EP0928828A1 - Alkylaminotriazole-containing granular components for automatic dishwashing compositions and process for preparing them - Google Patents

Abstract

Free-running granulate contains a solid alkylaminotriazole (I) and an alkali sulfate (II), in 1:100 to 2:1, preferably 1:70 to 3:2, especially 1:50 to 2:3 ratio, and has a particle size of 0.01-2, preferably 0.05-1.8, especially 0.1-1.6 mm. An Independent claim is also included for the production of the granulate.

Description

The application relates to alkylaminotriazole-containing granular components for use in MGSM and processes for its production
Granular cleaning agents for MGSM are known because they are easy to dose, pourable, free-flowing, storage-stable and visually appealing to the consumer.

Alkylaminotriazole is a corrosion protection component that in active oxygen Cleaners is widely used today. The chemical stability in these Systems exist only to a limited extent, however, since alkylaminotriazole is alkaline Substances is broken down. This is especially the case with longer storage, e.g. yellow colored and unpleasant smelling oxidation products that are used for Discoloration of the cleaner, loss of anti-corrosion effect and lead to lack of acceptance of the product by the consumer.

geeigneten" Prozesse, die Arbeit auf die Mixtur des organischen ertrudierbaren Feststoffs ausüben. Beispielhaft genannt für solche geeigneten Prozesse sind Mahlen, Pelletieren, Extrudieren, Stampfen und Pressen. Die Patentschrift deutet an, daß es durch die Verwendung von organischen Feststoffen in der Regel in Waschmitteln, die die erfindungsgemäßen Granulate enthalten, nicht zur Segregation von verschiedenartigen Teilchen kommen wird.From British patent step GB 1 400 444 (Unilever), granules are known which contain an organic extrudable solid, uniformly dispersed, which is selected from the group of corrosion inhibitors, such as benzotriazoles, bismethylene benzotriazoles, ethoxylated phosphate esters, oximes and hydroxamates and which are suitable for incorporation into detergent powder compositions. It is important that the extrudable solid is selected so that the granules are dissolved in water at 20 ° C. within 10 minutes, preferably within 2 minutes. The method described claims everyone

suitable "processes that work on the mixture of the organic extrudable solid. Examples of such suitable processes are grinding, pelletizing, extruding, tamping and pressing. The patent indicates that it is generally due to the use of organic solids in detergents which contain the granules according to the invention will not come to segregation of different types of particles.

WO 95/1416 (Procter & Gamble) describes a bleaching composition which is suitable for automatic dishwashing, the one Contains oxygen bleach, paraffin oil and a benzotriazole component, the entire component is intended for use in detergents. The Components can be powder, granules, pastes, liquids, gels, Tablets are present, with granular preparation forms being preferred. Poetry of at least 650 g / l or usually at least 700 g / l and preferred between 800 and 1200 g / l as well as particle sizes that are so distributed that not more than 5% of the particles larger than 1.4 mm in diameter and not more than 5% of the particles are less than 0.15 mm in diameter are preferred. In the application, several methods are described for these granules receive. A preferred process for making the connection involves this Premixing paraffin oil and a dispersant, this Premix is sprayed onto the rest of the composition. The The dispersant is advantageously nonionic surfactant. But also one Method of spraying paraffin oil and dispersant on the Bleach, with the associated reduction in dissolving speed of the bleaching agent in water, the so-called "coating", is preferred, the coated bleach particles thereafter in a dry mixing process with the rest the composition is mixed. The is also described Compact the bleach before mixing it with the rest of the ingredients the composition mixed dry. There is no instruction how Alkylaminotriazole homogeneously in a free-flowing dishwasher detergent component should be incorporated.

The US Pat. No. 4,321,166 (Procter & Gamble) describes builder-free, liquid detergent systems that act as a corrosion inhibitor aromatic triazoles and oligomeric olefinic fatty acids. The Anti-corrosion agents are said to discolor the metal wash baskets in automatic washing machines and the discoloration of fibers in contact prevent coming with the wash baskets. There is no reference to this in the scriptures given how organic redox-active substances homogeneous in Bleach components can be incorporated, and like silver protection can be achieved through these components.

The unpublished DE 196 31 787 describes a method for Production of a granular free-flowing component, including one at a temperature above 50 ° C meltable solid (I) from the group organic redox-active substances, preferably from the group of Benzotriazoles and a constituent component (II) which is fixed at its melting temperature selected from the group of those customary in dishwashing detergents Builder components and one or more other components from the group the hydrocarbons or their mixtures and one or more others Components from the group comprising the polar organic solvents and which contains surfactants, the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and is particularly preferably between 1 to 50 and 2 to 3 and the component a Particle size between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters.

The unpublished DE 197 01 031 describes the use of Alkylaminotriazoles as silver protection agents in automatic dishwashing detergents.

However, none of the above-mentioned patents shows how an alkylaminotriazole containing granular well poured component can be produced. The problem lies among other things in that alkylaminotriazole-containing mixtures according to the usual methods of granulation, such as the use of Grain build-up liquids that are produced are difficult to process, since the mixture tends to cake and is therefore difficult to pour. The The physical property of the pourability of the component should have one be kept stable for a long period of time. But also the chemical stability of Components containing alkylaminotriazole can be used with the knowledge of above writings can not be solved. This property becomes all the more important the background of the incorporation of these components in dishwasher detergents. Here are the properties of physical and chemical Stability of the granular components is particularly desirable. Alkylaminotriazole is said to be present in the presence of oxidative and alkaline Components remain stable so that it can still be effective as a silver protection agent can. Another serious problem is that alkylaminotriazole of production in a more acidic solution. If you give up such a recipe an alkaline carrier, the alkylaminotriazole decomposes immediately.

The task was to provide a free-flowing, storage-stable, homogeneous granulate to make, which contains alkylaminotriazole and as silver protection for the machine dishwashing is suitable. The one contained in the granulate Alkylaminotriazole should be protected against oxidative attack.

The present invention relates to a granular, free-flowing Component containing an organic solid (I) from the group of Alkylaminotriazoles and a component (II) selected from the group of Alkali metal sulfates, the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and is particularly preferably between 1 to 50 and 2 to 3 and the component a Particle size between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters.

The granular components according to the invention contain between 0.001 % By weight and 33% by weight, preferably between 0.05 and 20% by weight and particularly preferably between 0.5 and 10 wt .-% alkylaminotriazole compounds. Of the A person skilled in the art understands alkylaminotriazole compounds to be all chemical Derivatives of the alkylaminotriazole skeleton. Derivatives of alkylaminotriazole, in the sense of the present invention, above all, are all or part substituted compounds, suitable substituents being linear or can be branched alkyl chains with 1 to 20 carbon atoms. But also OH, SH, vinyl or halogen groups are conceivable.

For the purposes of the invention, means are preferred in which the ratio between Solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3.

An important parameter for the present means is the particle size of the Component that is between 0.01 and 2 millimeters, preferably 0.05 and 1.8 Millimeters and particularly preferably between 0.1 and 1.6 millimeters should.

in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen oder eine gegebenenfalls durch Hydroxy-, primäre, sekundäre, tertiäre Aminogruppen, Alkoxy- Alkylthio- oder Thiolgruppen substituierte Aryl-, Furyl-, Tetrahydrofuryl-, Thienyl-, Pyridyl-, Pyrrolidinyl-, 5-Oxo-2-pyrrolidinyl-, Pyrryl-, Imidazolyl-, Pyrimidylgruppe steht und ihre Salze mit Mineralsäuren, wie Kohlensäure oder organischen Carbonsäure. Als Beispiele der erfindungsgemäß einzusetzenden 3-Amino-5-alkyl-1,2,4-triazole können genannt werden.: 5,- -Propyl-, -Butyl-, -Pentyl-, -Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, - Dodecyl-, -Isononyl-, -Versatic-10-säurealkyl-, -Phenyl-, -p-Tolyl-, -(4-tert. Butylphenyl)-, -(4-Methoxyphenyl)-, -(2-, -3-, -4-Pyridyl)-, -(2-Thienyl)-, -(5-Methyl-2-furyl)-, -(5-Oxo-2-pyrrolidinyl)-, -3-amino-1,2,4-triazol.According to the invention, alkylaminotriazoles are understood to mean in particular the 3-amino-5-alkyl-1,2,4-triazoles or their salts of the general formula (I)

in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, Furyl, tetrahydrofuryl, thienyl, pyridyl, pyrrolidinyl, 5-oxo-2-pyrrolidinyl, pyrryl, imidazolyl, pyrimidyl group and their salts with mineral acids, such as carbonic acid or organic carboxylic acid. The following may be mentioned as examples of the 3-amino-5-alkyl-1,2,4-triazoles to be used according to the invention: 5, -propyl, butyl, pentyl, heptyl, octyl, nonyl -, -Decyl-, -Undecyl-, - Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4- Methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3-amino-1,2,4-triazole.

Preferred acids for salt formation are hydrochloric acid, sulfuric acid, Phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as Acetic, glycolic, citric, succinic acid.

Another object of the invention is the use of these granular trickle-shaped component as a silver protection agent in automatic dishwashing detergents.

Another object of the invention is a method for manufacturing granular free-flowing components, which is characterized in that the solid (I) in liquid form e.g. in the form of its hydrochloric acid solution optionally sprayed onto the solid (II) at elevated temperature.

This can be done continuously or in a batch process. Of the coarse-grained solid (I) is in a commercial mixer, preferably one Ploughshare mixer, with the lowest possible energy input and in a way which minimizes the abrasion of the grain, for example without the use of a Knife ring, within a short time, preferably between 1 and 5 minutes, particularly preferably 3 minutes with the organic solid (II) in liquid Form brushed, and optionally cooled or allowed to cool. In addition, other detergents that are common in detergent granulation can also be used Steps such as coating, impregnation, admixing flow improvers, Drying, extruding, etc. carried out to adjust the powder properties become. The addition of flow improvers is particularly suitable.

The melt of the organic solid (I) can be used in this process become. In a preferred embodiment of the invention, however, the Substance (I) in the form of a hydrochloric acid solution, preferably in concentrations of more than 30% by weight, particularly preferably 40% by weight. But you can also use a different solvent (III). This solvent (III) will preferably selected from the group consisting of methanol, ethanol, Isopropanol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, Polyethylene glycols and polypropylene glycols.

Also preferred as the solvent is the group of surfactants, the nonionic surfactants being particularly preferred. Most notably preferred in the sense of the invention are the surfactants from the group of Alkyl polyglycosides, the fatty alcohol ethoxylates or propoxylates and their esters. By using commercially available alkali sulfate, the decomposition of the Alkylaminotriazole can be prevented. However, it can be problematic that in some cases the mixture is very fine and bad can be pourable. Then compact the compound obtained for example on a roller compactor, you get a free-flowing, coarse-grained granules with a high bulk density. Through the granular Structure of the compound will significantly improve storage stability of alkylaminotriazole in alkaline cleaning agents. Besides, that is Demixing tendency reduced in powder formulations.

In certain cases, a final spraying of the granular components produced by the above process with Hydrocarbons or a mixture of hydrocarbons with a Melting point between 30 ° C and 120 ° C, preferably between 30 and 80 ° C, particularly preferably between 45 ° C and 65 ° C at elevated temperature. For the purposes of the present invention, use is particularly preferred macrocrystalline paraffins with melting points between 40 ° C and 60 ° C, microcrystalline paraffins with melting points between 60 ° C and 75 ° C and Mixtures between macro and micro crystalline paraffins with melting points from e.g. between 45 ° C and 65 ° C. But also other hydrocarbons and Mixtures of hydrocarbons can be used.

The granular component can also be colored, which in certain Embodiments can be of considerable advantage. The is then preferred Dye in a solvent applied to the solid (II), but also a Coloring the solution of the solid (I) has proven itself in some cases. After a possible cooling step, another solid (IV) from the group of builder substances, which makes a good free-flowing granular component is created, which is very good in Lets incorporate dishwashing detergent and storage-stable cleaning agents with good Silver protection results. In addition, more can be found at Detergent granulation usual steps, such as coating, impregnation, Admixing flow improvers, drying, extruding, etc. for adjustment the powder properties.

Another object of the invention is a dishwashing detergent containing granular component, preferably in amounts between 1 and 40% by weight based on the entire mixture, the dishwashing detergent also in Components typical of dishwashing detergents, such as builder substances, bleaching agents, Surfactants, corrosion protection agents, polymers, other silver protection agents, soil release compounds, Defoamers, perfumes and fragrances and others may contain.

Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used. Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues. Usual builders that are within the scope of the invention 10 and 90% by weight, based on the total preparation, can be present, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of disilicates used.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures the abovementioned substances, the preferred being in the sense of this invention Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used.

Bleach activators which are preferably used in the context of the invention Compounds which contain one or more N- or O-acyl groups, such as Substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, Tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, however also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767, as well as acetylated sorbitol and mannitol or those in European patent application EP 0 525 239 described mixtures (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetyl xylose and Octaacet yllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267 , which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411 , the manganese described in German patent application DE 44 16 438 , Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030 , the manganese complexes known from European patent application EP 0 693 550 xe, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and / or those described in European patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, Manganese complexes described in EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 . Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775 . Bleach activators from the group of multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-NOBMA are preferred , preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total composition, used.

Bleach-enhancing transition metal complexes, especially with the Central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, especially preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of Manganese sulfates are used in conventional amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferred from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used be used.

Soil-release compounds can also preferably be used in the dishwashing detergents according to the invention be introduced. To the invention Soil release connections used all count in the prior art known connections. Cationic polymers such as these are particularly suitable e.g. B. are known from the following publications:

In EP-A-0 167 382, EP-A-0 342 997 and DE-OS-26 16 404 cleaning agents are added to cationic polymers in order to achieve a streak-free cleaning of the surfaces.

EP-A-0 167 382 describes liquid detergent compositions which can contain cationic polymers as thickeners. Hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide are described.

EP-A-0 342 997 describes general-purpose cleaners which can contain cationic polymers, in particular polymers with imino groups being used.

DE-OS-26 16 404 describes cleaning agents for glass which contain cationic cellulose derivatives. The addition of the cationic cellulose derivatives in the agents a better drainage of the water in order to obtain streak-free cleaned glass.

In EP-A-0 467 472 e.g. B. cleaning agents for hard surfaces are described which contain cationic homo- and / or copolymers as soil-release polymers. These polymers have quaternized ammonium alkyl methacrylate groups as monomer units. These connections are used to equip the surfaces in such a way that the dirt can be removed more easily during the next cleaning process.

The cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammonium salts; polymer analog Reaction products of ethers or esters of polysaccharides with Ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternaries Quaternary ethyleneimine polymers and polyesters and polyamides Page groups as soil release connections.

According to the invention, between 0 and 5% by weight of the cleaning agent Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality. The most common Enzymes used include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Celluzym® 0.7 T and. Are particularly suitable cellulases and lipases Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T and Duramyl® from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades but also other enzymes can be used.

Surfactants can also be added to the dishwashing detergent according to the invention , in particular the nonionic surfactants, such as alkyl polyglycosides, ethoxylated fatty alcohols and glucamides are preferred.

Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes. Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.

The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or their mixtures with end groups capped Fatty alcohol ethoxylates.

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in SÖFW-Journal, 119, (1993), 794-808. Carbon chain lengths of C ₆ to C ₁₂ in the fatty acid residue are preferably used.

Dishwashing agents according to the invention can be used to protect the items to be washed or the machine contain other corrosion inhibitors, especially Silver protection agent in the field of automatic dishwashing a special one Have meaning as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are described. One finds in cleaner formulations In addition, active chlorine-containing agents which corrode the Can significantly reduce the silver surface. In chlorine-free cleaners according to the above writings especially oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Zinc compounds can also be used Prevention of corrosion on the wash ware.

The dishwashing detergents according to the invention can be used in all of the prior art known forms of supply are produced. These include powders, granules, Suspensions and moldings, such as pellets, extrudates and especially moldings. All possible three-dimensional shapes are suitable for the spatial shape of the moldings Bodies such as in the prior art patents and Standard works in the specialist literature (e.g. Riedel, "Die Tablette") but also in the Prior art patents are enumerated.

These include, in particular, cylindrical tablets, these tablets preferably a diameter of 15 to 60 mm, in particular 30 +/- 10 mm. The height of these tablets is preferably 5 to 30 mm especially 15 to 28 mm. Shaped bodies have been particularly advantageous a diameter of 32, 33, 34, 35, 36, 37, 38, and 39 mm. In special designs, the height is 24, 25, 26, 27 or 28 mm.

But also square, rectangular, trapezoidal, oval and irregular shaped bases can be used preferentially. The edge lengths are preferably between 15 to 60 mm, in particular 30 +/- 10 mm.

The weight of the individual tablets, in particular the tablets, is preferably 15 to 60 g and in particular 20 to 40 g per tablet or tablet; the consistency of the shaped bodies or tablets, however, usually has values above 1 kg / dm ³ , preferably from 1.1 to 1.4 kg / dm ³ .

Depending on the type of application, the water hardness range or the pollution can 1 or more, for example 2 to 4 moldings, in particular Tablets. Other moldings according to the invention can also smaller diameters or dimensions, for example around 10 mm, exhibit.

The moldings in which the dishwashing detergent is offered can be homogeneous or heterogeneous. Heterogeneous moldings can be in one simple case, for example, that the different Ingredients have different colors and / or a different one Wear fragrance component.

Another case of the non-uniform (heterogeneous) according to the invention Shaped bodies to count includes an embodiment in which a Molded body is pressed, the multiple layers (phases), so at least has two layers. It is e.g. B. possible that these different Layers have different disintegration and dissolution rates and / or carry different ingredients. This can result in advantageous application technology Properties of the molded articles result. If For example, ingredients are contained in the moldings influence each other negatively, so it is possible to separate them. Should in a defined sequence of cleaning conditions is created for a machine , it is possible to combine one (or more) component (s) in one (or the) more rapidly disintegrating and / or more quickly soluble layer and the other component (s) in one or the more slowly disintegrating Incorporate shift so that a component can work with lead time or has already reacted when another goes into solution.

A preferred embodiment of the invention is that two phases available. It is particularly favorable if the volume ratios of the both phases between 10: 1 and 1:10, preferably between 5: 1 and 1: 5, are particularly preferably between 2: 1 and 1: 2.

This is another particularly preferred embodiment characterized in that three or more further phases are present.

Another preferred form is a shaped body in which, in addition to one or two or three phases another area with regular or irregular Spatial shape is included, and not more than 30 vol% of the molded body occupies. In the preferred case, this is a trough.

Examples:

Production of the component according to the invention:

27.9 kg of sodium sulfate was placed in a Lödige ploughshare mixer without use of the knife ring within 3 min with 2.1 kg alkylaminotriazole (in 40 wt .-% hydrochloric acid solution) sprayed, after cooling A granular component was formed at room temperature.

The product was then compacted in a conventional manner Roller compactor to a granulate.

This component was in amounts up to 6 wt .-%, based on the finished Means in one or more subsequent mixing steps with other Recipe ingredients for a dishwashing detergent for the machine Dishwashing mixed. This consisted e.g. B from 25 g sodium citrate, 25 g Sodium carbonate, 10 g sodium perborate, 4 g tetraethylenediaminetetraacetic acid, 3.5 g of enzymes (such as amylase, protease and lipase) and 2 g of nonionic Surfactants (such as alkyl polyglycosides and ethoxylated fatty alcohols).

The components according to the invention can be incorporated very well into dishwashing detergents and give storage-stable cleaning agents with good silver protection. Table (I) shows the compositions of the granules used. Ingredients I. II III IV V VI VII Alkylaminotriazole 7 7 5 5 5 10th 4.5 Sodium sulfate 93 83 82 82 82 73 85 Surfactant - - 5 - 2.5 7 - Polyethylene glycol - - - 5 2.5 - 6.5 paraffin - 10th 8th 8th 8th 10th 4th Surfactants: e.g. Dehydol® LS4 (non-ionic surfactant: coconut alcohol-4EO), Dehypon® LS54 (non-ionic surfactant: coconut alcohol-5EO4PO), Plurafac® LF 403 (non-ionic surfactant C11-C13, 4EO-3PO),
Polyethylene glycols: Different molecular weights were used, e.g. B. 1500.
Paraffins: It was preferred to use macrocrystalline paraffins with melting points between 40 ° C and 60 ° C and microcrystalline paraffins with melting points between 60 ° C and 75 ° C, as well as mixtures of macrocrystalline and microcrystalline paraffins with melting points between 45 ° C and 65 ° C.

Components I-VII had a particle size between 0.1 and 1.6 millimeters.

Components I to VII were with percarbonate / TAED or perborate / TAED and the usual detergent components (citrate / phosphate, alkali carrier, enzymes) mixed up. The powder mixture is spread on crystallizing dishes and stored open for four days at 30 ° C and 80% relative humidity. Find it oxidative processes and decomposition of the alkylaminotriazole take place, so is the powder colored yellow and has an unpleasant smell of garlic or Almond oil.

The blends have been visually and olfactively examined by several machine dishwashers. The results of the storage test are summarized in Table (II). Ingredients I. II III IV V VI VII Oxidative yellowing low low no no no no no Oxidative odor change low low no no no no no Acceptable according to the present invention Yes Yes Yes Yes Yes Yes Yes

Other possible framework recipes that can be used are. A possible framework recipe (R) and experimental recipes (V) (figures in% by weight): ingredient Ra Va1 Phosphate (sodium tripolyphosphate) 30-60 54.8 sodium 5-25 15.9 Sodium disilicate 0-40 7.3 Polymer (Sokalan CP5) 0-10 2.2 Sodium metasilicate 0-10 Sodium bicarbonate 0-10 Bleach (sodium perborate) 2-20 9.0 Bleach Activator (TAED) (Co-pentammin-CI) 0-5 2.1 Enzyme (Amylase) (Duramyl 60 T) 0-5 2.0 Enzyme (Protease) (Blap 200 S) 0-5 1.8 Phosphonate or phosphonic acid 0-5 0.9 Nonionic surfactant (Dehypon LS 54) 0-5 2.0 Silver protection (alkylaminotriazole) 0-10 0.3 Tableting aid (polyethylene glycol) 0-10 Paraffin (mp: 53 ° C) 0-10 Perfume 0-1 0.2 dye 0-4 1.4

The builder system of the framework recipe above can also be composed as follows (all other ingredients are the same as in a). ingredient Rb Vb1 Vb2 Vb3 Vb4 Vb5 Vb6 Vb7 Phosphate (sodium tripolyphosphate) 30-60 59 56 53 48 48 48 47 Carbonate (sodium carbonate) 5-25 21.2 20.3 22.7 17th 20th 16 24th Polymer (Sokalan CP5) 0-10 2nd 10th 5 4th 5 Sodium metasilicate 0-10 1.8 Sodium bicarbonate 0-10 1 3rd

The following can also be used as the basic formulation (R) for the present application (% by weight): ingredient Rc Vc1 Vc2 Phosphate (sodium tripolyphosphate) 15-35 30th 35 Carbonate (sodium carbonate) 25-55 39 40 Sodium bicarbonate 10-20 14 15 Polymer (Sokalan CP5) 0-10 3rd Sodium disilicate 0-10 Sodium disilicate 0-10 0 0 Bleach (sodium perborate) 2-10 7 5 Bleach activator (TAED) 0-5 1 1 Enzyme (Amylase) (Duramyl 60 T) 0.4-2 1 0.5 Enzyme (Protease) (Blap 200 S) 0.4-2 1 0.5 Phosphonate or phosphonic acid 0-5 0 0 Nonionic surfactant (Dehypon LS 54) 0-5 2nd 1 Silver protection (alkylaminotriazole) 0-10 0.5 0.3 Paraffin (mp: 53 ° C) 0-10 0 Perfume 0-1 0 0.7 dye 0-4 0.5 1

The following can also be used as the basic formulation (R) for the present application (% by weight): ingredient Rd Vd1 Vd2 Trisodium citrate 20-55 44 34 Sodium bicarbonate 5-35 24th 9 Carbonate (sodium carbonate) 0-10 7 Polymer (Sokalan CP5) 0-10 6 Sodium disilicate 0-25 20th Bleach (sodium perborate) 0-22 9 16 Bleach activator (TAED) 0-25 3rd 1 Enzyme (Amylase) (Duramyl 60 T) 0.4-5 2.5 3rd Enzyme (Protease) (Blap 200 S) 0.4-5 2nd 3rd Phosphonate or phosphonic acid 0-5 1.5 2.3 Nonionic surfactant (Dehypon LS 54) 0-5 2.5 1.7 Silver protection (alkylaminotriazole) 0-10 0.5 0.5 Paraffin (mp. 53 ° C) 0-10 3rd 1.5 Perfume 0-1 0.9 0.5 dye 0-4 0.1 1.5

The following can also be used as the basic formulation (R) for the present application (% by weight): ingredient re Ve1 Ve2 Citrate (trisodium citrate) 20-55 38 24th Phosphate (trisodium polyphosphate) 20-55 24th 24th Carbonate (sodium carbonate) 1-15 11 15 Polymer (Sokalan CP5) 0-10 1.5 6 Silicate (sodium disilicate) 0-25 6 Bleach (sodium perborate) 2-20 12th 9 Bleach activator (TAED) 0-5 2nd 3rd Enzyme (Amylase) (Duramyl 60 T) 0-5 3rd 2nd Enzyme (Protease) (Blap 200 S) 0-5 0.5 2nd Phosphonate or phosphonic acid 0-5 2nd Tableting aid (polyethylene glycol) 0-10 5 0.8 Nonionic surfactant (Dehypon LS 54) 0-5 2.8 2nd Silver protection (alkylaminotriazole) 0-10 0.2 0.2 Paraffin (mp: 53 ° C) 0-10 Perfume 0-1 1 dye 0-4 1

The following can also be used as the basic formulation (R) for the present application (% by weight): ingredient Rf Vf1 Vf2 Vf3 Vf4 Phosphate (trisodium polyphosphate) 40-60 49 49 49 50 Carbonate (sodium carbonate) 0-20 17th 19th 5 Polymer (Sokalan CP5) 0-15 2nd 4th 1 6 Silicate (sodium disilicate) 0-30 24th 6 5 10th Bleach (sodium perborate) 0-15 10th 8th 10th 8th Bleach activator (TAED) 0-5 1.5 2nd 3rd 2nd Enzyme (Amylase) (Duramyl 60 T) 0-5 2nd 2nd 1.5 2.5 Enzyme (Protease) (Blap 200 S) 0-5 3.9 2nd 1.5 2.5 Phosphonate or phosphonic acid 0-8 0.8 1 1 2nd Tableting aid (polyethylene glycol) 0-10 0.2 4th 3.7 5 Nonionic surfactant (Dehypon LS 54) 0-8 1.5 2nd 4th 3rd Silver protection (alkylaminotriazole) 0-10 0.1 0.5 0.3 0.5 Perfume 0-2 1 0.5 0.5 0.5 dye 0-4 3rd 2nd 0.5 1

The following can be used as the basic formulation (R) for the present application (data in% by weight): ingredient Rg Vg1 Vg2 Vg3 Phosphate (sodium tripolyphosphate) 30-60 55.7 59.6 47 Sodium disilicate 5-40 22.3 17.5 24th Polymer (Sokalan CP5) 0-10 2.2 2.2 5 Sodium metasilicate 0-10 Sodium bicarbonate 0-10 Bleach (sodium perborate) 2-20 10th 10th 10th Bleach activator (co-catalyst) 0-2 1.1 1.1 0.5 Enzyme (Amylase) (Duramyl 60 T) 0-5 2.0 2.0 2.5 Enzyme (Protease) (Blap 200 S) 0-5 1.8 1.8 2.5 Phosphonate or phosphonic acid 0-5 0.9 0.9 1.5 Nonionic surfactant (Dehypon LS 54) 0-5 2.0 2.0 1.5 Silver protection (alkylaminotriazole) 0-10 0.3 0.3 0.5 Tableting aid (polyethylene glycol) 0-10 Paraffin (mp: 53 ° C) 0-10 2.0 3rd Perfume 0-1 0.2 0.2 0.5 dye 0-4 1.4 1.3 1.5

A further basic formulation (R) (% by weight) and experimental formulations (V) were tested: ingredient Ri1 Vi1 Vi2 sodium 35-55 43.5 45 Sodium bicarbonate 15-35 15 25th Polymer (Sokalan CP5) 3-10 5 3rd Sodium metasilicate 0-10 3rd 2nd Bleach (sodium perborate) 5-12 6 10th Bleach activator (TAED) 0-5 1 2nd Enzyme (Amylase) (Duramyl 60 T) 0.4-2 1 1 Enzyme (Protease) (Blap 200 S) 0.4-2 1 1 Phosphonate or phosphonic acid 0-5 0 2nd Nonionic surfactant (Dehypon LS 54) 0-5 1 2nd Tableting aid (polyethylene glycol) 0-5 3rd Silver protection (alkylaminotriazole) 0-10 0.5 1 Paraffin (mp: 53 ° C) 0-10 0 2nd Perfume 0-1 0 1 dye 0-4 1 1

Claims (10)

Including granular free-flowing component an organic solid (I) from the group of alkylaminotriazoles and a component (II) selected from the group of alkali sulfates
the ratio between solid (I) and solid (II) between 1 to 100 and 2 to 1, preferably between 1 to 70 and 3 to 2 and particularly preferably between 1 to 50 and 2 to 3 and the component has a particle size between 0 , 01 and 2 millimeters, preferably 0.05 and 1.8 millimeters and particularly preferably between 0.1 and 1.6 millimeters. Granular component according to claim 1, characterized in that between 0.001% and 33% by weight, preferably between 0.05 and 20 % By weight and particularly preferably between 0.5 and 10% by weight Alkylaminotriazole compounds are included Use of a granular free-flowing component according to the Claims 1 and 2 as silver protection agents in automatic dishwashing detergents. Process for the production of granular free-flowing components, thereby characterized in that the solid (I) from the group of Alkylaminotriazoles in liquid form, preferably in hydrochloric acid solution sprayed a solid (II). A method according to claim 4, characterized in that on a usual compactor is compacted. A method according to claim 4 or 5, characterized in that if necessary, further steps customary in detergent granulation, such as coating, impregnation, admixing of flow improvers, Drying, extruding, etc. for setting the powder properties be performed. Method according to claims 4 and 5, characterized in that a granular premix from a solid (II) placed in a mixer and then the substance (I) is sprayed on in liquid form and so Granules obtained are optionally dried and mixed is made up by flow improvers from the group of solids (IV). Method according to claim 7, characterized in that final further steps customary in detergent granulation, such as coating, Impregnation, admixing flow improvers, drying, extruding, etc. to adjust the powder properties. Dishwashing detergent characterized in that it is a granular component according to claims 1 to 3 and / or a component available according to one of the methods of claims 4-8, preferably in amounts between Contains 1 and 40 wt .-% based on the entire mixture. Dishwashing detergent according to claim 9, characterized in that also further components customary in dishwashing detergents, such as builder substances, Bleaching agents, surfactants, corrosion protection agents, polymers, other silver protection agents, Contains defoamers, perfumes and fragrances and others are.