EP1076685B1 - Method for producing granulates with detergent or cleaning action - Google Patents

Abstract

The invention relates to homogeneous granulates which are stable at storage, have active detergent or cleaning properties and present bulk densities which amount to no more than 85 % of the theoretical weight per litre and can be calculated using the standard calculation method. The granulates are obtained by the agglomeration of one or more solids with one or more granulating liquids in a free-falling mixer (13) which is divided into a mixing zone (1) and post-mixing zone (2) and comprises a strike-off bar (5) which is fixed to a frontal plate (4) from where it traverses the entire mixing zone (1) and possibly extends into the post-mixing zone (2). This allows for the production of products, especially special detergents, for example for washing delicates, woolens or curtains, which have bulk densities of approximately up to 500 g/l, corresponding to those of normal modern detergents, but in terms of their formulation constitute concentrates.

Description

The invention relates to a method for producing washable or cleaning-active granules with bulk weights below the value calculated using the normal calculation method is determined, the granules being free-flowing and homogeneous, by Mixing and agglomeration and, if necessary, subsequent processing.

Although the trend today is increasingly using heavy detergents or cleaning agents Bulk weights of 650 g / l and more, preferably above 700 g / l there is still a need for detergents or cleaning agents with bulk densities below of 700 g / l. Especially in geographic areas where hand washing is a plays a major role or in which, for example, mainly tub washing machines Machine wash are used, the detergents used must be quick and be soluble without too much mechanical action. In the case of mixed and granulated products So far this can only be ensured by the reduced bulk density of the funds become.

Usually, the requirements for modern, washing or cleaning-active granules are met sufficient storage stability regarding the flowability of the granular products posed. Today this requirement is usually referred to as Aid by so-called surface modifiers, which cover the surface of the granules and prevent the granules from sticking to one another. Another requirement namely a macroscopically homogeneous product that does not separate during production and filling as well as no separation of specifically different powder qualities shows to produce by mixing and granulating to separate the individual The skilled person can prevent components from being transported or stored however today still depends on the raw materials used and present problems to the available devices. Then comes as another Requirement to specify a specific bulk density with high formulation variability addition, it is necessary under the existing possibilities that the expert Compromises.

In conventional spray drying processes, relatively free-flowing and homogeneous Products received, however, must contain hydrolysis or temperature sensitive ingredients detergents or cleaning agents, for example peroxy bleach or enzymes, can be added later. Because the direct spray drying product usually only has bulk densities around 300 to 550 g / l, this - if higher bulk weights be desired - as is well known in the patent literature be granulated. If heavy ingredients are only mixed in, it happens although also to an increase in bulk density, but with the risk of segregation during transportation and storage. In addition, the spray drying process a costly process so that it is economically unfavorable, the main component a detergent by spray drying.

There are a number of mixers and granulators in which either can produce heavy or lighter granules. For example, in one Ploughshare mixer from Lödige achieves a high bulk density (roughly that will be the case Bulk weight achieved with the normal calculation method "sum of the weight Proportions of the individual solid raw materials multiplied by their bulk weights and the Liquid proportions multiplied by their density "or the bulk densities are predicted are only slightly less when the mixer is operating efficiently), but normally there is no sufficient agglomeration and therefore inhomogeneous granules as well as a relatively broad grain spectrum with coarse and fine particles. In addition, grain destruction of the coarser ones used occurs at least in part Solids instead. These products tend to separate.

While mixers and granulators like plowshare mixers move through rotating tools characterize, the so-called free-fall mixers are characterized by that they contain no tools and belong to the mixer with rotating containers. In them, the mix is raised and rubbed against the wall or fittings trickles over the surface of the bed under the influence of gravity.

In the so-called double cone mixer, which is one of the free-fall mixers and in which usually washing or cleaning-active granules with bulk weights are obtained, which confirm the theoretical calculation, the solid ingredients are different as mixed gently in the ploughshare mixer and without destroying the compressor; the inhomogeneity of the product remains. This is an indication of insufficient agglomeration.

With a few exceptions where granular raw materials are granulated, usually become one or more solids during mixing and agglomeration processed with the aid of granulating liquids. For example, in the international patent application WO97 / 21487 a process for the production of washing or described cleaning-active granules, the addition of water or aqueous Solutions and / or aqueous dispersions are made only in the amounts that the water binding capacity of the finished stable granules is not exceeded. The bulk weights the embodiments mentioned in the examples are between 650 g / l and 780 g / l. About the homogeneity of the product and an optionally adjustable bulk density no statements are made about the granules; however, the preferred choice leaves on mixers / granulators, which allow a high energy input, assume that the bulk weights cannot be freely adjusted for a given recipe and / or the finished ones Granules significant inhomogeneities due to the above explanations exhibit.

Another problem is the homogeneous incorporation of small components, which only in minor amounts, for example up to about 10% by weight in one Detergents or cleaning agents are used. These include cobuilders, optical Brighteners, sequestering agents, graying inhibitors, soap, colors and fragrances etc. The German patent application DE-A-196 51 072 proposes small components of this type for this purpose to accommodate in a separate additive, by using this additive a more precise dosage and a more homogeneous distribution of the small components in the entire detergent or cleaning agent is aimed for.

The two documents already mentioned show that in mixed products usually a Basic granulate is included, to which several other components are subsequently added or that several compounds (each with at least two washing or cleaning active Ingredients) separately and subsequently, if necessary, with admixture of other raw materials. Typical admixing components are, for example, peroxy bleaching agents such as perborate and / or percarbonate, which have bulk densities can have between 800 and 1000 g / l, or sodium sulfate, which a Has bulk density of up to 1500 g / l and still in quantities in some agents can contain up to 45 wt .-%. Also heavy sodium carbonates if necessary or bleach activators are suitable as admixing components. The admixing components mentioned with bulk weights above 700 g / l can be relative work easily into heavy detergents or cleaning agents; in detergents or cleaning agents, Which bulk weights should be below 650 g / l is not only necessary the other components have a correspondingly lower bulk density, there is also due to the bulk density differences of the individual granular components Risk of segregation. In the case of heavy sodium sulfate, there is also the fact that Sodium sulfate is relatively fine-grained and tends to be in the packaged package anyway during storage and especially during transport on the bottom of the package discontinued.

Tetraacetylethylenediamine (TAED), which is still the most widely used today Bleach activator, although only has bulk densities between 500 and 600 g / l; in washing or cleaning agents that have a bulk density of, for example, 400 g / l However, TAED is also a difficult and therefore problematic to use Raw material.

The object of the invention was to include granules which are active in washing or cleaning Bulk weights below the theoretical liter weight, which according to the normal Calculation method is determined to produce by mixing and agglomerating, where the finished granules in addition to sufficient storage stability (free-flowing) Above all, they should be homogeneous and at least the bulk density with a constant recipe should be variable within a certain range. Especially heavy ingredients with Bulk weights that are above the desired bulk density of the end product, should be able to be processed without the finished products tend to separate.

This object was achieved in that one solid or more Solids and one granulating liquid or several granulating liquids in one rotatable container without mixing tools (13) into a mixing zone (1) and a post-mixing zone (2) is divided and has a tee bar (5) which is attached to a stimulating plate (4) is fixed and from there crosses the entire mixing zone (1) and, if necessary, in the post-mixing zone (2) extends in, agglomerates and, if necessary, subsequently processed with a bulk density that is set to a maximum of 85% of the theoretical Liter weight, which is determined according to the normal calculation method becomes.

In the context of the present invention is under the normal calculation method understood the method in which the bulk density of the finished solid product like already stated above by adding up the individual bulk weights of a respective solid raw material or compounds weighted with its weight proportion in the finished solid product is calculated. The liquid components, i.e. the granulating liquid or the pelletizing fluids are analogous to their density.

Bulk weights are preferably set which are only a maximum of 80% and in particular only a maximum of 75% of the theoretical liter weight calculated as stated above turn off. Process end products with bulk weights below 650 g / l are particularly preferred.

Raw materials and / or compounds can be used as solids, the latter in the context of this invention at least two different ones usually in washing or Detergent ingredients contain and by conventional techniques such as Spray drying, granulation, roller compaction or extrusion have been prefabricated are. The raw materials used can be finely divided, but also of a coarser nature, whereby the method according to the invention has the advantage that even relatively fine-grained material can be processed without problems. Because the manufacturing and subsequent processing From an economic point of view, it can be quite unfavorable for compounds an embodiment of the invention preferred to use only 1 to 3 different compounds Use solids. It is particularly preferred in addition to the compounds at least one other solid raw material as a solid admixture to the To use compounds. In a particularly advantageous embodiment, none spray-dried compounds introduced into the process. It is also possible that no compounds at all, but only solid raw materials used as solids become. The method according to the invention has the advantage that so-called solid small components can be added directly. For example, proceed that the solids on a conveyor belt, a so-called component collection belt, be weighed together and the addition of the solid small components, especially those that are only used in amounts of at most 2% by weight as the last solid or the last solids directly before the introduction of the solids into the mixer. A separate premix of the solids in a separate one Mixer, i.e. the production of a so-called premix, which is used in other processes is quite common, is therefore not necessary in the method according to the invention.

Since it is preferred for economic reasons, neither the agglomeration process nor to connect a drying step to the treatment that may have been carried out, however, water can be added in the agglomeration phase and the end products of the process should not tend to stick, it is advantageous in another Embodiment of the invention preferred at least one over-dried solid (Raw material or compound) so that the water content of the solids used or the solid mixture as a whole is lower than the water binding capacity of the total solids or solid mixture corresponds. In another preferred The embodiment of the invention is the aqueous granulating liquid only in the amounts used that the water binding capacity of the agglomerates is not exceeded. to Determination of the water binding capacity and the addition of aqueous granulating liquids to solids with the proviso that the water binding capacity of the finished Products must not be exceeded, is expressly based on the disclosure international patent application WO-A-97/21487.

According to the invention, at least one granulating liquid will be, but preferably introduced at least two different granulating liquids in the process. All in all it is quite possible to have three, four or five, if desired even more different Introduce granulating liquids into the process. The granulating liquids can be non-aqueous or aqueous in nature. For example, it is possible that as single granulating liquid water, an aqueous solution or an aqueous dispersion is used. In a preferred embodiment of the invention, however, is used from a single granulating liquid a non-aqueous granulating liquid used. Within the scope of this invention, in particular, a non-aqueous Granulating fluid understood an auxiliary, which is a common ingredient - if necessary in aqueous solution or dispersion - of detergents or cleaning agents and at the process temperature is in the form of a liquid or melt.

In a further preferred embodiment of the invention, at least two different granulating liquids used. It is particularly advantageous that at least one of them is one of the above-mentioned non-aqueous granulating liquids is, while at least one further granulating liquid is water, an aqueous solution or is an aqueous dispersion.

In a further advantageous embodiment, the invention provides that 0.5 to 15 % By weight and in particular 1 to 10% by weight with a particular advantage of 1.5 to 7 % By weight of granulating liquid are introduced into the process.

Liquid or liquefied liquids are particularly suitable as the non-aqueous granulating liquid or melted nonionic surfactants, paraffins, silicone oils, fragrances, fatty acids, meltable polyester and known soil release ingredients of detergents.

The liquid or liquefied 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 20 moles of ethylene oxide (EO) per mole of alcohol, in particular up to an average of 14 EO per mole of alcohol, in of which the alcohol residue may be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols or C ₁₂ -C ₁₅ alcohols with 3 EO or 4 EO, C ₉ -C ₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO , 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol or C ₁₂ -C ₁₅ alcohol 3 EO and C ₁₂ -C ₁₈ alcohol with 7 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).

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, 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 fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.

Suitable fatty acids are in particular saturated fatty acids, such as lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived Mixtures.

Since the amount of water to be added depends on the case, there are no mandatory quantities that will definitely lead to success. In a preferred embodiment of the invention, however, is as a granulating liquid amount of water entered depending on the mixture to be agglomerated 0.5 to 10 wt .-% and in particular 1 to 7 wt .-%, each based on the total Mixture. It is irrelevant whether the water is the sole raw material or in In the form of an aqueous solution or in the form of an aqueous dispersion in the process is introduced. However, since preferably no drying step on the agglomeration process is connected, in a preferred embodiment of the invention, water not used as the sole agglomeration aid to the amount of registered To keep water as low as possible.

Aqueous solutions are those of inorganic and / or organic builder substances prefers. So here come in particular solutions of alkali silicates, Alkali carbonates, but also of polycarboxylates, for example citrates, (co) polymers Polycarboxylates and cellulose ethers such as carboxymethyl celluloses or Methyl celluloses into consideration. But also aqueous surfactant pastes of anionic and / or nonionic surfactants are suitable granulating liquids. For example, highly concentrated pastes of alkyl benzene sulfonates and alkyl sulfates are used become. The use of nonionic is particularly preferred at this point Surfactant pastes such as pastes of alkyl glycosides, polyhydroxy fatty acid amides or the like above-mentioned fatty acid methyl ester ethoxylates.

Alkyl glycosides are surfactants of the general formula RO (G) _x , in which R denotes a primary straight-chain or methyl-branched, in particular 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 1.1 to 1.4.

in der R¹CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.Polyhydroxy fatty acid amides obey the formula (I),

in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

In a further preferred embodiment of the invention it is provided that the invention manufactured agents are colored. This will be advantageous aqueous dye solutions or combinations of such dye solutions and one non-aqueous granulating liquid, in particular nonionic surfactant, used.

Mixtures of dye solutions and nonionic surfactants can also be used. In In a preferred embodiment, however, no aqueous dispersions of Nonionic surfactants used. Rather, it is preferred to use at least one non-aqueous one Granulating liquid to use at least one further aqueous granulating liquid. The use of at the process temperature is particularly preferred at temperatures around room temperature up to 60 ° C liquid non-ionic surfactants, Fragrances and / or paraffins. Aqueous liquids and non-aqueous liquids in weight ratios around 1.5: 1 to 1: 1.5 and in particular by 1.2: 1 to 1: 1.2.

The rotatable container to be used according to the invention without internal mixing tools (13) is preferably a conical mixing drum, which is arranged in a lying position, but can advantageously be inclined against the horizontal. The angle of inclination α is preferably less than 45 °, angle of inclination of less than 20 ° having proven particularly useful. The mixing drum (13) is divided into two parts, creating an actual mixing zone (1) and a post-mixing zone (2). In an advantageous embodiment of the invention, the length of the mixing zone (1): length of the post-mixing zone (2) is at least 1: 1, but preferably (70-55): (30-45). The mixing drum (13) has at least one possibility for adding solids (6), these being supplied in particular on the larger circular area. In addition, the mixing drum (13) also has at least one possibility for adding liquids (7), in particular nozzles, advantageously 1 to 5 nozzles, different granulating liquids being introduced via different nozzles, but one and the same granulating liquid can also be added via different nozzles. Single-substance nozzles are just as suitable here as multi-substance nozzles and / or spraying with gases, in particular air or water vapor, as aids. If, for example, two different nonionic surfactants such as C ₁₂ -C ₁₈ alcohol with 7 EO and C ₁₂ -C ₁₄ alcohol or C ₁₂ -C ₁₅ alcohol with 3 EO are used as granulating liquids, they can either be used as a mixture, via a two-component nozzle or introduced into the process via two nozzles.

In a preferred embodiment of the invention, the mixing drum (13) on the larger circular area of the mixing drum (13) on the solids feed (6) to which then the different nozzle lances (7) are attached. This can advantageously even small liquid components can be distributed homogeneously.

The mixing drum (13) is preferably driven by the drive (3), for example by a ring gear, divided into the mixing zone (1) and the post-mixing zone (2).

The essential part of the mixing drum (13) for the method according to the invention consists of a tee (5), which is attached to the end plate (4) of the first mixer part and from there crosses the entire mixing zone (1) and preferably into the Post-mixing zone (2) extends into it, but advantageously not over half the length of the Post-mixing zone (2) goes out. In particular, it is preferred that the tee (5) only extends into the first third of the length of the post-mixing zone (2). The tee (5) itself can have a width of, for example, 50 to 150 mm, preferably 75 to 130 mm. The upper edge of the tee (5) is at a distance from the inside Mixer wall (14), which is preferably a maximum of 10% of the smallest drum diameter in the mixing zone (1), preferably a maximum of 5% of the smallest drum diameter the mixing zone (1) and in particular 5 to 25 mm, advantageously less than 20 mm, for example 5 to 15 mm. The distance can be in the post-mixing zone (2) to the nearest inner mixer wall may be larger than in the mixing zone (1); Values between 100 and 300 mm are quite common.

Apparatus similar to the apparatus shown in FIG. 1, which are also used were, for example, in SÖFW, 99th year, pages 358 to 359 (1973) and in SÖFW, 94th year, pages 234 and 235 (1968).

After passing through the post-mixing zone (2), the finished product can either be used directly discharged via the discharge unit (8) and the discharge (9) or via the conveyor (10) are further processed, with further powders, in particular surface modifiers the well-known type added via the solids feed (11) can be. This conveyor and metering screw (10) leads into the post-mixing zone (2) into it (a direct connection of the conveyor device (10) to the discharge unit is also possible (8)), it is preferred that the screw (10) only in the second half of the length the post-mixing zone (2) and thus does not protrude into the part of the post-mixing zone (2), which still contains the tee (5). In a special embodiment of the The tee (5) is mounted on the screw (10).

All known, finely divided particles can be used as powdering agents or surface modifiers Representatives of this group are used. Amorphous and / or crystalline aluminosilicates, such as zeolite A, X and / or P, various types of silicas, Calcium stearate, carbonates, sulfates, but also fine-particle compounds, for example made of amorphous silicates and carbonates.

As solid starting materials, all can usually be in solid or solidified form Raw materials and / or compounds used in detergents or cleaning agents, in particular from the field of anionic, nonionic, cationic and / or amphoteric surfactants, inorganic and organic builder substances as well as organic builder acids, Peroxy bleach, bleach activators and bleach catalysts, inorganic in Water alkaline reacting salts such as sodium or potassium (bi) carbonate, amorphous or crystalline sodium silicates, neutral reacting salts such as sodium or potassium sulfate and the acidic salts such as sodium or potassium bisulfate, enzymes, discoloration inhibitors, Graying inhibitors, soil repellents, foam inhibitors, complexing agents, for example phosphonates, and optionally optical brighteners and pH regulators be used. For a more detailed description of these ingredients, see the numerous patent literature in the field of detergents or cleaning agents directed. It is also left to the expert which of the solid ingredients he considers Would like to use raw materials or as prefabricated compounds.

In particular, it is preferred that heavy solids, often from a wide variety Reasons are subsequently added to the agglomeration process become. These include sodium sulfate, which is still used in some countries up to 45 % By weight is contained in the detergents, but also sodium carbonate and sodium bicarbonate as well as peroxy bleaching agents such as perborate monohydrate, perborate tetrahydrate and / or percarbonate. Also granulated bleach activators, which often have a bulk density have from 500 to 600 g / l, count in detergents as desired Should have bulk density below 500 g / l, to the heavy ingredients that can also be used in the method according to the invention. It is from Advantage that bleach and bleach activator are introduced together in the process can be, without the use of water as agglomerating or granulating liquid a loss of bleaching activity would be feared. The same applies to granulated Enzymes and / or granulated foam inhibitors.

In addition to the usual spray-dried compounds, which have long been used as basic granules especially for detergents with bulk weights below 600 g / l, however also as a starting compound for further compacting granulations or extrusions are used and which often contain all components of the finished agent that are not hydrolysis and / or temperature sensitive are among the preferred ones Compounds those containing 10 to 75% by weight of organic components such as surfactants, Cosurfactants, which are also known as detergency boosters, and in particular organic ones Builders and cobuilders, especially polymeric and / or copolymeric salts for example acrylic acid and / or maleic acid. So-called highly concentrated surfactant compounds with a surfactant content of at least 30 % By weight, preferably of at least 50% by weight, based in each case on the compound, which can be granulated, for example, in the fluidized bed.

Another advantageous compound is a so-called builder compound that predominantly contains inorganic constituents and accordingly inorganic builders. You can set alkaline as desired by choosing the builders become. In an advantageous embodiment of the invention, builder compounds used, which a maximum of 30 wt .-%, preferably up to 20 wt .-% of organic Components, especially on anionic surfactants and / or nonionic surfactants. In particular, embodiments can be preferred which only have 2 to 15% by weight contain organic components and above all anionic surfactants. As special embodiments Builder compounds of this type are, in particular, those made from carbonates and called silicates, optionally up to 30% by weight, preferably up to 20 % By weight, surfactants, in particular anionic surfactants, but also anionic surfactants and nonionic surfactants, can have. Particularly preferred builder compounds have between 40 and 70% by weight sodium carbonate, 20 to 50% by weight sodium silicate of the module 2.0 to 3.3 and optionally about 2 to 18% by weight of anionic surfactant, in particular alkylbenzenesulfonate. On Another interesting compound contains essentially zeolite, crystalline layered Sodium disilicate and polymeric polycarboxylate or crystalline layered Sodium disilicate and citric acid.

In a preferred embodiment of the invention, a compound with high organic Proportions such as surfactants and optionally organic cobuilders and a builder compound, that should adjust the washing alkalinity of the finished product combined. These two compounds are preferably in weight ratios of 5: 1 to 1: 3 and in particular from 3: 1 to 1: 1.

a) 65 bis 95 Gew.-% Trägerstoff(en),

b) 0 bis 10 Gew.-% Hilfsstoff(en) sowie

c) 5 bis 25 Gew.-% Parfüm

einer Granulation oder Preßagglomeration unterworfen wird. Bevorzugte Trägerstoffe sind dabei ausgewählt aus der Gruppe der Tenside, Tensidcompounds, Di- und Polysaccharide, Silikate, Zeolithe, Carbonate, Sulfate und Citrate und werden in Mengen zwischen 65 und 95 Gew.-%, vorzugsweise von 70 bis 90 Gew.-%, jeweils bezogen auf das Gewicht der entstehenden Duftstoff-Formkörper, eingesetzt.On the one hand, fragrances can be introduced into the process in liquid form as a granulating liquid, as described. The process is also suitable for processing fragrances in the form of solid compounds. Such concentrated fragrance compounds can be produced separately, for example, by granulation, compacting, extrusion, pelletizing or using other agglomeration processes. Cyclodextrins, for example, have proven useful as carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. The special production of fragrance moldings is described, for example, in the older German patent application DE-A-197 46 780.6, in which a method is disclosed in which a solid and essentially water-free premix consists of

a) 65 to 95% by weight of carrier (s),

b) 0 to 10 wt .-% excipient (s) and

c) 5 to 25% by weight of perfume

is subjected to granulation or press agglomeration. Preferred carriers are selected from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates and are used in amounts between 65 and 95% by weight, preferably from 70 to 90% by weight, each based on the weight of the fragrance moldings formed.

As usual, the total content of surfactants in the finished product can be in a wide range vary and for example between 5 and 40 wt .-%, based on the finished agent, lie. As seen, anionic surfactants are preferably used as solids in the agglomerate Mixture given while nonionic surfactants both as part of the solids (Compounds) as well as agglomeration aids can be added. The weight ratio the anionic surfactants to the nonionic surfactants in the finished compositions can be 10: 1 to 1:10. In preferred embodiments, however, it is above 1, in particular even above 1.5: 1, for example at 5: 1 or 8: 1.

The agglomeration effect according to the invention is due to the special mode of action of the Mixer (13) used according to the invention supports. Especially relatively small particles and especially the fine particles with particle diameters smaller than 100 µm are moved up by the movement of the mixer (13), while relatively coarser particles becoming increasingly smaller in the rotary movement of the mixer (13) and instead towards the post-mixing zone (2) and then to exit from the Mixers (13) are transported into the discharge unit (8) or the conveying device (10), whereby, due to the rolling movement of the individual particle, it compresses the experience individual particles. Such a process is also roll agglomeration or Called roll granulation. From which particle size the particles predominantly only the Roll granulation subjected and no longer moved up by the movement of the mixer depend on the adjustable operating parameters of the Mixer, is dependent on the desired average and maximum Particle size distribution freely adjustable in a wide range. In particular applies that at higher speeds there is a shift to coarser particles.

The tapping bar (5) prevents the highly moved particles and in particular also the fines are only "driven in a circle", as soon as they hit the tee (5) hit, be stripped from this and fall vertically again. The geometry the mixer (13) allows that the injected liquid mist not only on the freshly added solids, but also directly into this curtain from relatively fine and sprayed themselves in the ascending and falling movement of the particles becomes. Furthermore, the chopping bar (5) prevents the powder from rotating the mixer (13) to the mixer wall (14) pressed and glued. In case should still build up adhesions - depending on the type of added Granulating liquids and their amount cannot always be excluded - see above the knock-off bar acts as a scraper and prevents the adhesive layer from continuing increases.

Since - as already explained above - the liquid components directly into the moving powder curtain are sprayed and this moistened powder in a first approximation only with the by the Rotary movement of the mixer (13) in small particles and fine particles whirled up Come into contact, the agglomeration effect takes place in the mixing zone (1) between the moistened powder on the one hand and the smaller particles and fine particles on the other instead, during an over-agglomeration by contacting the wetted powder or the remaining amounts of liquid components with the already further agglomerated and therefore coarser particles - in a first approximation - can almost be excluded. Be here that is, finer particles agglomerate into coarser particles, which in turn are dependent from their size less and less to no longer due to the rotary motion the mixer (13) are whirled up. In this way, minimization of the Fine grain fraction while minimizing the coarse grain fraction instead, as an over-agglomeration of the coarser particles can be largely prevented. It shows up here the big advantage over mixers with conveying tools such as the plowshares in the so-called ploughshare mixers. The tools reach into the mixed and agglomeration goods and therefore also convey coarser particles, "finished product," upwards, whereby on the one hand the risk of oversize grain generation increases, on the other hand the coarser ones Particles in terms of agglomeration in competition with the smaller particles and above all the fine grain proportions, i.e. the reduction of the fine grain fraction cannot be done effectively enough.

In principle, coarser particles can also be used in the mixer (13) used according to the invention be moved and agglomerated, and this happens the more the flatter the angle of inclination α, the longer the residence time of the material to be mixed in the mixer (13) and - how already said above - the higher the speed of the mixer. With a setting option of the angle of inclination α from 0 to about 30 ° and up to about 70 revolutions per Minute are for the reasons mentioned in a preferred embodiment of the Invention an angle of inclination of the mixer (13) from 10 to 20 °, in particular from 12 to 15 ° with a simultaneous movement of the mixer (13) via the drive (3) from 20 to 70 revolutions per minute and in particular from 30 to 60 revolutions per minute set.

The agents produced by the process according to the invention usually have Bulk density between about 350 and 750 g / l, preferably between 400 and 720 g / l, in particular above 450 g / l, but advantageously not above 700 g / l.

In a further preferred embodiment of the invention, the bulk density is below 700 g / l, especially below 650 g / l, even if according to the above specified normal calculation method a bulk density of well above 800 g / l would have been expected.

Such agents can be excellent as a detergent, but also as a compound for one processed detergent. The invention thus relates to another Embodiment of the invention laundry detergent, which consists of about 50 to 100 wt .-% of a Compound or product produced according to the invention.

The detergents or compounds produced according to the invention therefore have this not only have a relatively variable bulk density, they are also both in terms of pourability as well as the reduced to nonexistent tendency to segregate as highly stable to look at. This also applies to bleach and enzyme stability to because it is in storage due to the appropriate preferred control of the Water addition during the manufacturing process does not become one later during storage uncontrolled water intake comes. The particle size distributions of the finished Products can, for example, be set so that they roughly match those in the essential spray-dried product, which is subsequently hydrolysis and temperature sensitive Ingredients were mixed, are comparable. With regard to known Granulation processes have lower proportions of the agents produced according to the invention of fine and coarse grain, so that the end result is a higher product yield becomes. Nevertheless, fine and coarse-grained fractions that are still present can be made as desired have been screened so far. Fine particles can be returned directly to the agglomeration process while coarse particles due to the lack of tools in the mixer (13) must first be broken up separately before they can be recycled.

As has surprisingly been found, the so produced according to the invention Products also have application-technical advantages over products of the same composition, but which were produced by conventional granulation processes. These advantages relate in particular to the induction behavior in automatic Washing machines and / or the residue behavior on dark textiles.

As already stated, some contain funds, especially those with a relatively low level Bulk weights, which are still mainly produced by spray drying, and / or special detergents that are normally only used for very specific purposes, such as washing delicates, wool or curtains, are used, even today relatively high amounts of so-called fillers or fillers on. The best known filler or filler is probably the sodium sulfate. An exit of sodium sulfate from the slurry to be spray dried would increase the organic content in the slurry and thus mean high process uncertainty. A replacement the sulfate by other inorganic salts such as soda would indeed Ensure process reliability, but cause very alkaline products that are often not usable for the desired application. An exit the sulfate from the spray process and then adding the heavy sulfate to the Spray product would, like the conventional granulation of such agents with and without sulfate to much higher and too high bulk densities for the application purposes and at least in the case of spray drying and subsequent admixture of the Sulfate lead to products due to the different bulk densities of each Solids and particle size distribution tend to segregate.

With the aid of the method according to the invention, such products can, however now either with or without sulfate within the desired bulk density range become. In particular, the production of such so-called normal or Special detergents with bulk densities of up to 500 g / l, which do not contain sulfate or Containing sulfate only in amounts up to a maximum of 10% by weight is an innovation in particular in the area of the special detergents mentioned: concentrates are produced that but, unlike conventional manufacturing processes, it is still the low one Bulk weight of the "diluted" recipes. The dosage of these funds in a conventional washing process can be reduced accordingly.

Examples Example 1:

This example relates to the processing of compounds 1 and 2 according to the invention Add further raw materials to agent M1 according to the invention in a mixer according to Figure 1 (list of reference symbols see below). The angle of inclination α was 13 ° and the speed between 40 and 60 revolutions per minute. The comparative example contained V1 same compounds and raw materials as M1, but was in a commercially available Double cone mixer manufactured by Teltschik. Similar results were obtained for V1 achieved if, instead of the double cone mixer, a ploughshare mixer from Lödige was used. In comparative example V2, which has the same composition as M1 or V1 had, instead of Compounds 1 and 2, a spray-dried powder was produced and with the exception of sulfate and other organic material with the same raw materials edited.

Compound 1 contained 30% by weight of surfactant components, in particular 28% by weight of alkylbenzenesulfonate and / or alkyl sulfate and 3% by weight of nonionic surfactants such as C ₁₂ -C ₁₈ fatty alcohol with about 5 EO. The composition of the surfactants can vary within a wide range without affecting the result. For example, 25% by weight alkyl benzene sulfonate, 2% by weight alkyl sulfate and 3% by weight nonionic surfactant with different degrees of ethoxylation in the end product gave the same result. It was also possible to use 25% by weight of alkyl sulfate and 5% by weight of alkylbenzenesulfonate and no nonionic surfactants. Even increasing the surfactant content to over 40% by weight did not change the results given below.

Compound 1 additionally contained 50% by weight of inorganic builders, for example zeolite A, zeolite X, zeolite P, crystalline layered disilicate or any mixture from these, as well as 12 wt .-% organic cobuilders such as citric acid, citrate, other polycarboxylic acids or polycarboxylates and / or (co-) polymeric salts of acrylic acid and / or methacrylic acid and / or maleic acid with relative molecular weights between 3000 and 100000. The exact composition is also here for the end result irrelevant.

The water content of compound 1 was 7% by weight. The remaining quantities passed from salts from raw materials.

Compound 2 consisted of 50% by weight of sodium carbonate and 30% by weight of amorphous Sodium disilicate, 8% by weight of alkylbenzenesulfonate and 12% by weight of water.

Even the production of the compound (granulation in a mixer or extrusion or fluidized bed granulation) was for the final product results given below irrelevant.

30 parts by weight of compound 1, 10 parts by weight of compound 2 and 3 parts by weight of agglomeration aids, in particular 3 parts by weight of C ₁₂ -C ₁₈ fatty alcohol, were used to prepare agent M1 according to the invention and comparative example V1 with about 7 EO, 18 parts by weight of peroxy bleach (perborate monohydrate or percarbonate), 2.65 parts by weight of tetraacetylethylene diamine, 0.5 parts by weight of protease granules, 1.8 parts by weight of foam inhibitor granules, 38 parts by weight of perfume and 33.67 parts by weight of sodium sulfate are used, while for the preparation of V2 75 parts by weight of the spray-dried granules, 18 parts by weight of peroxy bleach (perborate monohydrate or percarbonate), 2.65 parts by weight Parts of tetraacetylethylenediamine, 0.5 parts by weight of protease granules, 1.8 parts by weight of foam inhibitor granules, 0.38 parts by weight of perfume and only 1.67 parts by weight of sodium sulfate were added.

The theoretical liter weight calculated in advance according to the normal calculation method of M1 was 872 g / l.

Table 1 shows the application properties of products M1, V1 and V2. It can be seen that M1 has advantages in solubility in spite of the higher bulk density than V2. It is also proven that the significant reduction in the bulk density of M1 compared to the value determined using the normal calculation method (only 71% of the theoretical liter weight) and the value of V1 (86% of the theoretical liter weight) brings about very clear advantages in terms of application technology. For V1 it was made more difficult that the residue remaining in the induction chamber hardened. The segregation tendencies were examined in three ways: 1. visually (when several visible layers appear, either recognizable by different particle sizes and / or in the case of partially stained products by concentration of a certain color in one layer), 2. analytically (samples from several layers were taken and analyzed for their composition) and 3. application technology (as in 2. samples were taken from several layers and examined for their flushing-in behavior and their residue behavior). Data from M1, V1 and V2 characteristics M1 V1 V2 Bulk density in g / l 620 g / l 750 g / l 550 g / l Wash-in test: residue in g less than 5 more than 5 less than 5 Sieving numbers (in% by weight): to 1.6 mm 3 5 1 to 0.8 mm 10 16 14 to 0.4 mm 36 24 39 to 0.2 mm 44 33 40 to 0.1 mm 7 11 6 through 0.1 mm 0 11 0 Residue notes on dark-colored textiles less than 3 5 between 3 and 5 storage stability free-flowing no segregation free-flowing segregation free-flowing no segregation

Einspültest:

To determine the induction behavior of the agents, the agents were used in household drum washing machines tested with induction drawer at a water pressure of 0.5 bar. test machines were Miele W918 and Quelle Privileg 1100. There were 5 in each machine Determinations carried out. From the 10 results, the one given below was then given Average formed. For this purpose, 100 g of the detergent were added to the dispenser compartment per wash cycle given. The tap water with which the funds in the respective machine, which was loaded with 3.5 kg of dry laundry, was washed in, had a water hardness of 16 ° d. After the wash-in was finished, the detergent residues were removed from the wash-in drawer and the induction chamber placed separately on a watch glass with a rubber wiper and balanced. 30% moisture was subtracted from these moist residues. The "dry residues" from the drawer and chamber were added and from the Sum formed the mean value, which is given in Table 1.

Determination of the residue behavior on dark-colored textiles:

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge

30 l of water were first introduced into a tub washing machine (TYPE Arcelik or comparable type), 150 g of the agent were added and dissolved by stirring. The laundry, consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, was then inserted and the machine heated to a temperature of 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, then the washing liquor was drained off, rinsed three times with 30 l of water each time and the laundry was spun for 15 seconds. The laundry was dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging):

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues

Note 3:

recognizable residues that are already annoying in the case of critical assessment

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity

Example 2:

Example 1 was repeated, except that agglomerating liquids were added to 2.5 parts by weight of nonionic surfactant now also used 2 parts by weight of an aqueous dye solution. A homogeneously colored product M2 was obtained, which despite the increased content Granulating liquid and especially water did not tend to stick.

Example 3:

Example 1 was repeated; However, in addition to the 3 parts by weight of nonionic surfactant, water was now added as a further granulating liquid in the amounts indicated in each case: with additions between 1 (M3) and 4.5 parts by weight of water, bulk densities between 620 and 640 g / l were obtained , However, the wash-in behavior deteriorated almost continuously. Additional subsequent surface treatment with solid raw materials (metering was carried out via the solids supply (11) and the conveyor (10)) not only improved the flushing behavior in M4 and M5, but surprisingly also significantly improved the residue marks (Table 2) , Products M3 M4 M5 Composition in parts by weight 100 M1
1 water 100 M1
2 water
2 compound 2 100 M1
4.5 water
2 compound 2 bulk weight 634 g / l 633 g / l 640 g / l theoretical liter weight 873 g / l 865 g / l 869 g / l Wash-in test: residue in g (measured twice) 6.3 / 9.9 6.0 / 7.0 5.5 / 4.6 Sieving numbers (in% by weight): to 1.6 mm 1 1 2 to 0.8 mm 3 7 12 to 0.4 mm 25 33 37 to 0.2 mm 56 56 47 to 0.1 mm 15 3 2 through 0.1 mm 0 0 0 Residue notes on dark-colored textiles 1.5 1.5 1.5 storage stability free-flowing no segregation free-flowing no segregation free-flowing no segregation

LIST OF REFERENCE NUMBERS

1

mixing zone

2

mixing zone

3

Drive, preferably ring gear; 0 to 70 revolutions per minute

4

faceplate

5

knock-down bar

6

Feed solids

7

Supply of liquid components (1 to 5 nozzle lances)

8th

discharge unit

9

discharge

10

Conveying device, preferably screw

11

Solid feed

12

Base frame with support block

13

Mixer without internal (mixing) tools

14

mixer wall

Claims (21)

1. A process for the production of detersive granules by mixing and agglomeration, optionally followed by aftertreatment, characterized in that one or more solids and one or more granulation liquids are agglomerated and optionally aftertreated in a rotatable container with no mixing tools (13) which is divided into a mixing zone (1) and an aftermixing zone (2) and which comprises a knock-down bar (5) which is fixed to a front plate (4) and from there crosses the entire mixing zone (1) and optionally extends into the aftermixing zone (2), a bulk density which makes up at most 85% of the theoretical weight per litre, as determined by the normal method of calculation, being established.
2. A process as claimed in claim 1, characterized in that the bulk density makes up at most 80% and more particularly at most 75% of the theoretical weight per litre, as determined by the normal method of calculation.
3. A process as claimed in claim 1 or 2, characterized in that the bulk density of the end product is between 400 and 720 g/l, more particularly above 450 g/l, but advantageously not above 700 g/l.
4. A process as claimed in claim 1 or 2, characterized in that the bulk density of the end product is below 650 g/l.
5. A process as claimed in any of claims 1 to 4, characterized in that, where a single granulation liquid is used, it is a nonaqueous granulation liquid, more particularly nonionic surfactants, perfumes, paraffins or silicone oils, fatty acids, fusible polyesters or soil release components which are present as a liquid or melt at the process temperature.
6. A process as claimed in any of claims 1 to 4, characterized in that at least two different granulation liquids are introduced into the process, at least one of which is a nonaqueous granulation liquid and, more particularly, at least one is water, an aqueous solution or an aqueous dispersion.
7. A process as claimed in any of claims 1 to 6, characterized in that 0.5 to 15% by weight, preferably 1 to 10% by weight and more particularly 1 to 7% by weight of granulation liquid(s) is introduced into the process.
8. A process as claimed in any of claims 1 to 7, characterized in that the compositions are coloured, for which purpose aqueous dye solutions or combinations of such dye solutions and a nonaqueous granulation liquid, more particularly nonionic surfactant, are used.
9. A process as claimed in any of claims 1 to 8, characterized in that raw materials and/or compounds are used as the solids, one to three different compounds advantageously being used.
10. A process as claimed in any of claims 1 to 9, characterized in that the solid minor components, more particularly those which are only used in quantities of at most 2% by weight, are introduced into the mixer as the last solid(s) immediately before the solids are added.
11. A process as claimed in any of claims 1 to 10, characterized in that the agglomeration process and the optional aftertreatment are not followed by drying.
12. A process as claimed in any of claims 1 to 11, characterized in that the water content of the solids used or the mixture of solids is lower than corresponds to the water binding capacity of the total solids or mixture of solids.
13. A process as claimed in any of claims 1 to 12, characterized in that the aqueous granulation liquid is only used in such quantities that the water binding capacity of the agglomerates is not exceeded.
14. A process as claimed in any of claims 1 to 13, characterized in that the ratio of the length of the mixing zone (1) to the length of the aftermixing zone (2) is at least 1:1.
15. A process as claimed in any of claims 1 to 14, characterized in that the knock-down bar (5) does not extend beyond half the length of the aftermixing zone (2).
16. A process as claimed in any of claims 1 to 15, characterized in that the upper edge of the knock-down bar (5) is at a distance from the mixer wall (14) which is preferably at most 10% of the drum diameter at the narrowest point of the drum (13) and more preferably at most 5% of the diameter of the drum (13) at its narrowest point.
17. A process as claimed in any of claims 1 to 16, characterized in that the mixer (13) is inclined at an angle α of 10 to 20° and more particularly 12 to 15° and simultaneously rotated via the drive (3) at 20 to 70 revolutions per minute and more particularly 30 to 60 revolutions per minute.
18. A process as claimed in any of claims 1 to 17, characterized in that the product is aftertreated with solids, so-called surface modifiers, via the feeder (10).
19. A detergent, characterized in that 50 to 100% by weight thereof consists of a compound produced by the process claimed in any of claims 1 to 18.
20. A detergent as claimed in claim 19, characterized in that the compound produced by the process claimed in any of claims 1 to 18 has a bulk density of at most 500 g/l and contains up to at most 10% by weight, if any, of sulfate.
21. The use of the detergent claimed in claim 19 or 20, more particularly a detergent consisting entirely of a compound produced by the process claimed in any of claims 1 to 17, as a special detergent, more particularly as a light-duty detergent, a detergent for woollens or a detergent for net curtains.

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