AU2971199A - Creación de Inventos y Patentes con Inteligencia Artificial

AU2971199A – Inkjet receptor media comprising metallic salts
– Google Patents

AU2971199A – Inkjet receptor media comprising metallic salts
– Google Patents
Inkjet receptor media comprising metallic salts

Download PDF
Info

Publication number
AU2971199A

AU2971199A
AU29711/99A
AU2971199A
AU2971199A
AU 2971199 A
AU2971199 A
AU 2971199A
AU 29711/99 A
AU29711/99 A
AU 29711/99A
AU 2971199 A
AU2971199 A
AU 2971199A
AU 2971199 A
AU2971199 A
AU 2971199A
Authority
AU
Australia
Prior art keywords
medium
metal
ink
organometallic salt
salt
Prior art date
1998-06-19
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.)

Granted

Application number
AU29711/99A
Other versions

AU751312B2
(en

Inventor
Omar Farooq
Clinton P. Waller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

3M Co

Original Assignee
Minnesota Mining and Manufacturing Co
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.)
1998-06-19
Filing date
1999-02-17
Publication date
2000-01-05

1999-02-17
Application filed by Minnesota Mining and Manufacturing Co
filed
Critical
Minnesota Mining and Manufacturing Co

2000-01-05
Publication of AU2971199A
publication
Critical
patent/AU2971199A/en

2002-08-15
Application granted
granted
Critical

2002-08-15
Publication of AU751312B2
publication
Critical
patent/AU751312B2/en

2019-02-17
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

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.]

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

Description

WO 99/65703 PCT/US99/03472 INKJET RECEPTOR MEDIA COMPRISING METALLIC SALTS 5 Field of Invention This invention relates to the use of organometallic salts for pigment management in microporous inkjet receptor media. Background of Invention 10 Inkjet imaging techniques have become vastly popular in commercial and consumer applications. The ability to use a personal computer and desktop printer to print a color image on paper or other receptor media has extended from dye-based inks to pigment-based inks. The latter provide brilliant colors and more durable images because pigment particles are contained in a 15 dispersion before being dispensed using a thermal inkjet print head, such as those commercially available from Hewlett Packard Corporation or LexMark Corporation in inkjet printers commercially available from Hewlett Packard Corporation, Encad Inc:. Mimaki Corporation, and others. Ink jet printers have been in general use for wide-format electronic 20 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. 25 The components of an ink jet system used for making graphics can be grouped into three major categories: I Computer. software, printer. 2 Ink. 3 Receptor sheet. 30 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 -1- WO 99/65703 PCT/US99/03472 provides the medium which accepts and holds the ink. The quality of the ink jet image is a function of the total system. However, the composition and interaction between the ink and receptor film is most important in an ink jet system. Image quality is what the viewing public and paying customers will 5 want and demand to see. Many other demands are also placed on the ink jet media/ink system from the print shop, such as rapid drying, humidity insensitivity, extended shelf life, waterfastness and overall handleability. Also, exposure to the environment can place additional demands on the media and ink (depending on the application of the graphic). 10 Porous membrane is a natural choice to use as a ink jet 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. However, in the past, when a porous coating or film has been employed to achieve desired quick dry, optical density has suffered greatly because the 15 colorant penetrates too deep into the porous network. This type of problem is magnified by printers that dispense high volumes of ink per drop because extra film thickness may be required to hold all the ink. When the pore size and pore volume of the membrane is opened to allow the pigments to penetrate, the pigments can be stratified in the membrane. Meaning, the black, cyan, magenta, 20 and yellow will be predominately found at different depths depending on order of application. Hence, some of the first color(s) applied is /are optically trapped in the image by subsequent application of other pigmented ink. Furthermore, lateral diffusion of the ink can also be a problem inherent in porous membranes used as receptive media. When pigmented inks are jetted onto a porous film that has a 25 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. 30 The chemical formulation of the pigmented inkjet ink has considerable complexity due to the requirement of continued dispersion of the WO 99/65703 PCTIUS99/03472 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 5 aqueous ink in which dye was dissolved. As inkjet inks have become more commercially oriented and pigmented-based inks have become more prevalent, different media have been tried in an attempt to control the management of fluids in the ink. Japanese Patent JP 61-041585 discloses a method for producing 10 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. 15 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 20 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. In the body of the patent, 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 25 until UV or heat curing after imaging. Hence, the current special ink jet media employ vehicle absorptive components, and sometimes optional additives to bind the inks to the media. As a consequence current media are inherently moisture sensitive and can be fragile to handling and subject to finger smearing. Moreover, the vehicle absorptive 30 components usually consist of water soluble (or swelling) polymers which result in slower printing speeds and dry times. -3- WO 99/65703 PCT/US99/03472 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 (Warner et al.) discloses a pigment management system in which a 5 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 10 protrusions that provide a suitable topography for pigment particle «nesting» and rocky protrusions that assist in media handling and the like. Other ink receptors have been disclosed, including U.S. Pat. Nos. 5,342,688 (Kitchin); 5,389,723 and 4,935,307 (both Iqbal et al.); 5,208,092 (Iqbal) 5,302,437 (Idei et al); U.S. Pat. No. 5,206,071 (Atherton et al.); and EPO Patent 15 Publication 0 484 016 Al. Summary of Invention In the present work, an organometallic salt improves on the art by rapidly releasing multivalent metal cation which takes care of the pigment 20 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. 25 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 30 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. -4- WO 99/65703 PCT/US99/03472 «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 5 receptor medium. Specifically, «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 10 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 15 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. 20 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. 25 Other features and advantages of the invention will be disclosed in relation to the embodiments of the invention. Embodiments of Invention Inkiet Receptor Medium 30 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 WO 99/65703 PCT/US99/03472 one major surface thereon. Preferably, 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. One embodiment of that medium is an inkjet receptor 5 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. Another embodiment is an inkjet receptor comprising a microporous membrane impregnated with a microporous fluorinated silica agglomerate together 10 with a binder and a surfactant or a combination of surfactants for the ink and membrane being employed. Another embodiment of that medium is an inkjet receptor comprising a microporous membrane impregnated with a microporous fluorinated silica agglomerate together with a binder and a surfactant or combination of 15 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. These receptors, when imaged in an inkjet printer, provide very high density and very high quality images which are tack-free and instantaneously dry 20 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 25 polymers/copolymers. Another embodiment of the present invention is 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 30 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 -6- WO 99/65703 PCT/US99/03472 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:. 5 Metal Sulfocarbolates MX 0 3 S OH M = Cu. Mg, Co (x-y = 12); M = AL, Ga (xy = 1:3, 23) Metal Hydroquinonesulfonates HO M , 0 3 S y OH M = Cu, Mg, Co (x-y = 12, 22); M = AL, Ga, Ti, Zr (x-y = 13, 2:3, 22) 10 -7- WO 99/65703 PCTIUS99/03472 Metal dihydroxybenzenedisulfonates HO 03 M0 3 S OH M =Cu, Mg, Co (xy =1:1, 12) ;M =Al, Ga, TZr (x-y1:1, 22, 4:3) 5 Metal Sulfosalicylates R M1 0 3 S& OH M = CuMg.,Co (x-y =12, 1:1); M =Al, Ga,TR Zr (xy 13, 23, 33) R = -COOH (LI’, Na’, K’-) Metal Sulfophthalates 10 Mx03S5 U 2 M = CuMg, Co (x-y= 1:1, 22,32); M =Al, Ga, TL Zr(x-y 1:3,22,2:3) R’ = R 2 = -COOH (Li , Na ,K) -8- WO 99/65703 PCT/US99/03472 Metal Carboxylates (a) R Mx ~OOC6 R2 M =Cu, Mg, Co (x-y= 1:1, 2 2, 32); M = AL Ga, Ti, Zr (x-y = 13, 22, 23) R = -COOH(Li,Na’,K’), R2=-OH 5 (b) R Mx OOC NR2 M =Cu, Mg, Co (x-y 1:1, 22, 32); M = Al Ga, Ti, Zr (x-y = 1:3, 22, 2:3)
R
1 = -COOH (Li , Na’, K’), R 2 = -OH 10 Metal Calix(n) arene sulfonates S3-M MM 03S OH H OH HO *~S3 -M 03S M M = Cu, Mg, Co, Ca, Al, Ti, Zr, Zn etc. n = 4-8 15 Another embodiment of the present invention is an inkjet medium -9- WO 99/65703 PCT/US99/03472 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 5 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 10 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 15 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 20 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. More preferably, the inkjet receptor medium uses a Thermally Induced Phase Separated (T.I.P.S.) microporous membrane according the 25 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. For optimization, the pore size and pore volume of the porous film can be adjusted for the model or make of the ink jet printer to correctly hold the volume of ink dispensed by the printer ensuring the highest possible image quality. The coating 30 on the preferred media/ink set has special utility in the demanding ink jet printing applications found in commercial printing. Thus, one can «fine tune» the -10- WO 99/65703 PCTIUS99/03472 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. Moreover, these media exhibit a complex porosity in its porous material that provides both a tortuous path for fluid management and a 5 tortuous path that ensnares the pigment initially and continually during ink delivery. Optional Additives Pigment Drying agents Pigment drying agents can be useful in the present invention and 10 can comprise aromatic or aliphatic acids having sulfonic, carboxylic, phenolic or mixed functionalities thereof. Preferably, 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. 15 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. At one end of the range of candidate acids, their higher solubility in water can interfere with other components in the media, such as a migration 20 inhibitor thereby perhaps requiring a greater concentration of drying agent to be included in the coating. One example of this type of acid is a sulfocarboxylic acid such as sulfosalicylic acid. At the other end of the range of candidate acids, the candidate acids with lower solubility in water would perform the drying function excellently but 25 could require more aggressive solvent(s) to be impregnated into the media. One example of 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. To overcome impregnating limitations, lower solubility acid candidates, such as aromatic carboxylic acids, can be derivatized to become a 30 monosodium salt (or any other similar alkali metal salt), the solubility of that salt in water is enhanced. One example of this type of acid-salt is an aromatic -11- WO 99/65703 PCT/US99/03472 carboxylic acid, sodium salt such as ortho-phthalic acid-sodium salt. Furthermore. the 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). Two examples 5 of these candidates are 5-sulfoisophthalic acid and also its monosodium salt. Other functional groups such as –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 10 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. Generally, 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 15 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. Thus, 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 20 range (e.g., about 5 weight percent). Moreover, 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 25 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. 30 Pigment Migration Inhibitors -12- WO 99/65703 PCT/US99/03472 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. 5 Nonlimiting examples of 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. 10 Other 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 15 methyloctylheptadecafluorosulfonylethylacrylate (MeFOSEA) (80/10/10); a copolymer of N-vinylpyrrolidone, acrylic acid, trimethoxysilylethylmethacrylate and N, N, N-ethyloctylheptadecafluorosulfonylethylacrylate (MeFOSEA) (83/10/2/5); and ); a copolymer of N-vinylpyrrolidone, acrylic acid, and Sulfonated Styrene–Sodium Salt (60/10/30). 20 Usefulness of the Invention and Examples It has been found that ink migration of the pigment particles can occur when capillary forces cause pigment particles of a portion of a printed inkjet medium is partially submerged in water. Only the area of printed ink above 25 migrates, and typically only after several hours of submersion of the other portion of the printed ink. This noticeable ink migration is in a manner like thin layer chromatography. It has also been found that ink migration of the pigment particles can occur when an overlaminate is used over the printed ink to protect the image. 30 However, at the edge of the overlaminate and the printed ink, water can ingress and cause capillary movement of the pigment underneath the overlaminate. -13- WO 99/65703 PCTIUS99/03472 In the present invention 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 5 water-fast within 2 minutes to 2 hrs of imaging without mechanical rubbing. The following examples illustrate the invention in more detail. Reaction of polyfunctional aromatic compounds containing sulfonic, carboxylic, hydroxyl groups and mixed groups thereof with certain metal halides, pseudo-halides and alkoxides lead to several classes of novel 10 organometallic salts. These salts have been prepared according to the following procedure. -14- WO 99/65703 PCT/US99/03472 Example-1: Various classes of organometallic salts were prepared by refluxing appropriate 5 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 1OOg 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 10 and dried. The product was characterized by the usual analytical techniques. 0 C-OH AiC1 3 + HO 3 S OH 1 3 Toluene/A 0 C-OH Al -03 S OHI + HCI Example-2: The same classes of materials were also prepared by using appropriate metal 15 alkoxides and hydroxysulfonic or sulfocarboxylic acids in water. Thus, aluminum isopropoxide was mixed with 5-sulfophthalic acid in 2:3 molar ratio and the mixture was heated to about 60’C for about 1/2 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 20 with the same acid in 1:2 molar ratio to obtain magnesium sulfophthalate in aqueous solution. -15- WO 99/65703 PCT/US99/03472 0 C -OH Al(O-iPr) 3 + HO 3 S OH -II 0 2 3 (24g= 0.12 mole) (45g = 0.18 mole) I H,0/A 0 C-OH AL) -0 3 S – j0 OH 47g 21g Example-3: The same class of salts were also prepared by yet another procedure Viz. 5 metathetical ion-exchange. Thus, 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 % hr. The solution was concentrated and sodium chloride was crystallized out. The solution was decanted to obtain 5 sulfoisophthalic acid-Mg salt in solution. -16- WO 99/65703 PCT/US99/03472 COOH Na ‘ O 3 S + MgCl2 COOH MeOH Reflux / 1/2 hr COOH Mg -0 3 S + NaCl COOH Example-4: Carboxy-derivative of the class of materials were prepared by hydrolyzing metal alkoxide with aromatic carboxylic acid or functionalized aromatic carboxylic acids. 5 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 % 2 hr, aluminum tris(5-sulfoisophthalate-Na salt) was obtained in solution. COOH Na~O 3 S + Al(i-PrO) 3 3 COOH I H,0 Reflux / 1/2 hr SO3~Na + Al ~OOC + HO COOH 10 -17- WO 99/65703 PCT/US99/03472 Example-5: The following 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 5 (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. COOH Cu 03S OH Al 0 3 S OH Copper(II)sulfocarbolate Aluminum 5-sulfosalicylate I II COOH COOH Al 2 0 3 S COO M -03 S COOH 2 Aluminum 5- sulfophthalate Magnesium 5-sulfophthalate 10 III IV Composition-I: 15 Aluminum 4-sulfophthalate – III 7.0% Dioctylsulfosuccinate (Dos’) 5.0%NVP/AA (copolymer) 2% IPA 25% De-ionized water 61% 20 Composition-II: Copper(II)sulfocarbolate – I 5.2% Aluminum sulfate (octadecahydrate) 4.1% Dioctylsulfosuccinate (Dos) 7.0% 25 NVP/AA (copolymer) 2.0% IPA 25% De-ionized water 45% -18- WO 99/65703 PCT/US99/03472 Composition-III: Aluminum 5-sulfosalicylate – II 7.0% 5 Dioctylsulfosuccinate (Dos 3 ) 6.0% NVP/AA (copolymer) 2% IPA 25% De-ionized water 60% 10 Composition-IV: Magnesium 5-sulfophthalate – IV 5.3% Dioctylsulfosuccinate (Dos 3 ) 6.0% 15 NVP/AA (copolymer) 2% IPA 25% De-ionized water 60% 20 The described 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: Bubble point 0.9 pim 25 Gurley 50cm 3 15 sec Porosity % void 38 % Surface wetting Energy (before treatment) 30 dynes/cm2 Caliper 0.178 mm (7 mil) 30 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 35 about 96 hours. During this time of submersion, the image did not show any deterioration due to pigment migration. The above described examples were repeated successfully using yet another microporous membrane prepared using thermally induced phase separation techniques according the disclosures of U.S. Pat. Nos. 4,539,256 (Shipman et al.), -19- WO 99/65703 PCT/US99/03472 4.726,989 (Mrozinski). and more particularly 5,120.594 (Mrozinski). This membrane had the following properties: Bubble point 0.75 pm Gurley 50cm 20 see 5 Porosity % void 41 % Surface wetting Energy (before treatment) 30 dynes/cm2 Caliper 0.178 mm (7 mil) 10 The film was dried at about 76 0 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 15 in the prior example. The invention is not limited to the above embodiments. The claims follows. -20-

Claims (19)

1. An inkjet receptor medium. comprising a composition of matter comprised of an organometallic salt of a multivalent metal cation and an 5 organic acid anion.

2. The medium of claim 1 wherein the multivalent metal cation is derived from group IIA to VIA and group IB to VIIIB in the Periodic Table having capability of forming organometallic salts/compounds with the 10 organic acid anion.

3. The medium of claim 1, wherein the organic acid anion is selected from the group consisting of acids having a carboxylic, sulfonic, phenolic and mixed functionalities thereof and wherein the organic acid anion is an aromatic 15 acid.

4. The medium of claim 3, wherein the aromatic acid comprises a sulfocarboxylic acid, a sulfosalicycylic acid, or a sulfophenolic acid. 20

5. The medium of claim I wherein the said organometallic salts are derived from the reaction of a metal halide or a pseudo-halide with an organic acid

6. The medium of claim I wherein the organometallic salts are derived from the reaction of a metal alkoxide with an organic acid via simple 25 hydrolysis in an aqueous medium.

7. The medium of claim I wherein the organometallic salt comprises any of monomeric, dimeric, trimeric salts whose solubility is dictated by the degree of complexation. 30 -21- WO 99/65703 PCT/US99/03472

8. The medium of claim 1, further comprising a porous substrate into which the organometallic salt is impregnated together with a surfactant. 5

9. The medium of claim 8, wherein the porous substrate is a microporous polypropylene membrane.

10. The medium of claim 1, wherein the organometallic salt is a metal sulfocarbolate of the formula: 10 Mx 0 3 S OH M = Cu, Mg, Co (x-y = 12); M = AL, Ga (x-y = 1:3, 2:3) 15

11. The medium of claim 1, wherein the organometallic salt is a metal hydroquinonesulfonate of the formula: HO Mx 0 3 S y OH M = Cu, Mg, Co (x-y = 12, 22); M = Al, Ga, Ti, Zr (x-y = 13, 2:3, 22)

12. The medium of claim 1, wherein the organometallic salt is a metal dihydroxybenzenedisulfonate of the formula: -22- WO 99/65703 PCT/US99/03472 HO 03 Mx 03S OH M Cu, Mg, Co (x-y = 1:1. 12); M = Al, Ga, T Zr (xy = 1:1 2-2,4:3)

13. The medium of claim 1, wherein the organometallic salt is a metal sulfosalicylate of the formula: 5 R Mx 0 3 S OH M Cu, Mg, Co (x-y = 12, 1:1); M = Al, Ga, Ti, Zr (x-y = 13, 2:3, 3-3) R = -COOH (Li’, Na’, K’)

14. The medium of claim 1, wherein the organometallic salt is a metal sulfophthalate of the formula: 10 R Mx ~0 3 S 2 y M =Cu, Mg, Co (x-y = 1:1, 22, 32); M = Al, Ga, Ti, Zr (x-y = 13, 22, 2:3) R’ = R2= -COOH (Lie, Nat, K+) 15

15. The medium of claim 1, wherein the organometallic salt is a metal carboxylate of the formulae: -23- WO 99/65703 PCT/US99/03472 R Mx ~OOC R2 M = Cu, Mg, Co (x-y= 1:1, 2:2, 32); M = AL Ga. Ti, Zr (x-y = 1:3. 22, 2:3) R = -COOH (Li’, Na, K’), R 2 = -OH RI Mx OOC NR2 M = Cu, Mg, Co (x-y = 1:1, 22, 32); M = AL Ga, Ti, Zr (x-y = 13, 22,2:3) R= COOH (Li’, NaT, K’), R 2 =-OH 5

16. The medium of claim 1, wherein the organometallic salt is a metal Calix(n)arene sulfonate of the formula: S3-M M 03S OH H OH HO * S3-M 03S M M = Cu, Mg, Co, Ca, Al, Ti, Zr, Zn etc. n = 4-8 10

17. A method of imaging a graphic on a porous substrate, comprising the steps of: -24- WO 99/65703 PCT/US99/03472 (a) impregnating an organometallic salt of claim 1 in the porous substrate; and (b) delivering ink to the porous substrate. 5

18. The method of claim 17, wherein the impregnating step (a) also includes impregnating a surfactant and a Migration inhibitor.

19. An image graphic, comprising ink in and on a porous substrate, wherein the porous substrate contains an organometallic salt of claim I 10 and wherein the ink interacts with the organometallic salt in a complexation of metal cation of the salt with dispersant in the ink. -25-

AU29711/99A
1998-06-19
1999-02-17
Inkjet receptor media comprising metallic salts

Ceased

AU751312B2
(en)

Applications Claiming Priority (3)

Application Number
Priority Date
Filing Date
Title

US09/099,983

US6703112B1
(en)

1998-06-19
1998-06-19
Organometallic salts for inkjet receptor media

US09/099983

1998-06-19

PCT/US1999/003472

WO1999065703A1
(en)

1998-06-19
1999-02-17
Inkjet receptor media comprising metallic salts

Publications (2)

Publication Number
Publication Date

AU2971199A
true

AU2971199A
(en)

2000-01-05

AU751312B2

AU751312B2
(en)

2002-08-15

Family
ID=22277540
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU29711/99A
Ceased

AU751312B2
(en)

1998-06-19
1999-02-17
Inkjet receptor media comprising metallic salts

Country Status (9)

Country
Link

US
(1)

US6703112B1
(en)

EP
(1)

EP1098775B1
(en)

JP
(1)

JP2002518215A
(en)

KR
(1)

KR20010052999A
(en)

CN
(1)

CN1306477A
(en)

AU
(1)

AU751312B2
(en)

BR
(1)

BR9911379A
(en)

DE
(1)

DE69920232T2
(en)

WO
(1)

WO1999065703A1
(en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US6773769B1
(en)

1999-05-18
2004-08-10
3M Innovative Properties Company
Macroporous ink receiving media

JP2001047734A
(en)

1999-08-06
2001-02-20
Three M Innovative Properties Co
Image recording medium

CA2398147A1
(en)

2000-02-08
2001-08-16
3M Innovative Properties Company
Ink fixing materials and methods of fixing ink

ATE304453T1
(en)

2000-02-08
2005-09-15
3M Innovative Properties Co

IMPROVED METHODS FOR COLD IMAGE TRANSFER

US20020052439A1
(en)

2000-08-08
2002-05-02
3M Innovative Properties Company
Ink receptive compositions and articles for image transfer

DE10309705B4
(en)

2003-03-06
2005-03-24
Felix Schoeller Jr. Foto- Und Spezialpapiere Gmbh & Co. Kg

Ink-jet recording sheet with improved ozone and light stability

KR100644607B1
(en)

2003-06-03
2006-11-13
삼성전자주식회사
Recording medium for ink jet printers

US20050170153A1
(en)

2004-02-02
2005-08-04
Celgard Inc.
Printable thin microporous membrane

US20110083573A1
(en)

2004-11-16
2011-04-14
Sappi Netherlands Services B.V.
Coating composition for offset paper

BRPI0516807A
(en)

2004-11-16
2008-09-23
Sappi Netherlands Services Bv

coating for offset paper and coated paper, method for producing this coating and use of a catalyst system

KR100707163B1
(en)

2005-10-12
2007-04-13
삼성에스디아이 주식회사
Solid acid, polymer electrolyte membrane comprising the same, and fuel cell employing the same

JP5503378B2
(en)

2010-03-31
2014-05-28
北越紀州製紙株式会社

Multi-layer inkjet postcard paper and method for producing the same

MX2013009977A
(en)

2011-03-02
2013-10-17
Futurefuel Chemical Co
Metal salts of a dialkyl ester of 5-sulfoisophthalic acid and method of preparing same.

CA2845087A1
(en)

2011-08-16
2013-02-21
Futurefuel Chemical Company
Salts of 5-sulfoisophthalic acid and method of making same

US8809565B2
(en)

2011-08-29
2014-08-19
Futurefuel Chemical Company
5-sulfoisophthalic acid salts and process for the preparation thereof

EP2925529B1
(en)

2012-11-28
2020-08-19
Välinge Innovation AB
Method of producing a building panel using digital printing

FR3000408B1
(en)

2013-01-03
2015-02-27
Commissariat Energie Atomique

METHOD FOR PRODUCING FILTER FOR FILTRATION OF NANOPARTICLES, FILTER OBTAINED AND METHOD FOR COLLECTING AND QUANTITATIVE ANALYSIS OF NANOPARTICLES THEREOF

US11104821B2
(en)

2017-03-31
2021-08-31
Dnp Fine Chemicals Co., Ltd.
Receptive solution, ink set containing said receptive solution and method for producing printed material using ink set

Family Cites Families (96)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US4247498A
(en)

1976-08-30
1981-01-27
Akzona Incorporated
Methods for making microporous products

JPS56159128A
(en)

1980-05-15
1981-12-08
Asahi Chem Ind Co Ltd
Thermoplastic resin porous film and production thereof

DE3024205A1
(en)

1980-06-27
1982-01-21
Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück

RECORDING PAPER FOR INK SPRAY RECORDING METHOD

JPS5769054A
(en)

1980-10-17
1982-04-27
Fuji Photo Film Co Ltd
Water proofing method of ink jet recording

US4539256A
(en)

1982-09-09
1985-09-03
Minnesota Mining And Manufacturing Co.
Microporous sheet material, method of making and articles made therewith

JPS6067190A
(en)

1983-09-22
1985-04-17
Ricoh Co Ltd
Ink jet recording medium

US4554181A
(en)

1984-05-07
1985-11-19
The Mead Corporation
Ink jet recording sheet having a bicomponent cationic recording surface

JPS6141585A
(en)

1984-08-03
1986-02-27
Canon Inc
Recording material

JPS6163476A
(en)

1984-09-06
1986-04-01
Canon Inc
Recording material

US4547405A
(en)

1984-12-13
1985-10-15
Polaroid Corporation
Ink jet transparency

EP0199874A1
(en)

1985-02-25
1986-11-05
The Mead Corporation
Ink jet recording sheet having an ink-receptive layer containing polyethylene oxide

JPS61261089A
(en)

1985-05-15
1986-11-19
Teijin Ltd
Recording sheet

JPS6294379A
(en)

1985-10-21
1987-04-30
Mitsubishi Yuka Fine Chem Co Ltd
Aqueous base ink recording sheet

JPS62124976A
(en)

1985-11-26
1987-06-06
Canon Inc
Recording material

US4732786A
(en)

1985-12-17
1988-03-22
James River Corporation
Ink jet printable coatings

US4649064A
(en)

1986-03-10
1987-03-10
Eastman Kodak Company
Rapid-drying recording element for liquid ink marking

US4775594A
(en)

1986-06-20
1988-10-04
James River Graphics, Inc.
Ink jet transparency with improved wetting properties

US4781985A
(en)

1986-06-20
1988-11-01
James River Graphics, Inc.
Ink jet transparency with improved ability to maintain edge acuity

US4726989A
(en)

1986-12-11
1988-02-23
Minnesota Mining And Manufacturing
Microporous materials incorporating a nucleating agent and methods for making same

JP2683019B2
(en)

1987-04-10
1997-11-26
キヤノン株式会社

Recording material and method for producing printed matter using the same

US4867881A
(en)

1987-09-14
1989-09-19
Minnesota Minning And Manufacturing Company
Orientied microporous film

US4892779A
(en)

1988-03-18
1990-01-09
Ppg Industries, Inc.
Multilayer article of microporous and substantially nonporous materials

US5102731A
(en)

1988-04-27
1992-04-07
Mitsubishi Kasei Corporation
Recording medium

US4935307A
(en)

1988-10-21
1990-06-19
Minnesota Mining And Manufacturing Company
Transparent coatings for graphics applications

US4903039A
(en)

1989-08-14
1990-02-20
Eastman Kodak Company
Transparent image-recording elements

US4903040A
(en)

1989-08-14
1990-02-20
Eastman Kodak Company
Transparent image-recording elements comprising vinyl pyrrolidone polymers

US5079319A
(en)

1989-10-25
1992-01-07
Ciba-Geigy Corporation
Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof

US5141790A
(en)

1989-11-20
1992-08-25
Minnesota Mining And Manufacturing Company
Repositionable pressure-sensitive adhesive tape

US5120594A
(en)

1989-11-20
1992-06-09
Minnesota Mining And Manufacturing Company
Microporous polyolefin shaped articles with patterned surface areas of different porosity

US5229207A
(en)

1990-04-24
1993-07-20
Minnesota Mining And Manufacturing Company
Film composite having repositionable adhesive by which it can become permanently bonded to a plasticized substrate

AR244825A1
(en)

1990-05-18
1993-11-30
Ciba Geigy
Procedure for uniformly dyeing the ends of cellulose fibres.

US5208092A
(en)

1990-10-24
1993-05-04
Minnesota Mining And Manufacturing Company
Transparent liquid absorbent materials for use as ink-receptive layers

US5389723A
(en)

1990-10-24
1995-02-14
Minnesota Mining And Manufacturing Company
Transparent liquid absorbent materials for use as ink receptive layers

US5443727A
(en)

1990-10-30
1995-08-22
Minnesota Mining And Manufacturing Company
Articles having a polymeric shell and method for preparing same

US5084340A
(en)

1990-12-03
1992-01-28
Eastman Kodak Company
Transparent ink jet receiving elements

US5126195A
(en)

1990-12-03
1992-06-30
Eastman Kodak Company
Transparent image-recording elements

US5126194A
(en)

1990-12-03
1992-06-30
Eastman Kodak Company
Ink jet transparency

DE69211333T2
(en)

1991-02-06
1997-01-23
Minnesota Mining & Mfg

HIGH SHEAR STRENGTH, REMOVABLE ADHESIVE SYSTEM

US5156674A
(en)

1991-06-21
1992-10-20
Mooney Chemicals, Inc.
Drier promoter compositions

US5302436A
(en)

1991-07-17
1994-04-12
Minnesota Mining And Manufacturing Company
Ink receptive film formulations

JP3213630B2
(en)

1991-07-25
2001-10-02
三菱製紙株式会社

Inkjet recording sheet

US5206071A
(en)

1991-11-27
1993-04-27
Arkwright Incorporated
Archivable ink jet recording media

FR2684676A1
(en)

1991-12-09
1993-06-11
Hoechst France

NOVEL WATER-INSOLUBLE CATIONIC COPOLYMERS, NEW DISPERSIONS AND THEIR APPLICATION IN COATING PAPERS.

US5220346A
(en)

1992-02-03
1993-06-15
Xerox Corporation
Printing processes with microwave drying

US5380044A
(en)

1992-04-16
1995-01-10
K & A Industries, Inc.
Identification card and method of making same

WO1993025595A1
(en)

1992-06-17
1993-12-23
Isp Investments Inc.
Cationic polymer compositions

DE59204608D1
(en)

1992-06-20
1996-01-18
Celfa Ag

Record carrier for the inclusion of coloring substances.

US5296277A
(en)

1992-06-26
1994-03-22
Minnesota Mining And Manufacturing Company
Positionable and repositionable adhesive articles

US5428383A
(en)

1992-08-05
1995-06-27
Hewlett-Packard Corporation
Method and apparatus for preventing color bleed in a multi-ink printing system

EP0587164B1
(en)

1992-09-10
1998-12-23
Canon Kabushiki Kaisha
Method and apparatus for ink jet recording

EP0949084B1
(en)

1993-03-02
2003-08-20
Mitsubishi Paper Mills, Ltd.
Ink jet recording sheet

DE69415190T2
(en)

1993-03-10
1999-05-20
Asahi Glass Co Ltd

Recording sheet with a dye absorbing layer

US5342688A
(en)

1993-03-12
1994-08-30
Minnesota Mining And Manufacturing Company
Ink-receptive sheet

US6482503B1
(en)

1993-03-19
2002-11-19
Xerox Corporation
Recording sheets containing pyrrole, pyrrolidine, pyridine, piperidine, homopiperidine, quinoline, isoquinoline, quinuclidine, indole, and indazole compounds

US5439739A
(en)

1993-06-03
1995-08-08
Mitsubishi Paper Mills Limited
Ink jet recording medium

DE4322179C2
(en)

1993-07-03
1997-02-13
Schoeller Felix Jun Papier

Recording material for ink jet printing processes

CA2138734C
(en)

1993-12-28
2000-11-14
Mamoru Sakaki
Recording medium and image-forming method employing the same

US5589277A
(en)

1994-02-15
1996-12-31
Xerox Corporation
Recording sheets containing amino acids, hydroxy acids, and polycarboxyl compounds

US5500668A
(en)

1994-02-15
1996-03-19
Xerox Corporation
Recording sheets for printing processes using microwave drying

US5429860A
(en)

1994-02-28
1995-07-04
E. I. Du Pont De Nemours And Company
Reactive media-ink system for ink jet printing

AU2143795A
(en)

1994-04-19
1995-11-10
Ilford A.G.
Recording sheets for ink jet printing

JPH0881611A
(en)

1994-07-11
1996-03-26
Canon Inc
Liquid composition, ink set and image-forming method using the same and apparatus therefor

US5747148A
(en)

1994-09-12
1998-05-05
Minnesota Mining And Manufacturing Company
Ink jet printing sheet

JP3635376B2
(en)

1994-12-12
2005-04-06
コニカミノルタホールディングス株式会社

Ink and sheet for ink jet recording and ink jet recording method

ATE197425T1
(en)

1994-12-14
2000-11-11
Rexam Graphics Inc

AQUEOUS INK RECEPTION INKJET RECEIVING MEDIUM WHICH RESULTS IN A WATER RESISTANT INKJET PRINT

US5686602A
(en)

1995-10-26
1997-11-11
Minnesota Mining & Manufacturing Company
Crosslinked cellulose polymer/colloidal sol matrix and its use with ink jet recording sheets

JP2921785B2
(en)

1995-04-05
1999-07-19
キヤノン株式会社

Recording medium, method for manufacturing the medium, and image forming method

FR2734005B1
(en)

1995-05-12
1997-07-18
Roquette Freres

COMPOSITION AND METHOD FOR GLUING PAPER

US5518534A
(en)

1995-08-04
1996-05-21
E. I. Du Pont De Nemours And Company
Ink set and process for alleviating bleed in printed elements

WO1997015455A1
(en)

1995-10-26
1997-05-01
Minnesota Mining And Manufacturing Company
Ink-jet recording sheet

AU6975896A
(en)

1995-10-26
1997-05-15
Minnesota Mining And Manufacturing Company
Composition for an ink-jet recording sheet

AU1276597A
(en)

1995-11-28
1997-06-19
Kimberly-Clark Worldwide, Inc.
Improved colorant stabilizers

US5679143A
(en)

1995-12-06
1997-10-21
Hewlett-Packard Company
Bleed alleviation in ink jet inks using acids containing a basic functional group

EP0865365A1
(en)

1995-12-07
1998-09-23
Minnesota Mining And Manufacturing Company
Ink jet printable microporous film

US5605750A
(en)

1995-12-29
1997-02-25
Eastman Kodak Company
Microporous ink-jet recording elements

US5681660A
(en)

1996-02-21
1997-10-28
Minnesota Mining And Manufacturing Company
Protective clear layer for images

US5948512A
(en)

1996-02-22
1999-09-07
Seiko Epson Corporation
Ink jet recording ink and recording method

CN1143885C
(en)

1996-02-26
2004-03-31
美国3M公司
Pressure sensitive adhesives

US5874143A
(en)

1996-02-26
1999-02-23
Minnesota Mining And Manufacturing Company
Pressure sensitive adhesives for use on low energy surfaces

KR19990087703A
(en)

1996-03-12
1999-12-27
스프레이그 로버트 월터

Inkjet recording media

US5863662A
(en)

1996-05-14
1999-01-26
Isp Investments Inc.
Terpolymer for ink jet recording

US5683793A
(en)

1996-06-03
1997-11-04
Xerox Corporation
Ink jet transparencies

US5695820A
(en)

1996-06-20
1997-12-09
Hewlett-Packard Company
Method for alleviating marangoni flow-induced print defects in ink-jet printing

DE19628341C2
(en)

1996-07-13
1998-09-17
Sihl Gmbh

Aqueous ink jet recording material and use for making waterfast and lightfast recordings on this material

WO1998005504A1
(en)

1996-08-01
1998-02-12
Seiko Epson Corporation
Ink jet recording method using two liquids

WO1998005512A1
(en)

1996-08-02
1998-02-12
Minnesota Mining And Manufacturing Company
Ink-receptive sheet

US6197397B1
(en)

1996-12-31
2001-03-06
3M Innovative Properties Company
Adhesives having a microreplicated topography and methods of making and using same

CA2277232C
(en)

1997-01-10
2005-11-01
Oce (Schweiz) Ag
Ink jet transfer systems, process for producing the same and their use in a printing process

DE19720833C1
(en)

1997-05-17
1999-04-08
Schoeller Felix Jun Foto

Recording material for the inkjet printing process

US5789342A
(en)

1997-06-19
1998-08-04
Eastman Kodak Company
Thermal dye transfer assemblage

US6632510B1
(en)

1997-07-14
2003-10-14
3M Innovative Properties Company
Microporous inkjet receptors containing both a pigment management system and a fluid management system

US6071614A
(en)

1997-07-14
2000-06-06
3M Innovative Properties Company
Microporous fluorinated silica agglomerate and method of preparing and using same

MY125712A
(en)

1997-07-31
2006-08-30
Hercules Inc
Composition and method for improved ink jet printing performance

JP3592044B2
(en)

1997-08-01
2004-11-24
キヤノン株式会社

Thermal bonding medium for inkjet, thermal bonding method, thermal bonding body, and method for manufacturing thermal bonding medium for inkjet

DE19733674A1
(en)

1997-08-04
1999-02-11
Itt Mfg Enterprises Inc

Method for increasing the driving stability of a motor vehicle

US6117527A
(en)

1997-08-22
2000-09-12
Xerox Corporation
Recording sheets and ink jet printing processes therewith

1998

1998-06-19
US
US09/099,983
patent/US6703112B1/en
not_active
Expired – Fee Related

1999

1999-02-17
KR
KR1020007014396A
patent/KR20010052999A/en
not_active
Application Discontinuation

1999-02-17
DE
DE1999620232
patent/DE69920232T2/en
not_active
Expired – Fee Related

1999-02-17
AU
AU29711/99A
patent/AU751312B2/en
not_active
Ceased

1999-02-17
CN
CN99807555A
patent/CN1306477A/en
active
Pending

1999-02-17
BR
BR9911379A
patent/BR9911379A/en
not_active
Application Discontinuation

1999-02-17
JP
JP2000554562A
patent/JP2002518215A/en
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
active
IP Right Grant

Also Published As

Publication number
Publication date

AU751312B2
(en)

2002-08-15

EP1098775B1
(en)

2004-09-15

WO1999065703A1
(en)

1999-12-23

KR20010052999A
(en)

2001-06-25

DE69920232D1
(en)

2004-10-21

BR9911379A
(en)

2001-03-13

JP2002518215A
(en)

2002-06-25

CN1306477A
(en)

2001-08-01

EP1098775A1
(en)

2001-05-16

US6703112B1
(en)

2004-03-09

DE69920232T2
(en)

2005-09-22

Información de contacto