Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/485—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the invention relates to coated particles, in particular particles with an inorganic content, preferably purely inorganic particles and particularly preferably coated magnetic particles, which are used as carrier particles in electrostatographic developers for electrostatographic imaging.
• a number of electrostatographic printing methods are known, e.g. direct electrostatic printing !, in which toner is applied to a receiving material which has no latent electrostatic image by means of an electronically addressable print head.
• toner images are placed on an imaging element in the form of a rotating drum that is electrostatic
• Contains layer which consists of a plurality of controllable electrodes in and under a dielectric layer. Electrical voltage is generated in the controllable electrodes, which attracts the toner particles from a toner source.
• a latent electrostatic image is generated by the steps a) uniformly charging a photoconductive element and b) imagewise discharging by means of an imagewise modulated exposure.
• a latent electrostatic image is generated by imagewise precipitation of electrically charged particles, for example by an electron beam or by ionized gas on a dielectric substrate.
• the latent images obtained are developed, that is to say converted into visible images, by selectively depositing light-absorbing substances thereon, which are called toners and are usually triboelectrically charged.
• the dry powder development can be carried out in different ways.
• One method is the one-component method, in which the toner itself is loaded by friction, transported with a roller and applied to the latent image. The quality is limited, especially when color prints are to be produced.
• Another method uses liquid development, in which colloidally charged toner particles are in a liquid insulating medium, e.g. a hydrocarbon for
• a disadvantage of this method is the emission of vaporized organic substances, especially when it comes to high printing speeds.
• a third method uses a two-component developer. In this case, magnetically mountable, coarse-grained carrier particles form a magnetic brush on the surface of the development roller by the magnetic
• Triboelectrically charged toner particles are present on the surface of the carrier particles. These are stripped from the carrier particles in accordance with the electrical charge of the latent electrostatic image, whereby the toner image is generated.
• the carrier particles are reused many times in this process; their mechanical stability is therefore of particular importance.
• non-magnetic electrophotographic developers made of two components can also be used.
• the developer consists of glass beads, which are optionally coated, and toner particles. The developer is allowed to fall onto the element carrying the latent image and in this way the development is carried out as described in BE 828 210. In this case too, the carrier particles are reused.
• a material with non-stick properties is preferred for the coating of the carrier particles in order to avoid sticking of the toner to the carrier surface. In most cases, however, this leads to a reduction in the adhesion of the coating to the carrier, which leads to a shortening of the service life, e.g. when using silicone resins as carrier coating agents.
• the silicone resin used consists of D and T units (in the case of D units the silicon atom is linked via 2 oxygen atoms, in the case of T units via 3 oxygen atoms it is linked to other silicon atoms), with other functional organosilanes, such as di- and trialkoxy-functional organosilanes and / or di- and trialkoxy-functional, nitrogen-containing organosilanes can be added.
• the application takes place, as can be seen from the examples, in a fluidized bed reactor; the coatings are then cured at 190 ° C to 296 ° C.
• the above-mentioned coatings with (polymeric) silicone resins have the disadvantage that high temperatures are necessary for complete curing (190 to 296 ° C.).
• many silicone resin coatings show non-stick properties, but necessarily poor adhesion to the substrate.
• di- and trialkoxy-functional organosilanes for example, must therefore be added to the silicone resins in order to improve the adhesion.
• the object of the present invention was therefore to provide coated particles, in particular particles with a content of inorganic material and in particular carrier particles for electrostatographic processes, the particles having a magnetic core and a coating of the core, which
• a) is tack-free, so that free-flowing, predominantly agglomerate-free particles are obtained.
• coated particles in particular coated particles containing inorganic material, are obtained which do not have the disadvantages mentioned above if the coating consists of monomeric polyfunctional organosilanes and / or their hydrolysis products and / or their reactants. onproducts with heteroatom-containing organosilanes and / or alkoxides is produced.
• the present invention therefore relates to particles (A) which are coated with a material (B), the particles (A) preferably containing inorganic material, in particular being inorganic particles and particularly preferably being magnetic carrier particles for electrostatographic processes, and the Material (B) is a monomeric, polyfunctional organosilane and / or a hydrolysis product thereof and / or a reaction product thereof with a heteroatom-containing organosilane and / or an alkoxide.
• Heteroatom-containing organosilanes for the purposes of the invention consist of at least one silicon atom with hydrolyzable and / or condensation-crosslinking groups such as -SiOR, where R in particular denotes alkyl, cycloalkyl or aryl, preferably alkyl, or SiOH and at least one heteroatom-containing organic radical bonded via a carbon atom, which is a May be alkyl, cycloalkyl or aryl.
• Heteroatoms of the heteroatom-containing organosilanes are preferably N, P, S, F, Cl, Br O, B and Al.
• Preferred heteroatoms are N and F, with nitrogen atoms being particularly preferred.
• Preferred nitrogen-containing organosilanes correspond to the formula (I)
• n 1 to 10, preferably 2 or 3
• n 0 to 2 preferably 2, o 0 to 2, preferably 0
• R 2 is H, alkyl or aryl, preferably H
• R 3 , R 4 are alkyl or aryl, preferably CH 3 or C 2 H 5 ,
• Preferred alkoxides correspond to the formula (II)
• M j is Si, Sn, Ti, Zr, B or Al
• R j is alkyl or aryl, preferably C ] -C 4 -alkyl and y in the case of Si, Sn, Ti, Zr 4 and in the case of B or Al 3.
• Polyfunctional organosilanes in the sense of the invention are characterized in that they contain at least 2, preferably at least 3 silicon atoms, each with 1 to 3 hydrolyzable and / or condensation-crosslinking groups, in particular alkoxy, acyloxy or hydroxy groups, and the silicon atoms each with an Si, C- Binding to a structural unit linked to the silicon atoms.
• the linked structural units in the sense of the invention are, for example, linear or branched C j to C j o-alkylene chains, C 5 to C j o-cycloalkylene radicals, aromatic radicals, such as phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals.
• aromatic radicals such as phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals.
• the aliphatic and aromatic radicals can also contain heteroatoms, such as Si, N, O, S or F.
• chain-shaped, ring-shaped or cage-shaped siloxanes such as silsequioxanes
• linking structural units are listed below, with X denoting Si atoms which have 1 to 3 hydrolyzable and / or condensation-crosslinking groups and with Y corresponding Si atoms which are bonded to the linking structural unit via an alkylene chain ; n stands for a number 1 to 10, m for a number 1 to 6:
• R is an organic residue, e.g. Is alkyl, cycloalkyl, aryl or alkenyl.
• polyfunctional organosilanes are compounds of the general formulas (IV), (V) and (VI): (R 5 ) 4 . i Si [(CH 2 ) p Si (OR 6 ) a (R 7 ) 3 . a ] i (IV)
• R 5 alkyl or aryl
• -Rg is hydrogen, alkyl or aryl if a is 1 and alkyl or aryl if a 2 or
• R 7 is alkyl or aryl, preferably methyl and a is 1 to 3;
• R 10 is alkyl or aryl, preferably methyl
• r 1 to 10 preferably 2 to 4, c 1 to 3, k 2 to 4, preferably 4 R alkyl or aryl, preferably methyl,
• R 13 is alkyl or aryl, preferably methyl and
• R 14 is alkyl or aryl.
• polyfunctional organosilanes examples are:
• Nitrogen-containing alkoxysilanes are, for example
• fluorine-containing alkoxysilanes examples are:
• x is 1 to 3 and R, R 'alkyl, cycloalkyl or aryl, preferably ethyl or methyl are.
• alkoxides which can be used to prepare the reaction products according to the invention, e.g. To improve the abrasion resistance or the tribological properties are:
• reaction products according to the invention can also be finely divided
• Conductivity-inducing agents for example carbon and charge-regulating agents, for example nigrosine, can also be added to the coating.
• Material B preferably contains 0.1 to 100% by weight of polyfunctional organosilane, 0 to 20% by weight of heteroatom-containing organosilane (I), 0 to 70% by weight of nanoparticles and 0 to 99.9% by weight Alkoxide (II).
• the material particularly preferably contains B.
• Magnetic inorganic particles are preferred as particles.
• the magnetic particles are preferably iron oxide pigments of the formula (III) (M 2 O) x (Fe 2 O 3 ) z (III)
• M 2 Li Mg, Sr, Ba, Mn, Fe (II), Co, Ni, Cu, Zn, Cd and
• the molar ratio of x to z is between 0 and 1, preferably between 0.3 and 1.
• composite particles consisting of 20 to 85% by weight of magnetic microparticles and an organic or inorganic binder, e.g. an organic polymer or a ceramic material. It is also possible to use non-magnetic cores such as glass beads.
• reaction products B) according to the invention are generally applied as a coating to the particles A).
• the polyfunctional organosilanes can be applied to the particles A in bulk or in a solvent, if appropriate in the presence of a catalyst.
• Coating B) is obtained after evaporation of the solvent and curing at a suitable temperature.
• the polyfunctional organosilanes are first mixed with alkoxides and, for example, heteroatom-containing organosilanes and / or nanoparticles, and, if appropriate in the presence of a catalyst, are applied to the particles A and cured.
• volatile starting materials such as tetraethyl orthosilicate
• this coating solution is applied to the iron oxide-containing materials using suitable methods, for example in a fluidized bed, the volatile constituents are evaporated and the coating thus obtained is optionally post-cured thermally.
• Suitable catalysts are organic and inorganic acids or bases, for example HCO 2 H, CH 3 COOH, HCl, NH 4 OH and alkali metal hydroxides, and F-containing salts such as NaF or NH 4 F.
• the added metal alkoxides themselves, such as Ti (OC H 5 ) 4 and Ti (Oi-C 3 H 7 ) 4 can be catalytically active.
• Metal soaps such as zinc octoate or dibutyltin laurate can also be used.
• polyfunctional organosilanes optionally in the presence of alkoxides
• the polyfunctional organosilanes are combined with the alkoxides, a solvent, water and a catalyst with stirring and reacted for a certain time before films can be obtained from these solutions or, after complete reaction (gelation), moldings can also be obtained.
• the film-forming properties of the reaction product (B) are a useful indicator that the solutions are suitable for coating the particles. If you coat e.g. a glass plate, a transparent, largely crack-free film wetting the entire area should be obtained after the volatile constituents have evaporated. However, the tendency to crack formation increases with the layer thickness of the film.
• the nitrogen-containing alkoxysilanes are only added after the polyfunctional organosilanes and optionally alkoxides have been reacted, as indicated above, and this precondensate has been diluted with further solvent.
• nitrogen-containing silanes such as H 2 N- (CH 2 ) 3 Si (OMe) 3 , catalyze the hydrolysis and condensation of alkoxysilanes. This can lead to the most reactive component, eg H 2 N- (CH 2 ) 3 Si (OCH 3 ) 3 , being hydrolyzed rapidly and condensed to an insoluble solid. This can prevent it by adding the nitrogen-containing alkoxysilanes to the diluted coating solution.
• solvents examples include Alcohols, such as methanol, ethanol, n-propanol, n-butanol, iso-propanol, sec-butanol or ethylene glycol, ketones, such as acetone or methyl ethyl ketone, amides, such as N-methylpyrrolidone or water. Because of their good miscibility with the precondensate, alcohols, in particular isopropanol, are particularly preferred. Mixtures of different solvents can also be used.
• Alcohols such as methanol, ethanol, n-propanol, n-butanol, iso-propanol, sec-butanol or ethylene glycol
• ketones such as acetone or methyl ethyl ketone
• amides such as N-methylpyrrolidone or water. Because of their good miscibility with the precondensate, alcohols, in particular isopropanol, are particularly preferred. Mixtures of different solvents
• the solvents can be applied after application of the coating solution, e.g. recovered by condensation and used again, if necessary after cleaning, in the process.
• the coating is preferably cured at temperatures from 25 to 220 ° C., particularly preferably from 80 to 180 ° C., very particularly preferably from 100 to 140 ° C.
• the amount of the coating applied, based on the core is between 0.1 and 10% by weight, preferably between 0.5 and 5% by weight and particularly preferably between 0.5 and 2% by weight.
• the coated inorganic particles in particular the carrier particles for electrophotography containing a magnetic core, are in particular spherical and have an average particle diameter of 20 to 200 ⁇ m, preferably 40 to 120 ⁇ m. It is also possible to apply two or more layers to the particles (A), for example first an electrically insulating layer and then a layer which improves the stability of the coated particles under mechanical stress.
• Suitable organic solvents for the oligomers are, for example, mono- and polyfunctional alcohols, such as methanol, ethanol, n-butanol, ethylene glycol.
• the oligomers can be prepared directly from the monomers of the formula (V) or from the starting products for the preparation of the monomers of the formula (V), those starting compounds being those of the formula (V) which have a halogen atom instead of the OR 9 group , for example a chlorine, bromine or
• oligomers are an example of the hydrolysis products used as material B.
• these oligomers are suitable for coating particles, in particular particles with an inorganic content, preferably purely inorganic particles.
• Alkoxides for example those of the formula II, and / or nanoparticles.
• the flowability is determined using an outlet cup and 500 g of the coated particles.
• the specific resistance ( ⁇ spec ) of the carrier was determined in a cylindrical measuring cell with an inner diameter of 22.5 mm, which was filled with carrier 4 mm high, on which a stamp was placed, which was loaded with 1 kg. At a voltage of 200 V, the current was read on the measuring device and ⁇ specifically calculated as follows:
• the charge acceptance (-Q / m) was determined by development. For this purpose, 100 parts by weight of carrier and 5 parts by weight of toner were used in the developer unit. mixes. The developer mixture was activated in a commercial copier for 10 minutes. After development, both the amount of toner discharged (m) and its charge (Q) were measured.
• the amount of coating given in the examples is given from the sum of the amount of polyfunctional organosilane and tetraethylorthosilicate used in% by weight compared to the amount of carrier.
• the proportion of the nitrogen-containing aminosilane (b-1) or (b-8) is given in% by weight compared to the coating material.
• Carrier mixed with 50 ceramic beads with a diameter of 10 mm in a bottle of 120 ml, so that the filling level of the bottle is about 50%.
• the bottle is rotated for 16 hours on a roller table at a speed of 25 m / min. This process partially rubs off the coating and determines the amount of coating material rubbed off as follows:
• the amount rubbed off is so small that it cannot be determined gravimetrically. But it can be very well homogeneously on a sheet of paper of a known optical
• the particles can be coated using various methods, e.g. in an industrial fluidized bed reactor or in a 2 1 three-necked flask with stirrer, injection system for the solution containing the coating material and a cooler for the recovery of the evaporated solvent.
• a coating temperature of 80 to 100 ° C at a slight negative pressure of 950 to 1,000 mbar absolute with a coating time of 15 to 60 minutes has proven to be expedient. Curing takes place in the same vessel at 120 to 190 ° C for 20 minutes to 4 hours. "X" in Tables 1 to 3 means that the substance was not used.
• Bontron N-O 2 is a nigrosine compound used for charge control; Spilon black TRH a Cr-azo complex that is used for charge control; Carbon black is a conductive soot.
• the coating was carried out at 70 ° C and 50 mbar.
• the product was dried at 90 ° C for 30 minutes and cured at 140 ° C for 16 hours.
• the results are shown in Table 5.
• the particles were sticky and therefore formed a lot of agglomerates or stuck to the kettle. A large amount of dust accumulated when drying.
• Coatings were applied in a fluidized bed reactor under the following conditions to 2 kg of the ferrite particles with solutions 22 to 27:
• the mixture was then cured for about 90 minutes at a bed temperature of 150 ° C. and finally cooled to room temperature.
• ⁇ spec was 4 x 10 5 ⁇ cm; -Q / m was 9.3 ⁇ C / g.
• Example 6 7.5 kg of a ferrite carrier as in Example 6 were coated with solution 30 at 85 ° C. and 980 mbar, dried and cured at 160 ° C. for 2 hours.
• the coating amount was 2.1% by weight, the content of b-7 1.0% by weight.
• ⁇ spec was 2.2 x 10 9 ⁇ cm; -Q / m was 16.1 ⁇ C / g; Abrasion: 0.12; Coarse fraction> 125 ⁇ m 0.9% by weight.
• Example 6 7.5 kg of ferrite camer as in Example 6 were coated with solution 32 at 85 ° C. and 980 mbar, dried and cured at 140 ° C. for 2 hours.
• the coating amount was 1.0% by weight, the proportion of b-7 2.0% by weight.
• s sp pe e z z was 1.5 x 10 8 ; -Q / m was 18 ⁇ C / g; abrasion: 0.12; coarse fraction> 125 ⁇ m 0.% by weight.
• Mn-Mg ferrite particles from Powdertech Co. Ltd. were used as particles containing iron oxide for the coating experiments.
• Tetraethyl orthosilicate, 8.25 g water and 0.16 g para-toluenesulfonic acid were combined with stirring in this order and stirred for another hour.
• the mixture was then diluted with 204.9 g of isopropanol and, in the case of solution 37, 0.2 g (b-7) were added.
• Ammonia was introduced through a gas inlet tube until saturation and the mixture was stirred for 4 hours. Excess ammonia was then removed and ammonium chloride was filtered off. The filtrate was neutralized with Na 2 CO 3 , mixed with filter aid (diatomaceous earth) and heated to 130 ° C. at a pressure of 10 mbar.
• the product was obtained as a clear liquid with a viscosity of 80 mPa.s, a density of 1.00 g / ml and a residual amount of hydrolyzable chlorine of 7 ppm.
• the condensation product of 1,3,5,7-tetramethyl-1,3,5,7-tetra- (2- (diethoxymethylsilyl) ethylene) cyclotetrasiloxane was a continuous molar mass distribution with an average number average (M j of 1 350 g / mol and an average weight average of

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Silicon Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Developing Agents For Electrophotography (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Glanulating (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Medicinal Preparation (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=26036768

Family Applications (2)

Family Applications Before (1)

Country Status (9)

Families Citing this family (45)

Family Cites Families (28)

• 1998
  • 1998-05-11 PT PT98924297T patent/PT981570E/pt unknown
  • 1998-05-11 AU AU76536/98A patent/AU7653698A/en not_active Abandoned
  • 1998-05-11 ES ES98924297T patent/ES2184268T3/es not_active Expired - Lifetime
  • 1998-05-11 AU AU76535/98A patent/AU7653598A/en not_active Abandoned
  • 1998-05-11 AT AT98924297T patent/ATE226226T1/de active
  • 1998-05-11 JP JP54988198A patent/JP2002502447A/ja active Pending
  • 1998-05-11 US US09/423,921 patent/US6413638B1/en not_active Expired - Fee Related
  • 1998-05-11 WO PCT/EP1998/002728 patent/WO1998052992A1/fr not_active Ceased
  • 1998-05-11 EP EP19980924297 patent/EP0981570B1/fr not_active Expired - Lifetime
  • 1998-05-11 US US09/423,498 patent/US6136939A/en not_active Expired - Lifetime
  • 1998-05-11 CA CA 2290455 patent/CA2290455C/fr not_active Expired - Fee Related
  • 1998-05-11 EP EP98924296A patent/EP0981780A1/fr not_active Withdrawn
  • 1998-05-11 WO PCT/EP1998/002727 patent/WO1998053372A1/fr not_active Ceased
  • 1998-05-11 JP JP54988298A patent/JP2001525833A/ja not_active Ceased

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events