-3 g / l used. The aluminum silicate: organic ion exchanger ratio is also found here in the range from 10: 1 to 1:10, preferably 4: 1 to 1: 4.

In addition, those in the patent ...........

(German Offenlegungsschrift 2 412 8) 6).

EXAMPLES The quantities given in the recipes refer to for the aluminum silicates on their anhydrous active substance, determined by one hour Dehydrate at 800 ° C. The water contained in the aluminum silicates is combined with other water contained in the agent indicated separately.

nDCIC't means the sodium or potassium salt of dichloroisocyanuric acid.

Under "water glass liquid" is a 35% solution of a sodium silicate the composition Na2O. 3.35 5102 to be understood. Only that is in the recipes Solids content (Suwne Na2O and SiO2) recorded and the water with another average contained water is indicated separately (see above).

The "Nonionic" is one available under the trade name "Pluronic L 61" Addition product of ethylene oxide with a polypropylene glycol ether of molecular weight 1900, the proportion of polypropylene glycol ether being 90 wt. - and the proportion of Polyethylene glycol ether makes up 10% by weight.

A substance based on a cross-linked was used as the ion exchanger S 100 Polystyrene sulfonic acid with a calcium binding capacity of 135 mg CaO / g active substance and a grain size of 0.3-0.8 mm is used (commercial product: "LEWATIT R S 100").

The preparation of the fully crystalline used in the examples Aluminum silicates I, II and V and the microcrystalline aluminum silicate XIIm in German Offenlegungsschrift 2,412,837. The products used had the following composition: I: 0.9 Na20. Al203. 2.04 SiO2. 4.3 H20 (= 21.6% H20) fully crystalline calcium binding capacity: 150 mg CaO / g AS II: 0.8 Na20. Al20 ». 2.65 SiO2. , 2 H20 fully crystalline calcium binding capacity: 120 mg CaO / g AS V: 1> 5 Na2O. A1203. 2 SiO2. 3 H20 (= 16.7% H20) X-ray amorphous calcium binding capacity: 140 mg CaO / g AS XIIm: 0.9 Na2O. Al203. 2 SiO2. 3 H20 (= 11 ffi H20) microcrystalline Calcium binding capacity: 175 mg CaO / g AS The following examples describe specific ones Embodiments of the means according to the invention for its implementation.

The recipes according to the state of the art are indicated by the letter "v" (= comparison) identified by the letters "a", "b", "c" and "d", respectively.

For the production of granulated, for use in household dishwashers certain cleaners of the formulations given below, the nonionic is dissolved in water, add the water glass and spray the solution onto a mixture of the remaining, powdery ingredients in motion, which is useful in a granulating device, e.g. B. happens on a granulating plate. After this the water is set as crystal water, the desired granulate is obtained.

Just like the detergents currently on the market, detergents with cation-exchanging agents are calling Aluminum silicates in the household normally, i. H. with normally sensitive items to be washed and over a variety of wash cycles, no significant glass damage emerged. Such Damage would only occur in long-term use. For the corrosion tests listed below test methods were therefore chosen that compared to the otherwise usual conditions of machine washing result in extremely increased glass corrosion. Just leave it like that the test duration can be reduced to an acceptable level.

For the corrosion tests with the given recipe examples For reasons of reproducibility, only round glasses made of less resistant soda glass were used used.

In order to avoid 'outliers' as much as possible and to always use the same starting material to use, previously unused undamaged glasses from the same batch used.

The test apparatus was deliberately kept simple. The round glasses were into pieces about the size of a slide (approx.

25 x 75 mm), marked with a diamond pen and firmly wedged into a 500 ml polyethylene bottle. Then 300 ml of rinsing solution were used added with the recipe to be tested.

The polyethylene bottles with the glasses stood during the inspection in thermostated water baths (65 + 2 00).

During the rinsing attempts, stirring was carried out continuously (approx. 150 revolutions) per minute). The stirrers passed through the lids of the sealed polyethylene bottles.

The corrosion tests in the examples given lasted in each case 165 hours (without interruptions for bath changers).

The cleaning solutions were renewed twice a day. To Diploma During the tests, the glasses were rinsed with deionized water and left in the air dried. The visual damage rating was versus white and black Background made. The type of damage was recorded in each case (e.g. iridescent Surfaces, cloudiness, deposits, punctiform damage or micro-cracks, etc.) as well as the shape, location and extent of the damage. After that first visual assessment The glasses were half concentrated for a few minutes with alcohol Methylene blue solution stained and immediately afterwards the strength and uniformity of the stainability judged.

This dyeability of the adsorptive substances produced by alkaline glass degradation The swelling layer is also a measure of glass corrosion. Damage can be so visible long before they would be visible to the naked eye without staining.

Table: Examples of recipes based on aluminum silicate Constituent% by weight of constituent in the formulations 1v 2v 3v 4v 5v 6v 7v 8v 9v 10v 11v 12v Aluminum silicate I 44 26 30 42 41 7 Aluminum silicate II 20 54 7 Aluminum silicate V 50 25 7 Aluminum silicate XIIm 31 7 46 20 Ion exchanger S 100 18 15 21 10 36 20 40 Pentasodium Phosphate 6 4 Sodium metasilicate 40 40 10 10 12 36 20 20 Liquid water glass 4 6 4 4 Na2SO4 16 16 22 Soda 22 25 22 Caustic soda (powdered) 12 12 10 Sodium polyacrylate 8 Nonionic 1 1 1 1 4 1 1 1 1 2 1 DCIC 2 4 2 2 2 2 1 2 Water 13 15 6 14 9 9 24 23 8 17 19 13 Example 1: This example demonstrates the state of the art under more stringent test conditions: The recipes iv to 12v listed in the table were used on Neckar cups 1812/14 from Glashütte Zwiesel (soda glass) in the test arrangement described above under conditions that were extreme compared to washing in the home 65 0 "was checked for its corrosion effect. For this purpose, the formulations were each used at 3 g / l in permuted water (softened Düsseldorf tap water at 1 0d).

After completion of the 165-hour endurance test, the glass was damaged judged.

All glasses showed significant damage. Severe opacities occurred concentric rings and towards the bottom of the glass. In some cases were observing iridescent spots. The glasses could be clearly colored.

Example 2: By replacing in each case 1/10 of the amount by weight of the aluminum silicates in the formulations lv to 8v and 10v to 12v as well as of a maximum of 5 wt. = 2.8 ffi CaO of the total detergent in recipe 9v through calcium carbonate became the recipes la to 12a formed. The formulations la to 12a were produced as above described; the powdery (technical) calcium carbonate was with the rest powdered recipe ingredients mixed before the liquid ingredients were sprayed on.

After endurance testing under the same conditions and on the same glass As in Example 1, the glasses all showed significantly less damage than with the recipes lv to 12 v. The dyeability was greatly reduced. Mostly the glasses were brilliant and without any damage.

Example): The corrosion tests were carried out as in Example 2 carried out analogously with the recipes la - 12a in Düsseldorf city water (16 ° d). The inhibition was at least as good, and in some cases slightly improved.

To determine the resulting water hardness in the wash liquor were In a separate experiment, the rinsing solutions were filtered after a rinsing time of 30 minutes and determines the water hardness in the usual way. The following values were obtained obtained: la 0.6 Od; 2a or 8 Od; 3a 0.4 Od; 4a 0.5 0d; 6a or 6 Od; 7a 0.9 Od; 8a or 8 ° d; 9a 0.9 ° d; lOa or 6 Od; lia 1.0 0d; 12a 0.7 ° d.

Example 4: As in Example 2, the inhibition additives the respective aluminum silicates loaded with Ca2 + ions are used and so are the recipes 1b bS 12b created The aluminum silicates were loaded with Ca2 + ions by using three times for about 15 minutes with ten times the weight of a ten percent calcium chloride solution were stirred at room temperature.

The aluminum silicates were then filtered off, washed and dried and mixed with the other powdery recipe ingredients.

The degree of exchange of those used in recipes 1b to 12b Aluminum silicates loaded with calcium ions was about 75% (i.e. 75% by weight Sodium ions previously present in the aluminum silicates were replaced by calcium ions replaced).

After the endurance test according to Examples 1 and 2, the same result Corrosion inhibition determined as with the formulations la to 12a.

Example 5: The organic ion exchangers can also be used as carriers of the inhibiting divalent or trivalent cations act.

By charging with a ten percent CaCl2 solution, the Ion exchanger in an exchange column at room temperature at 90 ffi with C. Loaded with Ca2 + ions. In the ion exchanger-containing recipes in the table 5% by weight of the ion exchanger, based on the total formulation, due to the calcium form of the exchanger and incorporated into the recipes in the same way. The low-corrosion formulations 2c-4c and 9c-12c were thus formed.

Example 6: Aluminum silicate I became 30 three times at room temperature Stirred for minutes with ten times the amount of a 20% zinc chloride solution, filtered and washed and thus loaded to approx. 75% with Zn2 + ions (analytically afterwards certainly). In the formulations lv to 12v, 1/10 of the aluminum silicates were used replaced by aluminum silicate 1 loaded with Zn2 + ions (with formulation 9v only 5% by weight, based on the total formulation). This results in the formulations 1d to 12d.

The corrosion test in permuted water according to the example 1 produced excellent corrosion inhibition, some of which was even stronger was as with the recipes la to 12a. The glasses were mostly brilliant and without any damage report.

Claims (7)

Claims Further training of the means for machine washing of dishes based on alkali silicates and / or carbonates and / or hydroxides for binding finely divided, water-insoluble, if necessary Compounds of the general formula (Alk2O) x containing bound water. Me203 (SiO2) y> is called "aluminum silicates", in the alk one which can be exchanged with calcium Alkali ion, x a number from 0.7 - 1.5, Me boron or aluminum and y a number from 0.8-6, preferably 1.3-4, which have a calcium binding capacity of 100 have up to 200 mg CaO / g anhydrous active substance (AS), and other usual Components of machine dishwashing detergents, according to patent ................... (German Offenlegungsschrift 2 412 836), characterized in that the means 0.5 to 5, preferably 1 to 3% by weight of compounds of divalent or trivalent cations, calculated as oxides, which are either sparingly soluble in water themselves or poorly soluble compounds result with detergent components, however, as a result of their addition, a maximum of only 20% of the original calcium binding capacity the aluminum silicates may be consumed. 2. Means according to claim 1, characterized in that it is in the frame of the following formulation: 10 - 6o wt .-% alkali silicates and / or carbonates and / or hydroxides, 10 - 80% by weight aluminum silicates (as active substance) 0.5 - 5% by weight of compounds of divalent or trivalent cations, calculated as oxides, included, but due to their addition a maximum of only 20% of the original calcium binding capacity of the aluminum silicates is consumed to be allowed to. O - 40% by weight of other common ingredients in dishwashing detergents. 3. Means according to claim 1 and 2, characterized in that it as other common ingredients of dishwashing detergents up to 10% by weight of active ingredients or substances releasing active oxygen, up to 10% by weight of surfactants, in particular contain nonionic surfactants, and up to 20 wt .-% sodium sulfate and / or water. 4. Means according to claim 1 to 3, characterized in that the compounds bivalent or trivalent metal ions, phosphates, carbonates, oxides or hydroxides, Silicates, aluminum silicates, borosilicates, sulfates or chlorides of calcium, magnesium, Are zinc or iron. 5. Composition according to claim 1 to 4, characterized in that cation-exchanging Organic exchange resins are used as carriers of the bivalent and trivalent cations will. 6. Composition according to claim 1-5, characterized in that the alkali silicates and / or carbonates and / or hydroxides partly by inorganic phosphorus-containing Complexing agents are replaced. 7. Means according to claim 1-6, characterized in that the content the agent of phosphorus compounds remains limited to such amounts that the The total P content of the agents does not exceed 6% by weight, preferably 3% by weight.