EP1226970B1 - Tintenstrahlaufzeichnungselement und Druckverfahren - Google Patents
Tintenstrahlaufzeichnungselement und Druckverfahren Download PDFInfo
- Publication number
- EP1226970B1 EP1226970B1 EP20020075169 EP02075169A EP1226970B1 EP 1226970 B1 EP1226970 B1 EP 1226970B1 EP 20020075169 EP20020075169 EP 20020075169 EP 02075169 A EP02075169 A EP 02075169A EP 1226970 B1 EP1226970 B1 EP 1226970B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording element
- particles
- ink jet
- cationic
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- the present invention relates to a porous ink jet recording element and printing method using the element.
- ink droplets are ej ected from a nozzle at high speed towards a recording element or medium to produce an image on the medium.
- the ink droplets, or recording liquid generally comprise a recording agent, such as a dye or pigment, and a large amount of solvent.
- the solvent, or carrier liquid typically is made up of water and an organic material such as a monohydric alcohol, a polyhydric alcohol or mixtures thereof.
- An ink jet recording element typically comprises a support having on at least one surface thereof an ink-receiving or image-receiving layer, and includes those intended for reflection viewing, which have an opaque support, and those intended for viewing by transmitted light, which have a transparent support.
- porous recording elements have been developed which provide nearly instantaneous drying as long as they have sufficient thickness and pore volume to effectively contain the liquid ink.
- a porous recording element can be manufactured by cast coating, in which a particulate-containing coating is applied to a support and is dried in contact with a polished smooth surface.
- EP 1,002,660 relates to a porous ink jet recording element comprising fine particles, hydrophilic binder and a water-soluble, cationic polymer.
- a porous ink jet recording element comprising fine particles, hydrophilic binder and a water-soluble, cationic polymer.
- this element there is a problem with this element in that the density of an image printed on such an element using a water-soluble cationic polymer is lower than one would like.
- U.S. Patent 6,089,704 relates to a nonporous ink jet recording element comprising cationic polymeric vinyl latex and a hydrophilic polymer.
- this nonporous recording element there is a problem with this nonporous recording element in that it images printed thereon dry too slowly.
- U.S. Patent 6,096,469 relates to an ink jet recording element comprising mesoporous particles dispersed in an organic binder.
- the organic binder can be a cationic latex polymer "having less than 10 mole percent of a copolymerizable monomer having a tertamino or quaternary ammonium functionality.”
- this element there is a problem with this element in that the density of an image printed on such an element with a binder having less than 10 mole percent of a cationic mordant functionality is lower than one would like.
- U.S. Patent 6,165,606 relates to an ink jet recording element comprising a support having thereon a porous image-receiving layer comprising: (a) particles having a primary particle size of 30 nm or less; and (b) cationic, polymeric particles comprising 30 to 100 mole percent of a mordant moiety.
- an ink jet recording element comprising a support having thereon a porous image-receiving layer comprising:
- a porous ink jet recording element is obtained that, when printed with dye-based inks, provides superior optical densities, good image quality and has an excellent dry time.
- Another embodiment of the invention relates to an ink jet printing method, comprising the steps of:
- Examples of (a) particles useful in the invention include alumina, boehmite, clay, calcium carbonate, titanium dioxide, calcined clay, aluminosilicates, silica, barium sulfate, or polymeric beads.
- the particles may be porous or nonporous.
- the particles are metallic oxides, preferably fumed. While many types of inorganic and organic particles are manufactured by various methods and commercially available for an image-receiving layer, porosity of the ink-receiving layer is necessary in order to obtain very fast ink drying. The pores formed between the particles must be sufficiently large and interconnected so that the printing ink passes quickly through the layer and away from the outer surface to give the impression of fast drying. At the same time, the particles must be arranged in such a way so that the pores formed between them are sufficiently small that they do not scatter visible light.
- the (a) particles may be in the form of primary particles, or in the form of secondary aggregated particles.
- the aggregates are comprised of smaller primary particles 7 to 40 nm in diameter, and being aggregated up to 300 nm in diameter.
- the pores in a dried coating of such aggregates fall within the range necessary to ensure low optical scatter yet sufficient ink solvent uptake.
- fumed metallic oxides which may be used in the invention as the (a) particles include silica and alumina fumed oxides. Fumed oxides are available in dry form or as dispersions of the aggregates mentioned above.
- the (b) water insoluble, cationic, polymeric particles comprising at least 20 mole percent of a cationic mordant moiety useful in the invention can be in the form of a latex, water dispersible polymer, beads, or core/shell particles wherein the core is organic or inorganic and the shell in either case is a cationic polymer.
- Such particles can be products of addition or condensation polymerization, or a combination of both. They can be linear, branched, hyper-branched, grafted, random, blocked, or can have other polymer microstructures well known to those in the art. They also can be partially crosslinked. Examples of core/shell particles useful in the invention are disclosed and claimed in U.S. Patent Application Serial No.
- the water insoluble, cationic, polymeric particles comprise at least 50 mole percent of a cationic mordant moiety.
- the (b) water insoluble, cationic, polymeric particles useful in the invention can be derived from nonionic, anionic, or cationic monomers. In a preferred embodiment, combinations of nonionic and cationic monomers are employed. In general, the amount of cationic monomer employed in the combination is at least 20 mole percent.
- the nonionic, anionic, or cationic monomers employed can include neutral, anionic or cationic derivatives of addition polymerizable monomers such as styrenes, alpha-alkylstyrenes, acrylate esters derived from alcohols or phenols, methacrylate esters, vinylimidazoles, vinylpyridines, vinylpyrrolidinones, acrylamides, methacrylamides, vinyl esters derived from straight chain and branched acids (e.g., vinyl acetate), vinyl ethers (e.g., vinyl methyl ether), vinyl nitriles, vinyl ketones, halogen-containing monomers such as vinyl chloride, and olefins, such as butadiene.
- addition polymerizable monomers such as styrenes, alpha-alkylstyrenes, acrylate esters derived from alcohols or phenols, methacrylate esters, vinylimidazoles, vinylpyridines, vinylpyrroli
- nonionic, anionic, or cationic monomers employed can also include neutral, anionic or cationic derivatives of condensation polymerizable monomers such as those used to prepare polyesters, polyethers, polycarbonates, polyureas and polyurethanes.
- the (b) water insoluble, cationic, polymeric particles employed in this invention can be prepared using conventional polymerization techniques including, but not limited to bulk, solution, emulsion, or suspension polymerization.
- the amount of (b) water insoluble, cationic, polymeric particles used should be high enough so that the images printed on the recording element will have a sufficiently high density, but low enough so that the interconnected pore structure formed by the aggregates is not filled.
- the weight ratio of (b) water insoluble, cationic, polymeric particles to (a) particles is from 1:2 to 1:10, preferably 1:5.
- (b) water insoluble, cationic, polymeric particles which may be used in the invention include those described in U.S. Patent 3,958,995. Specific examples of these polymers include:
- the image-receiving layer also contains a polymeric binder in an amount insufficient to alter the porosity of the porous receiving layer.
- the polymeric binder is a hydrophilic polymer such as poly(vinyl alcohol), poly(vinyl pyrrolidone), gelatin, cellulose ethers, poly(oxazolines), poly(vinylacetamides), partially hydrolyzed poly(vinyl acetate/vinyl alcohol), poly(acrylic acid), poly(acrylamide), poly(alkylene oxide), sulfonated or phosphated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan, tragacanth, xanthan, rhamsan and the like.
- the hydrophilic polymer is poly(vinyl alcohol), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, gelatin, or a poly(alkylene oxide).
- the hydrophilic binder is poly(vinyl alcohol). The polymeric binder should be chosen so that it is compatible with the aforementioned particles.
- the amount of binder used should be sufficient to impart cohesive strength to the inkjet recording element, but should also be minimized so that the interconnected pore structure formed by the aggregates is not filled in by the binder.
- the weight ratio of the binder to the total amount of particles is from 1:20 to 1:5.
- the recording element may also contain a base layer, next to the support, the function of which is to absorb the solvent from the ink.
- Materials useful for this layer include (a) particles, (b) particles, polymeric binder and/or crosslinker.
- the void volume must be sufficient to absorb all of the printing ink. For example, if a porous layer has 60 volume % open pores, in order to instantly absorb 32 cc/m 2 of ink, it must have a physical thickness of at least 54 ⁇ m.
- the support for the ink jet recording element used in the invention can be any of those usually used for ink jet receivers, such as resin-coated paper, paper, polyesters, or microporous materials such as polyethylene polymer-containing material sold by PPG Industries, Inc., Pittsburgh, Pennsylvania under the trade name of Teslin ®, Tyvek ® synthetic paper (DuPont Corp.), and OPPalyte® films (Mobil Chemical Co.) and other composite films listed in U.S. Patent 5,244,861.
- Opaque supports include plain paper, coated paper, synthetic paper, photographic paper support, melt-extrusion-coated paper, and laminated paper, such as biaxially oriented support laminates. Biaxially oriented support laminates are described in U.S.
- biaxially oriented supports include a paper base and a biaxially oriented polyolefin sheet, typically polypropylene, laminated to one or both sides of the paper base.
- Transparent supports include glass, cellulose derivatives, e.g., a cellulose ester, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate; polyesters, such as poly(ethylene terephthalate), poly(ethylene naphthalate), poly( 1,4-cyclohexanedimethylene terephthalate), poly(butylene terephthalate), and copolymers thereof; polyimides; polyamides; polycarbonates; polystyrene; polyolefins, such as polyethylene or polypropylene; polysulfones; polyacrylates; polyetherimides; and mixtures thereof.
- the papers listed above include a broad range of papers, from high end papers, such as photographic paper to low end papers, such as newsprint. In a preferred embodiment, polyethylene-coated paper is employed.
- the support used in the invention may have a thickness of from 50 to 500 ⁇ m, preferably from 75 to 300 ⁇ m.
- Antioxidants, antistatic agents, plasticizers and other known additives may be incorporated into the support, if desired.
- the surface of the support may be subjected to a corona-discharge treatment prior to applying the image-receiving layer.
- Coating compositions employed in the invention may be applied by any number of well known techniques, including dip-coating, wound-wire rod coating, doctor blade coating, gravure and reverse-roll coating, slide coating, bead coating, extrusion coating, curtain coating and the like.
- Known coating and drying methods are described in further detail in Research Disclosure no. 308119, published Dec. 1989, pages 1007 to 1008.
- Slide coating is preferred, in which the base layers and overcoat may be simultaneously applied. After coating, the layers are generally dried by simple evaporation, which may be accelerated by known techniques such as convection heating.
- crosslinkers which act upon the binder discussed above may be added in small quantities. Such an additive improves the cohesive strength of the layer.
- Crosslinkers such as carbodiimides, polyfunctional aziridines, aldehydes, isocyanates, epoxides, polyvalent metal cations, and the like may all be used.
- UV absorbers may also be added to the image-receiving layer as is well known in the art.
- Other additives include pH modifiers, adhesion promoters, rheology modifiers, surfactants, biocides, lubricants, dyes, optical brighteners, matte agents, antistatic agents, etc.
- additives known to those familiar with such art such as surfactants, defoamers, alcohol and the like may be used.
- a common level for coating aids is 0.01 to 0.30 % active coating aid based on the total solution weight.
- These coating aids can be nonionic, anionic, cationic or amphoteric. Specific examples are described in MCCUTCHEON's Volume 1: Emulsifiers and Detergents, 1995, North American Edition.
- the coating composition can be coated either from water or organic solvents, however water is preferred.
- the total solids content should be selected to yield a useful coating thickness in the most economical way, and for particulate coating formulations, solids contents from 10-40% are typical.
- the ink jet inks used to image the recording elements of the present invention are well-known in the art.
- the ink compositions used in ink jet printing typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, and the like.
- the solvent or carrier liquid can be solely water or can be water mixed with other water-miscible solvents such as polyhydric alcohols.
- Inks in which organic materials such as polyhydric alcohols are the predominant carrier or solvent liquid may also be used. Particularly useful are mixed solvents of water and polyhydric alcohols.
- the dyes used in such compositions are typically water-soluble direct or acid type dyes.
- Such liquid compositions have been described extensively in the prior art including, for example, U.S. Patents 4,381,946; 4,239,543 and 4,781,758.
- a coating solution for a base layer was prepared by combining fumed alumina (Cab-O-Sperse® PG003, Cabot Corp.), poly(vinyl alcohol) (Gohsenol® GH-23A, Nippon Gohsei Co., Ltd.) and 2,3-dihydroxy-1,4-dioxane (Clariant Corp.) in a ratio of 88:10:2 to give an aqueous coating formulation of 30% solids by weight.
- a coating solution for an image-receiving layer was prepared by combining fumed alumina (Cab-O-Sperse® PG003, Cabot Corp.), poly(vinyl alcohol) (Gohsenol® GH-23A, Nippon Gohsei Co.) and Polymer A in a ratio of 85:3:12 to give an aqueous coating formulation of 10% solids by weight.
- the fumed alumina particles have a primary particle size of from 7 to 40 nm in diameter and are aggregated up to 150 nm.
- Surfactants Zonyl® FSN E. I. du Pont de Nemours and Co.
- Olin@ 10G Dixie Chemical Co.
- the above coating solutions were simultaneously bead-coated at 40°C on polyethylene-coated paper base which had been previously subjected to corona discharge treatment.
- the image-receiving layer was coated on top of the base layer.
- the coating was then dried at 60°C by forced air to yield a two-layer recording element in which the thicknesses of the bottom and topmost layers were 40 ⁇ m (43 g/m 2 ) and 2 ⁇ m (2.2 g/m 2 ), respectively.
- Element 2 was prepared the same as Element 1 except that Polymer B was used instead of Polymer A.
- Element 3 was prepared the same as Element 1 except that the ratio for the image-receiving layer was 73:6:21 for fumed alumina to poly(vinyl alcohol) to Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-1 was used instead of Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-2 was used instead of Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-3 was used instead of Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-4 was used instead of Polymer A.
- This element was prepared the same as Element I except that Polymer C-5 was used instead of Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-6 was used instead of Polymer A.
- This element was prepared the same as Element I except that Polymer C-7 was used instead of Polymer A.
- This element was prepared the same as Element 1 except that Polymer C-8 was used instead of Polymer A.
- This element was prepared the same as Element I except that the image-receiving layer contained only fumed alumina.
- This element was prepared the same as Element 1 except that the image-receiving layer contained only fumed alumina and poly(vinyl alcohol) in a ratio of 98:2.
- This element was prepared the same as Comparative Element 10 except that the ratio of fumed alumina to poly(vinyl alcohol) was 90:10.
- This element was prepared the same as Element 3 except that Polymer C-9 was used instead of Polymer A.
- Test images of cyan, magenta, yellow, red, green and blue patches at 100% ink laydown were printed using an Epson Stylus® Color 740 using inks with catalogue number S020191 or an Epson Stylus® Photo 870 using inks with catalogue number T008201.
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Claims (10)
- Tintenstrahl-Aufzeichnungselement mit einem Träger, auf dem sich eine poröse Bildaufzeichnungsschicht befindet mit:(a) Teilchen mit einer primären Teilchengröße von im Durchmesser 7 bis 40 nm, die bis zu 300 nm aggregiert sein können; und(b) wasserunlöslichen, kationischen, polymeren Teilchen mit mindestens 20 Mol-% eines kationischen Beizmittelrestes.
- Aufzeichnungselement nach Anspruch 1, in dem das Gew.-Verhältnis von (b) wasserunlöslichen, kationischen, polymeren Teilchen zu (a) Teilchen bei 1:2 bis 1:10 liegt.
- Aufzeichnungselement nach Anspruch 1, in dem die poröse Bildaufzeichnungsschicht ferner ein polymeres Bindemittel in einer Menge enthält, die unzureichend ist, um die Porosität der porösen Bildempfangsschicht wesentlich zu verändern.
- Aufzeichnungselement nach Anspruch 3, in dem das Gew.-Verhältnis vom Bindemittel zur Gesamtmenge an Teilchen bei 1:20 bis 1:5 liegt.
- Aufzeichnungselement nach Anspruch 3, in dem das polymere Bindemittel ein hydrophiles Polymer ist.
- Aufzeichnungselement nach Anspruch 5, in dem das hydrophile Polymer aus Poly(vinylalkohol), Hydroxypropylcellulose, Hydroxypropylmethylcellulose, Gelatine oder einem Poly(alkylenoxid) besteht.
- Aufzeichnungselement nach Anspruch 3, in dem das polymere Bindemittel aus Poly(vinylalkohol) besteht.
- Aufzeichnungselement nach Anspruch 1, in dem die Teilchen (a) Teilchen aus metallischen Oxiden sind.
- Aufzeichnungselement nach Anspruch 1, in dem die Teilchen (a) porös sind.
- Tintenstrahl-Druckverfahren mit den Stufen:A) Bereitstellung eines Tintenstrahl-Druckers, der auf digitale Datensignale anspricht;B) Beladung des Druckers mit einem Tintenstrahl-Aufzeichnungselement wie in Anspruch 1 beschrieben;C) Beladung des Druckers mit einer Tintenstrahl-Tintenzusammensetzung; undD) Bedrucken der Bildempfangsschicht unter Verwendung der Tintenstrahl-Tintenzusammensetzung entsprechend den digitalen Datensignalen.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US770433 | 1985-08-29 | ||
US09/770,433 US6543891B1 (en) | 2001-01-26 | 2001-01-26 | Ink jet printing method |
US770814 | 2001-01-26 | ||
US09/770,814 US6630212B2 (en) | 2001-01-26 | 2001-01-26 | Ink jet recording element |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1226970A2 EP1226970A2 (de) | 2002-07-31 |
EP1226970A3 EP1226970A3 (de) | 2002-12-11 |
EP1226970B1 true EP1226970B1 (de) | 2004-04-07 |
Family
ID=27118311
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20020075169 Expired - Lifetime EP1226970B1 (de) | 2001-01-26 | 2002-01-16 | Tintenstrahlaufzeichnungselement und Druckverfahren |
Country Status (3)
Country | Link |
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EP (1) | EP1226970B1 (de) |
JP (1) | JP3939990B2 (de) |
DE (1) | DE60200328T2 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6773102B2 (en) * | 2002-09-27 | 2004-08-10 | Eastman Kodak Company | Inkjet printing method for an ink/receiver combination |
US6764173B2 (en) * | 2002-09-27 | 2004-07-20 | Eastman Kodak Company | Inkjet printing method |
EP1630600A3 (de) * | 2004-07-29 | 2006-03-22 | Rohm and Haas Electronic Materials, L.L.C. | Hotmeltzusammensetzung und Verfahren einschliesslich Erzeugung einer Maske |
CN106274110B (zh) * | 2015-05-13 | 2018-11-06 | 广东聚华印刷显示技术有限公司 | 一种低温喷墨印刷纳米金属图案的方法 |
CN106335298B (zh) * | 2015-07-09 | 2018-08-10 | 广东聚华印刷显示技术有限公司 | 喷墨印刷金属图案及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4059356B2 (ja) * | 1997-02-06 | 2008-03-12 | コニカミノルタホールディングス株式会社 | インクジェット記録用紙及びインクジェット記録方法 |
JP3920412B2 (ja) * | 1997-07-01 | 2007-05-30 | コニカミノルタホールディングス株式会社 | インクジェット記録方法 |
DE69932991T2 (de) * | 1998-06-10 | 2007-03-08 | Konica Minolta Holdings, Inc. | Tintenstrahlaufzeichnungspapier |
US6096469A (en) * | 1999-05-18 | 2000-08-01 | 3M Innovative Properties Company | Ink receptor media suitable for inkjet printing |
-
2002
- 2002-01-16 EP EP20020075169 patent/EP1226970B1/de not_active Expired - Lifetime
- 2002-01-16 DE DE2002600328 patent/DE60200328T2/de not_active Expired - Lifetime
- 2002-01-25 JP JP2002016869A patent/JP3939990B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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DE60200328D1 (de) | 2004-05-13 |
JP2002301866A (ja) | 2002-10-15 |
DE60200328T2 (de) | 2005-05-04 |
EP1226970A3 (de) | 2002-12-11 |
EP1226970A2 (de) | 2002-07-31 |
JP3939990B2 (ja) | 2007-07-04 |
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