Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/52—Bases or auxiliary layers; Substances therefor
  • G03C8/56—Mordant layers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
  • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

• This invention relates to a metal ion-crosslinked cellulose polymer network and in particular, it relates to one impregnated with a colloidal sol containing metal oxide-hydroxide particles. This invention further relates to the use ofthe above material with inkjet recording sheets.
• Water-soluble metal ion-crosslinked cellulose polymer gels are known in the art.
• the gels are formed by crosslinking cellulose polymer with appropriate polyvalent metal cations such as Fe +3 , Cr +3 , Pb +2 , Ca +2 , AT 3 , Zr +4 , Tf 4 , and the like.
• U.S. Pat. No. 4,486,335 discloses a water-soluble carboxymethyl hydroxyethyl cellulose polymer which is crosslinked to a gelled state by reacting the polymer with a suitable aluminum ion in the form of an aluminum salt (such as aluminum acetate or aluminum sulfate) in aqueous solution.
• the gel exhibits no significant thinning at temperatures less than about 200°F.
• Metal ion-crosslinked cellulose gels have been disclosed for such diverse uses as the secondary production of petroleum (see U.S. Pat. No. 4,396,433); stabilizing clay soils to deactivate water and thereby assist in preventing water from fluidizing the clay soil (see U.S. Pat. No. 4,425,165); and the controlled release of and the substantial reduction ofthe leaching of agricultural chemicals from the site of application (see U.S. Pat. No. 5,077,314). None ofthe foregoing patents disclose the formation of metal ion-crosslinked cellulose polymers containing a colloidal sol.
• Polymers and polyvalent metal salts have found applications in recording surfaces for inkjet recording sheets.
• Inkjet recording processes have emerged as one ofthe most important technologies for high speed electronic printing. With their emergence there has arisen a need for specialty papers having particular recording properties.
• the basic imaging technique in inkjet recording involves the use of one or more inkjet assemblies connected to a source of ink.
• Each inkjet includes a small orifice which is electromagnetically energized by magnetorestrictive, piezoelectric, thermal, or similar means to emit uniform droplets of ink as a continuous stream or as individual droplets on demand. The droplets are directed onto the surface of a moving web and controlled to form printed characters.
• the quality ofthe record obtained in an inkjet recording process is highly dependent on jet operation and the properties ofthe ink and the recording paper.
• the ink must be capable of forming stable ink droplets under pressure and must readily emerge from the ink jet orifice.
• Aqueous inks containing a water soluble dye and a humectant to prevent the ink from drying out in the jet assembly have been found to be particularly desirable.
• the absorption of these inks by the recording sheet has been somewhat problematic particularly in the area of multicolor printing where two or more ink drops may overlap on the surface ofthe recording sheet.
• the recording sheet must absorb the ink rapidly and at the same time insolubilize the ink dye on the sheet surface.
• the former property reduces the tendency for set-off (i.e., transfer ofthe ink from the paper to sheet handling rollers and the like) whereas the latter property insures that images having high optical density are obtained.
• These two properties are in conflict with one another. Papers having high absorbency draw the ink deeply into the paper and as a result, the optical density ofthe image formed at the paper surface is reduced. They also suffer from feathering, poor edge acuity, and show-through. Papers with low absorbency, such as highly sized papers, provide good optical density by retaining the ink at the paper surface, but have a high tendency to set-off because the ink vehicle is not absorbed rapidly.
• the perfect inkjet recording sheet has been described as a blotter with a magic film.
• the blotter rapidly absorbs the ink vehicle while the magic film insures that the colorant is retained at the surface ofthe sheet where its light-absorbing and reflecting properties are greatest. If the colorant is carried deeply into the paper web, its absorbing strength is reduced, web fibers conduct the ink laterally, and poor image sha ⁇ ness and show-through occurs. See P.A. McManus et al., "Paper Requirements for Color Imaging with Ink Jets". TAPPI, Vol. 66, No. 7, July 1983, pp. 81-85.
• U.S. Pat. No. 4,371,582 describes a recording sheet containing a cationic polymer latex which is designed to be used in inkjet recording with water soluble dyes to improve water fastness.
• the preferred cationic polymers are water insoluble and copolymers of a monomer containing a tertiary amino group or a quaternary ammonium group and a copolymerizable ethylenically-unsaturated compound.
• the insoluble polymer is applied to one surface ofthe recording sheet as a latex and interacts with water-soluble dyes containing a sulfo group for which it has strong mordanting power.
• 4,381, 185 discloses a process for printing with water soluble polymeric dyes in which the paper contains cationic groups.
• the cationic groups can be introduced into the paper through the addition of an organic additive such as a cationic polyamine or an inorganic additive such as calcium chloride, barium acetate, or aluminum nitrate.
• U.S. Pat. No. 4,554, 181 discloses an inkjet recording sheet having a recording surface which includes a combination of a water-soluble polyvalent metal salt and a cationic polymer.
• the polymer has cationic groups which are available in the recording surface for insolubilizing an anionic dye.
• a metal ion-crosslinked cellulose polymer network is formed, the crosslinked polymer network containing a colloidal sol comprising metal oxide-hydroxide particles which are entrapped within the crosslinked polymer network
• cellulose polymers contain pendant hydroxyl groups.
• a chelated structure is formed by coordinate bonding ofthe oxygen atoms ofthe pendant hydroxyl groups ofthe cellulose polymer to the metal ion crosslinking agent. This helps create a microporous crosslinked polymeric structure which entraps the metal oxide-hydroxide particles ofthe colloidal sol and which is optically transparent.
• the inventive material makes an excellent transparency film for inkjet recording sheets.
• the present invention provides a cellulose polymer network crosslinked with metal ions selected from the group consisting of: AT 3 , Zr +4 , and Ti +4 , the crosslinked cellulose polymer network having inco ⁇ orated therein a colloidal sol comprising metal oxide-hydroxide particles wherein the metal is Al, Zr, or Ti.
• the inventive material is optically clear and can be used to cast microporous films, either supported or unsupported.
• the presently preferred cellulose polymer is hydroxypropyl methylcellulose (HPMC).
• HPMC hydroxypropyl methylcellulose
• Af 3 is presently preferred as the metal ion crosslinking agent
• the present invention provides a recording sheet useful in inkjet recording comprising a substrate having a recording surface comprising the above-disclosed metal ion-crosslinked cellulose/colloidal sol matrix; glycol; and nonionic surfactant.
• This single-layer coating is optically clear and enhances the capillary properties ofthe film when droplets from an inkjet orifice are applied to the recording sheet.
• the presently preferred glycol is polyethylene glycol.
• the present invention provides a dual-layer coating for inkjet receptors. Positioned between (1) the previously described layer containing metal ion-crosslinked cellulose polymer/colloidal sol matrix; glycol; and nonionic surfactant and (2) the substrate is a layer comprising polymeric mordant for dye or pigment and at least one water-absorbent resin.
• Preferred water- absorbent resins include poly( vinyl alcohol), cellulose, poly(ethylene glycol), and polyvinylpyrrolidone.
• colloidal sol means an aqueous solution or a suspension with a pH of from about 3 to 6 and having a particle size of from l-300nm
• metal oxide-hydroxide means either a metal oxide, a metal hydroxide, or a mixture thereof
• chelation means bonding to a metal with two or more coordinate bonds from a ligand
• Coordinat bonding means bonding to a metal center involving electron donation
• microporous means a material containing sufficient capillaries to have sorbent qualities; and "optically clear” or “optically transparent” mean having greater than 90% transmittance of visible light.
• the inventive metal ion-crosslinked cellulose/colloidal sol matrix is prepared by first hydrolyzing the appropriate metal (i.e., Al, Zr, or Ti) alkoxide with an acid, organic or inorganic, in the presence ofthe cellulose polymer.
• suitable metal i.e., Al, Zr, or Ti
• acid organic or inorganic
• Non-limiting examples of such acids include, but are not limited to, CH 3 COOH; CF 3 COOH; CF 3 SO 3 H; HCl; HNO 3 , etc.
• the particular acid used will control the rate of hydrolysis and consequently, the degree of crosslinking of the cellulose.
• the above-disclosed metal ion-crosslinked cellulose polymer impregnated with a colloidal sol containing metal oxide-hydroxide particles can be used as a single-layer coating on a receptor surface for inkjet recording
• the single-layered construction containing the metal ion-crosslinked cellulose polymer/colloidal sol matrix also contains glycol and nonionic surfactant
• the thickness of this layer is preferably about 1-5 microns and more preferably, about 1-2 microns
• Non-limiting examples of cellulose polymers include methylcellulose, hydroxypropyl ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose (e g , METHOCELTM available from Dow Chemical Co , Midland, MI), etc
• Non-limiting examples of glycols or resins include poly(ethylene glycol), poly(propylene glycol), poly(propylene glycol-Z>-ethylene glycol), polytetrahydrofuran, poly(tetrahydrofuran-cc9-ethylene oxide), and the like
• Non-limiting examples of nonionic surfactants include nonionic hydrocarbon surfactants, and nonionic fluorocarbon surfactants
• Common nonionic hydrocarbon surfactants include ethoxylated alkylphenols (e g , TRITONTM X-100, X-l 14, and X-405 and their reduced forms available from Rohm and Haas, Philadelphia, PA)
• a preferred nonionic hydrocarbon surfactant is TRITONTM X-l 00
• Nonionic fluorocarbon surfactants include linear perfluorinated polyethoxylated alcohols (e.g., ZONYL FSNTM, FSNTM-100, FSOTM, and FSOTM-100 surfactants available from DuPont Specialty Chemicals, Wilmington, DE), fluorinated alkyl polyoxyethylene ethanols (e.g , FLUORADTM FC-170C available from 3M, St Paul, MN), fluorinated alkyl alkoxylate (e.g., FLUO
• fluorinated alkyl esters e.g., FLUORADTM FC-430, FC-431, and FC-740 available from 3M, St. Paul, MN
• Preferred nonionic fluorocarbon surfactants include ZONYL FSOTM, FLUORADTM FC-170C, and FLUORADTM FC-171.
• the crosslinked cellulose polymer/colloidal sol matrix-containing layer is the top layer and underneath is a layer containing polymeric mordant for dyes or pigments and at least one water- absorbent resin (e.g, poly( vinyl alcohol), cellulose, poly(ethylene glycol), polyvinylpyrrolidone, etc.).
• the thickness of the underlayer containing polymeric mordant for dyes, etc. is preferably about 8-20 microns and more preferably, about 8-12 microns.
• Non-limiting examples of polymeric mordants for dyes and pigments include those disclosed in U.S. Patent Nos. 5,342,688 and 5,354,813, both of which are herein inco ⁇ orated by reference.
• these polymeric mordants contain quaternized nitrogen heterocycles as groups pendant to the polymer backbone.
• Non-limiting examples of water-absorbing resins include polyvinylpyrrolidone and its copolymers, poly(vinyl alchohol) and its copolymers, poly(2-dimethylaminoethyl methacrylate) and its copolymers, poly(acrylic acid) and its copolymers, poly(ethylene oxide), polyacrylamide, poly(ethylene imine), gelatin, etc.
• the substrate ofthe inkjet receptor can be any conventional substrate known to those skilled in the art. Preferred are optically clear or transparent materials.
• suitable substrates include poly( ethylene terephthalate) ("PET”), poly( vinylidene chloride) (PVDC) primed PET, corona or flame-treated PET, poly(aryI ether ketone), poIy(aryl ether sulphone), etc.
• the coatings of this invention may be applied to the substrate by conventional coating methods such as knife coating, roll coating, gravure coating, bar coating, etc.
• the following non-limiting examples further illustrate the present invention.
• EXAMPLES The materials employed below were obtained from Aldrich Chemical Co (Milwaukee, WI) unless otherwise specified
• the mordant used in the following examples is a polyvinylpyridine that has been alkylated with the chloroacetonehydrazone of aminoguanidinium hydrochloride as disclosed in U S Patent
• Example 1 This example demonstrates the preparation of an aluminum ion-crosslinked cellulose polymer network impregnated with a colloidal aluminum oxide-hydroxide sol.
• a solution of 36 g hydroxypropyl methylcellulose (HPMC), (METHOCEL- F-50, Dow Chemical, MW 22,000 daltons, 50 mPa viscosity for a 2% solution) was prepared in 800 g water according to Dow Chemical's procedure (METHOCEL Cellulose Ethers, Technical Handbook, Dow Chemical)
• To this solution was added 94 g aluminum triisopropoxide with high-speed mechanical stirring
• the mixture was stirred at about 60°C for 1-2 hrs to obtain a fine slurry.
• To this mixture was added 1 lg of 37% hydrochloric acid with stirring.
• the sol was prepared using vigorous stirring for 36 hours with intermittent addition of water to a total volume of 1.0-1.2 liter.
• the desired 6-7% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol with an average particle size of 161 nm.
• a 2 % by weight aqueous solution ofthe above sol had a viscosity of 52.9 MPa at 10°C, 27.7 MPa at 25°C, 13.6 MPa at 40°C, and 7 5 MPa at 55°C.
• a 6% solution was coated using a #4 wire wound rod onto 4 mil PVDC primed PET and dried at 1 10°C for 1 minute to give a 0.4 micon thick clear, transparent coating. Scanning electron microscopy showed that the film had a semi-microstructured surface This material is useful for applications requiring water and/or solvent abso ⁇ tive properties, such as for receptor properties for printing media, particularly those requiring transparent materials.
• Example 2 The procedure of Example 1 was repeated except that 1 1 g of 69% nitric acid was used instead of hydrochloric acid. The desired 7% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol with an average particle size of 181 nm
• a 2 % by weight aqueous soulution ofthe above sol had a viscosity of 20.2 MPa at 10°C, 11.2 MPa at 25°C, 6.3 MPa at 40°C, and 0 8 MPa at 55°C.
• a 6% solution was coated using a #4 wire wound rod onto 4 mil PVDC primed PET and dried at 1 10°C for 1 minute to give a 0 4 micon thick clear, transparent coating Scanning electron miscroscopy showed that the film had a microstructured surface. This material is useful for applications requiring water and/or solvent abso ⁇ tive properties, such as for receptor properties for printing media, particularly those requiring transparent materials.
• Example 3 The procedure of Example 1 was repeated except that 9 g of glacial acetic acid was used instead of hydrochloric acid The desired 6% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol A clear and transparent film was prepared by casting the above solution on PVDC-primed PET
• Example 4 The procedure of Example 1 was repeated except that the amount of hydroxypropyl methylcellulose used was reduced to 18 g The desired 6% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol A clear and transparent film was prepared by casting the above solution on PVDC-primed PET
• Example 5 The procedure of Example 1 was repeated except that the amount of hydroxypropyl methylcellulose used was reduced to 12 g After 60 hours of digestion, additional hydrochloric acid was added to complete the hydrolysis The desired 6% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol A clear and transparent film was prepared by casting the above solution on PVDC-primed PET
• Example 6 The procedure of Example 1 was repeated except that the amount of hydroxypropyl methylcellulose used was reduced to 9 g After 60 hours of digestion, additional hydrochloric acid was added to complete the hydrolysis The desired 6% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol A clear and transparent film was prepared by casting the above solution on PVDC-primed PET
• Example 7 The procedure of Example 1 was repeated except that trifluoro ⁇ methanesulfonic acid was used instead of hydrochloric acid The desired 6% sol concentration was obtained by slow evaporation of water with stirring, resulting in a clear and transparent sol A clear and transparent film was prepared by casting the above solution on PVDC-primed PET
• Example 8 (Comparative Example) The procedure of Example 1 was repeated except that no hydroxypropyl methylcellulose was used After 7 days of digestion, a white, turbid-appearing sol was obtained with an average particle size of 100 nm
• Example 9 The following coating solution was made by mixing aqueous solutions ofthe following components COMPONENT Parts by Weight Copolymer-958 (50 % by weight) 52 0
• Airvol-523 (10 % by weight) 31 2 Gohsenol KP-O6 (10 % by weight) 3 5 Carbowax-600 (50 % by weight) 7 8 Mordant (20 % by weight) 3 8 Methocel F-50 (4 0 % by weight) 1 4
• aqueous solution was coated at 0 8-1 0 g/ft 2 on 4 mil PVDC-primed PET using an automated knife coater and dried at 260°F to give a bottom layer for a transparency film
• the following coating solution was made by mixing aqueous solutions ofthe following components
• the PEG blend was prepared by mixing polyethylene glycols) of varying MW (I e , 600, 1,000. 4,500, and 22,000) in equal parts by weight
• a small portion ofthe above aqueous solution was diluted to 2 % by weight and found to have a viscosity of 25 2 MPa at 10°C, 15 5 MPa at 25°C, 8 1 MPa at 40°C, and 4 3 MPa at 55°C
• the above solution was coated on the bottom layer prepared above using an automated knife coater adjusted to give a 5 mil wet thickness, and running at 7 5 ft /min web speed
• the coating was dried at 250°F to give a two layer transparency film
• Example 10 This example demonstrates the color densities obtained when the transparency film of Example 9 was imaged at 360 dpi with an Epson Color Stylus Writer The example also compares the densities obtained with other commercially available films Color densities were measured in a MacBeth densitometer Color shift means a visually observable hue shift as compared to ink printed on plain or coated inkjet receptive paper Coalescence means droplets of ink merged together, leaving a grainy image Dry time is the time required for ink to dry so that it does not transfer under moderate finger pressure Films Drv time Color densitv Comment

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  • 1995-10-26 US US08/548,580 patent/US5686602A/en not_active Expired - Fee Related
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