EP0675401B1 - Bildelement - Google Patents

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Publication number
EP0675401B1
EP0675401B1 EP95200756A EP95200756A EP0675401B1 EP 0675401 B1 EP0675401 B1 EP 0675401B1 EP 95200756 A EP95200756 A EP 95200756A EP 95200756 A EP95200756 A EP 95200756A EP 0675401 B1 EP0675401 B1 EP 0675401B1
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EP
European Patent Office
Prior art keywords
film
imaging element
forming
layer
particles
Prior art date
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Expired - Lifetime
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EP95200756A
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English (en)
French (fr)
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EP0675401A1 (de
Inventor
Yongcai C/O Eastman Kodak Company Wang
Charles Chester C/O Eastman Kodak Co. Anderson
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/221,719 external-priority patent/US5366855A/en
Priority claimed from US08/221,432 external-priority patent/US5447832A/en
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Publication of EP0675401A1 publication Critical patent/EP0675401A1/de
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Publication of EP0675401B1 publication Critical patent/EP0675401B1/de
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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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/853—Inorganic compounds, e.g. metals
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142—Inert intermediate layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas
    • 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
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/32—Matting agents
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/38—Dispersants; Agents facilitating spreading
    • G03C1/385—Dispersants; Agents facilitating spreading containing fluorine
    • 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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters
    • 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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

  • This invention relates to imaging elements and more particularly to photographic imaging elements.
  • Support materials for imaging elements often employ layers comprising glassy, hydrophobic polymers such as polyacrylates, polymethacrylates, polystyrenes, or cellulose esters, for example.
  • One typical application is as a backing layer to provide resistance to scratches, abrasion, blocking, and ferrotyping.
  • the latter two properties relate to the propensity of layers applied onto the support material or imaging element to stick together as a result of the adverse humidity, temperature, and pressure conditions that may occur during the manufacture and use of the imaging element.
  • Tg glass transition temperatures
  • these polymers are used in priming or "subbing" layers which are applied onto the film support to act as adhesion promoting layers for photographic emulsion layers.
  • Such low Tg polymers although useful when they underly an emulsion layer, are not suitable as, for example, backing layers since their blocking and ferrotyping resistance are poor.
  • US Patent No. 4,822,727 describes a silver halide photographic light-sensitive material having on a support at least one light-sensitive silver halide emulsion layer and at least one light-insensitive upper layer on the emulsion layer, in which at least one light-insensitive upper layer contains a polymer latex having a glass transition point of at least 20°C and said light-insensitive layer and/or at least one other light-insensitive layer contains a polymer latex having a glass transition point of lower than 20°C.
  • the invention provides an imaging element comprising a support, at least one light-sensitive layer e.g. a silver halide emulsion layer, and at least one coalesced layer coated from a continuous aqueous phase having dispersed therein a mixture of film-forming colloidal polymeric particles having an average particle size of from 10 to 500 nm and non-film-forming colloidal polymeric particles having an average particle size of from 10 to 500nm.
  • a support at least one light-sensitive layer e.g. a silver halide emulsion layer, and at least one coalesced layer coated from a continuous aqueous phase having dispersed therein a mixture of film-forming colloidal polymeric particles having an average particle size of from 10 to 500 nm and non-film-forming colloidal polymeric particles having an average particle size of from 10 to 500nm.
  • the coalesced layers are especially suitable for imaging elements due to their high transparency and toughness.
  • coalesced layers can be employed as subbing layers, overcoat layers, backing layers, receiving layers, barrier layers, timing layers, antihalation layers, antistatic layers, stripping layers, mordanting layers, scavenger layers, antikinking layers, transparent magnetic layers.
  • coalesced layers in accordance with this invention are particularly advantageous due to superior physical properties including transparency, toughness necessary for providing resistance to scratches, abrasion, blocking and ferrotyping, in addition to environmental considerations such as, the preparation of layers substantially free of solvents and general procedural advantages including ease of preparation together with short drying times.
  • the invention further provides an imaging element comprising a support having disposed thereon an antistat layer and an overlying protective layer of a coalesced layer of film-forming colloidal polymeric particles and non-film-forming colloidal polymeric particles.
  • the protective layer is coated from an aqueous composition comprising a mixture of film-forming, water dispersible polymeric particles and non-film-forming, water dispersible polymeric particles.
  • the mixture of polymers with different film-forming characteristics yields an overcoat composition that readily forms a high quality, continuous transparent film that prevents the loss of antistatic properties during film processing and provides scratch and abrasion resistance.
  • the antistatic layer described in U.S. Patent 4,203,769 is prepared by coating an aqueous colloidal solution of vanadium pentoxide.
  • the vanadium pentoxide is doped with silver.
  • a polymer binder such as vinylidene chloride-containing terpolymer latex or a polyesterionomer dispersion, is preferably employed in the antistatic layer to improve the integrity of the layer and to improve adhesion to the undercoat layer.
  • the weight ratio of polymer binder to vanadium pentoxide can range from about 1:5 to 200:1, but, preferably 1:1 to 10:1.
  • the antistatic coating formulation may also contain a wetting aid to improve coatability.
  • the antistat layer is coated at a dry coverage of from about 1 to 200 mg/m 2 .
  • Antistatic layers described in U.S. Patent No. 4,070,189 comprise a crosslinked vinylbenzene quaternary ammonium polymer in combination with a hydrophobic binder wherein the weight ratio of binder to antistatic crosslinked polymer is about 10:1 to 1:1.
  • the antistatic compositions described in U.S. Patents 4,237,194; 4,308,332; and 4,526,706 comprise a coalesced, cationically stabilized latex and a polyaniline acid addition salt semiconductor wherein the latex and semiconductor are chosen so that the semiconductor is associated with the latex before coalescing.
  • Particularly preferred latex binders include cationically stabilized, coalesced, substantially linear, polyurethanes.
  • the weight ratio of polymer latex particles to polyaniline in the antistatic coating composition can vary over a wide range. A useful range of this weight ratio is about 1:1 to 20:1. Typically, the dried coating weight of this antistatic layer is about 40 mg/m 2 or less.
  • colloidal polymeric particles are film-forming or non-film-forming is determined by the following test:
  • aqueous coating formulation of 3% by weight of colloidal polymeric particles free of organic solvent or coalescing aid, is applied to a sheet of polyethylene terephthalate in a wet coverage of 10 ml/m 2 and dried for 2 minutes at 75°C.
  • Polymers that form clear, transparent continuous films under these conditions are film-forming, while those that do not form clear, transparent continuous films are non-film-forming, for the purpose of this invention.
  • the coalesced layers in accordance with this invention are formed from colloidal polymeric particles that are a discontinuous phase of solid, water-insoluble particles suspended in a continuous aqueous medium.
  • the solid, water insoluble particles of both the film-forming and non-film-forming polymers have an average particle size of from 10 to 500 nm, preferably from 10 to 200 nm.
  • the film forming polymer is present in the coalesced layer in an amount of from 20 to 70 percent by weight and preferably from 30 to 50 percent by weight based on the total weight of the layer.
  • the imaging elements in accordance with this invention comprise a support material having thereon at least one coalesced layer coated from an aqueous composition comprising a mixture of a film-forming, water dispersible polymer and a non-film-forming, water dispersible polymer.
  • the support material may comprise various polymeric films including cellulose esters, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose propionate; polycarbonate, polystyrene, polyolefins, such as, polyethylene, polypropylene; polyesters, such as polyethylene terephthalate, polyethylene naphthalate; and paper or glass. Polyester film support is preferred. The thickness of the support is not critical.
  • polyester support thickness of 50 ⁇ m to 254 ⁇ m (2 to 10 mil) can be employed, for example, with very satisfactory results.
  • the polyester support typically employs an undercoat or primer layer well known in the art that comprise, for example, a vinylidene chloride/methyl acrylate/itaconic acid terpolymer or vinylidene chloride/acrylonitrile/acrylic acid terpolymer as described in U.S. Patent Nos. 2,627,088; 2,698,235; 2,698,240; 2,943,937; 3,143,421; 3,201,249; 3,271,178; and 3,501,301.
  • Coating compositions for preparing coalesced layers in accordance with the invention comprise a continuous aqueous phase having dispersed therein a mixture of film-forming polymeric particles (component A) and non-film-forming polymeric particles (component B).
  • component A comprises 20 to 70% of the total weight of components A and B of the coating composition.
  • additional compounds may be added to the coating composition, depending on the function of the particular layer, including surfactants, emulsifiers, coating aids, matte particles, rheology modifiers, crosslinking agents, inorganic fillers such as metal oxide particles, pigments, magnetic particles e.g. cobalt doped gamma iron oxide and biocides.
  • the coating composition may also include small amounts of organic solvents, preferably the concentration of organic solvent is less than 1 weight % of the total coating composition.
  • the non-film-forming polymer (B) comprises glassy polymers that provide resistance to blocking, ferrotyping, abrasion and scratches.
  • Non-film-forming polymer B is present in the coating composition and in the photographic layer in an amount of from 30 to 80 and preferably from 50 to 70 percent based on the total weight of film-forming polymer (A) and non-film-forming polymer (B).
  • polymers include addition-type polymers and interpolymers prepared from ethylenically unsaturated monomers such as acrylates including acrylic acid, methacrylates including methacrylic acid, acrylamides and methacrylamides, itaconic acid and its half esters and diesters, styrenes including substituted styrenes, acrylonitrile and methacrylonitrile, vinyl acetates, vinyl ethers, vinyl and vinylidene halides, and olefins.
  • ethylenically unsaturated monomers such as acrylates including acrylic acid, methacrylates including methacrylic acid, acrylamides and methacrylamides, itaconic acid and its half esters and diesters, styrenes including substituted styrenes, acrylonitrile and methacrylonitrile, vinyl acetates, vinyl ethers, vinyl and vinylidene halides, and olefins.
  • crosslinking and graft-linking monomers such as 1,4-butyleneglycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, diallyl phthalate, divinyl benzene may be used.
  • Other polymers that may comprise component B include water-dispersible condensation polymers such as polyesters, polyurethanes, polyamides, and epoxies. Polymers suitable for component B do not give transparent, continuous films upon drying when the above-described test is applied.
  • the film-forming polymer (A) comprises polymers that form a continuous film under the extremely fast drying conditions typical of the photographic film manufacturing process.
  • Polymers that are suitable for component A are those that give transparent, continuous films when the above-described test is applied and include addition-type polymers and interpolymers prepared from ethylenically unsaturated monomers such as acrylates including acrylic acid, methacrylates including methacrylic acid, acrylamides and methacrylamides, itaconic acid and its half esters and diesters, styrenes including substituted styrenes, acrylonitrile and methacrylonitrile, vinyl acetates, vinyl ethers, vinyl and vinylidene halides, and olefins.
  • crosslinking and graft-linking monomers such as 1,4-butyleneglycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, diallyl phthalate, divinyl benzene may be used.
  • suitable polymers useful as component A are film-forming dispersions of polyurethanes or polyesterionomers.
  • the colloidal polymeric particles can be prepared either by emulsion polymerization or by emulsifying pre-formed polymers in water with a proper dispersing agent. In both cases, chain transfer agents including mercaptans, polymercaptans, and halogen compounds can be used in the polymerization mixture to moderate the polymer molecular weight.
  • the weight average molecular weight of prepared polymers may vary from 5,000 to 30,000,000 and preferably from 50,000 to 10,000,000.
  • Preparation of polyurethane dispersions is well-known in the art and involves chain extending an aqueous dispersion of a prepolymer containing terminal isocyanate groups by reaction with a diamine or diol.
  • the prepolymer is prepared by reacting a polyester, polyether, polycarbonate, or polyacrylate having terminal hydroxyl groups with excess polyfunctional isocyanate.
  • This product is then treated with a compound that has functional groups that are reactive with an isocyanate, for example, hydroxyl groups, and a group that is capable of forming an anion, typically this is a carboxylic acid group.
  • the anionic groups are then neutralized with a tertiary amine to form the aqueous prepolymer dispersion.
  • polyesterionomer refers to polyesters that contain at least one ionic moiety. Such ionic moieties function to make the polymer water dispersible. These polyesters are prepared by reacting one or more dicarboxylic acids or their functional equivalents such as anhydrides, diesters, or diacid halides with one or more diols in melt phase polycondensation techniques as described in U.S. Patents 3,018,272; 3,929,489; 4,307,174; 4,419,437. Examples of this class of polymers include, for example, Eastman AQ polyesterionomers, manufactured by Eastman Chemical Co.
  • the ionic moiety is provided by some of the dicarboxylic acid repeat units, the remainder of the dicarboxylic acid repeat units are nonionic in nature.
  • Such ionic moieties can be anionic or cationic, but, anionic moieties are preferred for the present invention.
  • the ionic dicarboxylic acid contains a sulfonic acid group or its metal salt. Examples include the sodium, lithium, or potassium salt of sulfoterephthalic acid, sulfonaphthalene dicarboxylic acid, sulfophthalic acid, and sulfoisophthalic acid or their functional equivalent anhydride, diester, or diacid halide.
  • the ionic dicarboxylic acid repeat unit is provided by 5-sodiosulfoisophthalic acid or dimethyl 5-sodiosulfoisophthalate.
  • nonionic dicarboxylic acid repeat units are provided by dicarboxylic acids or their functional equivalents represented by the formula: where R is an aromatic or aliphatic hydrocarbon or contains both aromatic and aliphatic hydrocarbons.
  • R is an aromatic or aliphatic hydrocarbon or contains both aromatic and aliphatic hydrocarbons.
  • Exemplary compounds include isophthalic acid, terephthalic acid, succinic acid and adipic acid.
  • Suitable diols are represented by the formula: HO-R-OH, where R is aromatic or aliphatic or contains both aromatic and aliphatic hydrocarbons.
  • R is aromatic or aliphatic or contains both aromatic and aliphatic hydrocarbons.
  • the diol includes one or more of the following: ethylene glycol, diethylene glycol, or 1,4-cyclohexanedimethanol.
  • the polyesterionomer dispersions comprise from about 1 to about 25 mol %, based on the total moles of dicarboxylic acid repeat units, of the ionic dicarboxylic acid repeat units.
  • the polyesterionomers have a glass transition temperature (Tg) of about 60°C. or less to allow the formation of a continuous film.
  • the film-forming polymeric particles, the non-film-forming polymeric particles or both type particles may include reactive functional groups capable of forming covalent bonds by intermolecular crosslinking or by reaction with a crosslinking agent (i.e., a hardener).
  • Suitable reactive functional groups include: hydroxyl, carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, amide, allyl.
  • the coating compositions in accordance with the invention may also contain suitable crosslinking agents that may effectively be used in the coating compositions of the invention including aldehydes, epoxy compounds, polyfunctional aziridines,. vinyl sulfones, methoxyalkyl melamines, triazines, polyisocyanates, dioxane drivatives such as dihydroxydioxane, carbodiimides, chrome alum, and zirconium sulfate.
  • the crosslinking agents may react with functional groups present on either the film-forming polymers, the non-film-forming polymers or on both.
  • Matte particles well known in the art may be used in the coating composition of the invention, such matting agents have been described in Research Disclosure No. 308, published Dec 1989, pages 1008 to 1009.
  • the polymers may contain reactive functional groups capable of forming covalent bonds by intermolecular crosslinking or by reaction with a crosslinking agent (i.e., a hardener) in order to promote improved adherence to the film-forming and non-film-forming polymers of the invention.
  • Suitable reactive functional groups include: hydroxyl, carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, amide, allyl.
  • the coating compositions of the present invention may also include lubricants or combinations of lubricants to reduce sliding friction of the photographic elements in accordance with the invention.
  • lubricants or combinations of lubricants to reduce sliding friction of the photographic elements in accordance with the invention.
  • Virtually any type of water soluble or dispersible lubricants can be used.
  • water soluble or dispersible paraffin or wax-like materials including vegetable waxes, insect waxes, mineral waxes, petroleum waxes, synthetic waxes, carnauba wax, as well as wax-like components that occur individually in these waxes
  • perfluoro- or fluoro- or fluorochloro-containing materials which include poly(tetrafluoroethylene), poly(trifluorochloroethylene), poly(vinylidene fluoride), poly(trifluorochloroethylene-co-vinyl chloride), poly(meth)acrylates containing fluoro or perfluoroalkyl side groups, (3) poly(meth)acrylates or
  • the above lubricants also may contain reactive functional groups such as hydroxyl, carboxyl, carbodiimide, epoxide, aziridine, vinyl sulfone, sulfinic acid, active methylene, amino, and amide.
  • the lubricants can be incorporated in the coating composition in an amount from 0.1 to 150 mg/m 2 , preferably from 0.1 to 90 mg/m 2 .
  • compositions of the present invention may be applied as aqueous coating formulations containing up to about 50% total solids by coating methods well known in the art. For example, hopper coating, gravure coating, skim pan/air knife coating, spray coating, and other methods may be used with very satisfactory results.
  • the coatings are dried at temperatures up to 150°C. to give dry coating weights of 20 mg/m 2 to 10 g/m 2 .
  • the invention is applicable to thermal imaging elements wherein the coalesced layer may be employed as supports, dye-donor elements, dye-image receiving layers, barrier layers, overcoats, binders as described in U.S. Patents 5,288,689; 5,283,225; 4,772,582; 5,166,128.
  • Aqueous coating solutions comprising 3 weight % total solids were coated with a doctor blade onto polyethylene terephthalate film support that had been subbed with a terpolymer latex of acrylonitrile vinylidene chloride, and acrylic acid.
  • the coating was dried at 90°C. for one minute and the coating appearance recorded, the results are listed in Table 2. Transparent, high-quality films that are comparable in appearance to organic solvent applied coatings were obtained for the coating compositions of the invention.
  • the following examples show that the coating compositions of the invention provide void-free, impermeable films that are comparable with organic solvent applied layers.
  • a subbed polyester film support as previously described was coated with an aqueous antistatic formulation comprising 0.025 weight % of silver-doped vanadium pentoxide, 0.075 weight % of a terpolymer latex of methylacrylate, vinylidene chloride, and itaconic acid (15/83/2) and dried at 100°C. to yield an antistatic layer having a dry weight of about 8 mg/m 2 .
  • Aqueous coating compositions of the invention containing 1 to 3 weight % solids were applied over the antistatic layer and dried for 90 seconds at 100°C.
  • PCF Paper Clip Friction
  • Single Arm Scratch Example 40 P-2/P-11 70/30 ratio, with aziridine.
  • This example illustrates the incorporation of a conductive metal oxide particle in the coatings used in the invention.
  • a coating comprising a 15/35/50 weight ratio of polymer P-2/polymer P-11/conductive tin oxide particles was applied onto a subbed polyester support to give a transparent coating with a total dried weight of 1000 mg/m 2 .
  • the conductive tin oxide was Keeling & Walker CPM375 antimony-doped tin oxide that had been milled to an average particle size of about 50nm.
  • the surface resistivity of the coating measured at 20% RH before and after film processing using a two-point probe was 9.9 and 10.3 log ⁇ /square, respectively.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Paints Or Removers (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Claims (16)

  1. Abbildungselement mit einem Träger, mindestens einer lichtempfindlichen Schicht und mindestens einer zusammengeflossenen Schicht, die aus einer stetigen wässrigen Phase erzeugbar ist, in der eine Mischung aus filmbildenden, nicht wasserlöslichen kolloidalen Polymerpartikeln mit einer mittleren Partikelgröße von 10 bis 500 nm und nicht filmbildenden, nicht wasserlöslichen, kolloidalen Polymerpartikeln mit einer mittleren Partikelgröße von 10 bis 500 nm dispergiert ist, wobei die filmbildenden, kolloidalen Polymerpartikel klare, transparente, durchgehende Filme bilden, und wobei die nicht filmbildenden, kolloidalen Polymerpartikel keine klaren, transparenten, durchgehenden Filme bilden, wenn eine wässrige Beschichtungsformulierung von 3 Gew.-% kolloidaler Polymerpartikel und ohne ein organisches Lösemittel oder eine Koaleszenzhilfe auf einen Bogen aus Polyethylenterephthalat in einem Nassauftrag von 10 ml/m2 aufgetragen und für 2 Minuten bei 75°C getrocknet wird.
  2. Abbildungselement mit einem Träger, einer lichtempfindlichen Schicht und einer Antistatikschicht, wobei auf die Antistatikschicht eine Schutzschicht einer zusammengeflossenen Schicht aufgetragen ist, wie in Anspruch 1 dargelegt.
  3. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel in der zusammengeflossenen Schicht in einer Menge von 20 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Schicht, vorliegen.
  4. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die lichtempfindliche Schicht eine Silberhalogenid-Emulsionsschicht ist.
  5. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die lichtempfindliche Schicht eine thermische Abbildungsschicht ist.
  6. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polymer der filmbildenden, kolloidalen Partikel ein Additionspolymer ist.
  7. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polymer der filmbildenden, kolloidalen Partikel ein Kondensationspolymer ist.
  8. Abbildungselement nach Anspruch 1, dadurch gekennzeichnet, dass die zusammengeflossene Schicht Metalloxidpartikel enthält.
  9. Abbildungselement nach Anspruch 8, dadurch gekennzeichnet, dass die Metalloxidpartikel leitfähige Metalloxide sind.
  10. Abbildungselement nach Anspruch 9, dadurch gekennzeichnet, dass das leitfähige Metalloxid Zinnoxid ist.
  11. Abbildungselement nach Anspruch 10, dadurch gekennzeichnet, dass das Zinnoxid antimondotiert ist.
  12. Abbildungselement nach Anspruch 1, dadurch gekennzeichnet, dass die zusammengeflossene Schicht Magnetpartikel enthält.
  13. Abbildungselement nach Anspruch 12, dadurch gekennzeichnet, dass die Magnetpartikel kobaltdotiertes Gammaeisenoxid sind.
  14. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel oder die nicht filmbildenden, kolloidalen Polymerpartikel vernetzt sind.
  15. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel Additionspolymere und Interpolymere enthalten, die aus ethylenisch ungesättigten Monomeren hergestellt sind.
  16. Abbildungselement nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die filmbildenden, kolloidalen Polymerpartikel filmbildende Dispersionen von Polyurethan oder Polyesterionomeren enthalten.
EP95200756A 1994-03-31 1995-03-25 Bildelement Expired - Lifetime EP0675401B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/221,719 US5366855A (en) 1994-03-31 1994-03-31 Photographic support comprising an antistatic layer and a protective overcoat
US08/221,432 US5447832A (en) 1994-03-31 1994-03-31 Imaging element
US221719 1994-03-31
US221432 1994-03-31

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EP0675401A1 EP0675401A1 (de) 1995-10-04
EP0675401B1 true EP0675401B1 (de) 2003-05-14

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US5695920A (en) * 1996-04-22 1997-12-09 Eastman Kodak Company Aqueous coating compositions useful in the preparation of auxiliary layers of imaging elements
US6168911B1 (en) 1998-12-18 2001-01-02 Eastman Kodak Company Formulations for preparing metal oxide-based pigment-binder transparent electrically conductive layers

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JPS5834443A (ja) * 1981-08-26 1983-02-28 Fuji Photo Film Co Ltd 製版用ハロゲン化銀写真感光材料及びその減力処理方法
JPS59121327A (ja) * 1982-08-17 1984-07-13 Fuji Photo Film Co Ltd 製版用ハロゲン化銀写真感光材料及びその減力処理方法
JPS59149357A (ja) * 1983-02-15 1984-08-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS61140939A (ja) * 1984-12-12 1986-06-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS61251844A (ja) * 1985-04-30 1986-11-08 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
DE4308274C2 (de) * 1993-03-16 1996-07-18 Schoeller Felix Jun Papier Schichtträger für fotografische Aufzeichnungsmaterialien

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DE69530719D1 (de) 2003-06-18
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EP0675401A1 (de) 1995-10-04

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