DE10045977A1 - Cleaning of hollow objects such as bottles, pots or vases uses a cleaning substance in densified form e.g. tablets or agglomerate to reduce or eliminate need for brushing - Google Patents

Abstract

Manual cleaning of hollow objects is effected using a cleaning substance in the form of compressed (densified) bodies.

Description

The present invention relates to a method for manual cleaning of hollow bodies.

Hollow objects such as bottles, jugs, vases etc. are cleaned in the household as before, manually using appropriate brushes. On the one hand, the reason is that some of these items are not suitable for household dishwashers Dishwashers are unable to satisfy the interior of the hollow body to be cleaned.

In particular, hard-to-reach places in hollow bodies, such as the area of bottles Bottle shoulder or the angles formed by the bottle wall and bottom etc. are included inadequate cleaning of conventional processes. Residues often remain especially in the case of hollow bodies made of glass, also for optical reasons.

Also for the mechanical cleaning of hollow bodies with the help of suitable brushes cleaning agents are usually added. The funds are dosed arbitrarily, whereby often added in large quantities. In addition, the commercially available The composition of the cleaner does not address the special problems involved in cleaning of hollow bodies occurs are coordinated.

The object of the present invention was to provide a method len, with which it is possible to clean hollow bodies in a simple manner, including impurities cleaning in hard-to-reach places and without the cleaning shares Substances overdosed are used.

The solution to the problem is a method of the type mentioned, which thereby is characterized in that the cleaning-active substances in the form of compacted form bodies are used.  

It was found that, in particular in the household, hollow bodies using reini gungsactive substances that are used in the form of compressed moldings in can be easily cleaned even in hard-to-reach places. The shape bodies contain the cleaning-active substances preferably in an amount that corresponds to a defined volume is coordinated. With larger volumes, the number of used th moldings can be multiplied accordingly.

The use of mechanical aids, such as brushes, can be minimized and, if necessary, entirely waived it. Especially when cleaning heavily soiled hollow bodies However, it may be desirable if mechanical aids for supporting Rei be used.

Hollow bodies in the sense of the present invention are, in particular, objects which have one or more opening (s), such as mugs, cups, bowls, bottles, Va sen, cans including thermos jugs, etc. The method according to the invention are particularly advantageous for cleaning hollow bodies, the opening (s) in relation to the Cavity is relatively small, i.e. H. insufficient to tear with mechanical aids are. The hollow body to be cleaned can consist of any materials, such as Glass, plastic, metal etc.

The moldings used according to the invention can be used in combination with water or egg nem ecologically harmless organic solvents are used, whereby What is preferred.

When carrying out the method according to the invention, it has proven to be suitable if the moldings and water used in the invention in the to be cleaned Hollow bodies are given. The hollow body should be filled with water so far that the Sections to be cleaned are wetted with the detergent solution. Then you leave the Soak the detergent solution for a sufficient period of time until the desired detergent success. The exposure time can range from a few minutes to several Hours, such as B. Allow to act overnight.  

The cleaning process can be done by shaking the hollow body or by using a bur be supported.

The water used does not require any special treatment and can directly do what serhahn can be removed. The water temperature is preferably from 5 ° C to 25 ° C, depending on the season and the point at which the water is drawn. With especially difficult-to-remove dirt or to speed up the cleaning process warm to boiling water can also be used.

The spatial shape of the moldings used is preferably the shape in its dimensions adapted from the usual opening of the hollow body to be cleaned, so that the moldings per can be easily placed in the hollow body. In a preferred embodiment the largest dimension of the moldings used according to the invention is between 1 and 50 mm, particularly preferably between 2.5 and 40 mm and in particular between 5 and 20 mm.

The moldings used according to the invention can have a wide variety of geometries forms are provided. For example, in a predetermined spatial shape and a predetermined size can be made, practically all come as a spatial shape Configurations that can be meaningfully handled come into consideration, for example the end Formation as a board, the shape of bars or bars, cubes, cuboids and corresponding space elements elements with flat side surfaces and, in particular, cylindrical configurations circular or oval cross section. This last embodiment covers the darbie form from tablets to compact cylinder pieces with a ratio of height to diameter above 1.

The shaped bodies can each be designed as separate individual elements be the ent of the predetermined dosage of the ingredients used per volume speaks. But it is also possible to design the individual parts so that a plurality such mass units is connected, e.g. B. in a compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is seen.  

The cleaning-active substances can be made from any known substances be chosen. Surfactants, builders, bleaching agents and bleaching agents are preferred gates, enzymes and antimicrobial agents as well as their mixtures.

Anionic, nonionic, katio African and / or amphoteric surfactants or mixtures of these are used become. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acid ren with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, caprin acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of application technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine,  available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and preferred by average 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred non-ionic surfactants, either alone or non-ionic surfactant or in combination with other non-ionic surfactants are set, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated  Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular their fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-di methylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half there of.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula I,

in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hy droxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula II

in which R ² for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ³ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁴ for a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, at for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N- Alkoxy- or N-aryloxy-substituted compounds can then be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Po lyhydroxy fatty acid amides are transferred.

In the context of the present invention, preference is given to using moldings which are anio niche (s) and non-ionic (s) surfactant (s) contain, with application technology advantages from certain proportions in which the individual surfactant classes are used will result.

For example, moldings in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Shaped bodies are also preferred Surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 up to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight us in particular from 12.5 to 25 wt .-%, each based on the molded body important, included.

From an application point of view, it can have advantages if the molding used per has several phases and certain classes of surfactants in some phases or in ge velvet molded body, d. H. in all phases, are not included. The individual phases can have a different solubility, so that certain ingredients immediately after are released into contact with water and other ingredients only at a later time Time.

Conversely, the content of individual phases or the entire form can also be used body, d. H. all phases, certain surfactants have a positive effect. The The introduction of the alkyl polyglycosides described above has proven to be advantageous  so that moldings are preferred in which at least one phase of the moldings Contains alkyl polyglycosides.

Similar to the nonionic surfactants can also be left out of anioni tensides result from individual or all phases of shaped bodies which are suitable for certain areas of application are better suited. It is therefore within the scope of the present Invention molded articles can also be used in which at least one phase of the molded articles is free of anionic surfactants.

Only weakly foaming nonionic surfactants are preferably used as surfactants in moldings used according to the invention. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. Moldings used according to the invention particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The given degrees of ethoxylation are statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another preferred surfactant can be represented by formula III

R ⁵ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ⁶ ] (III)

describe in which R ^{5 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ⁶ denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15.

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

R ⁵ O [CH ₂ CH (R ⁷ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ⁶ (IV)

in which R ⁵ and R ^{6 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{7 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ⁷ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ⁷ can be selected to form ethylene oxide (R ⁷ = H) or propylene oxide (R ⁷ = CH ₃ ) units which can be joined together in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ⁵ O [CH ₂ CH (R ⁷ ) O] _x CH ₂ CH (OH) CH ₂ OR ⁶

simplified. In the last-mentioned formula, R ⁵ , R ⁶ and R ^{7 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ⁵ and R ^{6 has} 9 to 14 C atoms, R ⁷ stands for H and x assumes values from 6 to 15.

The total surfactant content of the moldings used according to the invention is preferably below 5% by weight, particularly preferably below 4% by weight, and in particular below 2% by weight, based in each case on their total weight.

The moldings used according to the invention preferably contain builders which again preferably from the groups of zeolites, silicates, carbonates, bicarbonates, Phosphates and polymers come from. Especially in the case of non-pressing processes Ren, such as curing, manufactured molded parts come from preferred ingredients the group of phosphates, with alkali metal phosphates being particularly preferred. This Fabrics are used in the manufacture of the masses in anhydrous or poor form and the desired plastic properties of the masses with water and optional Plating tools set.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as do decahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in water-free form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trina triumphosphate is easily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, flowable, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1%. solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. For the latter in particular, a large number of terms are used: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's theorem. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt free of water of crystallization dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these phosphates are exactly like sodium tripolyphosphate and potassium tripoly phosphate or mixtures of these two can be used; also mixtures of sodium tri polyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Ka Lithium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

In preferred moldings, at least one non-compressed portion contains phosphate (s) preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the non-compressed part.

If phosphates are used as the only hydratable substances in hardening compositions, so should the amount of water added not exceed their water binding capacity, in order to adhere to the free water content of the moldings to a low degree. Overall, have become Adherence to the above-mentioned limit values where the weight ratio of phosphate (s) to water in the deformable mass is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0.2.

Other ingredients instead of or in addition to phosphates in the moldings may be included are carbonates and / or hydrogen carbonates, the alkali metal salts and especially the potassium and / or sodium salts are preferred. before Drawn molded articles contain carbonate (s) and / or hydrogen carbonate (s), preferably alka licarbonate, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on a non-compressed part.

The same applies here in the case of production via curing with regard to the water content Masses the above. There have been procedures in particular as before emphasized where the weight ratio of carbonate (s) and / or hydrogen carbonate (s)  to water in the deformable mass less than 1: 0.2, preferably less 1: 0.15 and in particular less than 1: 0.1.

Other ingredients instead of or in addition to the phosphates mentioned and / or carbonates / bicarbonates in the moldings used according to the invention pern can be contained are silicates, the alkali metal silicates and below in particular the amorphous and / or crystalline potassium and / or sodium disilicate are preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

Moldings preferred in the context of the present invention contain silicate (s) preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in Amounts from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the entire molded body.

The same applies here for the production via curing with regard to the water content of the mas the above. In particular, methods have been preferred underlined, in which the weight ratio of silicate (s) to water in the deformed baren mass less than 1: 0.25, preferably less than 1: 0.2 and in particular less than 1: 0.15 is.

Substances from the group of zeolites, which are preferred builders, are also suitable as an important component in the moldings according to the invention. Zeolites have the general formula

M _{2 / n} O.Al ₂ O ₃ .xSiO ₂ .yH ₂ O

where M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can assume values between 0 and 20. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. The intercrystalline "zeolitic" water can be released continuously and reversibly depending on the type of zeolite, while for some types of zeolite there are also structural changes associated with the release or uptake of water.

In the structural subunits, the primary binding units "(AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called" secondary binding units ", which have the form of single or multiple rings. For example, 4-, 6- and 8- link rings on (referred to as S4R, S6R and S8R), other types are connected via four- and six-link double ring prisms (most common types: D4R as a square or D6R as a hexagonal prism.) These "secondary subunits" connect different polyhedra with The most widespread is a polyhedron, which is made up of six squares and eight equilateral hexagons and is called "β". With these units, a variety of different zeolites can be realized. So far, 34 natural zeolite minerals and approximately 100 synthetic zeolites known.

The best known zeolite, 4 A zeolite, is a cubic assembly of β-cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Å and 4.2 Å in size, the formula unit in the unit cell can be modified with Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27 Describe H ₂ O.

Zeolites of the faujasite type are preferred in the moldings according to the invention set. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite Types within the zeolite structure group 4 by the double six-ring subunit D6R is marked (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). About the zeolite structure In addition to the faujasite types mentioned, group 4 also includes the minerals chabazite and Gmelinit as well as the synthetic zeolites R (Chabazit-type), S (Gmelinit-type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Zeolites of the faujasite type are composed of β-cages which are linked tetrahedrally via D6R subunits, the β-cages being arranged in a manner similar to the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approx. 13 Å and can be represented by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .264 H ₂ O. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites that form the faujasite subgroup of zeolite structure group 4. Next  According to the invention, zeolite X also includes zeolite Y and faujasite and mixtures of these compounds can be used according to the invention, the pure zeolite X being preferred. Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites then, which do not necessarily have to belong to the zeolite structure group 4, are inventive usable according to, the advantages of the method according to the invention being particularly clear Lich emerge when at least 50 wt .-% of the powdering agent from a zeolite then of the faujasite type. It is also conceivable, for example, that the minimum Amount of a faujasite type zeolite (0.5% by weight based on the weight of the first the molded body) and conventional zeolite as the remaining powdering agent A used. However, it is preferred in any case that the powdering agent exclusively consists of one or more zeolites of the faujasite type, with zeolite X in turn is preferred.

The aluminum silicates, which are preferably used in the moldings according to the invention are commercially available and the methods for their presentation are in Stan dardmonographien described.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

in which x can have values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å exhibit.

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta S. p. A. is sold under the brand name VEGO BOND AX® and through the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .xH ₂ O,

K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .xH ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å, describe.

Shaped bodies used with preference contain zeolite (s), preferably zeolite A, zeolite P, Zeolite X and mixtures of these, in amounts of 10 to 60 wt .-%, preferably of 15 to 50 wt .-% and in particular from 20 to 40 wt .-%.

The particle sizes of the faujasite-type zeolites used are present preferably in the range of 0.1 to 100 microns, preferably between 0.5 and 50 microns and in particular between 1 and 30 microns, each with standard particle size determination methods measured.

It is generally preferred to use finely divided solids, regardless of what kind of solids it is. Generally speaking, processing is over Curing preferred process variants in which the average particle size of the set solids below 400 µm, preferably below 300 µm and especially below 200 µm lies.

The mean particle size is the arithmetic mean of the individual particles are sizes that can still fluctuate. This makes particularly preferred methods characterized in that less than 10 wt .-%, preferably less than 5 wt .-% and ins particularly less than 1% by weight of the solids used in the deformable mass (es)  Have particle sizes above 1000 microns. The upper particle size range leaves narrow even further, so that particularly preferred methods are characterized are less than 15 wt%, preferably less than 10 wt% and especially less than 5% by weight of the solids used in the deformable mass (s) have sizes above 800 µm.

In general, however, narrower particle size distributions are preferred, in which the Fluctuation range around the average particle size at most 50%, preferably at most The particle size is 40% and in particular a maximum of 30% of the average particle size a minimum of 0.7 and a maximum of 1.3 times the average particle size chen.

After processing, this water is preferably bunched in the form of water of hydration the, so that the end products of the process preferably have a significantly lower content have free water. Preferred end products of the process according to the invention are thereby essentially anhydrous, d. H. in a state where the liquid, d. H. not in the form of water of hydration and / or constitutional water below 2% by weight, preferably below 1% by weight and in particular even below 0.5% by weight, each based on the molded body. Accordingly, the shape of the invention body preferred, the less than 10 wt .-%, preferably less than 5 wt .-%, esp preferably less than 1 wt .-% and in particular less than 0.5 wt .-% free what included. Accordingly, water can essentially only in chemical and / or physically bound form or as a component of the raw materials present as a solid or compounds, but not as a liquid, solution or dispersion in the end products available. The moldings advantageously have at the end of the manufacturing process a total water content of not more than 15 wt .-%, so this water not in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix not more than 10 wt .-% and in particular is not more than 7% by weight.

Moldings used with particular preference in the context of the present invention Zen not only have an extremely low proportion of free water, but are preferred  still able to bind more free water. In preferred moldings be the water content of the moldings carries 50 to 100% of the calculated water binding capacity gens.

The water binding capacity is the ability of a substance (here: the shaped body) to absorb water in a chemically stable form and ultimately indicates how much water can be bound by a substance or a shaped body in the form of stable hydrates. The dimensionless value of the water binding capacity (WBV) is calculated from:

where n is the number of water molecules in the corresponding hydrate of the substance and M is the molar mass of the non-hydrated substance. This results, for example, in the water binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate)

The value WBV can be used for all hydrate-forming substances in the invention masses to be processed are calculated. About the percentages Proportions of these substances then result in the total water binding capacity of the recipes door. In preferred end products of the process, the water content is then between 50 and 100% of this calculated value.

In addition to the water content of the moldings and the ratio of water to certain Raw materials can in the case of the production of the non-pressed molded part Hardening also provides information about the absolute water content of the ver working masses. In particularly preferred methods, the deformable mass (es) during processing a water content of 2.5 to 30% by weight,  preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight, in each case based on towards the crowd.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one of the like use for ecological reasons is not objectionable, as well as mixtures of this. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipine acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, glucon are here acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the Alka limetal salts of polyacrylic acid or polymethacrylic acid, for example those with egg ner molecular weight of 500 to 70,000 g / mol.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecule mass, based on free acids, is generally from 2000 to 70,000 g / mol, preferably as 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the moldings is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, as in for example, contain allyloxybenzenesulfonic acid and methalylsulfonic acid as a monomer.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Mo nomere salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives th.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, de ren salts or their precursors. Polyaspa are particularly preferred Ragic acids or their salts and derivatives, which in addition to cobuilder properties also have a bleach-stabilizing effect.  

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehydrogenated with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have pen, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcar receive bonic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches that can. The hydrolysis can be carried out according to customary methods, for example acid or enzyme catalysis based procedures. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharids compared to dextrose, which has a DE of 100. So are usable probably maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol.

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

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Continue to be In this connection, glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are in formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acid ren or their salts, which may also be in lactone form and which  at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) from special of importance as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As an aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, it can be, especially if the moldings also contain bleach be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures gene from the phosphonates mentioned.

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

The moldings used according to the invention can contain bleaching agents as a further cleaning-active substance. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Here, "sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated set, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the per carbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. Basically, all commercially available percarbonate types can be used according to the invention, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Other usable bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthlo-looperoperic acid or diperdodecanedioic acid. Even when using the bleach, it is possible to do without the use of surfactants and / or builders, so that pure bleach tablets can be produced. In a preferred embodiment, a combination of sodium percarbonate with sodium sesquicarbonate is used, irrespective of which other ingredients are contained in the shaped bodies. In a further embodiment, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. Di benzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoper phthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalonic acid [ε-phthalimide [ Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyaocanoic acid, diperoxyacid, diacid acid, diacid acid, diacid acid, diacid acid, 2-diacid acid, 2-diacid acid, diacid acid, 2-diacid acid, diacid acid, 2-diacid acid, diacid acid, 2-diacid acid, 2-diacid acid, 2-diacid acid, 2-diacid acid, 2-diacid acid -Decyldiperoxybutan-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents, being based on this when used in open systems, d. H. in open hollow bodies, preferably is waived. Come under the appropriate chlorine or bromine releasing materials for example heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The moldings can contain bleach activators as further ingredients. Bleichaktivato Examples of compounds which support the action of the bleaching agents are compounds which contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylene diamine (TAED), tetraacetyl methylene diamine (TAMD) and tetraacetylhe xylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahy dro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple acy are preferred lated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazinderi vate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Gly colored, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic acid anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and Enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated  Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzo ylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also considered trains used. Combinations of conventional bleach activators can also be used become.

In addition to the conventional bleach activators or in their place can also bleaching catalysts mentioned are incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru-amine complexes can be used as bleaching catalysts.

Bleach activators from the group of polyacylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the ge whole molded body, 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 consisting of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese, the manganese sulfate are in usual amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the molded body, used. But in In special cases, more bleach activator can be used.

The inventive method for cleaning hollow bodies made of metal sets, it has proven to be advantageous if the form used according to the invention body contain corrosion inhibitors. Examples of such substances are triazoles Benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts  or complexes, particularly preferably benzotriazole and / or alkylamino triazole. In chlorine-free moldings, oxygen and nitrogen-containing organs in particular are used African 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-like and complex-like inorganic compounds, such as Salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred the transition metal salts selected from the group consisting of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also act as corrosion inhibitors gates are used. These compounds are preferably used in an amount of 0.01 up to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, each based on the finished molded article used.

If anti-corrosive agents are used in multi-phase moldings, it is preferred to separate them from the bleach. Shaped body in which one of the non-pressed Parts therefore contain bleach, while another contains anti-corrosion agents prefers.

The separation of the bleaching agents from other ingredients can also be advantageous. OF INVENTION Shaped body according to the invention, which contains bleach in one phase, while another Phase containing enzymes are also preferred.

Enzymes in the moldings used according to the invention include, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned hold. All of these hydrolases contribute to the removal of soiling such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching become. Bacterial strains or fungi such as Bacillus subti are particularly suitable lis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus are used. There are enzyme mixtures, for example  from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, Lipase or lipolytic enzymes, but especially protease and / or lipase containing mixtures or mixtures with lipolytically active enzymes of particular Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight, based in each case on the shaped body.

The moldings used according to the invention can be used to control microorganisms contain antimicrobial agents. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, fungio Statics and fungicides etc. Important substances from these groups are, for example, benz alkoniumchloride, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, also these connections can be dispensed with entirely.

The moldings used according to the invention can be further application technology contain partial components, such as disintegration aids, shower systems, dyes, Fragrances, antioxidants, fluorescent agents, foam inhibitors, silicone and / or paraffin oils. These substances are described below.

To facilitate the disintegration of highly compressed moldings, it is possible to disintegrate tools, so-called tablet disintegrants, to incorporate into them to reduce the disintegration times To shorten. These substances are suitable, for example, for the release of individual forms to accelerate body areas compared to other areas. Taking tablets or decay accelerators are according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) auxiliaries  understood that for the rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effects, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid tel are, for example, carbonate / citric acid systems, with other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modifi graced natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred moldings contain disintegration aids based on cellulose, preferably wise in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight %, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%, each based on the Tablet weight.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred moldings contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 % By weight. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable cellulosics consist of approx. 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based integration agent.

The cellulose used as disintegration aid is preferably not in finely divided form Form used, but before mixing to the premixes to be pressed in transferred a coarser form, for example granulated or compacted. Shaped body that Disintegrants in granular or optionally cogranulated form are included in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). this Fonts are also more detailed information on the production of granulated, compacted or cogra to take out of the pulverized cellulose disintegrant. The particle sizes of such disintegration medium are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The coarser ones mentioned above and described in more detail in the cited documents Disintegration aids based on cellulose are within the scope of the present invention preferably used as disintegration aids and commercially, for example, under Description Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and for example compactible to granules with an average particle size of 200 microns are.  

The moldings used according to the invention can also be a contain gas-evolving shower system that can be processed in one or more of the Masses is incorporated. The gas-developing shower system can be made from a single Substance exist that releases a gas on contact with water. Under these Compounds should be mentioned in particular the magnesium peroxide, which in contact with Water releases oxygen. The gas-releasing bubble system usually exists however, in turn, from at least two constituents, which together form gas react. While here a multitude of systems is conceivable and executable, the release nitrogen, oxygen or hydrogen, for example Shaped bodies preferably used bubble system based on both economic and also choose based on ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and one Acidifying agent which is suitable from the alkali metal salts in aqueous solution Release carbon dioxide.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Selbstver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and bicarbonates may be preferred for technical reasons.

In preferred moldings used, 2 to 20% by weight are used as the shower system preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% an acidifying agent, based in each case on the entire molded body puts. The content of individual substances in the substances mentioned can be quite high lying here.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution zen, are for example boric acid and alkali metal bisulfates, alkali metal dihydro gene phosphates and other inorganic salts can be used. However, or are preferred ganic acidifiers are used, with citric acid being a particularly preferred acidifier. However, the other fixed ones can also be used in particular  Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also used bar. Commercially available and as an acidifying agent within the scope of the present invention sokalan® DCS (trademark of BASF), a Ge mix of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipine acid (max. 33% by weight).

In the context of the present invention, preference is given to moldings in which the acidification agent in the shower system is a substance from the group of organic di-, tri- and oligo carboxylic acids or mixtures of these are used.

In order to improve the aesthetic impression of the moldings used according to the invention sern, they can be colored in whole or in part with suitable dyes. Beson their optical effects can be achieved if in the case of the production of mold the masses to be processed are colored differently from several masses are. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other contents substances of the molded body and against light as well as no pronounced substantivity the treated substrates such as glass, plastics, metal surfaces etc., so as not to stain them.

Preferred for use in moldings according to the invention are all colorants which are used in Cleaning process can be destroyed oxidatively as well as mixtures of the same neten blue dyes, so-called blue tones. It has proven to be a beneficial colorant use in water or at room temperature in liquid organic substances are soluble. For example, anionic colorants, e.g. B. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) part 1: Acid Green 1; Part 2: 10020), which as a commercial product, for example as Basacid® Green 970 is available from BASF, Ludwigshafen, as well as mixtures of these with suitable ones blue dyes. Pigmosol® Blue 6900 (CI 74160), Pig mosol® green 8730 (CI 74260), Basonyl® red 545 FL (CI 45170), Sandolan® rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051),  Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, C1 Acidblue 221), Nylosan® Yellow N-7GL SGR (CAS 61814-57- 1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0) for Commitment.

When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity for the materials from which the hollow bodies to be cleaned are made. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the shaped bodies varies. If the water-soluble dye is good, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmo sol® dyes, the suitable concentration of the colorant in the moldings is typically against some 10 ^-3 to 10 ^-4 wt .-%.

Fragrances are added to the moldings according to the invention in order to improve the aesthetics Improve product impression and consumer in addition to the performance of the pro products a visually and sensorially "typical and distinctive" product to deliver. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and carbon type Hydrogen can be used. Fragrance compounds of the ester type are e.g. B. Ben cyanoacetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbene zyl-carbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Tough to the ethers len for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C- Atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones z. B. the Jonone, ∝-isomethylionon and methyl-cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene  and pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural che fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom ten oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content is usually in the form used according to the invention body up to 2% by weight of the total formulation. The fragrances can be directly in the he molded bodies used according to the invention can be incorporated, but it can also be advantageous be necessary to apply the fragrances to carriers. As such carrier materials have become For example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

As foam inhibitors used in the moldings used according to the invention can be, for example, soaps, paraffins or silicone oils into consideration can optionally be applied to carrier materials.

To unwanted, caused by oxygen and other oxidative processes To prevent changes to the shaped bodies and / or the substrates to be cleaned, the moldings can contain antioxidants. This connection class includes for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

For all of the above-mentioned ingredients, advantageous properties can be derived therefrom to separate them from other ingredients or to mix them with certain other ingredients to assemble contents together. In the case of multi-phase moldings, the one individual phases also have different contents of the same ingredient, whereby advantages can be achieved.

The moldings used according to the invention have a 1% by weight solution of whole molded body in water preferably a pH in the range of 7 to 11, preferably  from 7.5 to 10 and in particular from 8 to 9.5, be on the prior art known pressing or non-pressing processes can be produced.

The molded body used according to the invention can be any of the prior art Technically known compressive or non-compressive molding processes are obtained become.

The pressing method includes e.g. B. the tableting. For this, the individual Ingredients that can be partially or fully pre-granulated, dry mixed, then cut to shape and pressed. The premix is used to produce the moldings in this embodiment in a so-called die between two stamps to one solid compressed compacted.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high throughputs is preferably via a volumetric dosage of Premix reached. As the tableting continues, the upper stamp touches this Premix and continues to lower towards the lower stamp. With this compression the particles of the premix are pressed closer together, the void vo lumen within the filling between the stamps decreases continuously. From a be agreed position of the upper stamp (and thus from a certain pressure on the front mixture) begins the plastic deformation, in which the particles flow together and it comes to the formation of the shaped body. Depending on the physical properties Part of the premix particles is crushed and it is crushed sintering of the premix occurs at even higher pressures. With increasing Pressing speed, i.e. high throughput, becomes the phase of elastic deformation mung continuously shortened, so that the resulting molded body more or less large Can have cavities. In the last step of tableting, the finished molding pressed out of the die by the lower stamp and by subsequent trans port facilities transported away. At this point, only the weight of the molded article is pers finally determined because the compacts due to physical processes (stretching,  crystallographic effects, cooling etc.) can still change their shape and size NEN.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this press stamp is comparable to the way a conventional four-stroke engine works. The pressing can be done with one upper and one lower stamp, but several stamps can also be made be attached to an eccentric disc, the number of die holes corresponding is expanded accordingly. The throughputs of eccentric presses vary depending on the type of some hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The number of the matrices varies between 6 and 55 depending on the model, whereby larger matrices in Are available commercially. Each die on the die table is an upper and lower stamp assigned, with the pressing pressure again being active only through the upper or lower stamp, but can also be built using both stamps. The matrix table and the stamp move around a common vertical axis, using the stamp rail-like cam tracks during the circulation in the positions for filling, Ver sealing, plastic deformation and ejection. In the places where a particularly serious raising or lowering of the stamp is required (filling len, compression, ejection), these cam tracks by additional low pressure pieces, low-tension rails and lifting tracks supported. Filling the die follows via a rigidly arranged feed device, the so-called filling shoe, which with egg nem storage container for the premix is connected. The pressure on the premix is individually adjustable via the press paths for upper and lower punches, the pressure construction by rolling the punch shaft heads past adjustable pressure rollers schieht.  

Rotary presses can also use two filling shoes to increase throughput hen be, only a semicircle are run through to produce a tablet got to. Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the lightly pressed first layer before the next Filling is ejected. Through appropriate process control, too Shell and dot tablets can be produced, which have an onion-shell-like structure, where in the case of the point tablets, the top of the core or core layers does not have is covered and thus remains visible. Rotary tablet presses are also available with single or Multiple tools can be equipped so that, for example, an outer circle with 50 and one inner circle with 35 holes can be used for pressing at the same time. The throughputs modern rotary tablet presses are over one million pieces (tablets) each Hour.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Ver packungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses AG, Berlin, and Rornaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the HPF 630 hydraulic double pressure press is particularly suitable Company LAEIS, D. Tabletting tools are, for example, from the company Adams Tablettier tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werk zeugbau, Tamm available. Other providers are e.g. B. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

Particularly preferred production variants for non-pressing processes are the sintering, the casting, the hardening of deformable masses and the production of particles, for. B. by granulation, pelleting, extrusion, agglomeration, etc. These are methods familiar to the person skilled in the art, in which it is not necessary to use high pressures. In the context of the present invention, “not compressed” means in particular “not produced by tableting”. According to the invention, pressure exertion of more than 5 kN / cm ² , preferably more than 2.5 kN / cm ² , particularly preferably more than 1 kN / cm ² and in particular more than 0.1 kN / cm ² should be avoided. The end products of processes in which particulate premixes are formed into shaped bodies by using pressures above 5 kN / cm ² by reducing the intra-particle and inter-particle spaces are usually referred to as "non-compressed part". The use of lower pressures, for example to shape deformable masses or particle piles, without achieving a self-adhering composite (a tablet) can, however, be advantageous in individual cases.

Sintering provides a possibly preformed particle pile represents that under the influence of external conditions (temperature, radiation, reactive gases, Liquids, etc.) is converted into a compact unit. Examples of sintering processes are the production of moldings by microwaves known from the prior art or radiation curing.

Another preferred sintering process for the production of non-pressed molded articles is reactive sintering. This is where the starting substances are brought into shape and then connected solidified by a compound A and a compound B to react with each other are brought, the compounds A and B mixed with the starting substances, applied to it or added after informing.

When this process is carried out, the compounds A and B react with Verfesti the individual ingredients. The reaction product formed from the ver bonds A and B connects the individual starting substances in such a way that a solid, relatively break-resistant molded body is obtained.

With this process, moldings with good decay are obtained. Because the bond of the individual ingredients by reactive sintering and not by the "sticky If the granule of the premix is conditioned, it is not necessary to adapt the recipe to the Adapt binding properties of the individual ingredients. These can be selected in depending on their effectiveness.  

In order to react the compounds A and B with one another, it has proven to be advantageous if the starting substances are mixed with the compound A or are coated with them before they are brought into shape. Examples of compounds A are the alkali metal hydroxides, in particular NaOH and KOH, alkaline earth metal hydroxides, in particular Ca (OH) ₂ , alkali metal silicates, organic or inorganic acids, such as citric acid, or acidic salts, such as hydrogen sulfate, anhydrous, hydratable salts or hydrate-containing salts, such as soda, acetates , Sulfates, alkali metalates, where the aforementioned compounds can, if possible, also be used in the form of their aqueous solutions.

The compound B is selected in such a way that 43561 00070 552 001000280000000200012000285914345000040 0002010045977 00004 43442she reacts with the compound A without the application of higher pressures or substantial temperature increases to form a solid, solidifying the other starting substances present. Examples of compounds B are CO ₂ , NH ₃ , water vapor or spray, salts containing hydrate water, which may react with the anhydrous salts present as compound A by hydrate migration, hydrated anhydrous salts which react with the hydrate-containing salts of component A with hydrate migration react, SO ₂ , SO ₃ , HCl, HBr, silicon halides such as SiCl ₄ or kiselsäureester S (OR) _x R ' _4-x .

The above-mentioned compounds A and B are interchangeable if two Compounds are used that react with one another during sintering.

In a preferred embodiment of this production route, the starting substances are mixed or coated with compound (s) A and then mixed with compound (s) B. It has proven particularly suitable if the compounds B are gaseous. The initial forms brought into shape (hereinafter referred to as preforms) can then either be gassed in simple form or introduced into a gas atmosphere. A particularly preferred combination of the compounds A and B are concentrated solutions of the alkali metal hydroxides, in particular NaOH and KOH, and alkaline earth metal hydroxides, such as Ca (OH) ₂ , or alkali metal silicates as the compound A and CO ₂ as the compound B.

To carry out the method according to the invention, the starting substances are first brought into shape, ie they are usually filled into a die which has the outer shape of the molded body to be produced. The starting substances are preferably in powdery to granular form. First, they are mixed or coated with a compound A. After filling into the matrix or tablet tenform, it has proven to be preferred to lightly press the starting substances in the matrix, e.g. B. by hand or with a stamp at a pressure which is below the above values, in particular below 100 N / cm ² . It is also possible to compress the premix by vibration (knock compression).

Subsequently, unless compound A is already mixed with the off is present, coated with it and mixed with compound B. After expiration the reaction becomes a break-stable molded body without the action of pressure or temperature receive.

If one of the compounds A or B is a gas, a preform may e.g. B. with this ver be set so that the gas flows through it. This procedure enables one uniform hardening of the molded body within a short time.

In a further process variant, a preform is placed in an atmosphere of reactive Gases introduced. This variant is easy to carry out. It is possible to use molded articles to produce a hardness gradient, d. H. Shaped body that is just a harder one Surface to shaped bodies that are fully hardened.

A preform or the premix can also be pressurized with the reactive gas be implemented. This process variant has the advantage that the surface is quick cures to form a hard shell, the curing process already stopped here or, as described above, via increasing hardening levels fully cured molded articles can be produced.

The above process variants can also be combined by going to next reactive gas flows through the preform to displace air. subsequently, The preform is then exposed to a gas atmosphere at normal pressure. Through the reaction  between the gas and the second component, gas is automatically in the mold sucked in.

In one possible embodiment of the present invention, the output is not mix but a preform already formed with the compound A be layers and then reacted with compound B. It hardens itself layer on the surface of the preform, while in the core the loose or slightly compacted structure is retained. Such moldings are characterized by particularly good decay behavior.

Unpressed molded articles can also be produced by casting. This is either which can be influenced by the choice of the starting materials, or by suspending the ge to achieve the desired ingredients in a meltable matrix.

The solidification of solutions with ambient temperature is also a way to produce non-pressed molded articles. Aqueous solutions can be prepared according to the state of the art Technique known by adding thickeners to cut-resistant molded articles be thickened. Examples of such thickeners that form solid jellies are Alginates, pectins, gelatin, etc.

Suitable for the production of gelatinous, dimensionally stable, non-compressed molded bodies from aqueous or non-aqueous solutions are preferred polymeric thickeners. These too Organic high-molecular substances called swelling agents that soak up liquids genes, swell and finally convert into viscous real or colloidal solutions hen, come from the groups of natural polymers, the modified natural Polymers and the fully synthetic polymers.

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

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

A large group of thickeners, widely used in the different The most common fields of application are the fully synthetic polymers such as polyacrylic and Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, poly amides and polyurethanes.

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

Shaped bodies that are produced by using thickeners preferably contain as a thickener 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular dere 0.4 to 1.5 wt .-%, a thickener, particularly preferably a polysaccharide.

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

Xanthan can be described by the following formula:

Preferred molded articles produced by non-pressing processes contain as Ver Thickeners, based in each case on the total average, 0.2 to 4% by weight, preferably 0.3 up to 3% by weight and in particular 0.4 to 1.5% by weight, xanthan.

Other suitable thickeners are polyurethanes or modified polyacrylates usually, based on the total non-compressed portion, in amounts of 0.2 to 5% by weight be used.

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

in which R ^{8 represents} a low molecular weight or polymeric diol radical, R ^{9 represents} an aliphatic or aromatic group and n represents a natural number. R ⁸ is preferably a linear or branched C _2-12 -alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula IV in that the radical R ⁸ further -O-CO-NH groups are bound.

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

Commercial polyurethane-based thickeners are, for example, under the Na men Acrysol®PM 12V (mixture of 3-5% modified starch and 14-16% PUR resin in Water, Rohm & Haas), Borchigel® L75-N (non-ionic PU dispersion, 50% in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol, Henkel-Nopco), Verdic ker QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.

Preferred molded articles produced by non-pressing processes contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight of a polyu Rethans.

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

in which R ^{10 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ¹² or O, R ^{11 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl residue, R ^{12 stands} for H or R ¹¹ and n stands for a natural number. Such modified polyacrylate esters or amides of acrylic acid or a substituted acrylic acid are common. Preferred among these polymers are those in which R ^{10 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ¹² ), both single (R ¹² = H) and double (R ¹² = R ¹¹ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another can be selected from optionally alkoxylated branched or unbranched C _8-22 alk (en) yl radicals. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, degrees of alkoxylation between 10 and 15 being particularly preferred.

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

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

in which R ^{13 is} a preferably unbranched, saturated or unsaturated C _{8-22 -alk} (en) yl radical, R ¹⁴ and R ¹⁵ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number Number between 2 and 30, preferably between 10 and 20. R ¹³ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol preferably being ethoxylated (R ¹⁵ = H).

Products of the formula VIa are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% by weight dispersions in water. In the mentioned commercial product, R ^{13 represents} a stearyl radical, R ¹⁴ is a hydrogen atom, R ¹⁵ is H or CH ₃ and the degree of ethoxylation a is 20.

Preferred molded articles produced by means of non-pressing processes contain on the entire molded body 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and esp in particular 0.5 to 1.5% by weight of a modified polyacrylate of the formula VI.

In a further preferred embodiment of the present invention, the Shaped bodies are produced by curing formable masses, which by molding Exercise procedures were previously brought into the desired shape.

The deformable mass (es) can be hardened by different mechanisms follow, whereby the time-delayed water binding, the cooling below the melting point, evaporation of solvents, crystallization, by chemical reaction (s), ins special polymerization and the change in rheological properties such. B. by changed shear of the mass (es) as the most important hardening mechanism besides the already radiation curing by UV, alpha, beta or gamma rays or microwaves are to be mentioned.  

In this preferred embodiment, a deformable, preferably plastic, Mass produced that can be shaped without great pressure. After shaping processing then takes place by suitable initiation or Ab wait a certain period of time. Masses are processed without further initiation have self-curing properties, this must be taken into account when processing, for hardening during the shaping process and thus blockages and disturbances to avoid procedural changes.

The curing of in the context of the present invention preferably by non-pressing Transmitting processes produced takes place by delayed water binding.

The time-delayed water binding in the masses can in turn be below can be realized in different ways. For example, there are masses that hy derivable, water-free raw materials or raw materials in low hydration levels, which in stable higher hydrates can pass as well as contain water. The formation of the hy drate, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to hardening of the masses. A shaping processing with low pressures After that, ken is no longer possible, and there are shaped articles which are stable in handling and which if necessary, can be further processed and / or packaged.

The time-delayed water binding can also take place, for example, by salts containing hydrate water that form in their own water of crystallization when the temperature rises solve, incorporated into the masses. If the temperature drops later, the crystal water becomes tied again, resulting in a loss of formability with simple Means and leads to a solidification of the masses.

The swelling of natural or synthetic polymers as time-delayed water Binding mechanism can be used in the context of the inventive method. Here Mixtures of unswollen polymer and suitable swelling agent, e.g. B. water, Diols, glycerin, etc., are incorporated into the masses, with swelling and curing after the shaping.  

The most important mechanism of hardening by delayed water binding is that Use a combination of water and water-free or low-water raw materials that last long hydrate sam. For this purpose, there are in particular substances that are in the cleaning pro contribute to cleaning performance. In the process of the invention be Preferred ingredients of the deformable materials are, for example, phosphates, car bonates, silicates and zeolites.

It is particularly preferred if the hydrate forms formed have low melting points have, because in this way a combination of the curing mechanisms by in drying and cooling is achieved. Preferred processes are characterized thereby characterized in that the deformable mass (es) 10 to 95 wt .-%, preferably 15 to 90 wt .-% %, particularly preferably 20 to 85 wt .-% and in particular 25 to 80 wt .-% anhydrous Contain substances, which by hydration into a hydrate form with a melting point below 120 ° C, preferably below 100 ° C and in particular below Go over 80 ° C.

The deformable properties of the masses can be increased by adding plasticizer auxiliaries such as polyethylene glycols, polypropylene glycols, waxes, paraffins, non-ioni tensides etc. are influenced. Further information on the substance class mentioned can be found below.

Another mechanism for curing the process in the inventive method Masses in the cooling process when processing the masses is above their expanse chung neutralization point. Process in which the hardening of the deformable mass (s) by Cooling below the melting point is preferred.

Masses softenable under the influence of temperature can be easily assembled, in which the desired further ingredients with a meltable or softenable substance mixed and the mixture at temperatures in the softening range of this substance warms and is shaped at these temperatures. Particularly preferred waxes, paraffins, polyalkylene are used as meltable or softenable substances glycols etc. used. These are described below.  

The meltable or softenable substances should have a melting range (Solidification range) in such a temperature range at which the others Ingredients of the masses to be processed are not exposed to excessive thermal stress become. On the other hand, however, the melting range must be sufficiently high to be too to provide a manageable molded body at least slightly elevated temperature. In Compositions preferred according to the invention have the meltable or softenable substances a melting point above 30 ° C.

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

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances that usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as Beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin wax or micro wax.  

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. As meltable or softenable substances for the through Compounds made of other materials can also be used as cooling-curing compositions Classes of substances that meet the requirements for the softening point. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic waxes made from lower are also suitable Carboxylic acids and fatty alcohols, for example Dimyristyl Tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or Semi-synthetic esters from lower alcohols with fatty acids from native sources can be used. In this class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), is also usable according to the invention as meltable or softenable substances.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols come in the form of wax esters of higher molecular fatty acids, for example (Wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The The solid particles coated according to the invention can optionally also be coated Wool wax alcohols, including triterpenoid and steroid alcohols, for example Lanolin, understands that, for example, under the trade name Argowax® (Pamentier & Co) is available. Also at least partially as part of the meltable or softenable Substances can be used in the context of the present invention, fatty acid glycerol esters or Fatty acid alkanolamides but also water-insoluble or only slightly water soluble polyalkylene glycol compounds.

Particularly preferred meltable or softenable substances in those to be processed Masses are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols  (PPG) contains, with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with Molar masses from 3000 to 5000 are particularly preferred. Appropriate procedure Ren, which are characterized in that the plastically deformable mass (es) minde least a substance from the group of polyethylene glycols (PEG) and / or polypropylene glycol cole (PPG) contains / are preferred. Here are to be processed according to the invention Tending masses particularly preferred, the only meltable or softenable substances Contain propylene glycols (PPG) and / or polyethylene glycols (PEG). These substances were described in detail above.

In a further preferred embodiment, they contain according to the invention processing masses in the majority of paraffin wax. That is, at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (related on the total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight are particularly preferred. In a particular embodiment of the invention the total amount of meltable or softenable substances used at least one Made exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline detergent environment there is no hydrolysis of the waxes (as is the case, for example, with the wax esters is to be expected), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residue usually and should result in an unsightly appearance on the cleaned surface therefore be avoided.  

Masses to be processed preferably contain as meltable or softenable substances at least one paraffin wax with a melting range of 50 ° C to 60 ° C, before drafted processes are characterized in that the deformable mass (es) is a paraf contains / contain wax with a melting range of 50 ° C to 55 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing share of solid wax components increase the resilience of the process end products Impacts or friction on other surfaces, resulting in longer-lasting protection leads. High levels of oils or liquid wax components can weaken them lead the shaped body or of areas of the shaped body, whereby pores are opened and the active substances are exposed to the environmental influences mentioned at the beginning.

In addition to paraffin, the meltable or softenable substances can also be the main constituent contain one or more of the above-mentioned waxes or wax-like substances. In Another preferred embodiment of the present invention should Mixture forming meltable or softenable substances must be such that the mass and the molded body formed therefrom or a component thereof at least largely are insoluble in water. The solubility in water should be at a temperature of around 30 ° C Do not exceed 10 mg / l and are preferably below 5 mg / l.

In such cases, however, the meltable or softenable substances should, if possible have low water solubility, even in water at an elevated temperature, in order to temperature-independent release of any active substances contained, if possible largely avoided.

Preferred masses to be processed according to the invention are characterized in that as meltable or softenable substances, one or more substances with a melt range from 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight  and in particular from 10 to 20 wt .-%, each based on the weight of the Mass, included.

Another mechanism by which the masses can harden is the Ver evaporation of solvents. For this purpose, solutions or dispersions of the desired ingredients in one or more suitable, volatile solvents are, the solvent after the shaping processing step give and harden. Lower alkanols, for example, are suitable as solvents, Aldehydes, ethers, esters, etc., their selection depending on the further composition of the processing masses is made. Particularly suitable solvents for such Processes in which the deformable mass (s) are cured by evaporation of Solvents, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-pro panol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1- Hexanol and the acetic acid esters of the above-mentioned alcohols, especially Es sigsäureethylester.

The evaporation of the solvents mentioned can by the shape and Ab elongation subsequent heating, or accelerated by air movement. Also Combinations of the measures mentioned are suitable for this, for example the attachment the preformed shaped body with warm or hot air.

Another mechanism that forms the hardening of the shaped bodies or parts thereof The basis for processed masses is crystallization. Procedure at which harden the deformable mass (s) by crystallization are also prefers.

Crystallization as the mechanism underlying curing can be used for example by melting crystalline substances as the basis of one or more serve formable masses. Such systems go in after processing a higher order state, which in turn to harden the entire gebil leads the molded body. However, crystallization can also be carried out by crystallization supersaturated solution. Supersaturation is within the scope of the present invention  the term for a metastable state in which in a closed System has more of a substance than is required for saturation. One at for example, supersaturated solution obtained by hypothermia contains more dissolved Most substance than it should contain in the thermal equilibrium. The excess of dissolved Substance can be inoculated with germs or dust particles or by shaking the System for instantaneous crystallization. As part of the present Invention, the term "oversaturated" always refers to a temperature of 20 ° C. To solve in a certain solvent at a temperature of 20 ° C × from a substance Grams in liters, the solution in the context of the present invention is considered to be "oversaturated" designate if it contains (x + y) grams of the substance in liters, where y <0 applies. So are in Within the scope of the present invention, solutions are also referred to as "oversaturated", which are associated with serve as the basis of a mass to be processed and at this temperature can be processed at which there is more of a dissolved substance in the solution than would dissolve in the same amount of solvent at 20 ° C.

The term "solubility" in the present invention means the maximum amount of one Substance that the solvent can absorb at a certain temperature, d. H. the Proportion of the solute in a solution saturated at the temperature in question. A solution contains more solute than it does at a given temperature in ther should contain dynamic equilibrium (e.g. with hypothermia), that is what they are called oversaturated. By inoculating with germs can cause the excess as a soil by which now only saturated solution fails. One saturated in terms of a substance However, the solution can also dissolve other substances (e.g. one can use a saturated one Saline solution dissolve sugar).

The state of supersaturation can, as described above, be reduced slowly cool or achieve by subcooling a solution as long as the solute in the sol solvent is more soluble at higher temperatures. Other ways to be littered solutions, for example, are combining two solutions, their React ingredients to another substance that does not fail immediately (prevented or delayed precipitation reactions). The latter mechanism is the basis of the bil Formation of masses to be processed according to the invention is particularly suitable.  

In principle, the state of supersaturation can be achieved with any type of solution, albeit the application of the principle described here in the manufacture of Detergents and cleaning agents are used. As a result, some systems are principally tend to form supersaturated solutions, use less well according to the invention bar, since the underlying substance systems are ecological, toxicological or economically reasons cannot be used. In addition to non-ionic surfactants or all Non-aqueous solvents are therefore methods according to the invention with the last mentioned curing mechanism is particularly preferred, in which as a basis min at least one mass to be processed is a supersaturated aqueous solution.

As mentioned above, the state of supersaturation relates to the present invention on the saturated solution at 20 ° C. By using solutions conditions that have a temperature above 20 ° C, the state of supersaturation can be easily reached. Processes according to the invention in which the crystallization hardening mass during processing a temperature between 35 and 120 ° C, before preferably between 40 and 110 ° C, particularly preferably between 45 and 90 ° C and esp in particular between 50 and 80 ° C, are within the scope of the present invention vorzugt.

Since the moldings produced are generally neither stored at elevated temperatures even later applied at these elevated temperatures, the cooling of the Mixture to precipitate the proportion of solute from the supersaturated solution, the was in the solution above the saturation limit at 20 ° C. The supersaturated Solution can thus cool down into a saturated solution and a soil body divide. But it is also possible that by recrystallization and hydration phenomena the supersaturated solution solidifies upon cooling to a solid. For example, this is the case when certain hydrated salts are in their crystal water when heated dissolve it. When cooling, supersaturated solutions are often formed here, which are caused by mechani influence or germ addition to a solid - the water containing salt as the thermodynamically stable state at room temperature - solidify. This is known Phenomenon of, for example, sodium thiosulfate pentahydrate and sodium acetate trihydrate, in particular the latter salt containing hydrate water in the form of the supersaturated Solution can be used advantageously in the inventive method. Also special ingredients,  such as phosphonates, show this phenomenon and are suitable in form of the solutions excellent as a granulation aid. For this, the corresponding Phosphonic acids (see below) are neutralized with concentrated alkali lye, whereby the Solution heated up by the heat of neutralization. When cooling down, these solids form solutions solids of the corresponding alkali phosphonates. By incorporating further In Contents in the still warm solutions can be processed according to the invention produce different compositions. Particularly preferred fiction Moderate processes are characterized in that the as the basis of the curing Mass serving supersaturated solution solidified at room temperature to a solid. Be It is preferred that the previously supersaturated solution becomes a solid after solidification by heating to the temperature at which the supersaturated solution was formed, cannot be converted back into a supersaturated solution. This is for example at the phosphonates mentioned.

The supersaturated solution serving as the basis of the hardening mass can - as before mentioned above - received in several ways and then after optional addition further ingredients are processed according to the invention. An easy way is at for example in that the supersaturated serving as the basis of the hardening mass Solution is made by dissolving the solute in heated solvent. In this way, higher amounts of the solute are in the heated solvent solved than would dissolve at 20 ° C, is one in the sense of the present invention supersaturated solution that is either hot (see above) or cooled and in the metastable Condition can be added to the mixer.

It is also possible to dehydrate salts containing hydrate by "dry" heating and dissolve in your own crystal water (see above). This is also a method in To produce usable supersaturated solutions within the scope of the present invention.

Another way is to use a gas or a non-supersaturated solution to add further liquid or solution so that the solute in the solution a poorly soluble substance reacts or is in the mixture of solvents worse solves. The combination of two solutions, each containing two substances, which reacting with each other to form a poorly soluble substance is also a method of  Preparation of supersaturated solutions as long as the poorly soluble substance is not instantaneous fails. Methods which are likewise preferred in the context of the present invention are there characterized in that the serving as the basis of the hardening mass littered is made by combining two or more solutions. examples for such ways to make supersaturated solutions are discussed below.

Preferred methods according to the invention are characterized in that the supersaturated aqueous solution by combining an aqueous solution of one or more acidic In substances, preferably from the group of surfactant acids, builder acids and Complexing acids, and an aqueous alkali solution, preferably an aqueous alka Iihydroxidlösung, in particular an aqueous sodium hydroxide solution, is obtained.

Among the representatives of the connection classes mentioned above the phosphonates in particular take one out in the context of the present invention protruding position. In preferred methods according to the invention, the is therefore littered Taken aqueous solution by combining an aqueous phosphonic acid solution with Konzentra ions above 45 wt .-%, preferably above 50 wt .-% and in particular above 55 wt .-%, each based on the phosphonic acid solution and an aqueous sodium hy hydroxide solution with concentrations above 35% by weight, preferably above 40% by weight and in particular above 45% by weight, based in each case on the sodium hydroxide solution, receive.

According to the invention, the deformable mass (es) can also be cured by chemical means Reaction (s), in particular polymerization, take place. In principle, all are chemical Suitable reactions starting from one or more liquid to pasty substance lead to solids by reaction with another substance (s). In particular che There are mixed recations that do not suddenly lead to the state change mentioned at suitable. From the variety of chemical reactions that lead to the solidification phenomenon, reactions are particularly suitable in which the construction of larger molecules from small ones ren molecules takes place. Again, this preferably includes reactions in which many small ones React molecules to a larger molecule (s). These are so-called polyreactions (Polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding  Polymers, polyadducts (polyadducts) or polycondensates (Po lycondensation products) then give the finished molded articles their strength.

Another molded body that is preferably used has a plate-like or sheet-like structure with alternating thick long and thin short segments, so that individual segments from this "bolt" at the predetermined breaking points, which represent the short thin segments, can be broken off and placed in the hollow body. This principle of "Bar-shaped" shaped detergent can also be used in other geometric shapes, For example, vertical triangles that are only along one side of their sides are interconnected, can be realized.

Claims (8)

1. A process for the manual cleaning of hollow bodies using cleaning-active substances, characterized in that the cleaning-active substances are used in the form of compressed moldings. 2. The method according to claim 1, characterized in that it is in the presence of Water is carried out. 3. The method according to claim 1 or 2, characterized in that the water and Shaped bodies are placed in the hollow body and one over a period of time from a few minutes to several hours. 4. The method according to claim 3, characterized in that the exposure time up to Is 24 hours. 5. The method according to any one of claims 1 to 4, characterized in that the cleaning-active substances are selected from tensides, builders, Bleaching agents, bleach activators, enzymes, antimicrobial agents and any Mixtures of the foregoing. 6. The method according to claim 5, characterized in that the Total surfactant content of the moldings used according to the invention below 5% by weight, particularly preferably below 4% by weight, and in particular below of 2% by weight, based in each case on their total weight. 7. The method according to any one of claims 1 to 6, characterized in that as other ingredients disintegration aids, shower systems, dyes, fragrances, Antioxidants, foam inhibitors, silicone and / or paraffin oils are included. 8. The method according to any one of claims 1 to 7, characterized in that the Shaped body using pressing processes, such as tableting, or non-pressing  Processes such as sintering, casting, hardening of deformable masses as well as by Granulation, pelleting, extrusion, agglomeration, etc. is produced.