+

WO1999018185A1 - Procede de preparation de pastilles detergentes stables a dissolution rapide - Google Patents

Procede de preparation de pastilles detergentes stables a dissolution rapide Download PDF

Info

Publication number
WO1999018185A1
WO1999018185A1 PCT/EP1998/006116 EP9806116W WO9918185A1 WO 1999018185 A1 WO1999018185 A1 WO 1999018185A1 EP 9806116 W EP9806116 W EP 9806116W WO 9918185 A1 WO9918185 A1 WO 9918185A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
acid
mixture
detergent
detergent tablets
Prior art date
Application number
PCT/EP1998/006116
Other languages
German (de)
English (en)
Inventor
Gerhard Blasey
Christian Block
Monika Böcker
Heinke Jebens
Hans-Friedrich Kruse
Andreas Lietzmann
Antoni Machin
Fred Schambil
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to PL98339651A priority Critical patent/PL339651A1/xx
Priority to EP98951468A priority patent/EP1025197A1/fr
Priority to JP2000514985A priority patent/JP2001519463A/ja
Publication of WO1999018185A1 publication Critical patent/WO1999018185A1/fr

Links

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
    • 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to the production of detergent tablets.
  • the invention relates to a process for the production of washing and cleaning-active foils which can be obtained by compression molding of particulate detergent and cleaning agent compositions and which are characterized by high strengths and nevertheless good decay and solubility characteristics.
  • washable and cleaning-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • the mixture to be tabletted is directly, i.e. pressed without prior granulation.
  • the advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required.
  • these advantages are offset by disadvantages.
  • a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die.
  • the usual way of producing detergent tablets starts from powdery components (“primary particles”), which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual additives and added to the tableting.
  • the properties of the granules are of crucial importance for the physical properties of the shaped bodies - particle sizes, moisture content and other parameters which can be controlled in the granules make a decisive contribution to the later properties of the shaped bodies.
  • two physical properties of moldings are of crucial importance, especially in the case of detergent tablets: the hardness and the rate of disintegration.
  • EP-A-0 522 766 discloses moldings made from a compacted, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • the molded articles are produced by mixing a detergent and cleaning agent granulate produced in a manner known per se with pulverulent preparation components and subsequent molding. Further documents which deal with the production of detergent tablets are EP-A-0 716 144 (Unilever), which describes tablets with an external shell made of water-soluble material, and EP-A-0 711 827 (Unilever), which contain a citrate with a defined solubility as an ingredient.
  • EP-A-0 716 144 Unilever
  • EP-A-0 711 827 Unilever
  • 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 manufacturing process for washing and cleaning-active moldings mentioned in the prior art is shaping pressing, which takes place in part at different temperatures.
  • only physical properties of the mixture to be pressed such as, for example, the particle size, the spatial distribution of individual components or the physical properties of individual components, are mentioned as further influencing variables.
  • Powdering granules is well known in the art.
  • inorganic salts for example sodium sulfate or carbonate, sodium silicates and aluminum silicates, and organic substances such as polymeric polycarboxylates are used as finely divided powdering agents.
  • This powdering is carried out both to reduce the stickiness of the granules and to increase the bulk density of the granules, which may result in advantages in terms of application technology.
  • the addition of fine particles Powdering agents for mixtures of granules and powdery substances and the effects of this procedure on the properties of the powdered mixtures are not described in the prior art.
  • the present invention was based on the object of providing, in addition to the selection of individual ingredients, a further influencing variable with which the physical properties of detergent tablets can be improved.
  • the object of the present invention was to provide a method which, by means of specific pretreatment of the mixture to be compressed, delivers hard and nevertheless rapidly disintegrating detergent tablets.
  • the invention therefore relates to a process for the production of detergent tablets by mixing detergent granules, prepared in a manner known per se, with pulverulent preparation components and subsequent shaping pressing, the mixture to be compressed being a pulverulent preparation component from 0.5 to 5% by weight. -% of a zeolite of the faujasite type, based on the weight of the resulting shaped body, are added.
  • the zeolite added as a powdery powdering component before the mixture is pressed has the general formula M 2 / n O ' Al 2 O 3 ' x SiO 2 'y H 2 O, in which M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can assume values between 0 and 20.
  • the zeolite structures are formed by linking AlO 4 tetrahedra with SiO 4 tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees.
  • the intercrystalline “zeolitic” water can be released continuously and reversibly, while for some types of zeolite structural changes are also associated with the water release or uptake.
  • the “primary binding units” AlO 4 tetrahedra and SiO tetrahedra form so-called “secondary binding units”, which have the form of one or more rings.
  • 2-, 6- and 8-membered rings appear in various zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ).
  • S4R, S6R and S8R zeolites
  • D4R most common types: D4R as a square prism or D6R as a hexagonal prism
  • These "secondary subunits" connect different polyhedra, which are denoted by Greek letters.
  • the best known zeolite, zeolite 4 A is a cubic combination of ß-cages that are linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 ⁇ and 4.2 ⁇ size, the formula unit in the unit cell can be with Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] " 27 H 2 O describe.
  • Zeolites of the faujasite type are used according to the invention, the use of which brings clear and unexpected advantages for the disintegration and dissolving properties of the detergent tablets produced.
  • the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double six-ring subunit D6R (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92.
  • the zeolite structure group 4 also includes the minerals chabazite and gmelinite and the synthetic zeolites R (chabazite type), S (gmelinite type) , L and ZK-5.
  • the latter two synthetic zeolites have no mineral analogues.
  • Faujasite-type zeolites are made up of ß-cages which are tetrahedral linked by D6R subunits, the ß-cages being arranged similar to the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities with a diameter of approximately 13 ⁇ and can be determined using the formula Na 86 [(AlO 2 ) 8 ⁇ (SiO 2 ) ⁇ o6] ' 264 H 2 O describe.
  • the network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).
  • zeolite of the faujasite type denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite X zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, pure zeolite X is preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to zeolite structural group 4 can be used according to the invention, the advantages of the process according to the invention being particularly evident when at least 50% by weight of the powdering agent consists of a zeolite of the faujasite type.
  • the minimum amount of a zeolite of the faujasite type (0.5% by weight, based on the weight of the shaped body formed) used and used as the remaining powdering agent conventional zeolite A.
  • the powdering agent consists exclusively of one or more zeolites of the faujasite type, with zeolite X again being preferred.
  • the aluminum silicates used in the process according to the invention are commercially available and the methods for their preparation are described in standard monographs.
  • x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 ⁇ .
  • a commercially available as part of the process of the invention can preferably be used, for example, also a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-%> zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ® is and through the formula
  • Y-type zeolites are also commercially available and can be expressed, for example, by the formulas Na 56 [(AlO 2 ) 5 6 (SiO 2 ) 13 6j • x H 2 O,
  • x stands for numbers between 0 and 276 and have a pore size of 8.0 ⁇ .
  • the particle sizes of the faujasite-type zeolites used in the process according to the invention are in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and in particular between 1 and 30 ⁇ m, each measured using standard particle size determination methods.
  • the actual manufacture of the shaped bodies according to the invention is first carried out by dry mixing the granular and powdery constituents and then bringing them to the table, in particular feeding them into tablets, whereby conventional methods can be used.
  • the premix produced by the process according to the invention is compacted in a so-called die between two punches to form a solid compact.
  • This process which is briefly referred to as tableting in the following, 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 molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing 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 stamp (and thus from a certain pressure on the premix) begins the plastic deformation, 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.).
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • 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 matrix table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • 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 molded articles 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 molded body can be manufactured in a predetermined spatial shape and a predetermined size.
  • 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 presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets can also be used without problems using a dosing aid.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered
  • the 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 application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, 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.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the 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 a molded body.
  • each individual layer consists of a pre-pressed premix, which according to the invention has been mixed with zeolite of the faujasite type. This results in the best disintegration times with good mold hardness.
  • the procedure according to the invention for the premix production can also be dispensed with in individual regions, inlays or layers of the molded body, which results in a delay in the dissolution of these regions, from which controlled-release effects can be realized.
  • Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article.
  • the articles to be coated can be sprayed with, for example, aqueous solutions or emulsions, or else using the process of melt coating Received coating.
  • the washing and cleaning agent shaped bodies After the molding, the washing and cleaning agent shaped bodies have a high stability.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured quantity of the diametrical breaking load. This can be determined according to
  • D diametrical fracture stress (DFS) in Pa
  • P is the force in N, which leads to the pressure exerted on the molded body, which causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • the mixture to be compacted from granulate (s), pulverulent preparation components and zeolite of the faujasite type is preferred at pressures between 100 and 1000 N / cm 2 between 200 and 800 N / cm and in particular between 250 and 500 N / cm and temperatures between 10 and 80 ° C, preferably between 15 and 70 ° C and in particular between 20 and 60 ° C.
  • the granular constituents of the mixture to be ves ⁇ ress are produced in a manner known per se with a composition known per se, the selection of the ingredients depending on the intended use of the molded article.
  • 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 molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9- sulfonates ⁇ -Alkylbenzolsul-, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 2 -i8-Monoolefmen with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 2 -i8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of D-sulfofatty acids for example the D-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Other 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.
  • Preferred sulfated fatty acid glycerol esters are the sulfate 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) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ⁇ -cis fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the CIO-C 20 oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7- ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9- u alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2- i 8 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8- ⁇ 8 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.
  • 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.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C] 2- ⁇ alcohols with 3 EO or 4 EO, C 9- ⁇ alcohol with 7 EO, C ⁇ 3- ⁇ 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C ⁇ 2- ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2- ⁇ alcohol with 3 EO and C 12-18 - alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • 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 aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms, in particular in 2-position methyl branch, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • 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 represents a linear, branched or cyclic alkyl radical or an aryl radical or is an oxyalkyl radical having 1 to 8 carbon atoms
  • C - alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are to be mentioned in particular as builders which can be contained in the detergent tablets according to the invention.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O ⁇ + ⁇ ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • 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 Na2Si2 ⁇ 5 -yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • 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.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray silicates which also have a delay in dissolution compared to conventional water glasses, are used, for example, in German Patent application DE-A-44 00 024 described. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used as builder is preferably zeolite A and / or P.
  • zeolite P zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures and / or co-crystallizates of A, X and / or P for example a cocrystallizate of 80% zeolite X and 20% of zeolite A, which (under the name VEGOBOND AX ® commercial product CONDEA Augusta SpA) is distributed.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 2 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups , -C 2 -C-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 that 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), as long as such use is not objectionable for ecological reasons, and mixtures of 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. These salts are used because of their builder properties and are not To be regarded as a component of the shower system, especially since the salts are not suitable, for example to release carbon dioxide from hydrogen carbonates.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the detergent tablets.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable are substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.
  • TAED
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Lack of Revelation, Ti, V and Cu complexes with Tripod ligands containing nitrogen and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • foam inhibitors for example, soaps of natural or synthetic origin come into consideration which have a high proportion of Ci8-24 fatty acids.
  • Suitable non-surfactant foam inhibitors are e.g. Organopolysiloxanes and their mixtures with microfine, optionally silanized silica 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.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand 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 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, based in each case on the nonionic cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid or of 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 obtained from Bacillus lentus are used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the shaped bodies 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-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Mo ⁇ holino group, have a diethanolamino group , a methyl amino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the washing and cleaning performance, to provide the consumer with a visually and sensorially “typical and unmistakable” product.
  • Individual fragrance compounds can be used as perfume oils or fragrances , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate,
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include the Te ⁇ ene such as limonene and pinene.
  • Te ⁇ ene such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the colorant content of the shaped bodies according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
  • a detergent granulate (composition according to Table 1) was placed in a mixer, sprayed with perfume and subsequently mixed with the preparation components mentioned in Table 2. Before the tablets were compressed, 4% by weight of cellulose (disintegrant) and 1% by weight of powdering component, based in each case on the weight of the molded body, were mixed in.
  • Zeolite X was used in the molded bodies 1 according to the invention, and comparative examples 2 were prepared using zeolite A as a powdering agent.
  • Comparative Examples 3 and 4 contained silicas as the powdering agent, the mixture in Example 3 being mixed with a hydrophobic precipitated silica (Sipernat ® D 17 ex Degussa) and in Example 4 with a hydrophilic precipitated silica (Sipernat ® 22 LS ex Degussa).
  • silicas as the powdering agent, the mixture in Example 3 being mixed with a hydrophobic precipitated silica (Sipernat ® D 17 ex Degussa) and in Example 4 with a hydrophilic precipitated silica (Sipernat ® 22 LS ex Degussa).
  • the hardness of the tablets (0 44 mm) was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood being determined.
  • two series of tablets 1 according to the invention and of the comparison tablets 2 to 4 were produced at different pressing forces, which is reflected in the two different hardnesses of the tablets, which are shown in Table 3 in the columns of the respective examples are given.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de préparation de corps moulés détergents et nettoyants par compactage d'une composition particulaire d'agents détergents et nettoyants, à des fins de modelage. Cette composition est obtenue par mélange d'un granulat détergent et nettoyant, produit de manière connue en soi, avec des constituants pulvérulents. On obtient des corps moulés particulièrement stables qui se caractérisent par des temps de désintégration réduits, si lors du mélange du granulat avec les constituants pulvérulents, on ajoute comme constituants pulvérulents, entre 0,5 et 5 % en poids d'un zéolithe de type faujasite, par rapport au poids du corps moulé obtenu.
PCT/EP1998/006116 1997-10-04 1998-09-25 Procede de preparation de pastilles detergentes stables a dissolution rapide WO1999018185A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL98339651A PL339651A1 (en) 1997-10-04 1998-09-25 Method of obtaining washing and cleaning agents in the form of solid formpieces
EP98951468A EP1025197A1 (fr) 1997-10-04 1998-09-25 Procede de preparation de pastilles detergentes stables a dissolution rapide
JP2000514985A JP2001519463A (ja) 1997-10-04 1998-09-25 安定性および急速な溶解性を示す洗剤錠剤の製法

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19743837A DE19743837A1 (de) 1997-10-04 1997-10-04 Verfahren zur Herstellung von stabilen und schnellöslichen Waschmitteltabletten
DE19743837.7 1997-10-04
CA002302811A CA2302811A1 (fr) 1997-10-04 2000-04-07 Procede pour produire des comprimes de detergent a dissolution rapide et stable

Publications (1)

Publication Number Publication Date
WO1999018185A1 true WO1999018185A1 (fr) 1999-04-15

Family

ID=25681670

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/006116 WO1999018185A1 (fr) 1997-10-04 1998-09-25 Procede de preparation de pastilles detergentes stables a dissolution rapide

Country Status (7)

Country Link
EP (1) EP1025197A1 (fr)
JP (1) JP2001519463A (fr)
CN (1) CN1273598A (fr)
CA (1) CA2302811A1 (fr)
DE (1) DE19743837A1 (fr)
PL (1) PL339651A1 (fr)
WO (1) WO1999018185A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057169A1 (fr) * 2000-02-03 2001-08-09 Cognis Deutschland Gmbh & Co. Kg Granulats tensioactifs
JP2003524067A (ja) * 2000-02-23 2003-08-12 ザ、プロクター、エンド、ギャンブル、カンパニー 錠剤型洗剤

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19828577A1 (de) * 1998-06-26 1999-12-30 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
DE19847280A1 (de) * 1998-10-14 2000-04-20 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Zeolithcompound
DE19910818A1 (de) * 1999-03-11 2000-09-14 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Tensid-Builderkombination

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264701A1 (fr) * 1986-10-13 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Comprimés de nettoyage pour le lavage de la vaisselle en machine
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
JPH06122900A (ja) * 1992-10-13 1994-05-06 Kao Corp 錠剤型洗浄剤組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264701A1 (fr) * 1986-10-13 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Comprimés de nettoyage pour le lavage de la vaisselle en machine
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
JPH06122900A (ja) * 1992-10-13 1994-05-06 Kao Corp 錠剤型洗浄剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 018, no. 415 (C - 1233) 4 August 1994 (1994-08-04) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057169A1 (fr) * 2000-02-03 2001-08-09 Cognis Deutschland Gmbh & Co. Kg Granulats tensioactifs
JP2003524067A (ja) * 2000-02-23 2003-08-12 ザ、プロクター、エンド、ギャンブル、カンパニー 錠剤型洗剤

Also Published As

Publication number Publication date
EP1025197A1 (fr) 2000-08-09
PL339651A1 (en) 2001-01-02
CN1273598A (zh) 2000-11-15
CA2302811A1 (fr) 2000-06-07
JP2001519463A (ja) 2001-10-23
DE19743837A1 (de) 1999-04-08

Similar Documents

Publication Publication Date Title
EP1060236A1 (fr) Perles parfumees sous forme de corps moules detergents
WO1999013043A1 (fr) Corps moules detergents et nettoyants presentant une solubilite amelioree
EP1015549A1 (fr) Corps moules de produit detergent et nettoyant a solubilite amelioree
EP1056832B1 (fr) Corps moules a plusieurs phases presentant une division de phases optimisee
EP1056833B1 (fr) Corps moules nettoyants et detergents contenant des agents de blanchiment
EP1051474B1 (fr) Comprimes detergents a phases multiples
WO1999024545A2 (fr) Procede pour la production de corps moules detergents stables et se decomposant rapidement
EP1037960B1 (fr) Corps moules de detergent a desintegration amelioree
WO2000044873A1 (fr) Pastilles detergentes a phases multiples
WO1999018185A1 (fr) Procede de preparation de pastilles detergentes stables a dissolution rapide
WO1999042556A1 (fr) Detergents et nettoyants sous forme de corps moules dont les proprietes presentent un profil renforce
EP1051475B1 (fr) Pastilles detergentes a phases multiples
WO1999055812A1 (fr) Corps moules detergents a proprietes de decomposition ameliorees
WO1999029825A1 (fr) Corps moules de detergent a desintegration amelioree
WO2000029541A1 (fr) Corps moules nettoyants et detergents exempts de parfums
WO2000027985A1 (fr) Corps moules d'agents nettoyants et detergents avec agents de solubilisation finement divises
WO2000000582A1 (fr) Procede de production de detergents et nettoyants sous forme de corps moules
EP1086203A1 (fr) Corps moules detergents stables a la rupture et se dissolvant rapidement
EP1155111A2 (fr) Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide
WO2000004114A2 (fr) Procede de fabrication de corps moules de produits de lavage et detergents renfermant des sulfates d'alcools gras
DE19841362A1 (de) ABS-haltige Wasch- und Reinigungsmittelformkörper
WO2000027984A1 (fr) Corps moules de detergent a forme optimisee

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98809861.X

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CN CZ HU JP PL RU SK US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1998951468

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1998951468

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09509922

Country of ref document: US

WWR Wipo information: refused in national office

Ref document number: 1998951468

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1998951468

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载