Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
  • C07C309/60—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
• • 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
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/508—Supports
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
  • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
  • C07C309/58—Carboxylic acid groups or esters thereof
• • 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
  • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249954—With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component

Definitions

• This invention relates to the use of organometallic salts for pigment management in microporous inkjet receptor media.
• Inkjet printers have been in general use for wide-format electronic printing for applications such as, engineering and architectural drawings. Because of the simplicity of operation, economy of ink jet printers, and improvements in ink technology the inkjet imaging process holds a superior growth potential promise for the printing industry to produce wide format, image on demand, presentation quality durable graphics.
• the components of an ink jet system used for making graphics can be grouped into three major categories:
• the computer, software, and printer will control the size, number and placement of the ink droplets and will transport the receptor film.
• the ink will contain the colorant or pigments which form the image and the receptor film provides the medium which accepts and holds the ink.
• the quality of the inkjet image is a function of the total system. However, the composition and interaction between the ink and receptor film is most important in an inkjet system.
• Porous membrane is a natural choice to use as a inkjet receptive media because the capillary action of the porous membrane can wick the ink into the pores much faster than the absorption mechanism of film forming water soluble coatings.
• optical density has suffered greatly because the colorant penetrates too deep into the porous network.
• pigmented inks When pigmented inks are jetted onto a porous film that has a pore size that is too small, color pigments will be filtered on the top of the membrane rendering high image density, but the pigments could easily smear and have the effect of never drying. Also, excess fluid from the ink can coalesce, or even worse, pool and run on the image before the water/glycol carrier is wicked away.
• the chemical formulation of the pigmented inkjet ink has considerable complexity due to the requirement of continued dispersion of the pigment particles in the remainder of the ink and during jetting of the ink.
• the typical consumer medium for receiving dye-based inkjet inks has been paper or specially coated papers. However, with too much inkjet ink in a given area of the paper, one can see the over-saturation of the paper with the aqueous ink in which dye was dissolved.
• Japanese Patent JP 61-041585 discloses a method for producing printing material using a ratio of PVA/PVP.
• the disadvantage is inadequate waterfastness and wet rub off properties.
• Japanese Patent JP61-261089 discloses a transparent material with cationic conductive resin in addition to a mixture of PVA/PVP. The material is water fast and smudge proof but the wet rub off properties are poor.
• European Patent Publication EP 0 716 931 Al discloses a system using a dye capable of co-ordinate bonding with a metal ion in two or more positions. Again binder resins are used with inorganic pigments in the paper or film. The metal ion was preferred to be jetted on before imaging and additional heating is necessary to complete the reaction. This system was not claiming to be water fast, the focus is long term storage without fading from heat or light.
• U.S. Pat. No. 5,537,137 discloses a system to achieve waterfastness by curing with heat or UV light.
• examples of their coatings contained Ca++ from CaCl 2 . This was added to provide reactive species for the acid groups on the dispersed polymer. The coating remains water soluble until UV or heat curing after imaging.
• the current special inkjet media employ vehicle absorptive components, and sometimes optional additives to bind the inks to the media.
• vehicle absorptive components usually consist of water soluble (or swelling) polymers which result in slower printing speeds and dry times.
• Pigmented ink delivery systems have also dealt with pigment management systems, wherein the resting location of the pigment particles are managed to provide the best possible image graphic. For example, U.S. Pat. No.
• 5,747,148 discloses a pigment management system in which a suitable supporting layer (including in a listing a microporous layer) has a two layer fluid management system: a protective penetrant layer and a receptor layer, both layers containing filler particles to provide two different types of protrusions from the uppermost protective penetrant layer. Electron microphotographs in that application show how the pigment particles of the ink encounter smooth protrusions that provide a suitable topography for pigment particle "nesting" and rocky protrusions that assist in media handling and the like.
• an organometallic salt improves on the art by rapidly releasing multivalent metal cation which takes care of the pigment management function and an organic anion which provides useful organic acid to control smudgeness and drying of the film.
• This work therefore, solves the need for an inkjet receptor to have both a pigment management system for flocculating or agglomerating of incoming ink and a drying agent for the humectants of the ink thus efficiently drying the pigmented inks within a porous substrate.
• One aspect of the invention is an inkjet receptor medium, comprising a composition of matter comprised of an organometallic salt of a multivalent metal cation and an organic acid anion.
• One aspect of the present invention is to provide a metal salt that releases a metal cation for pigment management and simultaneously releases an organic acid anion of a carboxylic or sulfocarboxylic or phenolic acid or hydroxy or mixed functionalities thereof to take care of the drying aspect of the ink system.
• "Drying agent'” means an agent, component, ingredient or compound which can dry or make the pigment feel dry to touch via chemically or physicochemically occlusion or interaction with certain components such as the humectant or other slow drying components in the pigmented inks used in printing the image onto the receptor medium.
• dry to touch " ' means, an indistinguishable "feel" between the imaged and the unimaged areas of the substrate regardless of whether, technically, all volatiles have evaporated from the imaged area.
• One feature of the present invention is a multivalent organometallic salt that releases a multivalent metal ion for pigment management and an anion of an organic acid consisting of a carboxylic and or a sulfonic acid or hydroxyl or a phenolic or a mixed functionality thereof in a composition in an aqueous solution wherein the acid works as an ink-drying agent in a film coated with the said composition.
• One advantage of the present invention is that both the multivalent metal cation and the organic acid can be derived from the same salt/component. This advantage avoids the necessity of providing two different components to a porous substrate. Furthermore, the procedure minimizes the possibility that the coating solutions become contaminated with any undesirable residue or components or by product-compounds as contaminants.
• Another feature of the present invention is that a composition including the organometallic salt, surfactant and the migration inhibitor uses a lesser amount of total solids to achieve comparable performance. Thus, one can minimize concentration to obtain equivalent performance or maximize concentration to achieve previously-unattainable performance.
• the inkjet receptor medium can be any porous membrane or film known to those skilled in the art wherein it is desired to print inkjet inks on at least one major surface thereon.
• the medium comprises an inkjet receptor medium, comprising a porous substrate having a fluid management system and having a pigment management system in contact with surfaces of pores of the substrate therein.
• an inkjet receptor comprising a microporous membrane impregnated with an inorganic multivalent metal salt together with a surfactant or combination of surfactants chosen for the ink and membrane being employed.
• an inkjet receptor comprising a microporous membrane impregnated with a microporous fluorinated silica agglomerate together with a binder and a surfactant or a combination of surfactants for the ink and membrane being employed.
• an inkjet receptor comprising a microporous membrane impregnated with a microporous fluorinated silica agglomerate together with a binder and a surfactant or combination of surfactants wherein the said surfactants are selected from the group of hydrocarbon-based anionic surfactants, silicon-based non-ionic surfactants or fluorocarbon-based non-ionic based surfactants or a combination thereof.
• receptors when imaged in an inkjet printer, provide very high density and very high quality images which are tack-free and instantaneously dry to touch.
• One embodiment of the present invention is an inkjet receptor comprising a microporous membrane impregnated with an organometallic multivalent salt together with a hydrophilic surfactant and an optional migration inhibitor polymer/copolymer chosen from a series of hydrophilic/hydrophobic polymers/copolymers.
• an inkjet medium comprising a microporous membrane impregnated with an organometallic multivalent salt wherein the said salts are derived from various aromatic acids consisting of sulfonic, carboxylic, phenolic, hydroxyl and mixed functionalities thereof and wherein the metal ions may be derived from group IIA to VIA and more preferably from group IB to VIIIB in the Periodic Table. Specific examples, include, but are not limited to, Al. Mg. Zn. Fe, Bi, Ga, Sn. Ca., Ti. Zr. Cu, Co etc.
• Nonlimiting examples of organometallic salts useful in the present invention include: .
• R -COOH (Li + , Na + , K + ;
• R 1 -COOH (Li + , Na + , K + ), R 2 - -OH
• n 4-8
• an inkjet medium comprising a microporous membrane impregnated with an organometallic multivalent salt wherein the said salt releases both a multivalent metal cation and an organic acid anion and wherein the metal cation plays the role of pigment management system and the organic acid anion plays the role of a dehydrating or drying agent thus making the image in the membrane smudge-free to touch.
• Another embodiment of the present invention is an inkjet medium comprising a microporous membrane impregnated with an organometallic multivalent salt wherein the said salt releases both a multivalent metal cation and an organic acid anion - both simultaneously being useful for pigment management system and humectant management system in the ink.
• Another embodiment of the present invention is an inkjet coating composition that incorporates an organometallic multivalent salt with a surfactant and a binder only to give a composition which provides 0.33 to 0.25 of the coating weight of that a composition consisting of an inorganic salt, a surfactant, organic acid and a binder.
• the ink colorant is typically a pigment dispersion having a dispersant that binds to the pigment that will destabilize, flocculate, agglomerate, or coagulate the pigments on contact with the media component.
• Depositing each of colors at or just below the surface of the membrane allowing the carrier fluid to wick into the membrane where the fluid management system can take over while providing a sheltered location for the pigments as managed by the pigment management system.
• the inkjet receptor medium uses a Thermally Induced Phase Separated (T.I.P.S.) microporous membrane according the disclosures of U.S. Pat. Nos. 4,539,256 (Shipman et al.), 4,726,989 (Mrozinski), and more particularly 5,120,594 (Mrozinski), and available from 3M.
• T.I.P.S. Thermally Induced Phase Separated
• the pore size and pore volume of the porous film can be adjusted for the model or make of the inkjet printer to correctly hold the volume of ink dispensed by the printer ensuring the highest possible image quality.
• the coating on the preferred media/ink set has special utility in the demanding ink jet printing applications found in commercial printing.
• these receptors can "fine tune" the properties of these receptors to deal with the variables of inkjet ink delivery, including without limitation: drop volume, porosity of media, and capacity of media to receive ink.
• these media exhibit a complex porosity in its porous material that provides both a tortuous path for fluid management and a tortuous path that ensnares the pigment initially and continually during ink delivery.
• Pigment drying agents can be useful in the present invention and can comprise aromatic or aliphatic acids having sulfonic, carboxylic, phenolic or mixed functionalities thereof.
• aromatic sulfonic and carboxylic acids have been found in this invention to be very effective in presence of multivalent metal salts and suitable surfactant and binder, to serve as drying agents for inkjet receptor media.
• These acids can be of various types, chosen according to properties and distinguished by extent of their solubility in water and how that solubility affects drying performance.
• sulfocarboxylic acid such as sulfosalicylic acid.
• the candidate acids with lower solubility in water would perform the drying function excellently but could require more aggressive solvent(s) to be impregnated into the media.
• This type of acid is a phthalic acid so long as it is recognized that impregnating the receptor media will be more challenging because of the acid's lower solubility.
• lower solubility acid candidates such as aromatic carboxylic acids
• the solubility of that salt in water is enhanced.
• this type of acid-salt is an aromatic carboxylic acid, sodium salt such as or/ ⁇ o-phthalic acid-sodium salt.
• aromatic carboxylic acids are also sufficiently soluble in water when the aromatic moiety contains at least one sulfonic acid group attached to the aromatic ring either as acid or as its sodium salt (or other alkali metal salts).
• sulfonic acid group attached to the aromatic ring either as acid or as its sodium salt (or other alkali metal salts).
• Two examples of these candidates are 5-sulfoisophthalic acid and also its monosodium salt.
• —OH group can be attached to the aromatic moiety to increase the solubility of the aromatic carboxylic group.
• Examples in this category are hydroxy-aryldicarboxylic acid isomers.
• a related factor to choice of lower water solubility candidate acid is the amount of the acid to be included in the receptor media.
• the relationship is generally such that the lower solubility acid candidates are needed in smaller amounts than the higher solubility acid candidates.
• an acid used in the present invention can be present in the receptor medium in an amount ranging from about 1 to about 20 weight percent of the total coating weight of compositions with which the medium is impregnated with a fluid management system/pigment management system. Preferably, the amount ranges from about 4 to about 15 weight percent.
• a sodium salt of an aromatic sulfocarboxylic acid should be present in an amount in the higher end of the range (e.g., about 15 weight percent), whereas a carboxylic acid should be present in an amount in the lower end of the range (e.g., about 5 weight percent).
• free acid and salt forms of that acid can be combined for controlled tailoring of impregnation processing and resulting drying performance.
• the acid or its salt can be impregnated into the media by adding it to a coating solution otherwise being impregnated into the media for fluid management and pigment management purposes.
• Suitable coating solutions comprise a multivalent inorganic salt, a suitable surfactant, an alcohol and water.
• the weight percent of the acid/salt being used usually ranges from about 40 to about 60 weight percent and more preferably from about 45 to about 55 weight percent of the total solids in the composition.
• Pigment migration inhibitors can be used in the present invention as an optional additive. These inhibitors can be homopolymers or copolymers having any number of hydrophilic monomers, each of whose homopolymers are hydrophilic. so long as the resulting copolymer is sparingly soluble in water.
• hydrophilic monomers are methacrylic, ethacrylic acids, acrylic acid, N-Vinylphthalimide, Vinylimidazole. Vinylpyridine and N-vinyl-2-pyrrolidinone. with the last and acrylic acid being presently preferred.
• the homopolymer is a polyvinylpyrrolidinone (PVP) of relatively high molecular weight available from commercial sources.
• ink receptive copolymers that are sparingly soluble in water include a copolymer of N-vinylpyrrolidone, acrylic acid, and trimethoxysilylethylmethacrylate (80/10/10); a copolymer of N-vinylpyrrolidone, acrylic acid, trimethoxysilylethylmethacrylate, and ethyleneoxide acrylate (75/10/5/10); a copolymer of N-vinylpyrrolidone, acrylic acid, and N, N, N- methyloctylheptadecafluorosulfonylethylacrylate (MeFOSEA) (80/10/10); a copolymer of N-vinylpyrrolidone, acrylic acid, trimethoxysilylethylmethacrylate and N, N, N-ethyloctylheptadecafluorosulfonylethylacrylate (MeFOSEA) (83/10/2/5);
• ink migration of the pigment particles can occur when an overlaminate is used over the printed ink to protect the image.
• water can ingress and cause capillary movement of the pigment underneath the overlaminate.
• the complexation of multivalent metal cation with the chemically released organic acid anions and the migration inhibitor provides not only efficient pigment and humectant management systems but also allows significant pigment inhibition on the film that it is found to be completely water- fast within 2 minutes to 2 hrs of imaging without mechanical rubbing.
• organometallic salts were prepared by refiuxing appropriate quantities of metal chlorides and hydroxysulfonic acids in toluene for 8-9 hrs. The materials were filtered, dried in air and stored. In a typical experiment, to a solution of 90g of 5-sulfosalicylic acid (0.35 mole) in lOOg toluene was added 15.7g (0.12 mole) of aluminum chloride and the mixture was heated to near-reflux temperature of the solvent for about 8 hrs. The white solid precipitated was filtered and dried. The product was characterized by the usual analytical techniques.
• the same classes of materials were also prepared by using appropriate metal alkoxides and hydroxysulfonic or sulfocarboxylic acids in water.
• aluminum isopropoxide was mixed with 5-sulfophthalic acid in 2:3 molar ratio and the mixture was heated to about 60°C for about '/_ hr.
• Aluminum isopropoxide was hydrolyzed and the salt was obtained as aqueous solution and was used as such for inkjet coatings.
• Magnesium ethoxide was similarly hydrolyzed from its mixture with the same acid in 1 :2 molar ratio to obtain magnesium sulfophthalate in aqueous solution.
• the same class of salts were also prepared by yet another procedure Viz. metathetical ion-exchange.
• a solution of 5-sulfoisophthalic acid-Na salt (20 g, 0.075 mole) in methanol was mixed with magnesium chloride (3.5 g, 0.0375 mole), and the mixture was refluxed for about VT. hr.
• the solution was concentrated and sodium chloride was crystallized out.
• the solution was decanted to obtain 5- sulfoisophthalic acid-Mg salt in solution.
• Carboxy-derivative of the class of materials were prepared by hydrolyzing metal alkoxide with aromatic carboxylic acid or functionalized aromatic carboxylic acids. Thus, refluxing a mixture of 24g (0.090 mole) 5-sulfoisophthalic acid-Na salt with 6.1g (0.030 mole) aluminum isopropoxide in 3:1 molar ratio in aqueous media for about Vz hr, aluminum tris(5-sulfoisophthalate-Na salt) was obtained in solution.
• organometallic salts (I-IV) were used in the following compositions.
• the compositions were coated onto oil-in microporous polypropylene membrane prepared by the techniques according the disclosures of U.S. Pat. Nos. 4,539,256 (Shipman et al.), 4,726,989 (Mrozinski), and more particularly 5.120,594 (Mrozinski).
• the impregnated membrane was dried and then imaged in an HP- 2500 series wide-format inkjet printers (Hewlett Packard Corporation of Palo Alto, CA, USA) to obtain instantaneously dry, smudge-free and water-fast images.
• composition-I Composition-I:
• composition-II Composition-II:
• Copper(II)sulfocarbolate - 1 5.2% Aluminum sulfate (octadecahydrate) 4.1% Dioctylsulfosuccinate (Dos 3 ) 7.0% NVP/AA (copolymer) 2.0% IPA 25% De-ionized water 45% Composition-Ill:
• composition-IV Composition-IV:
• compositions were coated onto a microporous polypropylene membrane prepared according the disclosures of U.S. Pat. Nos. 4,539,256 (Shipman et al.), 4,726,989 (Mrozinski). and more particularly 5,120,594 (Mrozinski) that had the following properties:
• the composition was coated onto the microporous inkjet receptor medium with a No. 4 Meyer bar.
• the printed medium was laminated with 3M Scotch No. 845 Book Tape and the laminated medium was adhered to a piece of anodized aluminum and approximately 75% percent was submerged in water for a period of about 96 hours. During this time of submersion, the image did not show any deterioration due to pigment migration.
• the film was dried at about 76°C-121°C within 1-2 minutes.
• the impregnated membrane when imaged in HP-2500 series printer provided very high quality and high-density image which was instantaneously dry, tack-free, feathering-free, and smudge-free.
• the image did not show any movement in any of the ink/color on water-challenging done in the same manner as disclosed above in the prior example.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Ink Jet (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)

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• 1998
  • 1998-06-19 US US09/099,983 patent/US6703112B1/en not_active Expired - Fee Related
• 1999
  • 1999-02-17 JP JP2000554562A patent/JP2002518215A/ja not_active Withdrawn
  • 1999-02-17 EP EP99910960A patent/EP1098775B1/en not_active Expired - Lifetime
  • 1999-02-17 WO PCT/US1999/003472 patent/WO1999065703A1/en not_active Ceased
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  • 1999-02-17 BR BR9911379A patent/BR9911379A/pt not_active Application Discontinuation
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