EP0032236A1 - Dishwashing detergent - Google Patents

Abstract

Machine dishwashing detergent with a high content of alkali metal hydroxides with the smallest possible surface and a content of finely granulated purest trichloroisocyanuric acid.

Description

The application concerns alkaline, active chlorine-containing granulated, machine-applicable dishwashing detergents.

For machine cleaning of heavily soiled dishes, especially in the commercial sector, alkaline cleaning agents are usually used, which essentially consist of builders, alkali metal silicates, alkali metal carbonates and / or alkali metal hydroxides, compounds containing active chlorine and optionally nonionic surfactants. The higher the active chlorine content of the cleaning agents, the better the stain cleaning, for example in the case of tea residues, and the higher the alkali metal hydroxide content, the better the cleaning effect, in particular for dishes with burnt-on food residues.

The cleaning agents are generally prepared by dry mixing the individual powdery or particulate constituents, for example in rotating drums, to form the desired mixed product, any liquid constituents such as, for example, nonionic surfactants and / or water glass as such, as a mixture or in aqueous solution by spraying on the moving powder or particulate constituents or groups of constituents, whereby granulation takes place. The active chlorine compounds who which is usually added at the end. In any case, an end product of free-flowing powdery to granular nature is sought, which does not cake during normal storage and is stable in terms of its constituents. This applies in particular to the compound containing active chlorine.

Polychlorinated cyanuric acids and their salts have proven particularly useful as active chlorine-containing compounds in powdered or granulated dishwashing detergents. Because of the highest content of active chlorine, trichloroisocyanuric acid is always of great interest. However, their low solubility in water and their poor shelf life are disadvantageous.

It is also known that powder and granule mixtures become more and more labile with storage, particularly with an increasing content of compounds containing active chlorine and alkali metal hydroxides. Under unfavorable storage conditions, for example at elevated temperature and / or when moisture enters the packs, exothermic self-decomposition of the chlorine carrier as well as reactions with other components of the cleaning agents can occur. This self-decomposition is all the more uncomfortable because it can still occur weeks after production. The cleaning agent remaining after self-decomposition is largely worthless, since it is baked together and hardly contains any active chlorine. In addition, this possible self-decomposition naturally represents an undesirable safety risk in storage and handling.

For stabilizing dishwashing detergents containing active chlorine compounds and Alkali metal hydroxides have been recommended in US Pat. No. 3,166,513 to use potassium dichloroisocyanurate in granulated form with a critical particle size as the active chlorine-containing component. Potassium dichloroisocyanurate is considered to be more stable than sodium dichloroisocyanurate, and the granular form is said to bring about further stabilization. The amount of potassium dichloroisocyanurate in these agents with a content of up to 30 percent by weight of alkali metal hydroxides does not exceed 5 percent by weight.

However, potassium dichloroisocyanurate is considerably more expensive than the corresponding sodium compound. The teaching of this patent therefore has only theoretical interest. In addition, DE-OS 16 17 095 states that despite a certain improvement in terms of the storage stability of these agents, there are still unacceptable losses of available chlorine, and recipes are therefore mentioned which contain granulated sodium dichloroisocyanurate in the presence of nonionic Contain surfactants and caustic alkalis and which are said to be more stable than cleaning agents containing granulated potassium dichloroisocyanurates. But here too the amount of sodium dichloroisocyanurate is preferably at most 5 percent by weight.

According to DE-OS 23 58 249, a further increase in stability is to be achieved if the anhydrous sodium dichloroisocyanurate is replaced by its dihydrate. Its proportion can be increased to 10 percent by weight. However, the dishwashing detergents thus produced no longer contain any free alkali metal hydroxides and therefore no longer stand up to a technical comparison.

From US Pat. No. 2,607,738 it is also already known to produce alkaline cleaning agents containing trichloroisocyanuric acid, which are also said to be stable in storage. However, these agents also do not contain any alkali metal hydroxide. This is understandable, because it is known, for example from "Soap, Cosmetics, Chemical Specialties", August 1974, pages 46 to 55, in particular page 48, Table 3, that trichloroisocyanuric acid is most decomposed in the presence of flaky sodium hydroxide as an alkaline compound, which however for potassium and sodium dichloroisocyanurate is also given there.

There has been no lack of attempts to use trichloroisocyanuric acid by using stabilizing agents such as dry trialkali salts of cyanuric acid or a mixture of equivalent amounts of cyanuric acid and alkali metal hydroxide (DE _- AS 11 67 473) or sodium acetate (DE-OS 23 40 910) enable. In both cases, however, the agents contain unwanted fiber such as cyanuric acid and sodium acetate. The practical use of trichloroisocyanuric acid in dishwashing detergents with a high content of alkali metal hydroxides has therefore not been able to prevail, even though this substance has the highest active chlorine content and was therefore repeatedly irritating to use.

It was therefore completely surprising when, according to the invention, it was found that the use of particularly large amounts of granulated trichloroisocyanuric acid with a certain particle size and high degree of purity with simultaneous use of large amounts of alkali metal hydroxides, in particular in the form of solid, coarse-grained or almost spherical prills with also a certain particle size, a self-decomposition of the resulting cleaning agents is practically completely prevented. This is all the more surprising since the combination of large amounts of such alkali metal hydroxides with commercially available granulated monoalkali salts of trichloroisocyanuric acid does not lead to sufficiently stable product formulations. Even a stabilizing addition of paraffin oils proposed in DE-AS 16 17 088 has become practically superfluous, unless it appears desirable for other reasons.

The fears that trichloroisocyanuric acid, because of its poor solubility in water, are unsuitable for use in dishwashing detergents, proved to be unfounded given the high alkali metal hydroxide content of the agents according to the invention, since it greatly accelerates the solubility.

The present invention therefore relates to alkaline, active chlorine-containing granulated, machine-applicable dishwashing detergents containing builder substances, alkali metal silicates, alkali metal carbonates, alkali metal hydroxides and optionally nonionic surfactants, which are characterized in that they contain 1 to 30, preferably 3 to 15 and in particular 5 to 15 percent by weight on finely divided trichloroisocyanuric acid in granulate or prill form with the smallest possible surface and a degree of purity determined by laser-raman spectroscopy ≥ 99% and 10 to 40, preferably 15 to 30 percent by weight of granulated alkali metal hydroxide with the smallest possible surface.

das mittels eines Sieb-Satzes nach DIN 4188 bestimmt wurde. Damit wurden Granulate eingesetzt, deren Teilchen zu mehr als 90, vorzugsweise zu mehr als 95 Gew.-% und insbesondere zu mehr als 98 Gew.-% durch ein Sieb mit der lichten Maschenweite von 1,6 mm hindurchgingen und zu mehr als 90, vorzugsweise zu mehr als 95 Gew.-% und insbesondere zu mehr als 99 Gew.-% von einem Sieb mit der lichten Maschenweite von 0,2 mm'zurückgehalten wurden. Man kann jedoch auch Trichlorisocyanursäuren einsetzen, deren Teilchen zu mehr als 98 Gew.-% von einem Sieb mit der lichten Maschenweite von 0,4 mm zurückgehalten werden, wobei die gesamte Korngrößenverteilung so zu bemessen ist, daß gleichzeitig vorzugsweise mehr als 55 Gew.-% der Teilchen von einem Sieb mit der lichten Maschenweite von 0,8 mm zurückgehalten werden.The finely divided trichloroisocyanuric acid used according to the invention essentially had the following grain spectrum:

which was determined using a sieve set according to DIN 4188. Granules were thus used, the particles of which more than 90, preferably more than 95% by weight and in particular more than 98% by weight passed through a sieve with a mesh size of 1.6 mm and more than 90% by weight. preferably more than 95% by weight and in particular more than 99% by weight have been retained by a sieve with an internal mesh size of 0.2 mm. However, it is also possible to use trichloroisocyanuric acids, the particles of which are more than 98% by weight retained by a sieve with a mesh size of 0.4 mm, the total grain size distribution being such that at the same time preferably more than 55% by weight % of the particles are retained by a sieve with a mesh size of 0.8 mm.

• Erregerwellenlänge 647,1 nm (Krypton Laser)
• Leistung 200 mW
• Spektrale Spaltbreite 4 cm^-1
• Empfindlichkeit 200 counts sec^-1 _full scale (10₀).
• Unter den genannten Meßbedingungen wurden neben den typischen Banden der Trichlorisocyanursäure Nebenbanden von Verunreinigungen bei ca. 600, 1060, 1310 und 1₆₈0 cm^-1 in einer Intensität von 20 bis 40 Skalenteil_en beobachtet.

The degree of purity of the trichloroisocyanuric acid was determined by using laser Raman spectroscopy with a Raman spectrometer, model 82 from Cary, and the following measurement conditions:

• Excitation wavelength 647.1 nm (Krypton laser)
• Power 200 mW
• Spectral slit width 4 cm ^-1
• Sensitivity 200 counts sec ^-1 _f ull scale (10 _0).
• Among the mentioned measuring conditions were in addition to the typical bands of trichloroisocyanuric minor bands of impurities at about 600, 1060, 1310 and 1 ₆₈ 0 cm _en observed at an intensity of 20 to 40 scale division ^-1.

With a changed sensitivity of 50 ₀₀ count sec ^-1 for _{full scale} deflection, the intensi was activity of the bands present due to impurities ≥ 1% of the intensity of the main bands of trichloroisocyanuric acid. This results in a purity of the anhydrous trichloroisocyanuric acid of ≥ 99%. Trichloroisocyanuric acids with a purity of ^> 97.5% have proven unsuitable for use in the dishwashing detergents according to the invention.

das heißt, mehr als 70, vorzugsweise zu mehr als 80 Gew.-% aller Teilchen passieren ein Sieb mit einer lichten Maschenweite von 1,6 mm und weniger als 10 Gew.-% aller Teilchen passieren ein Sieb mit einer lichten Maschenweite von 0,2 mm (Sieb-Satz nach DIN 4188).The nature of the alkali metal hydroxides is of minor importance. Particularly good, reliable and unambiguous results are achieved, however, if they are used as granulated alkali metal hydroxides with a surface that is as small as possible, ie as spherical as possible. Potassium and preferably sodium hydroxide are used, namely as coarse grains or preferably as so-called prills. The coarse grain essentially has the following grain size distribution:

that is, more than 70, preferably more than 80% by weight of all particles pass through a sieve with a clear mesh size of 1.6 mm and less than 10% by weight of all particles pass through a sieve with a clear mesh size of 0, 2 mm (sieve set according to DIN 4188).

das heißt, die Teilchen sind so groß, daß sie praktisch ein Sieb mit 0,2 mm lichter Maschenweite (Sieb-Satz DIN 4169) nicht mehr passieren.The prills preferably used according to the invention essentially have the following grain size distribution:

that is, the particles are so large that they practically no longer pass a sieve with a 0.2 mm mesh size (sieve set DIN 4169).

The entire grain size distribution> 0.2 mm is mainly determined by the other powder or granular components of the respective recipes. In order to avoid segregation phenomena within the products, it is advantageous to avoid larger differences in the grain sizes of the individual components.

• 1 - 30, vorzuasweise 3 bis 15 und insbesondere 5 - 15 Gewichtsprozent feinteilige Trichlorisocyanursäure mit möglichst kleiner Oberfläche und einem laser-raman-spektroskopisch ermittelten Reinheitsgrad ≥ 99 %,
• 10 - 40, vorzugsweise 15 bis 30 Gewichtsprozent feingranulierte Alkalimetallhydroxide mit möglichst kleiner Oberfläche,
• 5 - 60, vorzugsweise 20 bis 45 Gewichtsprozent Gerüstsubstanzen,
• 5 - 50, vorzugsweise 20 bis 40 Gewichtsprozent Alkalimetallsilikate,
• 5 - 50, vorzugsweise 10 bis 30 Gewichtsprozent Alkalimetallcarbonate sowie
• 0 - 5, vorzugsweise 0,5 bis 1,5 Gewichtsprozent .nichtionische Tenside.

The agents according to the invention have the following basic formulation:

• 1 to 30, preferably 3 to 15 and in particular 5 to 15 percent by weight of finely divided trichloroisocyanuric acid with a surface that is as small as possible and a degree of purity as determined by laser-raman spectroscopy ≥ 99%,
• 10 - 40, preferably 15 to 30 percent by weight of finely granulated alkali metal hydroxides with the smallest possible surface area,
• 5-60, preferably 20 to 45 percent by weight of builder substances,
• 5-50, preferably 20 to 40 percent by weight alkali metal silicates,
• 5-50, preferably 10 to 30 percent by weight alkali metal carbonates and
• 0 - 5, preferably 0.5 to 1.5 percent by weight. Nonionic surfactants.

Commercial alkali metal polyphosphates with a molar ratio of Na ₂ 0 or K ₂ 0 to P ₂ 0 _5, such as 1: 1 to 2: 1, can preferably be used as builders. These include sodium tripolyphosphate, which is preferred for cost reasons, sodium hexametaphosphate and sodium pyrophosphate and the corresponding potassium polyphosphates. In the case of the polyphosphates, the particle size is of no particular importance. It is therefore possible to use the commercially available products, with their hydrate water content being of minor importance.

in der Kat ein gegen Calcium austauschbares Kation der Wertigkeit n, vorzugsweise Natrium, x eine Zahl von 0,7 bis 1,5, vorzugsweise 0,9 bis 1,3 und y eine Zahl von 0,8 bis 6, vorzugsweise von 1,3 bis 4 bedeuten, die ein Calciumbindevermögen von 50 bis 200, vorzugsweise 100 bis 200 mg CaO/g wasserfreier anorganischer Aktivsubstanz aufweist, ersetzt werden. Derartige Verbindungen sind beispielsweise unter der Bezeichnung SASIL® von der Firma Henkel KGaA, Düsseldorf bekannt. Sie können bis zu 60, vorzugsweise 25 bis 50 % der Gerüstsubstanzen ausmachen.For the purpose of reducing the water reutrophication caused by them, the polyphosphates can also be produced, in part, by synthetically produced water-insoluble, bound water-containing aluminosilicates of the general formula which also bind the calcium hardness of the water

in the cat a cation of valence n, preferably sodium, exchangeable for calcium, x a number from 0.7 to 1.5, preferably 0.9 to 1.3 and y a number from 0.8 to 6, preferably of 1, 3 to 4, which have a calcium binding capacity of 50 to 200, preferably 100 to 200 mg CaO / g of anhydrous inorganic active substance, are replaced. Such connections are known, for example, under the name SASIL® from Henkel KGaA, Düsseldorf. They can make up up to 60, preferably 25 to 50% of the framework substances.

• 1 1 einer wäßrigen, 0,594 g CaCl₂ (= 300 mg CaO/l = 30° dH) enthaltenden und mit verdünnter NaOH auf einen pHwert von 10 eingestellten lösung wird mit 1 g Aluminiumsilikat versetzt (auf AS bezogen). Dann wird die Suspension 15 Minuten lang bei einer Temperatur von 22 °C (± 2 °C) kräftig gerührt. Nach Abfiltrieren des Aluminiumsilikates bestimmt man die Resthärte x des Filtrates. Daraus errechnet sich das Calciumbindevermögen in mg Ca0/g AS nach der Formel: (30 - x) . 10.

The calcium binding capacity of the aluminum silicates was determined in the following way:

• 1 g of an aqueous solution containing 0.594 g CaCl ₂ (= 300 mg CaO / l = 30 ° dH) and adjusted to a pH value of 10 with dilute NaOH is mixed with 1 g aluminum silicate (based on AA). Then the suspension is stirred vigorously for 15 minutes at a temperature of 22 ° C (± 2 ° C). After filtering off the aluminum silicate, the residual hardness x of the filtrate is determined. The calcium binding capacity in mg Ca0 / g AS is calculated from the formula: (30 - x). 10th

If you determine the calcium binding capacity at higher temperatures, for example at 60 ° C, you will find consistently better values than at 22 ° C. This fact distinguishes aluminum silicates from most of the soluble complexing agents previously proposed for use in detergents and represents a special technical advance in their use.

The alkali metal silicates used primarily act as corrosion inhibitors for the metal parts of the dishwashers. The soluble alkali metal silicates used are preferably sodium or potassium metasilicates in which the ratio of alkali oxide: silicon dioxide is approximately 1: 0.5 to 3.5. The anhydrous silicates are preferably used. Disilicates with a ratio of alkali oxide: silicon dioxide such as 1: 2 are also suitable for use in the cleaning agents according to the invention.

In the case of alkali metal carbonates, sodium and potassium carbonate in the form of water of hydration are primarily considered. The carbonates mainly serve as fillers. If appropriate, they can also be partially or completely replaced by corresponding sulfates.

Nonionic surfactants which may be used are those which do not decompose in the presence of compounds containing active chlorine and alkali metal hydroxides. Low-foaming surfactants are also expediently used. There are preferably ethylene oxide adducts of higher molecular weight polypropylene glycols of molecular weights from 900 to 4000 and also adducts of ethylene oxide or ethylene oxide and propylene oxide with higher fatty alcohols such as dodecyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol or mixtures thereof as well as synthetic, produced for example by oxo process alcohols of chain length C ₁₂ -C ₁₈ and corresponding alkylene oxide adducts with alkylphenols, preferably nonylphenol. Examples of suitable addition products are the adduct of 10 to 30 percent by weight of ethylene oxide with a polypropylene glycol of molecular weight 1750, the adduct of 20 moles of ethylene oxide or 9 moles of ethylene oxide and 10 moles of propylene oxide with nonylphenol, the adduct of 5 to 12 moles of ethylene oxide with a fatty alcohol mixture Chain lengths C ₁₂ -C ₁₈ containing about 30% oleyl alcohol and the like. This exemplary list is not a limitation.

If necessary, chlorine and alkali-resistant colors and fragrances can be added to the dish detergents.

The dishwashing detergents according to the invention were once produced by simply mixing the powdery or granular constituents in a conventional mixing drum.

However, granules can also be produced. For this purpose, a so-called basic granulate was first produced in a conventional manner, which contained the framework substances, alkali metal carbonates, silicates and surfactants, the mostly liquid nonionic surfactants and possibly liquid or water-based silicates individually or as a mixture with the liquid surfactants in a controlled manner on the dry ones moving and therefore well mixed solid granulate components were sprayed on. A Lödige and Eirich mixer were used as granulators. This basic granulate was then mixed with appropriate amounts of granulated trichloroisocyanuric acid and alkali metal hydroxides in the form of prills or coarse grains. The respective grain sizes were obtained by sieving. In order to counteract separations into individual mixture components, the basic granulate, the chlorine carrier and the alkali metal hydroxides were used in largely identical grain sizes. The dishes detergent granules obtained were loose and free-flowing and neither caked during storage nor did they show signs of segregation after a shaking process simulating transport conditions.

The trichloroisocyanuric acids I, II, III and IV used in the examples according to the invention and the comparative compositions given below and - 'NaOH coarse grain or NaOH prills had the following degree of purity and / or grain size distribution, determined in accordance with DIN 4188:

B e i s o p i e l e example 1

Example 2

Mit gleichen Mengen wurde ein entsprechendes Mittel mit der erfindungsgemäßen Trichlorisocyanursäure IV hergestellt, das sich ebenso verhielt wie ein Mittel der vorstehend angegebenen Zusammensetzung.

A corresponding agent with the trichloroisocyanuric acid IV according to the invention was prepared with the same amounts and behaved in exactly the same way as an agent of the composition given above.

Example 3

Example 4

Example 5

Mixed product from:

Example 6

Mixed product from:

Example 7

und der Zumischung von

Granulate from: basic granulate

and the admixture of

Example 8

und der Zumischung von

Granulate from: basic granulate

and the admixture of

comparative tests

The following tests were carried out to demonstrate the resistance of the inventive cleaning agents to commercial granules containing granulated sodium dichloroisocyanurate dihydrate: 50 kg of the powders or granules prepared according to Examples 1 to 4 were placed in 60 liter polyethylene plastic drums such as those used for shipping used, filled and provided with a cover seal and clamping ring. In double tests, the products in these containers were heated on a drum heating system to a floor temperature of 65 ° to 70 ° C. In this way, the investigation period could be reduced to a practical level. Under practical conditions of use, this period otherwise extends from a few days to 10 weeks. The temperature curve inside the container was continuously recorded depending on the time.

No self-decomposition occurred even after 200 hours at a floor temperature of 70 ° C with a fluctuation range of ± 4 ° C. However, if, in Example 1, the trichloroisocyanuric acid I had the same active chlorine content as a substitute for granulated sodium dichloroisocyanurate dihydrate, the double experiment started after 14.5 a violent self-decomposition occurs in about 12.5 hours. The temperature inside the product rose to about 165 ° to 170 ° C. After the self-decomposition had ended, the lid of the container had become wavy due to the influence of heat and had been discarded. After cooling, the product itself was solid and rock hard. The active chlorine content fell from the initial value of 4.55% to a final value of 0.43% and was therefore completely unusable. A product of the composition according to Example 2 was investigated under the same experimental conditions as stated above, again the feared self-decomposition did not occur. When replacing trichloroisocyanuric acid I with an active chlorine content. same amount of granulated sodium dichloroisocyanurate dihydrate, a violent self-decomposition process occurred after 7.5 hours. The final reaction temperature was 220 ° C. The plastic jacket of the polyethylene container had melted and the product came out. The active chlorine content dropped from 7.3% in the fresh mixture to a final value of 0.5%. Even the use of sodium hydroxide prills, which are practically free of dust, did not prevent the self-decomposition of this product.

Corresponding tests with a composition or comparative composition according to Examples 3 and 4 led to the start of self-decomposition after 3.5 or 16 hours with the use of granulated sodium dichloroisocyanurate dihydrate, with the development of a maximum temperature of 240 ° or 185 ° C.

In order to investigate the influence of the degree of purity of the anhydrous granular trichloroisocyanuric acid, further tests were carried out in the apparatus described below. Corresponding cleaning agents with a commercially available composition were also tested under these comparable conditions.

The experimental apparatus consisted of a cup-shaped, glass pressure vessel with a volume of 1 liter, which was surrounded by a heating jacket. This pressure vessel was filled with 1 kg each of one of the mixtures 1 to 4 specified below and sealed at the top with an insulating layer made of asbestos cardboard and rock wool. Through the patch, with a gas discharge nozzle and two. Temperature sensors provided with sensor inputs and connected to the pressure vessel by means of a clamping ring, temperature sensors were led to the edge of the pressure vessel and into the center of the mixture.

The pressure vessel was largely insulated so that heat exchange with the surroundings would be avoided. The pressure in the vessel was kept constant by evacuating gases. In order to initiate the self-decomposition of the powdered detergent mixtures, the pressure vessel was heated to a constant "base temperature" depending on the composition by means of an adjustable jacket and floor heating. The so-called "initial time" of self-decomposition was the time in minutes after which the heating was switched off automatically. This happened at the time when the temperature of the reaction mixture exceeded that of the base temperature. The temperature curve as a function of time was determined using iron / constantan Resistance thermocouples measured in the center and near the jacket of the pressure vessels. The highest temperature reached in the center of the reaction mixture as a function of time was determined. The results are shown in Table 2.

Trial 1

Trial 2

Qersucb 3

Trial 4

Trial 5

Trial 6

Trial 7

Trial 8

Trial 9

It can be seen from the test results given in Table 2 that the stability of the cleaning agent mixtures (= reaction mixtures) was greater in any case if trichloroisocyanuric acid was used instead of various known alkali metal dichloroisocyanurates (tests 4, 5 and 7 to 9 compared to the tests 1 to 3 and 6) and that it increased when using trichloroisocyanuric acid with higher purity and larger grain size (tests 4 and 7 compared to tests 5, 8 and 9).

Optimal results were obtained when NaOH in the form of prills is used with practically no fine grain fraction <0.2 mm (test 7). Here base temperatures of 125 ° C were required to get the self-decomposition going.

The cleaning agents listed in Examples 5 to 8 were each stored for 24 weeks at room temperatures between 17 and 24 ° C and at 35 ° C and 70% relative humidity in a climatic cabinet in watertight containers.

Examples 5 to 8 were further varied in such a way that the trichloroisocyanuric acid (TCIC) "I" used according to the invention was exchanged for two other trichloroisocyanuric acids "II" and "III", each with a low degree of purity (samples 1 to 4 A / B). In addition, the trichloroisocyanuric acid was replaced by correspondingly higher amounts of potassium dichloroisocyanurate (KDCIC) and sodium dichloroisocyanurate (NaDCIC) anhydrous and as dihydrate, which provided the same amounts of active chlorine. The pentasodium triphosphate content was reduced accordingly (samples 1-4 C). The To Compositions of the samples were exposed to the same storage conditions as those in Examples 5 to 8. Finally, the active chlorine content of all, still free-flowing, samples was determined iodometrically. Table 3 below shows that the storage behavior when using trichloroisocyanuric acid I is significantly better than that of the other active chlorine carriers.

Claims (6)

1. Alkaline, active chlorine-containing granulated, machine-applicable dishwashing detergents containing builders, alkali metal silicates, alkali metal carbonates, alkali metal hydroxides and optionally nonionic surfactants, characterized in that they contain 1 to 30, preferably 3 to 15 and in particular 5 to 15 percent by weight of finely divided trichloroisocyanuric acid in granular - Or prill form with a surface that is as small as possible and a degree of purity determined by laser raman spectroscopy ≥ 99% and 10 to 40, preferably 15 to 30 percent by weight of granulated alkali metal hydroxide with a surface that is as small as possible. 2. Composition according to claim 1, characterized in that 'they contain finely divided trichloroisocyanuric acid, the particles of which are more than 90, preferably more than 95 and in particular more than 98% by weight through a sieve with a mesh size of 1.6 mm pass through and are held back by a sieve with a clear mesh size of 0.2 mm to more than 90, preferably more than 95% by weight and in particular more than 99% by weight. 3. Composition according to claim 1, characterized in that they contain finely divided trichloroisocyanuric acid, the particles of which are more than 98% by weight from a sieve with a mesh size of 0.4 mm and at the same time more than 55% by weight of one Sieve with a mesh size of 0.8 mm should be retained. 4. Composition according to claim 1 to 3, characterized in that they contain coarse-grained sodium hydroxide, the particles of more than 70, preferably more than 80 wt .-% through a sieve with a mesh size of 1.6 mm and less than 10% by weight passed through a sieve with a mesh size of <0.2 mm. 5. Compositions according to claim 1 to 4, characterized in that they contain prill-shaped sodium hydroxide, the particles of which practically 100% by weight pass through a sieve with an internal mesh size of 1.6 mm and which have practically no particles with a size of 0, 2 mm. 6. Composition according to claim 1 to 5, characterized by the following composition: 1 - 30, preferably 3 to 15 and in particular 5 to 15 percent by weight of finely divided trichloroisocyanuric acid in granulate or prill form with the smallest possible surface and a degree of purity determined by laser-raman spectroscopy? 99%, 10-40, preferably 15 to 30 percent by weight granulated alkali metal hydroxides with the smallest possible surface, 5-60, preferably 20 to 45 percent by weight of builder substances, 5-50, preferably 20 to 40 percent by weight alkali metal silicates, 2-50, preferably 5 to 30 percent by weight alkali metal carbonates and 0-5, preferably 0.5 to 1.5 weight percent nonionic surfactants.