DE10125565A1 - Production of amorphous materials, useful for producing granules of e.g. dishwashing detergent containing active substances, comprises grinding materials under drying conditions - Google Patents

Abstract

Process (A) for producing amorphous materials comprises grinding materials under drying conditions. Independent claims are also included for the following: (1) a process (B) for producing granules containing active substances, in which one or more carriers are amorphized and then loaded with one or more active substances and granulated; (2) granules containing active substances, comprising one or more amorphized carriers.

Description

The present invention relates to a method for producing highly absorbent (carrier ) Materials that as such have a variety of uses. In another version The present invention relates to a method for producing active substance-containing substances Granules in which these (carrier) materials are used.

When producing many products, the problem arises that moist, sticky substances are processed must be processed, but the finished product should not have this property. Also in an Their areas of application, for example cosmetics, are the treatment of surfaces with State of the art moisture binding agents. For these and other areas of application there is a need for substances which have a high adsorption or absorption capacity and are based on this way suitable as carrier materials in granulation processes or as powdering agents etc.

Many carrier materials known from the prior art have to be used as Powder or carrier are converted into the finest possible form. The necessary for this Milling operations convert crystalline substances into amorphous powders, which are then distinguish higher absorption capacity. Unfortunately, such amorphized (carrier) materials cannot be stored arbitrarily, since recrystallization phenomena often appear. It also occurs in the situation tion - e.g. T. accompanied by recrystallization processes - a clumping in the silo instead of the Agglomerate formation tendency and hygroscopicity of the ground materials can be attributed. The The complications mentioned increase further with decreasing grain size. On Another problem can be that the capacity of the conventional grind Although substances for liquid to pasty substances have been increased, the rate of absorption is clearly too slow for these substances. This leads to extended production times towards the impossibility of realizing industrial scale.  

The object of the present invention was now to provide finely divided (carrier) materials to deliver which can be stored without clumping or losing their absorption capacity. Zusätz Lich, the materials to be provided should have highly absorbent properties and have a high absorption rate for liquid to pasty substances.

Another object of the present invention was to provide a granulation process rens, which enables the production of granules containing highly active substances.

It has now been found that the grinding with simultaneous drying is amorphous (carrier ) Supplies materials which are characterized by the above-mentioned and desired positive properties distinguish.

A first subject of the present application is therefore a process for producing amor pher (carrier) materials, in which the (carrier) material (s) under drying conditions be ground.

In contrast to conventional grinding processes in the process according to the invention Grist already dried during grinding. The drying conditions can be through technical measures such as working in heated mills, the use of infrared blasting or blowing hot air (hereinafter sometimes referred to as hot air) realize.

All materials that are ground and used in fine particles can be considered as regrind should. Depending on the type of industry for which the regrind is used should, the products of the process according to the invention can be used as support materials for use the following granulations or agglomerations, or as binders, powdering agents etc. - some examples of such ground products are powdered sugar, industrial powdering agents, kosme table powder without allergenic emulsifiers, oil binding agents, mold release agents, fire extinguishing powder etc.

The end products of the process according to the invention are preferably by the Invention appropriate methods to particle sizes in which 95 wt .-% of the particles smaller than 50 µm, preferably less than 20 µm.

The amorphous (carrier) materials produced by the process according to the invention are Stable without clumping and can be handled in seconds with liquid to pasty media be loaded, whereby they bind to silage-compatible compounds.

Further details on the method according to the invention are given in the explanations below Find out where the process is part of a granulation process.  

A particularly preferred area of application for the amorphous (carrier) materials is the one set as carrier material in agglomeration or granulation. Because these substances are characterized by high Characterize absorption or adsorption capacity, granulation liquids are excellent apply them and thus produce storage-stable and easily ensileable granules. It does not have to Total amount of the carrier material have been amorphized according to the invention, the advantageous Properties can also be achieved if only some of the solids to be granulated was subjected to the amorphization process according to the invention.

Another subject of the present application is therefore a process for the production of Granules containing active substance, in which one or more carrier material (s) amorphizes and then acted upon with active substance (s) and granulated.

The amophization of carrier materials occurs either according to the above be described methods according to the invention or by other methods for amorphization, for example by ultrasonic or shock wave techniques. However, the first is preferred hend described method to use for amorphization, so that Granu invention lationsverfahren for the production of active substance-containing granules are preferred, in which grind and then one or more carrier material (s) under drying conditions be loaded with active substance (s) and granulated.

As already mentioned, the total amount of the support materials need not be amorphized; mixtures of amorphous and crystalline support materials can also be used. Another object of the present invention is therefore a process for the production of granules containing active substance, which by the steps

• a) grinding one or more carrier material (s) under drying conditions;
• b) optional mixing of the ground material formed in step a) with further solids;
• c) Mixing the ground material formed in step a) or the Mi obtained in step b) creation with one or more active substance (s);
• d) granulation of the mixture obtained in step c) with optional addition of granules onshilfsmitteln

is marked.

Carrier materials that can preferably be amorphized also have their own be able to form inclusion compounds. Such substances are particularly suitable It is also good as a powder, carrier material, etc., because the molecular structure of these substances is hollow has spaces or channels in which other substances can be stored well, quickly and permanently can. A particularly preferred process variant therefore provides that that or at least one of the carrier material (s) is selected from the group of substances which form a final connections are suitable.  

Among the substances capable of clathrate formation is again a group of substances in the Particularly preferred within the scope of the present invention. These substances have a molecular one Structure that they have in the amorphized state especially to accommodate the in most industri The current process enables common liquid to pasty substances. More preferred methods are therefore characterized in that the or at least one of the carrier material (ien) out is selected from the group urea, thiourea, amylose, perhydrotriphenylene, zinc hydroxide as well as the montmorillonite and / or cyclodextrins.

The urea which can be used according to the invention is the diamide of carbonic acid, which is sometimes also referred to as carbamide and can be described by the formula H ₂ N-CO-NH ₂ . Urea forms colorless, odorless crystals with a density of 1.335, which melt at 133 ° C. Urea is soluble in water, methanol, ethanol and glycerin with a neutral reaction.

The production of urea can be carried out by evaporation of an aq solution of ammonium cyanate or in the laboratory by exposure to ammonia Phosgene, chloroformate, urethane or carbonic acid diester according to the usual acid mid-synthesis. Technically, urea is made from carbon dioxide and ammonia via ammonia umcarbamat, which at 135-150 ° C and 35-40 bar in the presence of three times the amount of ammonia Urea passes over. Under these conditions, the hydrolysis taking place as a side reaction suppresses the ammonium carbamate in ammonium carbonate or ammonia and carbon dioxide.

Thiourea, H ₂ N-CS-NH ₂ , is available in the form of colorless, rhombic prisms with a density of 1.40. Thiohranstoff does not have a real melting point, since it rearranges relatively quickly to ammonium thiocyanate from 135 ° C. When heated quickly, the melting point. Found 180 ° C. Thiourea is soluble in polar protic and aprotic solvents such as water, alcohol, dimethylformamide, dimethyl sulfoxide and others, insoluble in non-polar solvents.

Amylose is the component of the starch coated with amylopectin, the amylose content of which is approx. Is 20-30%. Amylose is water-soluble and gives a characteristic with iodine-potassium iodide solution blue coloration due to the formation of inclusion compounds. In the molecule Amylose differs from amylopectin by its unbranched structure, the one Degradation to oligosaccharides permitted by both α- and β-amylase and by the schrau ben-shaped conformation ver for the formation of inclusion compounds with alcohols etc. is answerable. The average molecular weight is 50,000-150,000 daltons.

Perhydrotriphenylene (octadecahydrotriphenylene) is the fully saturated derivative of triphe nylens, which can exist in various stereoisomeric forms, depending on the type of linkage four cyclohexane rings. The trans-anti-trans-anti-trans compound has a melting point of 124 ° C; the (all-S) form can be separated from the enantiomeric (all-R) form by racemate separation  become. Perhydrotriphenlylene is able to form channel inclusion compounds with carboxylic acids, Form alcohols, ketones etc.

Zinc hydroxide has 6 different crystalline modifications, of which only the colorless rhombic. ε-Zn (OH) ₂ is stable in equilibrium with water below 39 ° C. The compound is formed by precipitation from zinc salt solution with the calculated amount of alkali or ammonia as an amorphous precipitate, which slowly converts to the crystalline form.

Montmorillonites are clay minerals belonging to the dioctahedral smectites, which are described by the general formulas Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O and Al ₂ O _3. 4SiO ₂ .H ₂ O.nH ₂ O, respectively to let. These substances are predominantly white, gray-white to yellowish, completely amorphous, slightly friable, swelling in water but not becoming plastic. The layer packs in the three-layer structure of the montmorillonite can be reversible storage of water (in 2-7 times the amount), among other substances such. As alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy aluminosilicate ions, etc. swell; Montmorillonites make a significant contribution to soil fertility due to their ability to bind water, to provide inclusion compounds and cations useful in plant physiology.

In addition to the substances already mentioned, hydroquinone is also suitable, for example. hydroquinone comes in the form of colorless needles or prisms with a density of 1.33 and a melting point of 173-174 ° C in the trade. It sublimes without decomposing and boils at 285-287 ° C, is somewhat soluble in water, easily soluble in hot water, alcohol, ether and benzene.

Hydroquinone is usually produced via 1,4-benzoquinone ("quinone"), which is produced by oxidation of aniline and (without isolating it) reduced with iron and water at 50-80 ° C. Other processes are the air oxidation of 1,4-diisopropylbenzene; phenol oxidation with peroxycarboxylic acids or H ₂ O ₂ and mineral acids; the Reppe hydroquinone process, where hydroquinone is obtained directly from C ₂ H ₂ , CO and H ₂ O in the presence of catalysts.

The carrier materials can be ground to any particle size, the Mahlpro zess in step a) is preferably adjusted to achieve fine particle sizes. Here are Process according to the invention preferred, in which the carrier material (s) in step a) to average grain sizes <200 µm, preferably <100 µm, particularly preferably <50 µm and in particular <25 µm, are ground.

The grinding can take place in all efforts known in the prior art, single Lich example, pin mills, impact mills and air jet mills listed as suitable equipment become. Particularly preferred methods are characterized in that the grinding under drying conditions in an impact mill.  

According to the invention it is essential to adhere to drying conditions during the grinding process zesses. Under "drying conditions" is ver in the context of the present invention stood that the regrind is dried simultaneously during grinding, d. H. that the Water content of the regrind (can be determined, for example, as a loss on drying or according to Karl Fischer) decreases at the same time as the particle size is reduced.

According to the invention, the drying conditions can be achieved, for example, by - As already mentioned above - technical measures such as working in heated mills, the Use of infrared heaters or blowing hot air. Especially blowing hot air into the mills for carrying out the method is preferred step a), so that preferred methods are characterized in that the drying Be conditions in the grinding can be realized by blowing hot air. Here are sol che process variants preferred, in which the temperature of the hot air 25 to 200 ° C, preferred as 30 to 150 ° C and in particular 40 to 120 ° C.

After grinding, additional substances can be added to the regrind [step b) Procedure]. Mixtures of different materials can of course already be used in step a) are ground, provided the substances used survive the grinding process undamaged. Substances that could lose positive properties in the grinding process, or their use in fine particles ger form is not desired, are then preferably added in process step b). But substances which have already been pre-ground can also be added before or after process step a). This can be advantageous, for example, if these substances are ground together with the carrier materials is not desired, or if these substances are already in their delivery form are very finely divided and no longer need to be ground. For example, are invented Processes according to the invention are preferred in which the regrind formed in step a) is used in step b) Flow aids, preferably with finely divided silica, in amounts of 0.01 to 5% by weight preferably from 0.05 to 2% by weight and in particular from 0.1 to 0.5% by weight, in each case based on the mixture of regrind and flow aids is mixed.

Other substances that are added to the millbase in step b) of the process according to the invention that are, in particular, builders. These builders preferably come from the Groups of zeolites, silicates, carbonates, hydrogen carbonates, phosphates and polymers.

Alkali metal phosphates is the summary term for the alkali metal (especially 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, very easily soluble in water powder, which lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trime taphosphate (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 a pH of 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 light 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 set that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, and as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (accordingly 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-phase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 has a melting point of 1340 ° and is readily 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). In the case of substances, there are colorless crystals which 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 dehydrating 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. A large number of terms are used in particular for the latter: melt or glow phosphates, graham salt, Kurrol's and Maddrell's salt. 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 a non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O], which is water-free or crystallizes with 6 H ₂ O _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 60 ° approx. 20 g, at 100 ° around 32 g of the water free of crystal water; 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% 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 + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these phosphates are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tri polyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium Potassium tripolyphosphate can be used according to the invention.

Other ingredients that are mixed with the regrind instead of or in addition to phosphates can be, are carbonates and / or hydrogen carbonates, the alkali metal salts and especially the potassium and / or sodium salts are preferred. Carbo are preferred here nat (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably natri  umcarbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular dere from 10 to 30 wt .-%, each based on the mixture from step b).

Other ingredients instead of or in addition to the phosphates mentioned and / or Carbonates / bicarbonates can be admixed in step b) are silicates, the Alkali metal silicates and especially the amorphous and / or crystalline potassium and / or Sodium disilicates are preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H 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. 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 Na ₂ O: SiO ₂ modulus from 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. which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amor phen sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / 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-rays, 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 in such a way that the products have microcrystalline ranges 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 compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

Preferred silicate (s) in the context of the present invention are alkali silicates, especially before adds crystalline or amorphous alkali disilicates, in amounts of 3 to 60% by weight, preferably of 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass of Mixture from step b)

Substances from the group of zeolites are also suitable as an important component for admixing in step b). 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 coolly occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. Depending on the type of zeolite, the intercrystalline "zeolitic" water can be released continuously and reversibly, while for some types of zeolite structural changes are also associated with the water release or absorption.

In step c) of the process according to the invention, the ground material obtained in step a) or in Step b) the mixture obtained is mixed with active substance. The same applies to solid active substances according to the above, d. H. in principle, the active substance can also be ground, provided that it is not damaged in the grinding process. In the case of non-solid active substances, step d) - the granulation - take place together with step c) by mixing under agglomerating the conditions. This procedure is available, for example, for liquid to pasty sen active substances, which can then serve as a granulating liquid. Particularly preferred Processes according to the invention are therefore characterized in that the or at least one the active substance (s) is selected from the group of surfactants, fragrances, foam inhibitors or non-aqueous solvents.

The surfactants include in particular the anionic surfactants in acid form, aqueous solutions or Pastes of the neutralized anionic surfactant acids, nonionic surfactants and / or cationic surfactants or amphoteric surfactants.

One or more substances from the group of the car are preferred as anionic surfactants in acid form bonic acids, the sulfuric acid half-ester and the sulfonic acids, preferably from the group of Fatty acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids used. To be enough The compounds mentioned should have suitable surface-active properties have longer-chain hydrocarbon radicals, i.e. at least 6 in the alkyl or alkenyl radical Have carbon atoms. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carbon acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. Be preferred in the context of the present compound the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexotonic acid (melotonic acid), hexotonic acid (melotonic acid), as well as the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaiidic acid), 9c, 12c-octadolic acid) , 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreinsä For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as can be obtained from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6% by weight C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _{18 '} , 3 wt% C _18'' , 1 wt% C _18''' ), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C _{18 '} ), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 ''} , 0.5% by weight % C _{18 '''),} technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight of C ₁₆ , 5% by weight of C ₁₈ , 25% by weight of C _{18 '} , 45% by weight of C _18'' , 7% by weight of C _18''' ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention. Your alkali metal, especially sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids in question and subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most important industrial process in terms of quantity for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that can be used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, differ in comparison to the alkyl sulfates due to its higher water solubility and lower sensitivity to water hardness Characterize (solubility of Ca salts). Alkyl ether sulfuric acids are like the alkyl sulfur Acids synthesized from fatty alcohols, which with ethylene oxide to the fatty alcohols concerned  thoxylates are implemented. Instead of ethylene oxide, propylene oxide can also be used the. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfation reactors provides yields over 98% of the alkyl ether sulfuric acids concerned.

Alkanesulfonic acids and olefin sulfonic acids are also within the scope of the present invention Anionic surfactants can be used in acid form. Alkanesulfonic acids can terminal the sulfonic acid group bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulf fonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins with sulfur dioxide and chlorine are added under Be radiation with UV light converted to the corresponding sulfochlorides, which with hydrolysis Alkali directly the alkanesulfonates, when reacting with water the alkanesulfonic acids. There in the sulfochlorination di- and polysulfochlorides as well as chlorinated hydrocarbons as a side pro products of the radical reaction can occur, the reaction is usually only up to Um Settlements of 30% carried out and then canceled.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins can be reacted with sulfur dioxide and oxygen under irradiation with UV light. At this Radical reactions result in successive alkylsulfonyl radicals that carry oxygen to the alkyl persul fonylradiaklen continue to respond. The reaction with unreacted paraffin gives an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical falls. The reaction of the two radicals with unreacted paraffin gives the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. Around the yield of the two end products, alkyl sulfonic acid and sulfuric acid, is as high as possible hold and suppress side reactions, this reaction is usually only up to implementation degrees of 1% and then terminated.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis) these sultones react to Hy droxylalkanesulfonic acids or alkenesulfonic acids, both of which are also anionic surfactants can be used.

Alkylbenzenesulfonates as powerful anionic surfactants have been ours since the 1930s Century known. At that time, monochlorination of kogasin fractions and sub Sequential Friedel-Crafts alkylation prepared alkylbenzenes that sulfonated with oleum and with Na tron lye were neutralized. In the early 1950s, alkylbenzene was manufactured sulfonate propylene tetramerized to branched α-dodecylene and the product over a Friedel Crafts reaction using aluminum trichloride or hydrogen fluoride to the tetrapro  implemented pylenebenzene, which was subsequently sulfonated and neutralized. This economic Possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough This class of surfactants, hereinafter the soaps as the main surfactant in detergents and cleaning agents displaced.

Due to the lack of biodegradability of TPS, there was a need for new ones To represent alkylbenzenesulfonates, which are characterized by an improved ecological behavior to draw. These requirements are met by linear alkylbenzenesulfonates, which today are almost exclusively manufactured alkylbenzenesulfonates and with the abbreviation ABS or LAS can be occupied.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are made from linear olefins are accessible. For this purpose, petroleum fractions with molecules are used on an industrial scale larseven separated into the n-paraffins of the desired purity and dehy to the n-olefins driert, resulting in both α- and i-olefins. The resulting olefins are then in In the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear Alkylbenzenes has: When using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, becomes fluorine If hydrogen is used as a catalyst, the 2-phenyl isomer content can be increased to about 20% by weight. reduce. Finally, the sulfonation of linear alkylbenzenes is now possible on an industrial scale Oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the largest has interpretation. Special film or tube bundle reactors are used for the sulfonation Product to provide a 97 wt .-% alkylbenzenesulfonic acid (ABSS), which are within the scope of the invention can be used as anionic surfactant acid.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among these, the sodium salts of the ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. According to the invention, preferred as the anionic surfactant in acid form are C _8-16 , preferably C _9-13 alkylbenzenesulfonic acids. In the context of the present invention it is further preferred to use C _8-16 -, preferably C _9-13 - alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetraline content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkyl benzenesulfonic acids whose alkyl benzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkyl benzene sulfonic acids used have a 2-phenyl isomer content of less than 22% by weight. %, based on the alkylbenzenesulfonic acid.

The above-mentioned anionic surfactants in their acid form can be used alone or as a mixture with each other. But it is also possible and preferred that the anionic surfactant in acid reform before step c) of the process according to the invention further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably of 1 to 15 % By weight and in particular from 2 to 10% by weight, in each case based on the weight of the to be converted mixture, be mixed.

In the context of the present invention, in addition to the "Ten acidic acids "also the fatty acids, phosphonic acids, polymer acids or partially neutralized Polymer acids as well as "builder acids" and "complex builder acids" (details later in the text) alone as well as in any mixtures. Offer as ingredients of detergents and cleaning agents acid detergent and cleaning agent ingredients, for example phosphon acids, which in neutralized form (phosphonates) are part of many as incrustation inhibitors Detergents and cleaning agents are. The use of (partially neutralized) polymer acids such as for example polyacrylic acids, is possible according to the invention. But it is also possible to acidate to mix difficult ingredients with the anionic surfactant acid. Here, for example, so-called mentioned small components, which are otherwise added in complex further steps would have, for example optical brighteners, dyes, etc., the acidity in individual cases is to be checked.

In preferred embodiments of the present invention, the mixture contains active substance punch nonionic surfactants or nonionic surfactants are used as active substances.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular special primary alcohols with 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 is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, Alko holethoxylate 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 degrees of ethoxylation given represent 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.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes 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 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 nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fat säuremethyleste.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

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

in which RCO stands 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 hydroxyl 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 III

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example wise 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 polyhydroxy fatty acid amides leads.

It is particularly preferred for many applications if 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 is between 5: 1 and 1: 2. End products of the process according to the invention are preferred rens, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in quantities from 5 to 80% by weight, preferably from 7.5 to 70% by weight, particularly preferably from 10 to 60 % By weight and in particular from 12.5 to 50% by weight, in each case based on the process end pro product, included.

As already mentioned, the use of surfactants in cleaning agents for machine dishwashing is preferably limited to the use of nonionic surfactants in small quantities. If the end products of the process according to the invention are to be used in such products, they preferably contain only certain nonionic surfactants which are described below. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. 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 methyl or linear branching in the 2-position 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 ethoxy latex 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 degrees of ethoxylation given represent 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.

In particular in the case of process end products according to the invention for use in cleaning agents For machine dishwashing, it is preferred that they contain a nonionic surfactant ten, which has a melting point above room temperature, preferably a nonionic Surfactant with a melting point above 20 ° C. Nonionic tensi to be used with preference de have melting points above 25 ° C., particularly preferred nonioni to be used cal surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable non-ionic surfactants, the melting or softening points in the tempera mentioned have low-foaming nonionic surfactants, which at Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably have above 35 Pas and in particular above 40 Pas. Also non-ionic surfactants that are used in Room temperature waxy consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally more complex tensides such as polyoxypropy len / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.  

In a preferred embodiment of the present invention, the nonionic surfactant is included a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably minde at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units point. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 % By weight of the total molecular weight of such nonionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above room temperature temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends, which is 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block Copolymers of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane tend 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that can be used with particular advantage are, for example available under the name Poly Tergent® SLF-18 from Olin Chemicals.

Another preferred surfactant can be represented by the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

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

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

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 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. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ 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 ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = 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 larger, 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 group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula applies

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 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 ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

Fragrances can be used as active substance in the process according to the invention in order to to improve the aesthetic impression of the products and the consumer in addition to the performance of the A visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the syntheti  esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxy thylisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phenyls thylacetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyace taldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limes and pinene. However, different mixtures are preferred ner fragrances are used, which together produce an appealing fragrance. Such par Fu oils can also contain natural fragrance mixtures, such as those from vegetable sources are accessible, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lin denflower oil, juniper oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as oran gene flower oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the agents produced according to the invention is usually up to 2 % By weight of the total formulation, with high-dose fragrance compounds also far higher here can have contents. The fragrances can be used directly in the process according to the invention can be used, but it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the perfume to the laundry and by a slower fragrance release ensure a long-lasting fragrance of the textiles. Such carrier materials have, for example Wise cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes also having a wide range Ren auxiliaries can be coated.

As foam inhibitors that can be used in the agents produced according to the invention NEN, for example, soaps, paraffins or silicone oils come into consideration, which if necessary Carrier materials can be applied.

As already mentioned above, steps c) and d) of the method can be carried out according to the invention rens also run together by adding the active substance into the regrind or the mixture Step b) is granulated. The active substance can be part of the solid bed (she is then either milled in step a) or mixed in step b)) or as a sub Punch itself, as a melt, solution, emulsion or suspension component of the granulating liquid be. Processes according to the invention are particularly preferred here in which the vermi in step c) takes place under granulating conditions, the active substance (s) before are preferably part of the granulating liquid.  

The method according to the invention is suitable because of the special properties of the step a) produced carrier materials particularly well for the production of highly active Gra nulate. In the case of surfactant granules in particular, active substance contents that can be realized so far not with conventional methods or only with negative side effects (clump tendency, poor solubility, gel formation, etc.) were possible. According to the invention particular preferred process variants in which the active substance content of the granules latex at least 10% by weight, preferably at least 15% by weight, particularly preferably at least at least 30% by weight and in particular at least 50% by weight, in each case based on the process final product.

The use of amorphized glass obtained by grinding under drying conditions Germ materials in granules have so far not been described in the prior art. Such granu latex are characterized by high storage stability, low tendency towards bleeding and clumping as well as an excellent solubility behavior. Another subject of the present The invention is therefore an active substance-containing granulate which contains one or more amorphized Trä germateriel (ien) contains.

Regarding preferred carrier materials, active substances and contents of these substances in the inventions Granules according to the invention apply analogously to what has been stated above. Granules according to the invention with 3 to 60 wt .-% hydrophobic liquid - based on granules - are in this together hang particularly interesting.  

Examples

Commercially available urea (prills) was ground to a grain size of d ₅₀ = 20-32 µm. An "ultra-rotor" (impact mill) from Al tenburger-Jäckering was used for the example according to the invention, which includes a drying stage in the grinding. The comparative example V was ground in a Zirkoplex classifier mill 100 ZPS, which does not allow drying during the grinding.

The following table shows the properties of the urea regrinds obtained in this way:

Claims (15)

1. A process for producing amorphous (carrier) materials, characterized in that the (carrier) materials are ground under drying conditions. 2. Process for the preparation of granules containing active substance, characterized in that one or more carrier material (s) amorphized and then be with active substance (s) whipped up and granulated. 3. Process for the preparation of granules containing active substance, characterized in that one or more carrier material (s) are ground and dried under drying conditions finally acted upon with active substance (s) and granulated. 4. Process for the production of granules containing active substance, characterized by the steps

• a) grinding one or more carrier material (s) under drying conditions;
• b) optional mixing of the ground material formed in step a) with further solids;
• c) mixing the ground material formed in step a) or the mixture obtained in step b) with one or more active substance (s);
• d) granulation of the mixture obtained in step c) with optional addition of granulation auxiliaries.

5. The method according to any one of claims 1 to 4, characterized in that the or mind At least one of the carrier material (s) is selected from the group of substances used for formation of inclusion compounds are suitable. 6. The method according to any one of claims 1 to 5, characterized in that the or mind at least one of the carrier material (s) is selected from the group urea, thiourea, Amylose, perhydrotriphenylene, zinc hydroxide and the montmorillonite and / or cyclodextrins. 7. The method according to any one of claims 2 to 6, characterized in that the or mind at least one of the active substance (s) is selected from the group of surfactants, fragrances, Foam inhibitors or non-aqueous solvents. 8. The method according to any one of claims 4 to 7, characterized in that the or the Trä germ material (ien) in step a) to average grain sizes <200 microns, preferably <100 microns, be particularly preferably <50 µm and in particular <25 µm, are ground.   9. The method according to any one of claims 1 to 8, characterized in that the drying Grinding conditions can be achieved by blowing hot air. 10. The method according to claim 9, characterized in that the temperature of the hot air 25 to 200 ° C, preferably 30 to 150 ° C and in particular 40 to 120 ° C. 11. The method according to any one of claims 4 to 10, characterized in that in step a) regrind formed in step b) with flow aids, preferably with finely divided silica, in Amounts from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight and in particular from 0.1 to 0.5 wt .-%, each based on the mixture of regrind and flow aids, ver is mixed. 12. The method according to any one of claims 4 to 11, characterized in that the mixing in step c) is carried out under granulating conditions, the active substance (s) being preferred are part of the granulating liquid. 13. The method according to any one of claims 1 to 12, characterized in that the active substance Punch content of the granules at least 10 wt .-%, preferably at least 15 wt .-%, be particularly preferably at least 30% by weight and in particular at least 50% by weight in each case based on the end product of the process. 14. The method according to any one of claims 1 to 13, characterized in that the grinding done under drying conditions in an impact mill. 15. Active substance-containing granules, characterized in that it has one or more amorphous based carrier material (ien) contains.