EP1015550B1 - Procede de production de nettoyants et detergents particulaires - Google Patents

Procede de production de nettoyants et detergents particulaires Download PDF

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Publication number
EP1015550B1
EP1015550B1 EP98947499A EP98947499A EP1015550B1 EP 1015550 B1 EP1015550 B1 EP 1015550B1 EP 98947499 A EP98947499 A EP 98947499A EP 98947499 A EP98947499 A EP 98947499A EP 1015550 B1 EP1015550 B1 EP 1015550B1
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EP
European Patent Office
Prior art keywords
weight
process according
shaping
raw materials
liquid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP98947499A
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German (de)
English (en)
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EP1015550A1 (fr
Inventor
Kathleen Paatz
Wilfried Rähse
Peter Sandkühler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from PCT/EP1997/005945 external-priority patent/WO1999013045A1/fr
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP98947499A priority Critical patent/EP1015550B1/fr
Publication of EP1015550A1 publication Critical patent/EP1015550A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the invention relates to a process for the preparation of particulate detergents or cleaning agents or of multicomponent components which, in admixture with other ingredients, give rise to such agents, with the aid of a specially adapted granulation process and washing or cleaning agents prepared in this way.
  • Particulate detergents or cleaning agents with bulk densities above 600 g / l have been part of the state of the art for quite some time. In recent years, was associated with the increase in bulk density and a concentration of the washing and cleaning active ingredients, so that the consumer had to dose not only less volume, but also less mass per washing or cleaning process. The increase in bulk density, and in particular the higher concentration of agents on washing or cleaning-active substances was generally paid for by a subjective from the point of view of the consumer subjectively worse solubility, which was caused by the usually slower dissolution rate of the agent used.
  • European Patent EP 0 486 592 B1 describes granular or extruded detergents or cleaning compositions having bulk densities above 600 g / l and containing anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight. contain. They are prepared by a process in which a solid, free-flowing premix containing a plasticizer and / or lubricant of preferably aqueous surfactant pastes and / or aqueous polymer solutions, extruded at high pressures between 25 and 200 bar extruded and the strand after leaving the hole shape is cut by means of a cutting device to the predetermined granule dimension and rounded.
  • the premix consists at least partially solid ingredients, which optionally liquid ingredients such as liquid at room temperature nonionic surfactants are mixed.
  • aqueous formulations are used as plasticizers and / or lubricants in preferred embodiments.
  • plasticizers and / or lubricants in preferred embodiments.
  • organic liquids optionally in turn in admixture with water, in question.
  • the patent does not disclose any process conditions to be observed in the case of an anhydrous extrusion.
  • the extrudates produced can either already be used as detergents or cleaners or else subsequently be treated with other granules or powder components to form finished detergents or cleaners.
  • German patent application DE 195 19 139 A1 proposes to solve the conflict between high degree of compaction of the individual grain, in particular of the extrudate, on the one hand and the nevertheless required rapid and in particular gelgelever Reader disintegration of the finished detergents or cleaners in aqueous liquors before, particulate wash or detergent having a bulk density above 600 g / l, which contain anionic and / or nonionic surfactants in amounts of at least 15 wt .-%, to be designed such that at least two different granular components are used, of which at least one extruded and at least a non-extruded, wherein the surfactant content of the extruded component, including the soaps, a maximum of 15 wt.%, Based on the respective extruded component should be.
  • non-extruded component Additional surfactant components of the final detergent or cleaning agent are incorporated into the composition by one or more non-extruded component (s).
  • this method solves the problem of gelling high-density and high-surfactant detergents or cleaners when used in an aqueous liquor, but also involves a number of new problems. There may be segregation processes and corresponding fluctuations in the reproducibility of the desired washing or cleaning result.
  • the extruded portion of the agents is not only of high density, but the dried extrudates are also comparatively hard at the same time. Under the conditions of transport, storage and use, the comparatively softer granulate content of the non-extruded component (s) may thus be exposed to mechanical forces which lead in part to its reduction and thus to the formation of dust and fines by abrasion.
  • Another disadvantage of this method is that it can come to particle enlargements and crystallizations by the dissolution of solid and water-soluble constituents by the water contained, in particular under the influence of pressure during extrusion, which in turn in turn disadvantageous to the dissolving behavior of the finished. Affect funds.
  • a method for the production of heavy granules with the aid of an aqueous granulating aid is the two-stage granulation, initially plastic primary agglomerates are produced in a conventional mixer / granulator, which subsequently in apparatuses such as a Verrunder, Rotocoater, Marumerizer etc. with liquid binder and / or subsequently treated with dust and then usually dried become.
  • the granulation and simultaneous rounding can be carried out, for example, in fluidized-bed granulators which comprise a rotating disk.
  • solid starting materials are first fluidized in the fluidized bed and then with liquid binder which is introduced via tangentially oriented nozzles in the fluidized bed, agglomerated "(Size Enlargement by Agglomeration,” W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451).
  • this method can also be used for non-aqueous processes (melt-coating process), but then the advantage of the apparatus to be able to effect a simultaneous drying, is not exploited.
  • aqueous solutions, pastes or aqueous dispersions wherein the water is not used as structure breaker as said above and is usually dried away after the extrusion.
  • Extrusion without addition of water is not explicitly suggested; even in the example part, the addition of aqueous solutions takes place additionally and separately from the nonionic surfactant-structure breaker mixture; above all, however, this document does not mention any process conditions under which an anhydrous extrusion can be carried out.
  • European Patent Application EP 0 337 330 describes a process for increasing the bulk density of a spray-dried detergent by granulation in a mixer with addition of nonionic compounds.
  • nonionic compounds include ethoxylated and / or propoxylated nonionic surfactants such as primary or secondary alcohols having 8 to 20 carbon atoms and 2 to 20 moles of alkylene oxide per mole of alcohol, especially nonionic surfactants having 2 to 6 EO and HLB values of 11 or less added in the mixer become.
  • Ethylene glycols and propylene glycols can also be used there as nonionic compounds.
  • International patent application WO-A-96/10071 discloses a process for producing granules having bulk densities of at least 650 g / l and surfactant contents of at least 40 wt .-%, wherein the granulation is carried out in one step in a high shear mixer at temperatures between room temperature and 60 ° C.
  • the solid starting materials are particles having a particle size between 0.1 microns and 500 microns, wherein at least 15 wt -.% Of the particles should have a particle size above 50 microns, but sufficiently small, fine particles are present, so that a particularly large surface of the solid feed.
  • Surfactant mixtures of anionic surfactants and nonionic surfactants in weight ratios of 2: 8 to 8: 2, which may have up to 20% by weight of water, are used as binders.
  • nonionic surfactants primary C 12 -C 15 alcohols are given with 3 to 7 EO.
  • Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the process given, since this increases the viscosity of the mixture and makes the process more controllable.
  • the surfactant mixture may also contain polyethylene glycols.
  • US Pat. No. 5,108,646 describes the preparation of builder agglomerates in which 50 to 75 parts by weight of aluminosilicates or crystalline sheet silicates are agglomerated with 20 to 35 parts by weight of a binder.
  • Suitable binders are, above all, high-viscosity anionic surfactant pastes which may contain up to 90% by weight of water.
  • polymers such as polyethylene glycols having molecular weights between 1000 and 20,000 come into consideration, as well as mixtures of these and conventional nonionic surfactants such as C 9 -C 16 alcohols having 4 to 8 EO, as long as their melting range is not below 35 ° C or below 45 ° C begins.
  • the agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy input.
  • intensive mixer with a very specific, relatively high energy input.
  • a superagglomeration up to a dough-like mass occurs, at lower energy inputs only finely divided powders or very light agglomerates are obtained with an undesirably wide Komspektrum.
  • the object of the invention was to produce particulate detergents or cleaning compositions or multicomponent components which, when blended with other ingredients, produce such agents which, even with a reduced surface area, in particular with a spherical shape (bead shape), have improved disintegration in the aqueous solution Fleet exhibit.
  • the process should be economically advantageous and can dispense with costly drying steps.
  • the invention therefore relates to a process for the preparation of particulate laundry detergents or cleaning agents or multicomponent or treated raw materials which, when blended with other ingredients, provide such compositions with bulk densities above 600 g / l by combining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, initially producing a premix containing individual raw materials and / or compounds which are present as solids at room temperature and a pressure of 1 bar, and then converting this premix into a grain using compaction forces and optionally on it subsequently processed or processed, which is characterized in that the premix is substantially anhydrous and one under the molding conditions, especially at room temperature and a pressure of 1 bar, liquid molding In the form of a swollen in non-aqueous solution polymer.
  • substantially anhydrous is to be understood as meaning a state in which the content of liquid water, that is to say water not present in the form of water of hydration and / or water of constitution, is less than 2% by weight, preferably less than 1% by weight. % and in particular even less than 0.5% by weight, in each case based on the premix. Accordingly, essentially only in chemically and / or physically bound form or as part of the raw materials or compounds present as solids at temperatures below 45 ° C. at a pressure of 1 bar, water can be used as a solid, but not as a liquid, solution or dispersion in the process for the preparation of the premix are introduced.
  • the premix has a total water content of not more than 15 wt .-%, which water is thus not present in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the content of not zeolite and / or water bound to silicates in the solid premix not more than 10 wt .-%, preferably less than 7 wt .-% and with particular preference at most 2 wt .-% to 5 wt .-% is.
  • particulate detergents or cleaners are preferably understood as meaning those which have no dust-like constituents and in particular no particle sizes of less than 200 ⁇ m.
  • particle size distributions are preferred which comprise at least 90% by weight of particles having a diameter of at least 400 ⁇ m.
  • dough-shaped mass at lower energy inputs only finely divided powders or very light agglomerates are obtained with an undesirably broad particle size range.
  • the object of the invention was to produce particulate detergents or cleaning compositions or multicomponent components which, when blended with other ingredients, produce such agents which, even with a reduced surface area, in particular with a spherical shape (bead shape), have improved disintegration in the aqueous solution Fleet exhibit.
  • the process should be economically advantageous and can dispense with costly drying steps.
  • the invention therefore relates to a process for the preparation of particulate laundry detergents or cleaning compositions or multicomponent components or treated raw materials which, in admixture with other ingredients, results in such compositions having bulk densities of above 600 g / l by combining washing or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, initially producing a premix containing individual raw materials and / or compounds which are present as solids at room temperature and a pressure of 1 bar, and then converting this premix into a grain using compaction forces and optionally on it subsequently processed or prepared, characterized in that in the premix, the content of liquid water is less than 2 wt.% And in the shaping under the molding conditions, especially at room temperature and a pressure of 1 bar, liquid forming assistant in the form of a swollen in substantially nonaqueous solution polymer, the substantially non-aqueous liquid having not more than 20 wt.% Water containing the substantially non-aqueous liquid component of the forming aid from the liquid at room temperature di- or tri
  • the premix is "essentially anhydrous", which in the context of this invention means a state in which the content of liquid water, that is not in the form of water of hydration and / or water of constitution, is less than 2% by weight. preferably below 1% by weight and in particular even below 0.5% by weight, based in each case on the group-bearing starches or celluloses, phosphated starches such as starch disphosphate, but also inorganic polymers such as phyllosilicates and mixtures thereof.
  • the polyvinylpyrrolidones those having molecular weights of up to 30,000 are preferred.
  • relative molecular mass ranges of between 3,000 and 30,000, for example about 10,000.
  • the polymers which are preferably used also include hydroxypropyl starch and starch diphosphate.
  • the concentration of the polymers in the anhydrous liquids is preferably 5% by weight to 20% by weight. in particular about 6 wt .-% to 12 wt .-%.
  • the content of shaping aids is preferably at least 2% by weight but less than 20% by weight, in particular less than 15% by weight, with particular preference being given to amounts in the range from 3% by weight to 10% by weight.
  • the shaping aid for simplicity's sake, only one or the shaping aid will be mentioned. However, it should be made clear that it is always possible to use several, different shaping aids and mixtures of different shaping aids.
  • Detergents or cleansers are understood to mean compositions of this type which can be used for washing or cleaning without the need to generally add further ingredients.
  • a multi-substance mixture or compound consists of at least 2 components usually used in detergents or cleaners; However, compounds are normally only used in combination with other ingredients, preferably together with other compounds.
  • a treated raw material in the context of this invention is a relatively finely divided raw material which has been converted by the process according to the invention into a coarser particle. Strictly speaking, a treated raw material in the context of the invention is a compound if the treatment agent is an ingredient commonly used in detergents or cleansers.
  • ingredients used in the process of the invention may be prepared separately compounds, but also raw materials which are powdery or particulate (finely divided to coarse), but in any case at room temperature and a pressure of 1 bar - with the exception of those optionally present at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants - in solid form.
  • particulate detergents or cleaners may also be tablets having customary dimensions for washing or cleaning agent tablets for household use, for example with weights of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of about 35 mm to 40 mm, act.
  • Swollen polymers used in the context of the present invention as a component of the formulating aid are those which lead to gelatinous states in essentially non-aqueous liquids.
  • Suitable systems are those of essentially nonaqueous liquid and polymer which have at room temperature in the presence of the polymer at least 20 times, in particular 300 times to 5000 times higher viscosity than the substantially nonaqueous liquid alone.
  • the viscosity of the forming aid is preferably in the range of from 200 mPas to 100,000 mPas, especially from 400 mPas to 50,000 mPas, as measured, for example, by means of a Brookfield rotary viscometer.
  • the viscosity preferably deviates only relatively little from the values at room temperature and is preferably in the range from 250 mPas to 40,000 mPas.
  • the suitable constituents of the liquid component of the shaping assistant include liquid at room temperature, di- or trihydric alcohols having boiling points (at 1 bar) above 80 ° C, especially above 120 ° C, their mixtures and mixtures thereof with liquid at room temperature single-grade alcohols having boiling points (at 1 bar) above 80 ° C, especially above 120 ° C; such as, for example, n-propanol, isopropanol, n-butanol, s-butanol, isobutanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerol, di- or triethylene or -propylene glycol or mixtures thereof, in particular glycerol and / or ethylene glycol.
  • these liquids may also contain water, as long as it is observed that the molding agent is used only in amounts such that the above limit of 2% by weight of additional liquid water in the premix is not used is reached.
  • a substantially non-aqueous liquid in this sense contains not more than 20% by weight, in particular not more than 15% by weight of water, in one particularly preferred embodiment liquids having water contents below 1% by weight, in particular at most 2 to 5 wt .-% is. It is particularly advantageous if the premix contains no water that is not bound to the builders. This is technically difficult to realize; As a rule, at least always traces of water are introduced by the raw materials and compounds.
  • the content of solid compounds used in the premix at temperatures below 45 ° C non-aqueous liquid components, excluding the liquid at room temperature shaping auxiliary, is preferably up to 10 wt .-%, advantageously up to 6 wt.%, Each based on the premix.
  • solid compounds are used in the premix, which contain conventional at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants and which were prepared separately by all known methods of preparation - for example by spray drying, granulation or spraying of Shinbeads.
  • premixes can be prepared which, for example, up to about 10 wt .-%, preferably below, in particular up to a maximum of 8 wt .-% and for example between 1 and 5 wt.% Of nonionic surfactants, based on the finished composition, allow.
  • at least 80% by weight of the used compounds and individual raw materials have a softening point or melting point above 150 ° C at atmospheric pressure (1 bar).
  • the premix in addition to the solid constituents and the molding aid liquid at room temperature, may contain up to 10% by weight of liquid nonionic surfactants at temperatures below 45 ° C. and a pressure of 1 bar, in particular the alkoxylated alcohols customarily used in detergents or cleaners. such as fatty alcohols or oxo alcohols having a C chain length of between 8 and 20 and especially an average of 3 to 7 ethylene oxide units per mole of alcohol.
  • the addition of the liquid nonionic surfactants can be carried out in the amounts which still ensure that the premix is in free-flowing form. If such liquid nonionic surfactants are incorporated into the premix, it is preferred that liquid nonionic surfactants and the disintegrating styling aid be incorporated separately into the process.
  • the liquid surfactants are applied to the powder stream in a continuous production process, in particular by means of nozzles, and are absorbed by the latter.
  • the premix also contains at least one raw material or at least one compound which, as stated above, serves as a shaping aid.
  • the shaping aid in the form of the anhydrous swollen polymer can be mixed with the remaining constituents of the premix before the shaping step. This is particularly preferred when the shaping takes place by an extrusion step or by means of a tableting or other pressing operation. It can also be sprayed onto the premix during shaping or added dropwise to the premix, which is particularly preferred in shaping by build-up granulation.
  • the temperature during the shaping step is preferably in the case of room temperature or the temperature resulting from the energy input of the molding device, but it is also possible to increase the premix and, if appropriate, the molding aid to be added separately during molding to higher temperatures, for example 35 ° C. to 80 ° C. to heat, with temperatures in the range of 45 ° C to 65 ° C may be particularly advantageous.
  • the shaping aid in the process step of the compacting shaping as homogeneous as possible in the compacted Well distributed.
  • the Applicant is of the opinion that by a homogeneous distribution of the shaping aid in the sense of a binder within the premix under the process conditions of compression, the solid compounds and the optionally present individual raw materials so enclosed by the binder and then together be glued that the finished end products are composed almost exactly of these many small individual particles, which are held together by the binder, which performs the task of a preferred thin partition between these individual particles.
  • a honeycomb-like structure these honeycombs are filled with solids (compounds or Einzelrohstofien).
  • the forming aid must therefore be of the type that the adhesive properties come into play at the molding temperatures. On the other hand, it is also essential for the choice of the type and amount of forming aid used, that although the binding properties are not lost after the forming step within the final product, the cohesion of the final product is thus secured, but that the final product itself under normal storage and transport conditions not glued. It must be surprising that when using the molding aid at room temperature, a final product is still obtained which neither at room temperature nor at slightly elevated temperatures by 30 ° C, ie at summer temperatures and under storage or transport conditions, tends to stick.
  • the joining together of the washing or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping can be achieved by conventional methods in which compaction forces are applied, such as granulating, compacting, for example Roll compacting or extruding, or tableting, optionally with the addition of conventional disintegrants, and pelletizing done.
  • compaction forces such as granulating, compacting, for example Roll compacting or extruding, or tableting, optionally with the addition of conventional disintegrants, and pelletizing done.
  • spray-dried granules can be used as prefabricated compounds in the premix, but the invention is by no means limited thereto. Rather, in the process according to the invention, it is not advisable to use spray-dried granules, since even finely divided raw materials with dust-like proportions can be easily processed according to the invention without being precompounded beforehand, for example spray-dried.
  • the substantially anhydrous process allows not only that peroxy bleach can be processed without loss of activity, it is thereby also possible to process peroxy bleach and bleach activators together in a particle without having to fear serious loss of activity.
  • the compacting shaping of the process is carried out with the aid of an agglomeration step, wherein the premix is agglomerated in a suitable device and the shaping aid defined above assumes the role of a binder.
  • the granulation process can be carried out continuously or discontinuously.
  • the procedure is preferably such that the solid constituents of the premix to be compressed are introduced into a granulator in which a mixer may also be used, if appropriate by addition of a liquid nonionic surfactant and any dusts present, and the shaping assistant is introduced into the granulator ,
  • the desired average particle size of the granules can be adjusted by the type and amount of forming aid and by the machine and operating parameters, such as speed and residence time, and temperature.
  • Pelletizers, rotary drums, ploughshare mixers with chopper from Lödige®, high-performance mixers with rotating mixing vessels and swirlers, for example from Laeis Bucher® or Eirich®, intensive mixers with shaving heads, for example from LIPP Mischtechnik® or Imcatec®, Drais, can be used as suitable granulators ®, Fukae® or Forberg® mixers and the so-called Rotorcoater® from Glatt® with horizontal and inclined turntables up to 50 °. Less suitable are Lödige® CB mixers, PK-Niro® zig-zag mixers, a Ballestra® warp mix and Hosokawa® or Schugi® mixers.
  • a fluid bed or a horizontal mixer for example a Nautamixer®, is also less suitable.
  • compositions according to the invention in tablet form can be produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range of, for example, 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa.
  • the solids for the preparation of the solid and free-flowing premix are first mixed together at room temperature to slightly elevated temperatures, which are preferably in the range of room temperature to 35 ° C in a conventional mixing and / or granulating.
  • the compaction step of the process according to the invention is then carried out by means of an extrusion of the premix thus obtained, as described, for example, in European Patent EP 0 486 592 B1 or International Patent Applications WO-A-93/02176 and WO-A-94/09111.
  • the pre-mixture is extruded under pressure and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.
  • the homogeneous and solid premix usually contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry of specific work plastically softened and extrudable.
  • a plasticizer and / or lubricant which causes the premix under the pressure or under the entry of specific work plastically softened and extrudable.
  • anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also polymers such as polymeric polycarboxylates, are included.
  • the forming aid prevents or at least reduces the sticking of adhesions Apparatus walls and Verdichtungswerk-Leugen. This applies not only to the processing in the extruder, but equally also to processing, for example, in continuous mixers / granulators or rollers.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder with a co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
  • the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
  • the extrudate is reduced to approximately spherical to cylindrical granules by means of a rotating bladed knife.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of a substantially uniformly predictable particle size succeeds, wherein in detail the absolute particle sizes can be adapted to the intended use.
  • particle diameters of at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
  • the length / diameter ratio of the chopped primary granules in one important embodiment is in the range of about 1: 1 to about 3: 1.
  • extrusion / compression can also be performed in low-pressure extruders, in the Kahl press or in the Bextruder®.
  • any edges present on the primary granulate are rounded off after the compaction step, so that finally spherical to approximately spherical grains can be obtained, if these do not already arise in the first compacting shaping step.
  • small amounts of dry powder for example, zeolite powder, such as zeolite NaA powder, may be included in this stage.
  • the particle size distribution of the premix is applied substantially wider than that of the end product according to the invention and produced according to the invention.
  • the premix may contain much larger Feinkomanteile, even dust, possibly also coarser particles, but it is preferred that a premix having a relatively broad particle size distribution and relatively high levels of fine grain in a final product with relatively narrow particle size distribution and relatively low levels of fine grain is transferred.
  • the process according to the invention is essentially anhydrous - i.
  • impurities water contents
  • anhydrous - is not only the risk of gelling the surfactant raw materials already minimized in the manufacturing process to exclude, in addition, an environmentally valuable process is also provided, as by waiving a subsequent drying step not only energy is saved but also emissions, as they occur predominantly in conventional types of drying, can be avoided.
  • agents, compounds and treated raw materials thus have an improved dissolution rate compared to such agents, compounds and treated raw materials, although the same final composition but were not prepared by the process according to the invention, ie were not prepared under anhydrous conditions using an anhydrous swollen polymer as a shaping aid:
  • another object of the invention is a particulate detergent or cleaning agent, which was prepared by the process according to the invention and whose release behavior is dependent only on the dissolution behavior of the individual raw materials and compounds used.
  • Applicant believes that this particular release behavior is effected by a honeycomb-like structure of the particles, these honeycombs being filled with solids.
  • Another object of the invention are compounds prepared by the process of the invention and treated raw materials, such as builder granules, bleach activator granules or enzyme granules.
  • treated raw materials show a surprisingly high rate of dissolution in water, especially when the raw material was used in itself in very finely divided, optionally ground form.
  • base granules, compounds and treated raw materials are provided which have spherical shape or pearl shape.
  • the bulk density of process end products prepared according to the invention is preferably above 700 g / l, in particular between 750 and 1000 g / l. Even if the granules are treated with other ingredients which have lower bulk densities, the bulk density of the final product does not decrease to the extent that would normally have been expected. It is believed that approximately spherical means, and particularly extrudates made by the process of the invention, are more like the ideal shape of a sphere with a smooth, "smeared" surface than the agents and extrudates made by conventional and, in particular, aqueous processes. As a result, better space filling is achieved, which leads to a higher bulk density, even if components are admixed, which have neither spherical structure nor such a high bulk density.
  • the resulting particulate process end products can either be used directly as detergents or cleaning agents or aftertreated by conventional methods and / or be prepared.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients of detergents or cleaners, for example zeolites, whereby the bulk density is optionally further increased.
  • a preferred after-treatment is also the procedure according to the German patent applications DE 195 24 287 and DE 195 47 457, wherein dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products according to the invention, which serve as a core, and thus Means arise, which have these so-called fines as an outer shell.
  • this in turn is done by an agglomeration step, wherein as a binder, the shaping aids of the method according to the invention can be used.
  • agglomeration step wherein as a binder, the shaping aids of the method according to the invention can be used.
  • the particulate process end products of the present invention serve as a compound to which other ingredients, and optionally other compounds, are added.
  • bleach activators and foam inhibitors especially salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or other polycarboxylates, but also organic acids such as citric acid are mixed in the treatment.
  • the admixing components are used in granular form and with a particle size distribution which is tailored to the particle size distribution of the compositions and compounds according to the invention.
  • a particulate detergent which consists of at least 80% by weight of compounds prepared according to the invention and / or treated raw materials. In particular, it consists of at least 80 wt .-% of a base granules according to the invention.
  • the remaining ingredients may have been prepared and admixed by any known method. It is, however preferably that these remaining constituents, which may be compounds and / or treated raw materials, were prepared by the process according to the invention. In particular, this makes it possible to produce base granules and remaining constituents with approximately the same flowability, bulk density, size and particle size distribution.
  • Important ingredients of the agents and ingredients of the invention, which are used in the process according to the invention are surfactants, in particular anionic surfactants, which are preferably at least in amounts of 0.5 wt .-% in the inventive compositions or the inventively prepared compositions.
  • surfactants include in particular sulfonates and sulfates, but also soaps.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14- C 15 alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are normally only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • sulfosuccinates whose fatty alcohol residues are of ethoxylated fatty alcohols with narrow homolog distribution derive, more preferably.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are in particular soaps, preferably in amounts of 0.2 to 5 wt.%.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactants are contained or used in the compositions according to the invention or in the process according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.
  • nonionic surfactants are preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 12 -alcohols with 3 EO or 4 EO, C 9 -C 11 -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 of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 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.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 5 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 6 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • nonionic surfactants are C 12 -C 18 fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO.
  • nonionic surfactants of the amine oxide type for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 A1 or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061 A1.
  • End group-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 are distinguished in particular by their bi-and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955.
  • inorganic and organic builders are among the most important ingredients of detergents and cleaners.
  • the zeolite containing fine-crystalline, synthetic and bound water is preferably zeolite A and / or P.
  • the zeolite P used is, for example, zeolite MAP® (commercial product from Crosfield).
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt.%, Based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 . yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 of 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, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of 10 nm to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished composition.
  • tripolyphosphates already in small amounts up to a maximum of 10 wt .-%, based on the finished composition, in combination lead with other builders to a synergistic improvement of the secondary washing ability.
  • Suitable substitutes or partial substitutes for the zeolite are also phyllosilicates of natural and synthetic origin.
  • Such sheet silicates are known for example from the patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their usability is not limited to a specific composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Suitable phyllosilicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite.
  • small amounts of iron may be incorporated in the crystal lattice of the phyllosilicates according to the above formulas.
  • the layered silicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling state or on the type of processing.
  • Useful sheet silicates are known, for example, from US Pat. No. 3,966,629, EP 0 026 529 and EP 0 028 432.
  • phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.
  • Useful organic builders are, for example, usable in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • these acids when used in the premix according to the invention and are not subsequently added, used anhydrous.
  • Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the Hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000.
  • a preferred dextrin is described in the European patent application EP 0 703 292 A1 .
  • the oxidized derivatives of oligosaccharides for example of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are described, for example, in European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and in international patent applications WO 92/18542, WO 93/08251, WO 94/28030 , WO 95/07303, WO 95/12619 and WO 95/20608.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates are particularly preferred in this connection, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0 150 930 and Japanese Patent Application JP 93/339896.
  • Suitable amounts are in zeolite-containing and / or silicate-containing Fonnulmaschineen at 3 to 15 wt.%.
  • Suitable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in International Patent Application WO 95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% of maleic acid.
  • Their relative molecular mass, based on free acids, is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000.
  • the content of (co) polymeric polycarboxylates in the usual range is preferably from 1 to 10% by weight. %.
  • biodegradable polymers of more than two different monomer units for example those according to the German patent application DE 43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German Patent DE 42 21 381 as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids, their salts or their precursors are also particularly preferred.
  • polyaspartic acids or their salts and derivatives of which German Patent Application DE 195 40 086 discloses that they are co-builders. Properties also have a bleach-stabilizing effect.
  • Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • compositions may also contain components that positively affect oil and grease washout from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt.%,
  • nonionic cellulose ether as well as the known from the prior art polymeric esters of phthalic acid and / or terephthalic acid with monomeric and / or polymeric diols or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • Particularly preferred of these are the sulfonated derivatives of phthalic and
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving silicates or mixtures thereof; in particular, alkali metal carbonate and amorphous alkali metal silicate, above all sodium silicate with a molar ratio of Na 2 O: SiO 2 of from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of the sodium carbonate agent is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of the sodium silicate agent if it is not to be used as a builder, is generally up to 10% by weight and preferably between 2 and 8% by weight, but may otherwise be higher.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group-containing amino acids and / or salts thereof.
  • a partial to complete replacement of the alkali metal carbonates by glycine or glycinate takes place.
  • the other detergent ingredients include grayness inhibitors, foam inhibitors, bleach and bleach activators, optical brighteners, enzymes, fabric softening substances, dyes and fragrances and neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • acidic salts or slightly alkaline salts Bisulfates and / or bicarbonates or the abovementioned organic polycarboxylic acids, which can also be used simultaneously as builders, are preferred as the acidifying component. Particularly preferred is the use of citric acid, which is either added subsequently (customary procedure) or - in anhydrous form - is used in solid premix.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 25% by weight and in particular from 10 to 20% by weight, with perborate monohydrate or percarbonate being advantageously used.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoyisuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and the enol esters
  • TAED
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • the salts of polyphosphonic acids used are preferably the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 1.5% by weight.
  • Suitable enzymes are in particular those from the class of hydrolases, such as proteases, lipases, cutinases, amylases, cellulases or mixtures thereof in question.
  • Oxireductases are also suitable.
  • Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the agents may contain other enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • Diphenylstyryle for example, the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4 -Chlorstyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • the means E1 to E5 as well as for comparison the means V1 and V2 not according to the invention were prepared as follows:
  • the premix was plasticized and extruded through the extruder head hole die plate into fine strands with a diameter of 1.4 mm at the pressure indicated in Table 1, which were comminuted to approximately spherical granules by means of a doctor blade after nozzle exit ( Length / diameter ratio about 1, hot break).
  • the resulting warm granules were rounded for one minute in a commercially available Rumerier Marumerizer® type and optionally coated with a finely divided powder.
  • Another agent V3 was prepared, which contained the same ingredients in the final product as E2 , but in which the copolymer was not introduced in anhydrous swollen form, but as about 30 wt .-% aqueous solution in the process. The excess water was then dried away in a fluidized bed. The bulk density of the extrudate V3 was 770 g / l, the L-test gave a value of 28%.
  • compositions of spray-dried powders SP1 and SP2 are Compositions of spray-dried powders SP1 and SP2:
  • Spray dried powder 1 26.00% by weight of C 9 -C 13 -alkylbenzenesulfonate 8.50% by weight of sodium carbonate 41.33% by weight of zeolite A, based on anhydrous active substance punching 9.50 wt .-% copolymeric sodium salt of acrylic acid and maleic 1.00% by weight of phosphonate 12.00% by weight of water 0.42% by weight of optical brightener Residual salts from solutions
  • Spray dried powder 2 26.00 wt .-% C 9 -C 13 alkylbenzenesulfonate 42.83% by weight of zeolite A, based on anhydrous active substance punching 5.50 wt .-% copolymeric sodium salt of acrylic acid and maleic 1.00% by weight of phosphonate 5.00% by weight of sodium carbonate 6.00% by weight sodium sulfate 12.00% by weight of water 0.42% by weight of optical brightener Residual salts from solutions Table 1 composition E1 E2 E

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Claims (17)

  1. Procédé de préparation d'agents de lavage ou de nettoyage sous forme de particules resp. de composants à plusieurs substances ou de substances brutes traitées, qui résultent, lors du mélange avec d'autres constituants, en ces agents, présentant des densités apparentes supérieures à 600 g/l, par la réunion de compounds et/ou de substances brutes d'agents de lavage ou de nettoyage avec façonnage simultané ou consécutif, en préparant d'abord un prémélange, qui contient les différentes substances brutes et/ou les compounds, qui se trouvent à température ambiante et une pression de 1 bar sous forme de solides, puis on transforme ce prémélange en utilisant des forces de compactage en un grain puis, le cas échéant, on le transforme consécutivement davantage ou on le prépare, caractérisé en ce que dans le prémélange, la teneur en eau liquide est inférieure à 2% en poids et on utilise, lors du façonnage, un adjuvant de façonnage liquide dans les conditions de façonnage, en particulier également à température ambiante et à une pression de 1 bar, sous forme d'un polymère gonflé dans une solution essentiellement non aqueuse, le liquide essentiellement non aqueux ne présentant pas plus de 20% en poids d'eau, le composant liquide essentiellement non aqueux de l'adjuvant de façonnage étant choisi parmi les alcools divalents ou trivalents, liquides à température ambiante, présentant des points d'ébullition (à 1 bar) supérieurs à 80°C, leurs mélanges et leurs mélanges avec des alcools monovalents liquides à température ambiante, présentant des points d'ébullition (à 1 bar) supérieurs à 80°C et le système constitué par le liquide essentiellement non aqueux et le polymère présentant, à température ambiante, en présence du polymère, une viscosité au moins 20 fois supérieure à celle du liquide essentiellement non aqueux seul.
  2. Procédé selon la revendication 1, caractérisé en ce que le polymère gonflé dans une solution essentiellement non aqueuse est un système constitué par un liquide essentiellement non aqueux et un polymère, qui présente, à température ambiante, en présence du polymère, une viscosité 300 à 5000 fois supérieure à celle du liquide essentiellement non aqueux seul.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la viscosité de l'adjuvant de façonnage se situe, à température ambiante, dans la plage de 200 mPa.s à 100 000 mPa.s, en particulier de 400 mPa.s à 50 000 mPa.s.
  4. Procédé selon la revendication 3, caractérisé en ce qu'à une température plus élevée, la viscosité de l'adjuvant de façonnage ne s'écarte que relativement peu des valeurs à température ambiante et est située, à 60°C, dans la plage de 250 mPa.s à 40 000 mPa.s.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le composant liquide essentiellement non aqueux de l'adjuvant de façonnage est choisi parmi les alcools divalents ou trivalents liquides à température ambiante présentant des points d'ébullition (à 1 bar) supérieurs à 120°C, leurs mélanges et leurs mélanges avec des alcools monovalents liquides à température ambiante présentant des points d'ébullition (à 1 bar) supérieurs à 80°C, en particulier supérieurs à 120°C.
  6. Procédé selon la revendication 5, caractérisé en ce que le composant liquide essentiellement non aqueux de l'adjuvant de façonnage est choisi parmi le n-propanol, l'iso-propanol, le n-butanol, le s-butanol, l'iso-butanol, l'éthylèneglycol, le 1,2-propylèneglycol ou le 1,3-propylèneglycol, le glycérol, le diéthylèneglycol, le triéthylèneglycol, le dipropylèneglycol ou le tripropylèneglycol ou leurs mélanges.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le liquide essentiellement non aqueux ne contient pas plus de 15% en poids d'eau.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polymère, qui conduit dans le liquide essentiellement non aqueux à un système gonflé est choisi parmi la polyvinylpyrrolidone, le poly(acide acrylique), les copolymères de l'acide acrylique et d'acide maléique, le poly(alcool vinylique), le xanthane, les amidons partiellement hydrolysés (maltodextrines), les alginates, l'amylopectine, les amidons ou celluloses portant des groupes méthyléther, hydroxyéthyléther, hydroxypropyléther et/ou hydroxybutyléther, les amidons phosphatés tels que le diphosphate d'amidon et les polymères inorganiques, tels que les silicates à couches ainsi que leurs mélanges.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que dans l'adjuvant de façonnage, la concentration en polymère dans le liquide essentiellement non aqueux est de 1% en poids à 80% en poids, en particulier de 2% en poids à 60% en poids.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la teneur en adjuvant de façonnage, par rapport au prémélange à compacter, est de 2% en poids à moins de 25% en poids, en particulier de 3% en poids à 15% en poids.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'on utilise un adjuvant de façonnage qui se dissout complètement, à une concentration de 8 g dans 1 l d'eau à 30°C, en moins de 90 secondes.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le prémélange présente au total une teneur en eau qui n'est pas supérieure à 20% en poids, la teneur en eau non liée à une zéolithe et/ou des silicates n'étant pas supérieure à 15% en poids et en particulier inférieure à 12% en poids.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le façonnage de compactage est réalisé à l'aide d'une étape d'agglomération, le prémélange étant granulé par agglomération dans un dispositif approprié à cette fin et l'adjuvant de façonnage sous forme du polymère gonflé dans un liquide essentiellement non aqueux remplissant le rôle d'un liant.
  14. Procédé selon la revendication 13, caractérisé en ce qu'on dispose au préalable les constituants solides du prémélange à compacter dans un granulateur, pour lequel on peut également utiliser un mélangeur, on lie le cas échéant par l'addition d'un agent tensioactif non ionique liquide les poussières éventuellement présentes et on introduit l'adjuvant de façonnage dans le granulateur.
  15. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le façonnage est réalisé par extrusion, le prémélange étant compacté sous pression, plastifié, extrudé sous forme de brins fins dans la filière à trous dans la tête d'extrusion et enfin broyé au moyen d'un couteau rotatif, de préférence en grains de granulat sphériques (en forme de perles) à cylindriques.
  16. Agent de lavage granulé ou extrudé, préparé selon le procédé selon l'une quelconque des revendications 1 à 15, son comportement de dissolution dépendant du comportement de dissolution des différentes substances brutes et des compounds utilisés, caractérisé en ce qu'il est constitué à raison d'au moins 50% en poids du compound préparé selon l'invention et/ou des substances brutes traitées selon l'invention et en particulier à raison d'au moins 60% en poids par un granulat de base ou par un extrudat de base préparé selon l'invention, où il est particulièrement avantageux que les autres constituants soient également des compounds ou des substances brutes traitées qui ont été préparés selon le procédé selon l'une quelconque des revendications 1 à 15.
  17. Agent selon la revendication 16, caractérisé en ce qu'il présente comme enveloppe extérieure des constituants en forme de poussière ou des constituants au moins finement divisés (ce qu'on appelle les proportions fines), qui sont accolés par une agglomération en masse fondue.
EP98947499A 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires Expired - Lifetime EP1015550B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98947499A EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE19638599A DE19638599A1 (de) 1996-09-20 1996-09-20 Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels
PCT/EP1997/004975 WO1998012299A1 (fr) 1996-09-20 1997-09-11 Procede de production d'un detergent ou nettoyant particulaire
WOPCT/EP97/04975 1997-09-11
WOPCT/EP97/05945 1997-10-28
PCT/EP1997/005945 WO1999013045A1 (fr) 1997-09-11 1997-10-28 Procede pour la production de detergents particulaires
PCT/EP1998/005548 WO1999013046A1 (fr) 1997-09-11 1998-09-02 Procede de production de nettoyants et detergents particulaires
EP98947499A EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

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EP1015550A1 EP1015550A1 (fr) 2000-07-05
EP1015550B1 true EP1015550B1 (fr) 2006-02-01

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EP98947499A Expired - Lifetime EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

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JP (1) JP2001500557A (fr)
KR (3) KR20010029500A (fr)
CN (1) CN1187435C (fr)
AT (1) ATE256176T1 (fr)
CZ (1) CZ296295B6 (fr)
DE (2) DE19638599A1 (fr)
ES (1) ES2213222T3 (fr)
PL (1) PL331987A1 (fr)
RU (1) RU2200190C2 (fr)
SK (1) SK285376B6 (fr)
TR (1) TR199900582T2 (fr)
UA (1) UA64724C2 (fr)
WO (1) WO1998012299A1 (fr)

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DE19723616A1 (de) * 1997-06-05 1998-12-10 Henkel Kgaa Granulares Waschmittel
DE19746781A1 (de) * 1997-10-23 1999-04-29 Henkel Kgaa Verfahren zur Herstellung duftverstärkter Wasch- oder Reinigungsmittel
DE19753310A1 (de) * 1997-12-02 1999-06-10 Henkel Kgaa Rohstoff-Compounds mit hohem Schüttgewicht
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
CN1346400A (zh) * 1998-09-25 2002-04-24 宝洁公司 溶解性改进的粒状洗涤剂组合物
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
DE19858887A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Kompaktat mit silicatischem Builder
DE10031619A1 (de) 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE10137925A1 (de) 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
WO2008054335A1 (fr) * 2006-10-30 2008-05-08 Eduard Valerievich Belinskiy Moyen de lavage granulé synthétique et cabine de douche associée
US8119112B2 (en) * 2008-01-31 2012-02-21 Bausch & Lomb Incorporated Ophthalmic compositions with an amphoteric surfactant and hyaluronic acid
GB0915572D0 (en) * 2009-09-07 2009-10-07 Reckitt Benckiser Nv Detergent composition
KR102184251B1 (ko) * 2013-03-22 2020-11-30 바스프 에스이 계면활성제로서의 알킬 글리코시드
CN104152293A (zh) * 2014-07-28 2014-11-19 张洪山 洗涤用碱性蛋白彩色粒子成套生产线
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
US9512388B2 (en) * 2015-02-18 2016-12-06 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD784819S1 (en) 2015-02-18 2017-04-25 Henkel Us Iv Corporation Container for a solid state detergent
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
WO2020050426A1 (fr) * 2018-09-03 2020-03-12 주식회사 프랜드 Procédé de préparation de billes de gommage à propriétés antibactériennes à base d'amidon

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DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions

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RU99108122A (ru) 2001-02-20
JP2001500557A (ja) 2001-01-16
UA64724C2 (uk) 2004-03-15
CZ296295B6 (cs) 2006-02-15
EP1015550A1 (fr) 2000-07-05
DE19638599A1 (de) 1998-03-26
EP0931137B1 (fr) 2003-12-10
CN1230984A (zh) 1999-10-06
ES2213222T3 (es) 2004-08-16
PL331987A1 (en) 1999-08-16
WO1998012299A1 (fr) 1998-03-26
KR20010023926A (ko) 2001-03-26
KR20010029500A (ko) 2001-04-06
EP0931137A1 (fr) 1999-07-28
CZ97799A3 (cs) 1999-09-15
SK285376B6 (sk) 2006-12-07
CN1187435C (zh) 2005-02-02
SK35299A3 (en) 1999-07-12
RU2200190C2 (ru) 2003-03-10
TR199900582T2 (xx) 1999-06-21
KR20010023917A (ko) 2001-03-26
ATE256176T1 (de) 2003-12-15

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