EP0962817A1 - Formule rutile polymère pour des supports d'imagerie - Google Patents

Formule rutile polymère pour des supports d'imagerie Download PDF

Info

Publication number
EP0962817A1
EP0962817A1 EP99201617A EP99201617A EP0962817A1 EP 0962817 A1 EP0962817 A1 EP 0962817A1 EP 99201617 A EP99201617 A EP 99201617A EP 99201617 A EP99201617 A EP 99201617A EP 0962817 A1 EP0962817 A1 EP 0962817A1
Authority
EP
European Patent Office
Prior art keywords
imaging
resin
support
tio
rutile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99201617A
Other languages
German (de)
English (en)
Inventor
Valerie Jean Eastman Kodak Company Harris
William Andrew Eastman Kodak Company Mruk
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak 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.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0962817A1 publication Critical patent/EP0962817A1/fr
Withdrawn legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • 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
    • B41M5/506—Intermediate 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
    • B41M5/502—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • the present invention relates to imaging papers and, more particularly to imaging papers having high sharpness, whiteness and excellent manufacturability.
  • a second method to improve sharpness is to use two or more layers of water-proof resin laminated on the imaging side of the paper having differing contents ofTiO 2 (US 5,429,916).
  • the water-proof resin layer with the lowest level of TiO 2 is placed in the resin layer nearest to the paper base (US 5,573,898).
  • US 5,573,898 teaches the use of either a rutile or anatase TiO 2 for the photographic support.
  • US 5,573,898 teaches to use an anatase TiO 2 to achieve a white support and a rutile TiO 2 to achieve a sharp support.
  • the anatase TiO 2 required to make a white support is costly and has poor filterability and runnability problems during extrusion coating.
  • the third method to improve sharpness is to change from the anatase to rutile TiO 2 .
  • the refractive index of anatase TiO 2 is 2.52, while rutile TiO 2 is 2.76.
  • Rutile TiO 2 's higher refractive index allows for a lower loading of TiO 2 to get the same sharpness as a highly loaded anatase support.
  • rutile TiO 2 could not provide as white and as bright a support as one with anatase TiO 2 .
  • Imaging supports require a very white support.
  • TiO 2 increases the reflectivity or lightness of the support. Blue colorants are added to the resin coated support to increase the apparent whiteness. As you add blue colorant the support gets darker.
  • rutile TiO 2 is intrinsically lighter than the anatase structure, the large particle rutile (>0.26 micrometers) is yellower. Therefore, substantially more blue colorant is needed for the rutile than the anatase to get an equivalently blue support. The end result is that a support loaded with rutile TiO 2 looks darker than a support having anatase TiO 2 .
  • a fourth method to improve sharpness but maintain a white support is to combine the rutile and anatase TiO 2 (US 5,569,577).
  • Our studies show that imaging supports with more than 5 weight percent rutile TiO 2 in combination with anatase TiO 2 eliminates the whiteness advantage of the anatase TiO 2 . Additionally, the manufacturability is poor and material costs high for the anatase/rutile blend.
  • Inkjet and thermal imaging sharpness is not determined by the TiO 2 type or level but by the quality of the original image and the printer.
  • the problem for these type of imaging supports is obtaining a very white and opaque support.
  • the hiding power and opacity of rutile TiO 2 is superior to anatase TiO 2 but the rutile TiO 2 is too yellow.
  • anatase TiO 2 An additional problem with anatase TiO 2 is its thermal instability. Anatase TiO 2 yellows during extrusion processing unless large amounts of a metal soap, such as calcium stearate, is added to the resin layer. The calcium stearate prevents the anatase TiO 2 from yellowing during extrusion. However, the stearate produces by-products that build up on the external extruder parts and drips down onto the finished imaging sheet causing costly defects.
  • a metal soap such as calcium stearate
  • Rutile TiO 2 can be made by the sulfate or chloride process while the anatase TiO 2 can only be made by the sulfate process.
  • the chloride process is environmentally more friendly than the sulfate process. The sulfate process produces a large amount of acid waste and contaminated by products.
  • the present invention provides an imaging support using rutile TiO 2 that has high sharpness, whiteness and excellent manufacturability.
  • the present invention is an imaging resin which includes a polyolefin having dispersed therein rutile TiO 2 having a particle size from 0.1 to 0.26 microns at a concentration of at least 10 weight percent, and a dispersing agent.
  • the resin is applied to a support to create an imaging base.
  • a imaging layer can be superposed on the the imaging base to provide an imaging element.
  • the imaging element is a photographic element.
  • imaging element is a material that may be used with the laminated support for the transfer of images to the support by techniques such as ink jet printing or thermal dye transfer as well as a support for silver halide images.
  • photographic element is a material that utilizes photosensitive silver halide in the formation of images.
  • the image layer that is coated on the imaging element may be any material that is known in the art such as gelatin, pigmented latex, polyurethane, polyesters, (poly(vinyl chloride), poly(styrene-co-acrylonitrile) polycaprolactone, polyvinyl alcohol, polycarbonate, polyvinyl pyrrolidone, starch, methacrylate, polymers and co-polymers of acrylic acid, polyethylene oxide, cellulosics such as hydroxymethyl cellulose and porous receivers containing silica, sol-gels, alumina, calcium carbonate, clays, talc, zinc oxide, zeolites, barium sulfate, zinc sulfide, TiO 2 or mixtures thereof.
  • the dye image-receiving layer may be present in any amount which is effective for the intended purpose.
  • the photographic elements can be single color elements or multicolor elements.
  • Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
  • the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
  • the reflective support of the present invention includes one or more resin coating layers on the support.
  • One or more imaging layers may be superposed on the waterproof resin coating layers.
  • the rutile TiO 2 is included in one or all of these resin coated layers. It is preferred to incorporate the resin layer with the lowest TiO 2 level next to the paper base.
  • the average pigment diameter of the rutile TiO 2 is most preferably in the range of 0.1 to 0.26 micrometers. Pigments that are greater than 0.26 micrometers are too yellow for an imaging element application and the pigments that are less than 0.1 micrometers are not sufficiently opaque when dispersed in polymers.
  • the rutile TiO 2 content of the resin coated layer is preferably greater than 10% and less than 50% by weight of the resin layer. If the rutile TiO 2 content is less than 10% the imaging element is inferior for sharpness and opacity. If the rutile TiO 2 content greater than 50% it will cause problems with melt fracture during extrusion.
  • the rutile pigment may be present in one or all of the layers.
  • the concentration of the small particle rutile in each layer preferably ranges from 0-50% by weight of the individual layer. In the layer with the highest concentration of TiO 2 , the rutile concentration may be from 10 to 50 weight percent of the layer.
  • the surface of the rutile TiO 2 can be treated with inorganic compounds such as aluminum hydroxide, alumina or silica with a fluoride compound or fluorine ions, silicon hydroxide, silicon dioxide, boron oxide, barium modified silica as described in US Pat. 4,781,761, phosphates, zinc oxide, ZrO 2 , etc. and with organic treatments such as polyhydric alcohol, polyhydric amine, metal soap, alkyl titanate, polysiloxanes, etc or with a combination of the inorganic and organic treating agents.
  • the amount of the surface treating agents is preferably in the range of 0.2 to 2.0% for the inorganic treatment and 0.1 to 1% for the organic treatment, relative to the weight of the titanium dioxide.
  • a sharp and white support is achieved when small particle rutile TiO 2 is incorporated in the resin layers of an imaging support.
  • the small particle rutile TiO 2 resin layers provides an imaging support that is as white and as bright as the current anatase system.
  • the small particle TiO 2 imparts high sharpness and opacity to the imaging supports.
  • Small amounts of the small particle rutile TiO 2 can be added to an imaging support resin layer to get the same sharpness and opacity as a highly loaded anatase resin layer.
  • the lower loading of the rutile pigment reduces cost and the propensity for die lines.
  • rutile TiO 2 does not thermally yellow during extrusion.
  • the use of the small particle rutile TiO 2 eliminates the need to use large amounts of stearate slip agents. Reduction in stearate levels reduces the build-up of stearic acid on external extruder parts and consequently reduces imperfections and the need for cleaning of the extruder.
  • the polymer and the rutile TiO 2 are mixed with each other in the presence of a dispersing agent.
  • dispersing agents are metal salts of higher fatty acids such as sodium palmitate, calcium palmitate, sodium laurate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, etc, higher fatty amides, and higher fatty acids.
  • the preferred dispersing agent is sodium stearate and the most preferred dispersing agent is zinc stearate. Both of these dispersing agents give superior whiteness to the resin coated layer.
  • the layers of the water-proof resin coating preferably contain colorants such as a bluing agent and magenta or red pigment.
  • Applicable bluing agents include commonly know pigments, such as ultramarine blue, cobalt blue, oxide cobalt phosphate, quinacridone pigments, and a mixture thereof.
  • Applicable red or magenta colorants are quinacridones and ultramarines.
  • the water-proof resin may also include a fluorescing agent which absorbs energy in the UV region and emits light largely in the blue region. Any one or a combination of the optical brighteners referred to in US patent 3,260,715 can be incorporated into the resin coating.
  • the water-proof resin coating may also contain an antioxidant(s) such as hindered phenol primary antioxidants used alone or in combination with a secondary antioxidants.
  • antioxidants such as hindered phenol primary antioxidants used alone or in combination with a secondary antioxidants.
  • hindered phenol primary antioxidants include pentaerythrityl tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate] (such as Irganox 1010), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate (such as Irganox 1076), benzenepropanoic acid 3,5-bis(1,1-dimethyl)-4-hydroxy-2[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)hydrazide (such as Irganox MD1024), 2,2'-thiodiethylene
  • Secondary antioxidants include organic alkyl and aryl phosphites including examples such as triphenylphosphite (such as Irgastab TPP), tri(n-propylphenyl-phophite) (such as Irgastab SN-55), 2,4-bis(1,1-dimethylphenyl) phosphite (such as Irgafos 168).
  • triphenylphosphite such as Irgastab TPP
  • tri(n-propylphenyl-phophite) such as Irgastab SN-55
  • 2,4-bis(1,1-dimethylphenyl) phosphite such as Irgafos 168.
  • Suitable polyolefins for the water-proof layer(s) include polyethylene, polypropylene, polymethylpentene, polystyrene, polybutylene and mixtures thereof.
  • Polyolefin copolymers including copolymers of polyethylene, propylene and ethylene such as hexene, butene, and octene are also useful.
  • Polyethylene is preferred, as it is low in cost and has desirable coating properties.
  • As polyethylene usable are high-density polyethylene, low-density polyethylene, linear low density polyethylene, and polyethylene blends.
  • suitable dicarboxylic acids include terephthalic, isophthalic, phthalic, naphthalene dicarboxylic acid, succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1,4-cyclohexanedicarboxylic, sodiosulfoisophthalic and mixtures thereof.
  • glycols examples include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, other polyethylene glycols and mixtures thereof.
  • Preferred continuous matrix polyesters are those having repeat units from terephthalic acid or naphthalene dicarboxylic acid and at least one glycol selected from ethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol.
  • Poly(ethylene terephthalate) which may be modified by small amounts of other monomers, is especially preferred.
  • suitable polyesters include liquid crystal copolyesters formed by the inclusion of suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • examples of such liquid crystal copolyesters are those disclosed in U.S. Pat. Nos. 4,420,607, 4,459,402 and 4,468,510.
  • Useful polyamides include nylon 6, nylon 66, and mixtures thereof Copolymers of polyamides are also suitable continuous phase polymers.
  • An example of a useful polycarbonate is bisphenol-A polycarbonate.
  • Cellulosic esters suitable for use as the continuous phase polymer of the composite sheets include cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, and mixtures or copolymers thereof.
  • Useful polyvinyl resins include polyvinyl chloride, poly(vinyl acetal), and mixtures thereof. Copolymers of vinyl resins can also be utilized.
  • the small particle rutile TiO 2 , colorants, slip agents, optical brightener, antioxidant are incorporated either together or separately with the polymer using a mixer.
  • a concentrate of the additives in the form of a pellet is typically made.
  • the concentration of the rutile pigment can be from 20% to 80% by weight of the masterbatch. The master batch is then adequately diluted for use with the waterproof resin.
  • the support to which the water-proof resin layer is laminated may be a polymeric, a synthetic paper, cloth, woven polymer fibers, or a cellulose fiber paper support, or laminates thereof.
  • the base also may be a microvoided polyethylene terephthalate such as disclosed in U.S. Patent Nos. 4,912,333; 4,994,312 and 5,055,371.
  • the preferred support is a photographic grade cellulose fiber paper.
  • Chemical sensitization of the emulsion typically employs sensitizers such as: sulfur-containing compounds, e.g., allyl isothiocyanate, sodium thiosulfate and allyl thiourea; reducing agents, e.g., polyamines and stannous salts; noble metal compounds, e.g., gold, platinum; and polymeric agents, e.g., polyalkylene oxides.
  • sensitizers such as: sulfur-containing compounds, e.g., allyl isothiocyanate, sodium thiosulfate and allyl thiourea; reducing agents, e.g., polyamines and stannous salts; noble metal compounds, e.g., gold, platinum; and polymeric agents, e.g., polyalkylene oxides.
  • heat treatment is employed to complete chemical sensitization.
  • Spectral sensitization is effected with a combination of dyes, which are designed for the wavelength range of interest within
  • the emulsion is coated on a support.
  • Various coating techniques include dip coating, air knife coating, curtain coating and extrusion coating.
  • the silver halide emulsions utilized in this invention may be comprised of any halide distribution. Thus, they may be comprised of silver chloride, silver chloroiodide, silver bromide, silver bromochloride, silver chlorobromide, silver iodochloride, silver iodobromide, silver bromoiodochloride, silver chloroiodobromide, silver iodobromochloride, and silver iodochlorobromide emulsions. It is preferred, however, that the emulsions be predominantly silver chloride emulsions. By predominantly silver chloride, it is meant that the grains of the emulsion are greater than 50 mole percent silver chloride. Preferably, they are greater than 90 mole percent silver chloride; and optimally greater than 95 mole percent silver chloride.
  • the silver halide emulsions can contain grains of any size and morphology.
  • the grains may take the form of cubes, octahedrons, cubooctahedrons, or any of the other naturally occurring morphologies of cubic lattice type silver halide grains.
  • the grains may be irregular such as spherical grains or tabular grains. Grains having a tabular or cubic morphology are preferred.
  • the photographic elements of the invention may utilize emulsions as described in The Theory of the Photographic Process , Fourth Edition, T.H. James, Macmillan Publishing Company, Inc., 1977, pages 151-152.
  • Reduction sensitization has been known to improve the photographic sensitivity of silver halide emulsions. While reduction sensitized silver halide emulsions generally exhibit good photographic speed, they often suffer from undesirable fog and poor storage stability.
  • Reduction sensitization can be performed intentionally by adding reduction sensitizers, chemicals which reduce silver ions to form metallic silver atoms, or by providing a reducing environment such as high pH (excess hydroxide ion) and/or low pAg (excess silver ion).
  • a silver halide emulsion unintentional reduction sensitization can occur when, for example, silver nitrate or alkali solutions are added rapidly or with poor mixing to form emulsion grains.
  • ripeners such as thioethers, selenoethers, thioureas, or ammonia tends to facilitate reduction sensitization.
  • reduction sensitizers and environments which may be used during precipitation or spectral/chemical sensitization to reduction sensitize an emulsion include ascorbic acid derivatives; tin compounds; polyamine compounds; and thiourea dioxide-based compounds described in U.S. Patents 2,487,850; 2,512,925; and British Patent 789,823.
  • Specific examples of reduction sensitizers or conditions, such as dimethylamineborane, stannous chloride, hydrazine, high pH (pH 8-11) and low pAg (pAg 1-7) ripening are discussed by S.Collier in Photographic Science and Engineering, 23,113 (1979).
  • EP 0 348934 A1 (Yamashita), EP 0 369491 (Yamashita), EP 0 371388 (Ohashi), EP 0 396424 A1 (Takada), EP 0 404142 A1 (Yamada), and EP 0 435355 A1 (Makino).
  • the photographic elements of this invention may use emulsions doped with Group VIII metals such as iridium, rhodium, osmium, and iron as described in Research Disclosure , September 1996, Item 38957, Section I, published by Kenneth Mason Publications, Ltd., Dudley Annex, 12 a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND. Additionally, a general summary of the use of iridium in the sensitization of silver halide emulsions is contained in Carroll, "Iridium Sensitization: A Literature Review," Photographic Science and Engineering, Vol. 24, No. 6, 1980.
  • a method of manufacturing a silver halide emulsion by chemically sensitizing the emulsion in the presence of an iridium salt and a photographic spectral sensitizing dye is described in U.S. Patent 4,693,965.
  • emulsions show an increased fresh fog and a lower contrast sensitometric curve when processed in the color reversal E-6 process as described in The British Journal of Photography Annual, 1982, pages 201-203.
  • a typical multicolor photographic element of the invention comprises the invention laminated support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler; a magenta image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler; and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
  • the element may contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
  • the support of the invention may also be utilized for black and white photographic print elements.
  • the photographic elements may also contain a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support, as in U.S. Patents 4,279,945 and 4,302,523.
  • a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support, as in U.S. Patents 4,279,945 and 4,302,523.
  • the element will have a total thickness (excluding the support) of from 5 to 30 ⁇ m.
  • the photographic elements can be exposed with various forms of energy which encompass the ultraviolet, visible, and infrared regions of the electromagnetic spectrum as well as with electron beam, beta radiation, gamma radiation, x-ray, alpha particle, neutron radiation, and other forms of corpuscular and wave-like radiant energy in either noncoherent (random phase) forms or coherent (in phase) forms, as produced by lasers.
  • the photographic elements can include features found in conventional radiographic elements.
  • the photographic elements are preferably exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image, and then processed to form a visible image, preferably by other than heat treatment. Processing is preferably carried out in the known RA-4TM (Eastman Kodak Company) Process or other processing systems suitable for developing high chloride emulsions.
  • the pellet containing the pigment and other additives is subjected to hot-melt coating onto a running support of paper or synthetic paper. If desired, the pellet is diluted with a polymer prior to hot melt coating.
  • the resin layer may be formed by lamination.
  • the layers may be formed through either successive lamination or other laminations using a multi-layer extrusion die such as a die employing a feed block, a die of a multi-slot type or a multi-manifold.
  • the die is not limited to any specific type and may be any one of the common dies such as a T-slot or coat hanger die.
  • An exit orifice temperature in heat melt extrusion of the water-proof resin ranges from 500-660°F.
  • the support may be treated with a activating treatment such as corona discharge, flame, ozone, plasma, or glow discharge.
  • the total thickness of the single layer or multi-layerwater-proof resin, which are applied to a base paper of the reflective support used in the present invention at a side for imaging, is preferably in the range of 5 to 100 micrometers and most preferably in the range of 10 to 50 micrometers.
  • the thickness of each layer is preferably in a range from 0.5 to 50 micrometers.
  • a thickness of each layer ranges from 0.5 to 50 micrometers and the total thickness is in the range of 5 to 100 micrometers and most preferably in the range of 10 to 50 micrometers.
  • the thickness of the resin layer applied to a base paper on the side opposite the imaging element is preferably in a range from 5 to 100 micrometers and more preferably from 10 to 50 micrometers.
  • the surface of the water-proofresin coating at the imaging side may be a glossy, fine, silk, grain, or matte surface.
  • On the surface of the waterproof coating on the side which is not coated with an imaging layer may also be glossy, fine, silk, or matte surface.
  • the preferred waterproof surface for the side away from the imaging element is matte.
  • a photographic paper support was produced by refining a pulp furnish of 100% bleached hardwood Kraft through a double disk refiner, then a Jordan conical refiner. To the resulting pulp furnish was added 0.8% sodium stearate, 0.5% aluminum chloride, 0.15% stilbene triazine FWA, 0.2% polyamideepichlorohydrin, 0.7% anionic polyacrylamide, and 0.6% TiO2 on a dry weight basis. An about 31.5 lbs. per 1000 sq. ft. (ksf) bone dry weight base paper was made on a fourdrinier paper machine, wet pressed to a solid of 42%, and dried to a moisture of 3% using steam-heated dryers achieving an apparent density of 0.70 g/cc.
  • the paper base was then surface sized using a vertical size press with a 16% hydroxyethylated cornstarch solution to achieve a loading of 4.2 wt. % starch.
  • the surface sized support was dried to a moisture of 8.8% using steam-heated dryers and calendered to an apparent density of 1.08 gm/cc.
  • a blend of high and low density polyethylene was melt extruded at 600°F and a coverage of 6.0 lbs/1000ft 2 onto one side of the paper described above.
  • 5.5 lb./1000ft 2 of a low density polyethylene resin containing 12% of a 0.22 ⁇ m rutile TiO 2 , available from Dupont, 0.3% zinc stearate, 0.05% optical brightener, 0.1% antioxidant, 0.6% blue colorant, and 0.002% red colorant were extrusion coated at 600 °F and 30 micrometers thickness.
  • the resulting resin coated support was sensitized as described below.
  • Blue sensitive emulsion (Blue EM-1) was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener. Cesium pentachloronitrosylosmate was added from during the making process and potassium iodide was added towards the end of the making process to form a band of silver iodide in the grain.
  • the resultant emulsion contained cubic shaped grains of 0.6 mm in edgelength size.
  • This emulsion was optimally sensitized by the addition of glutaryldiaminophenyldisulfide followed by the addition of a colloidal suspension of aurous sulfide and heat ramped to 60°C during which time blue sensitizing dye, BSD-4, potassium hexachloroiridate, Lippmann bromide and 1-(3-acetamidophenyl)-5-mercaptotetrazole were added.
  • Green sensitive emulsion (Green EM-1) was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener. Cesium pentachloronitrosylosmate was added during most of the making process. The resultant emulsion contained cubic shaped grains of 0.3 mm in edgelength size. This emulsion was optimally sensitized by the addition of a colloidal suspension of aurous sulfide and heated to 55°C. The following were then added, potassium hexachloroiridate, Lippmannbromide and green sensitizing dye, GSD-1. The finished emulsion was then allowed to cool and 1-(3-acetamidophenyl)-5-mercaptotetrazole was added a few seconds after the cool down began.
  • Green sensitive emulsion (Green EM-2) was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener. Cesium pentachloronitrosylosmate was added during most of the making process and potassium iodide was added at towards the end of the making process to form a band of silver iodide in the grain. Further, pentachlorothiazoleiridate (III) potassium salt was added towards the end of the making process. The resultant emulsion contained cubic shaped grains of 0.22 mm in edgelength size.
  • This emulsion was optimally sensitized by the addition of glutaryldiaminophenyldisulfide, followed by the addition of a colloidal suspension of aurous sulfide and heat ramped to 60°C during which time green sensitizing dye, GSD-1, potassium hexachloroiridate, Lippmann bromide and 1-(3-acetamidophenyl)-5-mercaptotetrazole were added.
  • Red sensitive emulsion (Red EM-1) was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a well-stirred reactor containing gelatin peptizer and thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.4 mm in edgelength size.
  • This emulsion was optimally sensitized by the addition of Bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate)gold(I)fluoroborate and sodium thiosulfate followed by heat digestion at 65°C. The following were then added, 1-(3-acetamidophenyl)-5-mercaptotetrazole, potassium hexachloroiridate and potassium bromide.
  • the emulsion was cooled to 40°C and the red sensitizing dye, RSD-1, was added.
  • Coupler dispersions were emulsified by methods well known to the art, and the following layers were coated on a polyethylene resin coated paper support, that was sized as described in U.S. Patent 4,994,147 and pH adjusted as described in U.S. Patent 4,917,994.
  • the polyethylene layer coated on the emulsion side of the support contained a mixture of 0.1 % (4,4'-bis(5-methyl-2-benzoxazolyl) stilbene and 4,4'-bis(2-benzoxazolyl) stilbene, 12.5 % TiO2, and 3 % ZnO white pigment.
  • the layers were hardened with bis(vinylsulfonyl methyl) ether at 1.95 % of the total gelatin weight.
  • a blend of high and low density polyethylene was melt extruded at 600°F and a coverage of 6.0 lbs/1000ft 2 onto one side of the paper described above.
  • 5.5 lb/1000ft 2 of a polyethylene resin containing 12 weight % of a 0.22 ⁇ rutile TiO 2 , 0.3 weight % sodium stearate, 0.05 weight % optical brightener, 0.1 weight % antioxidant, 0.6 weight % blue colorant, and 0.002 weight % red colorant are extrusion coated at 600F onto photographic paper.
  • the resulting resin coated support was sensitized as described in Example 1.
  • a blend of high and low density polyethylene was melt extruded at 600°F and a coverage of 6.0 lbs/1000ft 2 onto one side of the paper described above.
  • 5.5 lb./1000ft 2 of a polyethylene resin containing 12 weight % of a 0.22 ⁇ rutile TiO 2 , 0.3 weight % Kemamide w40 fatty bisamide , 0.05 weight % optical brightener, 0.1 weight % antioxidant, 0.6 weight % blue colorant, and 0.002 weight % red colorant are extrusion coated at 600 °F onto photographic paper.
  • the resulting resin coated support was sensitized as described in Example 1.
  • a blend of high and low density polyethylene was melt extruded at 600 °F and a coverage of 6.0 lbs/1000ft 2 onto one side of the paper described above.
  • 5.5 lb./1000ft 2 of a polyethylene resin containing 14.5 weight % of a 0.18 ⁇ m anatase TiO 2 , 0.5 weight % calcium stearate, 0.05 weight % optical brightener, 0.1 weight % antioxidant, 0.6 weight % blue colorant, and 0.002 weight % red colorant are extrusion coated at 600 °F onto photographic paper.
  • the resulting resin coated support was sensitized as described in Example 1.
  • the polyethylene resin containing 12% of a 0.22 ⁇ m rutile TiO 2 , 0.5 weight % zinc stearate, 0.05 weight % optical brightener, 0.1 weight % antioxidant, 0.6 weight % blue colorant, and 0.002 weight % red colorant from example 1 was tested for die line propensity by extruding the resin on a 1.5" Egan extruder.
  • the resin was dried for 17 hours in a desiccant (-7.5°F dew point) hot air (180°F) drier.
  • the resins were extruded are 587°F at a rate of about 50-60 lb/hour with a die gap of 30 mils.
  • the resins were extruded in the drool mode (no coating just running into a cool water bath) at 130 RPM's. Six pounds of resin blend per 1000 square feet was coated onto standard photographic grade paper every 30 minutes. The metric used to determine the time to die-lines was the time it took for the first die-line to show up on the resin coated sheet.
  • the polyethylene resin containing 12 weight % of the 0.22 ⁇ m rutile TiO 2 , 0.3 weight % Kemamide w40 fatty bisamide , 0.05 weight % optical brightener, 0.1 weight % antioxidant, 0.6 weight % blue colorant, and 0.002 weight % red colorant from example 3 was tested for die line propensity by extruding the resin on a 1.5" Egan extruder.
  • the resin was dried for 17 hours in a desiccant (-7.5 °F dew point) hot air (180 °F) drier.
  • the resins were extruded are 587 °F at a rate of about 50-60 lb./hour with a die gap of 30 mils.
  • the resins were extruded in the drool mode at 130 RPM's (no coating just running into a cool water bath). Six pounds of resin blend per 1000 square feet was coated onto standard photographic grade paper every 30 minutes. The metric used to determine the time to die-lines was the time it took for the first die-line to show up on the resin coated sheet.
  • the resin formulation from comparative example 1 was tested for die line propensity by extruding the resin on a 1.5" Egan extruder.
  • the resin was dried for 17 hours in a desiccant (-7.5 °F dew point) hot air (180 °F) drier.
  • the resins were extruded are 587 °F at a rate of about 50-60 lb./hour with a die gap of 30 mils.
  • the resins were extruded in the drool mode at 130 RPM's (no coating just running into a cool water bath).
  • Six pounds of resin blend per 1000 square feet was coated onto standard photographic grade paper every 30 minutes. The metric used to determine the time to die-lines was the time it took for the first die-line to show up on the resin coated sheet.
  • Example 1 Samples of example 1-3 and comparative example 1 were chemically photo processed (with no exposure) to yield a sample of minimum dye density. The samples minimum dye samples were tested for color using a spectrogard colorimeter (Table 1). Colorimetry Resin UVO L* UVO a* UVO b* UVI L* UVI a* UVI b* Example 1 91.61 -0.21 -2.17 91.76 0.12 -3.54 Example 2 91.73 -0.10 -2.10 91.86 0.25 -3.60 Example 3 91.70 -0.65 -2.05 91.87 -0.35 -3.48 Comparative Example 1 91.65 -0.57 -1.33 91.84 0.05 -3.51 L* is the lightness, a* the redness, and b* the blueness of the support.
  • L* is a function of b*. To make a support more blue, one can add more blue colorant, but the lightness will be reduced.
  • UVO measurements are equivalent to tungsten lighting, UVI is equivalent to fluorescent lighting.
  • UVO measurements at equivalent L* values the rutile support is ⁇ 0.7 b* units bluer while UVI, the support are essentially equivalent in b*.
  • a value of 0.4 b* is noticeably bluer to the average person. Therefore, in typical room light the rutile support will appear whiter than the anatase support and in florescent lighting the rutile and anatase support will appear to be equally white.
  • Both examples of the invention ran over 2X longer than the anatase comparison sample.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
EP99201617A 1998-06-04 1999-05-21 Formule rutile polymère pour des supports d'imagerie Withdrawn EP0962817A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9059998A 1998-06-04 1998-06-04
US90599 1998-06-04

Publications (1)

Publication Number Publication Date
EP0962817A1 true EP0962817A1 (fr) 1999-12-08

Family

ID=22223491

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99201617A Withdrawn EP0962817A1 (fr) 1998-06-04 1999-05-21 Formule rutile polymère pour des supports d'imagerie

Country Status (3)

Country Link
EP (1) EP0962817A1 (fr)
JP (1) JP2000010241A (fr)
CN (1) CN1238472A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582552A1 (fr) * 2004-04-02 2005-10-05 Felix Schoeller jr Foto- und Spezialpapiere GmbH & Co. KG Masterbatch
WO2013154583A1 (fr) 2012-04-13 2013-10-17 Hewlett-Packard Development Company, L.P. Support d'enregistrement

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3890985B2 (ja) * 2001-02-16 2007-03-07 東洋インキ製造株式会社 着色樹脂組成物の製造方法およびその利用
JP5178201B2 (ja) * 2005-11-07 2013-04-10 日本製紙株式会社 無臭性紙製液体容器用マスターバッチ、該無臭性紙製液体容器用マスターバッチを用いて形成されたポリオレフィン層を有する無臭性紙製液体容器用積層材料及び該積層材料を用いて成形された無臭性紙製液体用容器
JP7100933B1 (ja) 2022-03-03 2022-07-14 株式会社Tbm 積層シート及び食品包装容器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3942733A1 (de) * 1988-12-23 1990-06-28 Mitsubishi Paper Mills Ltd Verfahren zum herstellen eines fotografischen traegers
DE4120402A1 (de) * 1990-06-20 1992-01-09 Mitsubishi Paper Mills Ltd Verfahren zur herstellung eines titandioxidpigmentes fuer die fotografie, sowie fotografische unterlage, enthaltend dasselbe
US5714310A (en) * 1989-03-28 1998-02-03 Mitsubishi Paper Mills Limited Photographic support comprising a resin layer containing TiO2 pigments being coated with an alkaline earth metal-containing compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3942733A1 (de) * 1988-12-23 1990-06-28 Mitsubishi Paper Mills Ltd Verfahren zum herstellen eines fotografischen traegers
US5714310A (en) * 1989-03-28 1998-02-03 Mitsubishi Paper Mills Limited Photographic support comprising a resin layer containing TiO2 pigments being coated with an alkaline earth metal-containing compound
DE4120402A1 (de) * 1990-06-20 1992-01-09 Mitsubishi Paper Mills Ltd Verfahren zur herstellung eines titandioxidpigmentes fuer die fotografie, sowie fotografische unterlage, enthaltend dasselbe

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582552A1 (fr) * 2004-04-02 2005-10-05 Felix Schoeller jr Foto- und Spezialpapiere GmbH & Co. KG Masterbatch
WO2013154583A1 (fr) 2012-04-13 2013-10-17 Hewlett-Packard Development Company, L.P. Support d'enregistrement
EP2836368A4 (fr) * 2012-04-13 2015-02-18 Hewlett Packard Development Co Support d'enregistrement
US9821588B2 (en) 2012-04-13 2017-11-21 Hewlett-Packard Development Company, L.P. Recording media

Also Published As

Publication number Publication date
JP2000010241A (ja) 2000-01-14
CN1238472A (zh) 1999-12-15

Similar Documents

Publication Publication Date Title
US5888714A (en) Adhesives such as metallocene catalyzed ethylene plastomers for bonding biaxially oriented polyolefin sheets to paper
US5968695A (en) Roughness elimination by control of strength of polymer sheet in relation to base paper
US5866282A (en) Composite photographic material with laminated biaxially oriented polyolefin sheets
US5888643A (en) Controlling bending stiffness in photographic paper
US5888681A (en) Photographic element with microvoided sheet of opalescent appearance
US5853965A (en) Photographic element with bonding layer on oriented sheet
US5935690A (en) Sheets having a microvoided layer of strength sufficient to prevent bend cracking in an imaging member
US5902720A (en) Photographic element that resists curl using oriented sheets
EP0964301B1 (fr) Papier de base pour un papier photographique
US5998119A (en) Imaging element with a substrate containing low molecular weight hindered amine stabilizer
EP0926548A1 (fr) Matériau photographique composé avec des feuilles stratifiées de polyoléfine biaxialement orientée à performance optique améliorée
US6001547A (en) Imaging element with thin biaxially oriented color layer
US6171751B1 (en) Imaging element with hindered amine stabilizer in the base
US5994045A (en) Composite photographic material with laminated biaxially oriented polyolefin sheets with controlled water vapor transmission rate
EP0962817A1 (fr) Formule rutile polymère pour des supports d'imagerie
US6344310B1 (en) Thin durable photographic element
US6017686A (en) Translucent display paper with biaxially oriented polyolefin sheets
US6291150B1 (en) Reflective photographic material with foil layer
US6114102A (en) Imaging substrate with oxygen barrier layer
US6040124A (en) Imaging element with biaxially oriented sheet with fluoropolymer
US5968722A (en) Biaxially oriented sheet photographic film for better photofinishing
US6521399B1 (en) Imaging member with biaxially oriented sheets containing optical brighteners
US6348304B1 (en) Impact resistant photographic element
US6824936B1 (en) Hindered amine light stabilizer for improved yellow dark stability
US6268117B1 (en) Photographic clear display material with coextruded polyester

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000513

AKX Designation fees paid

Free format text: DE FR GB

17Q First examination report despatched

Effective date: 20010601

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20011212