FIRM ONE CLEANING AGENT PREPARATIONS

The invention concerns firm cleaning agent preparations for machine Geschirrspülen as well as a procedure for the their production.

Weak-alkaline means for the machine table-ware uniting are well-known. In the DE 4232170 such highly effective means for the machine table-ware uniting are described, with which Pentaalkalitriphosphat completely replaced and also the content of phosphate substitutes like native and synthetic polymers strongly reduce or one limited completely. Typical cleaning agents can gemäß sodium CIT advice, citric acid, soda, sodium silicate, Natriumhydrogencarbonat, sodium perborate, sodium percarbonate, bleaching activators, Tenside and enzymes of this teachings contain.

When the processing and using these means it can come however to problems. The Darreichungsform of the powder substance often offered in herkömmfichen cleaning agents has the disadvantage, daß it with the production and the use often strongly makes dust. Auß erdem powders bend exactly like usual mixture granulates, in which the dust formation is already importantly minimized, to the Entmi single components, which can affect a reproducible cleaner achievement unfavorably. Beyond that sticking and cheeks of the individual bases together are often not auszuschlie&szlig with conventional granulates ion procedures, which often work using water or aqueous solutions; EN, which negatively affects the pourability of the cleaning agents and thus their dosing ability, and/or their stability in storage. This can be prevented so far only by complex, often multi-level, drying procedures.

From the DE 39 26 253 procedures for the production of Extrudaten are admit whereby a homogeneous, firm Vorgemisch under pressure are strangförmig injected and the strand from withdrawal from the hole form by means of a Schneidevorrichtung to the pre-determined granulates dimension cut. The homogeneous and firm Vorgemisch contains a Plastifizierund/or lubricant, which causes, daß the Vorgemisch under pressure and/or under the entry of specific work vividly softened and extrudable becomes. Preferential Plastifizierund/or lubricants is Tenside and/or polymers, which preferably in liquid, preparation form in the form of paste or gel-like use will. The Vorgemisch can auß erdem powder and/or granulates contained whereby the granulates among other things by granulation processes or also by conventional spray drying processes to be received. After the withdrawal from the hole form no more shearing stresses influence and the viscosity of the system increase thereby, in such a manner da&szlig on the system; the extruded strand on predetermineable Extrudatdimensionen to be cut can. The disadvantages of the powder form are avoided here, but by the use wäß riger solutions, wäß riger Plastifizierund lubricant, and/or strongly hydrate-aqueous components it can come to sticking together and cheeks of the products, whereby drying processes are necessary.

Against the background this state of the art it is task of the invention, new, firm cleaning agent for machine Geschirrspülen in the form of Preß lingen to make available, those with high Schüttgewicht as freifließ end, to do not bake bending products to be offered can. A further task of the invention is to suggest a suitable manufacture procedure for such products which work water-poor or water-free and get along with a minimum on drying processes.

“Water arm” meant in this connection a quantity water those, as a function of the Wasseraufnahmefähigkeit of the materials used, no additional drying step makes more necessary.

The subject of the invention is thus a procedure for the production of firm cleaning agent preparations, where one prepares firm and liquid components to a homogeneous, form-giving injectable mass by mixing, which injects mass over hole forms with apertures of of the pre-determined Presslingdimension at temperatures above 30°C strangförmig at above 50 bar, which by means of a Schneidevorrichtung to the pre-determined Presslingdimension and gewünschtenfalls the received still plastic particles cut withdrawing consolidated material strands form-giving changed, by the fact characterized that the ingredients contain between 30°C and 60°C, in particular between 35°C and 45°C, melting paraffin as auxiliary component, and one these after the cut procedure/or after that-further shaping by cooling solidifies läß t. This can happen for example in an extrusion.

A further the subject of the invention is a firm cleaning agent preparation for machine Geschirrspülen in the form of Presslingen into rieselförmiger Komform, which are on Schüttgewichte of at least 700 g/l, containing firm of ingredients, at least anteilsweise of the class of the Builder, alkali carriers, oxygen bleaches and/or bleaching activators to belong and further at least anteilsweise materials (Flüssigphase), vividly liquid at temperatures over 30°C, ductile or, which the class of the Tenside belong can, by the fact characterized that the Flüssigphase between 30°C and 60°C, in particular between 35°C and 45°C, melting paraffin in quantities from 1 to 15 Gew. - % contains.

Without daß the invention on a certain theory to be restricted is, is assumed, daß into that erfindungsgemäß EN products assigned component with a fusion point between 30 and 60 °C in the context of the processing process as liquid manufacturing aid is present and their solidifying after end of the processing to solidification of the developed Preß linge contributes. Decisive is daß this component, even if it is present in merging with other liquid components, solidifies itself, i.e. at least partly crystallizes. One accepts, daß the further liquid portions of the cooled down Flüssigphase in the Porenvolumen of the solids to be absorbed, where however the confirmed portions contribute to the solidification.

In a preferential execution form those contain erfindungsgemäß EN cleaning agent the Flüssigphase in portions from 5 to 20 Gew. - % particularly prefers in 10 to 15 Gew. - %

The descriptive Flüssigphase contains the Parraffine in quantities from 1 to 15 Gew. - % related to the entire preparation, in particularly preferential execution forms in 2 to 5 Gew. - %. The fusion point of the Pataffine is to be thereby preferentially between 35 °C and to 45 °C.

Further parts of the Flüssigphase can be selected thereby in the sense of the registration for example from the group of the Tenside. (Aniontenside, Kationtenside, Nichtioni Tenside).

For the solution of the available task is particularly preferential the use of nichtionischen Tensiden, which from the group of the ethoxylierten Fettalkohole, which Alkylpolyglycoside and/or the Fettsäureglucamide are selected.

The specialist generally understands the reaction products by alkoxylierten alcohols about alkyl oxide, prefers Ethylenoxid, with alcohols, preferentially in the sense of the available invention the längerkettigen alcohols. Usually moles Ethylenoxid and a mol alcohol enstehen, dependent on the reaction conditions a complex mixture on addition products different Ethoxylierungsgrades from n. A further execution form exists in the use of mixtures of the alkyl oxides bevozugt the mixture of Ethylenoxid and propylene oxide. Also one can gewünschtenfalls by one abschließ end to Veretherung with kurzkettigen alkyl groups, as the Butylgruppe prefers, at the substance class of the “locked” Alkoholethoxylaten arrives, which can be likewise used in the sense of the invention. In the sense of the available invention thereby hochethoxylierte Fettalkohole or their mixtures with finalgroup-locked Fettalkoholethoxylaten are completely particularly preferential.

Alkylpolyglycoside are Tenside, which will receive by the reaction from sugars and alcohols in the relevant procedures of präparativen organic chemistry can, whereby it comes depending upon kind of the production to a mixture monoalkylated, oligomerer or polymere sugar. Preferential Alkylpolyglykoside can be Alkylpolyglucoside, whereby the alcohol particularly prefers langkettiger Fettalkohole is or a mixture of langkettiger Fettalkohole is and the Oligomerisierungsgrad of the sugars between 1 and 10 is.

Fettsäurepolyhydroxylamide (Glucamide) are acylierte Reakionsprodukte of the reductive Aminierung of a sugar (glucose) with ammonia, whereby as acylation means usually langkettige fatty acids, langkettige fatty acid esters or langkettige fatty acid chloride are used. Secondary amides, if one reduces instead of with ammonia with Methylamin or ethyl amine, originate in as e.g. in SÖFW journal, 119, (1993), to 794-808 are described. Preferred one uses carbon chain lengths from C6 to C12 in the fatty acid remainder.

Beyond that procedures know still further components to be used in the cleaning agent and that below described, how is exemplarily clarified in the following.

Into that erfindungsgemäß EN cleaning agents can be used water-soluble and water-insoluble Builder particularly for binding calcium and magnesium. Water-soluble Builder are preferentially, there them on table-ware and hard surfaces in addition usually less tend insoluble arrears to form. Usual Builder, those in the context of the invention between 10 and 90 Gew. - % related to the entire preparation present to be can homopolymeren, are the low-molecular Polycarbonsäuren and their salts, and copolymers the Polycarbonsäuren and their salts, the carbonates, phosphates and silicates. Among water-insoluble Buildern the zeolites, which can be used likewise, rank just like mixtures of the aforementioned Buildersubstanzen. For those erfindungsgemäß EN cleaning agent prefers tri sodium CIT advice and/or pentane atrium tripolyphosphate and silikatische Builder from the class of the Disilikate begun.

As further components alkali carriers can be present. As alkali carriers are considered alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, Alkalimetallsesquicarbonate, alkali silicates, Alkalimetasilikate, and mixtures of the aforementioned materials, whereby in the sense of this invention prefer the alkali carbonates, in particular Natriumcarbonat, Natriumhydrogencarbonat or Natriumsesquicarbonat in quantities of 2 and 50 Gew. - % related to the entire preparation to be used.

Further possible components are oxygen bleaches. Typical oxygen bleaches are those alkali metal perborate and their hydrates and the alkali metal percarbonates, whereby in the context of the invention sodium perborate, as mono - or Tetrahydrat, prefers or sodium percarbonate and their hydrates in quantities from 2 to 12 Gew. - % related to the entire preparation use find.

Typical components of cleaning agent preparations for machine Geschirrspülen, those for technical reasons that erfindungsgemäß EN preparation in form of a powder, granulates or as liquid to be also later added can, are bleaching activators, enzymes, perfume oils, corrosion protection agents and manufacturing aids.

Well-known bleaching activators are connections, one or more Nbzw. O-acyl groups contain, like substances from the class of the anhydrides, the ester, of the imides and the acylierten Imidazole or Oxime. Examples are Tetraacetylethylendiamin TAED, Tetraacetylmethylendiamin TAMD and Tetraacetylhexylendiamin TAHD, in addition, Pentaacetylglucose PAG, 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin DADHT and Isatosäureanhydrid ISA. For the available invention bleaching activator portions between 1 and 5 Gew have themselves. - works satisfactorily % related to the entire preparation.

Erfindungsgemäß can the cleaning agent between 0 and 5 Gew. - % enzymes related to the entire preparation to be added, in order to increase the achievement of the cleaning agents or to ensure under milder conditions the cleaning achievement in same quality. To the most frequently verwendeteten enzymes belong Lipasen, Amylasen, Cellulasen and Proteasen. Preferential Proteasen e.g. is. BLAP® 140 of the company Biozym, Optimase® - M-440 and Opticlean® M-250 of the company Solvay of enzyme; Maxacal® CX and Maxapem® or Esperase® the company Gist Brocades or also Savinase® the company Novo. Particularly suitable Cellulasen and Lipasen are Celluzym® 0.7 T and Lipolase® 30 T of the company Novo Nordisk. Termamyl&reg find special use as Amylasen; 60 T, and Termamyl® 90 T of the company Novo, Amylase LT® the company Solvay of enzyme or Maxamyl® P5000 of the company Gist Brocades in addition, other enzymes can be used.

Erfindungsgemäß e table-ware detergents can contain of the Spülgutes or the machine corrosion inhibitors to the protection, whereby particularly silver protective agents within the range of the machine table-ware rinsing have a special meaning, as them e.g. in the DE 43 25 922, which DE 41 28 672 or the DE 43 38 724 are descriptive. One finds in formulations of cleaner in addition frequently active-chloric means, which can decrease a corroding of the silver surface clearly. In cleaners free from chlorine become gemäß the above writings particularly sauerstoffund nitrogenous organic redox-active compounds, like zweiund trivalent phenol, e.g. Hydrochinon, pyrocatechol, Hydroxyhydrochinon, Gallussäure, Phloroglucin, Pyrogallol and/or derivatives of these connecting classes. Also salzund complex-like inorganic compounds, like salts of the metals Mn, Ti, Zr, Hf, V, CO and Ce find frequently use. Likewise zinc connections to the prevention of the corrosion at the Spülgut can be used.

Further well-known components for Waschund cleaning agent are often inferred from the group of the perfume oils. Also they can into that erfindungsgemäß EN cleaning agent compositions contained its.

In addition still different additives can be used for manufacturing, like for example to the Abpudern of the residual moisture in some preparations purify-hasty reference fitting materials, those the specialist usually from the group of the precipitation silicic acids, the alkali carbonates (particularly Natriumcarbonat), the alkali hydrogencarbonates (particularly Natriumhydrogencarbonat), which can select zeolites and similar suitable means.

A preferential cleaning agent preparation gemäß of the available invention contains so for example 20 to 70 Gew. - % sodium CIT advice, 2 to 10 Gew. - % Tenside, 2 to 15 Gew. - % soda, 10 to 50 Gew. - % Natriumhydrogencarbonat, 2 to 12 Gew. - % sodium perborate, 0 to 30 Gew. - % Polycarbonsäure in each case related to the entire preparation.

One can do that erfindungsgemäß EN cleaning agent preparations as mixing component also later 1 to 5 Gew. - % bleaching activator, 0 to 5 Gew. - % enzyme and/or 0 to 1 Gew. - % perfume oil for manufacturing beige-add.

To erfindungsgemäß EN solution of the task can be fed the extrusion equipment used in the procedure descriptive down in different way with material. So e.g. everything can be supplied components in a Vorgemisch, which can be extruded, or in extrusion to be mixed, whereby then prefers the liquid components by a separate connecting piece are added. Can erfindungsgemäß the further active substances, like in particular bleaching activators, corrosion inhibitors for silver, enzymes and such a thing, in granulates form or than liquid or firm of aggregates being added.

One plastifiziert the mixture by pressure build-up before the perforated disks, energy entry by the snails and additional warming up by the Mantelheizung of extrusion. The grouting of the cleaning agent mass which can be extruded takes place at pressures above 50 bar. The particularly preferred execution form of the procedure works at pressures above 100 bar.

The temperature, at which the mass plastifiziert in such a way, daß injecting by the perforated tile and cutting to cylindrical molded articles are possible, without daß it for sticking together comes, depends on the prescription components and lies preferentially between 45 and 60 °C, particularly preferentially above 50°C.

In extrusion becomes on as gleichmä&szlig as possible; igen throughput by all openings of the perforated disk respected, so daß the strands by the circulating measurers to be homogeneously cut can. A preferential execution form for spherical Presslinge consists of it, daß the diameter of the material strand approximately the height of the particles corresponds.

As a check of the temperature of the withdrawing plastifizierten strands it can be desired these by shock cooling, in particular by means of cool air to cool down forwards and/or during division at least superficially.

Afterwards effected then prefers a reinforcement of the still plastic bodies in a usual market round, whereby in the Anschluß the spherical parts still by Abpudern to be manufactured can. One uses purify-hasty reference fitting materials, in particular precipitation silicic acids, Natriumcarbonat, Natriumhydrogencarbonat, zeolites and such a thing.

By working in the fundamentally water-free environment under simultaneous receipt of the ability for the shaping of the plastifizierten mass can usually erfindungsgemäß without drying steps to be done. However, perhaps as a function of the Wasseraufnahmefähigkeit of the materials used, still if remainder liquid should be present, then also a drying step can be accomplished. Preferred the quantity of water is below 5 Gew. - Gew particularly prefers % under 3. - % and completely particularly prefers under 2 Gew. - %. Such a small quantity of water, which does not make an additional drying step more necessary, can be very useful with the controlling of the Plastifizierfähigkeit of the mixture. Therefore is with selected examples, if the plasticizing not with other well-known Maß took one controls and one changes, a water content above 1 Gew. - % prefers.

After the cooling of the product on ambient temperature (under 30°C) can so freifließ do not end to cheeks bending products with a Schüttgewicht from 600 to 1000 g/l to be received.

For in the following the descriptive cleaning agent preparations in a double snail laboratory extrusion of the company Leistritz were processed.

The plasticizing of the continuously metered mixture of the components 1-8 took place in extrusion via the energy entry of the snails, if necessary via additional Mantelheizung and via pressure build-up before the perforated disk. The temperature, at which the mass plastifiziert in such a way, daß injecting by the 1.6 mm of drillings of the perforated tile and cutting to cylindrical Formkörpem is possible, without daß it for sticking together comes, was in the available case about 54 - 58 °C. The cylindrical molded articles with a length/diameter relationship of 1:1 were converted in a usual market round to spherical particles. Under standard temperature became freifließ end, not to cheeks bending product receive, which with the components 9-11 to a finished product with a Schüttgewicht of 860 g/l one mixed.

One leads the procedure with the components in this composition so, daß one the solids 1-4 and the liquid components 5-8 as mixture into extrusion proportions in each case, then one receives after processing likewise a finished product with the characteristics the example of the 1

By the employment of a mixture of the components 1-8 with the production of the Rohextrudates under the conditions the example of the 1 became well flie&szlig after remainder merging with the components 9 and 10; capable product with a Schüttgewicht from 880 g/l receive.