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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0086—Laundry tablets
• • 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
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0082—Coated tablets
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• EP-A-0 716 144 (Unilever), which describes tablets with an external shell made of water-soluble material
• EP-A-0 711 827 (Unilever), which contain a citrate with a defined solubility as an ingredient.
• binders which may have an explosive action (in particular polyethylene glycol) is disclosed in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material be produced, always being pressed below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.
• the present invention is therefore based on the object of providing detergent tablets with further improved disintegration and dissolving properties by targeted incorporation of a cellulose-based disintegrant.
• the invention relates to a detergent tablet made of compressed, particulate detergent, comprising surfactant (s), builder, a cellulose-based disintegrant and, if appropriate, further detergent and detergent constituents, the disintegrant in the molded body being separated from hydrophobizing substances in a defined manner Region of the molded body is present.
• the detergent tablets of the present invention solve the problem of inadequate disintegration of these tablets due to insufficient disintegration activity of the cellulose-based disintegration agent by spatially separating hydrophobizing components which can reduce the disintegration activity from the disintegration agent.
• a preferred embodiment of the present invention provides that the delimited region which contains the disintegrating agent does not contain the disintegrating agent alone but in a mixture with other non-hydrophobic substances.
• Preferred detergent tablets contain the disintegrant and other non-hydrophobizing ingredients of detergents in the defined region.
• the delimited region contains the disintegrant and at least part of the total amount of the builders and ionic surfactants contained in the molded body.
• Particularly preferred washing and cleaning Molded agent bodies have a delimited region which contains bleach and / or bleach activator in addition to the disintegrant.
• the applicant assumes that the separation of the hydrophobizing substances from the disintegrant has the effect that the water access to the disintegrant is facilitated and the disintegration of the shaped bodies is thereby accelerated.
• hydrophobizing substances are understood to mean those substances which reduce the water wettability of the disintegrant or of the secondary particles which contain the disintegrant.
• the typically hydrophobic substances such as paraffins and silicones (used as defoamers in detergents and cleaning agents) or perfume oils are not present in the delimited region.
• Other hydrophobic substances are, for example, the nonionic surfactants, which do not spontaneously dissolve in water, but tend to gel. Although not all nonionic surfactants have this hydrophobic character, a theoretically derived division into hydrophobic and non-hydrophobic nonionic surfactants is difficult.
• the person skilled in the art will possibly have no difficulty in finding out nonionic surfactants which have an excessively hydrophobic character and keeping them out of the defined region.
• the HLB values of the non-ionic surfactants are indicative.
• Non-ionic surfactants with HLB values below 10 tend to be hydrophobic, while those with HLB values above 12 can be considered non-hydrophobic.
• the spatially delineated region containing the disintegrant is preferably devoid of nonionic surfactants.
• Preferred moldings contain, as hydrophobizing substances, nonionic surfactants which are spatially separated from the delimited region.
• foam inhibitors soaps of natural or synthetic origin come into consideration which have a high proportion of C I8 . 24 fatty acids.
• Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
• the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. Provided that they are used in the moldings according to the invention, these substances are not present in the delimited region which contains the disintegrant.
• Preferred detergent tablets contain foam inhibitors as the hydrophobizing substance, which are spatially separated from the delimited region.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate Benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate, ethers include, for example, benzylethyl ether, aldehydes include linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetalde- hyd, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, oc-
• the dyes used in detergents and cleaning agents are generally readily water-soluble and do not absorb onto the treated goods, they can also be used together with the disintegrant in the spatially defined region.
• the fragrances which have a pronounced hydrophobic character should be spatially separate from the disintegrant.
• Preferred detergent tablets contain perfume as a hydrophobizing substance, which is spatially separated from the delimited region.
• spatial separation is understood to mean that the separate layer, covering or individual insert which contains the disintegrant is completely free from the hydrophobic substances mentioned.
• this can be achieved, for example, by producing a separate secondary granulate which, in addition to the disintegrant, contains only non-hydrophobizing substances and, after mixing with other constituents and / or compounds, is pressed to give shaped articles.
• Hydrophobic substances can then be used in the other layer (s).
• the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
• the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant.
• Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%>) undamaged.
• microcrystalline celluloses which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
• the detergent tablets of the present invention preferably additionally contain further ingredients customary in detergents and cleaners from the group of the surfactants, builders, bleaching agents, bleach activators, enzymes, optical brighteners and other auxiliaries or active ingredients. These substances are described in more detail below.
• Anionic, nonionic, cationic and / or amphoteric surfactants can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
• the total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the moldings, with surfactant contents above 15% by weight being preferred.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• Preferred surfactants of the sulfonate type are C 9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C 12 are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
• Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
• R * for hydrogen
• [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar. can be obtained with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 represents a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms
• C M - alkyl or phenyl radicals being preferred
• [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.
• the builders that can be contained in the detergent tablets according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 'H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• M sodium or hydrogen
• x is a number from 1.9 to 4
• y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• Such crystalline layered 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 represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na ⁇ O ⁇ y ⁇ O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP ⁇ R (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and or P are also suitable.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
• small additions 18 fatty alcohols can contain nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C I2 -C having 2 to 5 ethylene - Oxide groups, C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• bleach activators can be incorporated as the sole constituent or as an ingredient of component b).
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give ahphatic peroxocarboxylic acids with 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• bleach catalysts can also be incorporated into the moldings.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru lack of revelation, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts .
• the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
• Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• the moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
• brighteners of the substituted diphenylstyryl type may be present, e.g.
• the particulate detergent and cleaning agent to be compressed is pressed at temperatures below 30 ° C. and pressing forces below 15 N / cm 2 .
• the molded articles according to the invention are actually produced first by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular pressing them into tablets, whereby conventional methods can be used.
• the premix is compacted in a so-called die between two punches to form a solid concentrate. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
• the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
• the constant dosage tion is preferably achieved by volumetric metering of the premix.
• the upper punch touches the premix and lowers further in the direction of the lower punch.
• the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed.
• the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
• the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
• the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
• rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
• the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
• Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
• the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
• Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
• several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before the further filling.
• jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
• Rotary tablet presses can also be equipped with single or multiple tools so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
• the throughputs of modern rotary tablet presses are over one million tablets per hour.
• Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
• the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
• the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
• the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
• the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic Liquor presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
• the spatial shape of another embodiment of the shaped body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process.
• the detergent tablets can also be used without problems via a metering aid and are preferred in the context of the present invention.
• Another preferred molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments are broken off from this “bar” at the predetermined breaking points, which represent the short thin segments, and into the This principle of the “bar-shaped” shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
• the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
• a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while the two cover layers are used in the case of the stacked shaped body and the is in the case of the shell-shaped shaped body outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
• Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash liquor; rather, it is also possible in such cases to put the molded body in direct contact with the textiles in the machine without fear of bleaching and the like.
• the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else by means of the melt coating method Received coating.
• the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
• Table 2 Composition of the basic granulate [% by weight]:
• the perfume was added to the base granules separately from the cellulose before being mixed with the pulverulent preparation components.
• Comparative example 3 represents a tablet in which the nonionic surfactants were not introduced via the base granules, but instead were placed on a mixture of anionic surfactant granules and powdered processing components. The perfume was sprayed onto the mixture as the last substance.
• the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
• the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.
• 3 tablets of 40 g each were placed in the wash-in chamber of the washing machine in question. After the induction process, the residue was dried in the chamber and weighed out.

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• 1997
  • 1997-09-09 DE DE1997139384 patent/DE19739384A1/de not_active Withdrawn
• 1998
  • 1998-08-29 JP JP2000510832A patent/JP2001515953A/ja active Pending
  • 1998-08-29 CN CN 98808922 patent/CN1269825A/zh active Pending
  • 1998-08-29 EP EP98951327A patent/EP1015549A1/de not_active Withdrawn
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