EP0672544B1 - Elément d'enregistrement thermosensible avec couche intermédiaire adhésive - Google Patents

Elément d'enregistrement thermosensible avec couche intermédiaire adhésive Download PDF

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Publication number
EP0672544B1
EP0672544B1 EP95200593A EP95200593A EP0672544B1 EP 0672544 B1 EP0672544 B1 EP 0672544B1 EP 95200593 A EP95200593 A EP 95200593A EP 95200593 A EP95200593 A EP 95200593A EP 0672544 B1 EP0672544 B1 EP 0672544B1
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EP
European Patent Office
Prior art keywords
layer
imaging
thermally processable
poly
adhesive interlayer
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EP95200593A
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German (de)
English (en)
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EP0672544A1 (fr
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Charles Leo C/O Eastman Kodak Company Bauer
Wayne Arthur C/O Eastman Kodak Company Bowman
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/213,784 external-priority patent/US5393649A/en
Priority claimed from US08/213,778 external-priority patent/US5418120A/en
Priority claimed from US08/213,496 external-priority patent/US5422234A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0672544A1 publication Critical patent/EP0672544A1/fr
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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
    • B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • 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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • 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
    • G03C2200/00—Details
    • G03C2200/35—Intermediate layer

Definitions

  • This invention relates in general to imaging elements and in particular to thermally processable imaging elements. More specifically, this invention relates to imaging elements comprising a thermographic or photothermographic layer, an overcoat layer and an adhesive interlayer interposed between the overcoat layer and the thermographic or photothermographic layer.
  • Thermally processable imaging elements including films and papers, for producing images by thermal processing are well known. These elements include photothermographic elements in which an image is formed by imagewise exposure of the element to light followed by development by uniformly heating the element. These elements also include thermographic elements in which an image is formed by imagewise heating the element. Such elements are described in, for example, Research Disclosure , June 1978, Item No. 17029 and U.S. Patents 3,080,254, 3,457,075 and 3,933,508.
  • a protective overcoat layer for such imaging elements should: (a) provide resistance to deformation of the layers of the element during thermal processing, (b) prevent or reduce loss of volatile components in the element during thermal processing, (c) reduce or prevent transfer of essential imaging components from one or more of the layers of the element into the overcoat layer during manufacture of the element or during storage of the element prior to imaging and thermal processing, (d) enable satisfactory adhesion of the overcoat to a contiguous layer of the element, and (e) be free from cracking and undesired marking, such as abrasion marking, during manufacture, storage, and processing of the element.
  • EP-A-0 568 023 describes a heat-developable photosensitive material comprising a support, a photothermographic imaging layer, a hydrophobic polymeric overcoat layer and an interlayer between the imaging and overcoat layers which may comprise polyvinylpyrrolidone or polyethylene oxide.
  • a particularly preferred overcoat for thermally processable imaging elements is an overcoat comprising poly(silicic acid) as described in U.S. Patent 4,741,992, issued May 3, 1988.
  • water-soluble hydroxyl-containing monomers or polymers are incorporated in the overcoat layer together with the poly(silicic acid).
  • the combination of poly(silicic acid) and a water-soluble hydroxyl-containing monomer or polymer that is compatible with the poly(silicic acid) is also useful in a backing layer on the side of the support opposite to the imaging layer as described in U.S. Patent 4,828,971, issued May 9, 1989.
  • the support is typically a polyester, most usually poly(ethylene terephthalate), and migration of the alcohol into such a support causes a highly undesirable width-wise curl which makes the imaging element very difficult to handle. A serious consequence of such width-wise curl, even though it may be very slight in extent, is jamming of processing equipment.
  • Unwanted curl can be reduced by use of a barrier layer which is comprised of poly(silicic acid) and a water-soluble hydroxyl-containing monomer or polymer that is compatible therewith and which is interposed between the support and the image-forming layer, as described in U.S. Patent 5,264,334, issued November 23, 1993.
  • this method also requires the use of an additional coating step.
  • Unwanted curl can also be reduced by incorporating a pre-hydrolyzed polyalkoxysilane in the imaging composition as described in U.S. Patent No. 5,294,526, issued March 15, 1994.
  • a pre-hydrolyzed polyalkoxysilane By utilizing a pre-hydrolyzed polyalkoxysilane, the by-products of hydrolysis, such as the ethyl alcohol that is formed by hydrolysis of tetraethoxysilane, are not present in the image-forming layer and thus the problems caused by their migrating into the support are avoided.
  • this method requires very exacting control of all process parameters.
  • An adhesive interlayer comprising a polymer having pyrrolidone functionality or a polymer having epoxy functionality or a polyalkoxysilane has been found to serve as an effective adhesion-promoting layer which overcomes the difficult problem of providing good adhesion between an overcoat which is typically hydrophilic and an imaging layer which is typically hydrophobic. Moreover, use of such polymers for this purpose not only provides very effective adhesion but causes no adverse sensitometric effects and involves the use of low cost, readily available materials which are easily handled and coated and are environmentally advantageous.
  • the overcoat layer utilized in the thermally processable imaging elements of this invention performs several important functions as hereinabove described. It can be composed of hydrophilic colloids such as gelatin or poly(vinyl alcohol) but is preferably composed of poly(silicic acid) and a water-soluble hydroxyl-containing monomer or polymer as described in U.S. Patent 4,741,992, issued May 3, 1988.
  • the thermally processable imaging element of this invention can optionally include additional layers such as a backing layer.
  • Particularly useful backing layers are those comprising poly(silicic acid) and a water-soluble hydroxyl-containing monomer or polymer that is compatible therewith as described in U.S. Patent 4,828,971, issued May 9, 1989.
  • the improved thermally processable imaging element of this invention can contain three different layers each of which is comprised of poly(silicic acid), namely, (1) an overcoat layer whose purpose is to protect the element as described in U.S. Patent 4,741,992, (2) a backing layer whose purpose is to improve conveyance, reduce static electricity and eliminate formation of Newton Rings as described in U.S. Patent 4,828,971 and (3) a barrier layer whose purpose is to protect the support against migration from the imaging layer of hydrolysis by-products and thereby prevent width-wise curl as described in U.S. Patent 5,264,334.
  • the thermally processable imaging elements of this invention also include an electroconductive layer to provide antistatic protection as described in United States Patent No. 5,310,640, issued May 10, 1994.
  • the thermally processable imaging element of this invention can be a black-and-white imaging element or a dye-forming imaging element. It can be of widely varying construction as long as it includes the aforesaid support, imaging layer, overcoat layer and adhesive interlayer.
  • Typical imaging elements within the scope of this invention comprise at least one imaging layer containing in reactive association in a binder, preferably a binder comprising hydroxyl groups, (a) photographic silver halide prepared in situ and/or ex situ, (b) an image-forming combination comprising (i) an organic silver salt oxidizing agent, preferably a silver salt of a long chain fatty acid, such as silver behenate, with (ii) a reducing agent for the organic silver salt oxidizing agent, preferably a phenolic reducing agent, and (c) an optional toning agent.
  • References describing such imaging elements include, for example, U.S. Patents 3,457,075; 4,459,350; 4,264,725 and 4,741,992 and Research Disclosure , June 1978, Item No. 17029.
  • Polymers having pyrrolidone functionality that are useful in this invention can vary widely in structure and include homopolymers of N-vinyl-2-pyrrolidone, copolymers formed by polymerizing two polymerizable monomers one of which provides pyrrolidone functionality, and interpolymers formed by polymerizing three or more polymerizable monomers at least one of which provides pyrrolidone functionality.
  • Polymers having epoxy functionality that are useful in this invention can vary widely in structure and include homopolymers of epoxy monomers, copolymers formed by polymerizing two polymerizable monomers one of which provides epoxy functionality and interpolymers formed by polymerizing three or more polymerizable monomers at least one of which provides epoxy functionality.
  • Polyalkoxysilanes useful in this invention to form the adhesive interlayer include those represented by the formulae I or II as follows: Si(OR 1 ) 4 R 2 -Si(OR 3 ) 3 wherein R 1 and R 3 are individually unsubstituted or substituted alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl, and R 2 is unsubstituted or substituted alkyl, such as alkyl containing 1 to 22 carbon atoms, such as methyl, ethyl, propyl, butyl, and n-octadecyl; or unsubstituted or substituted phenyl.
  • Polyalkoxysilanes can also be utilized in the thermally processable imaging elements of this invention to form overcoat layers, backing layers or barrier layers or as components of the imaging layer.
  • the optimum layer thickness of the imaging layer, the overcoat layer and the adhesive interlayer depends upon various factors, such as the particular element, processing conditions, thermal processing means, desired image and the particular components of the layers.
  • a particularly useful imaging layer thickness is typically within the range of 1 to 10 ⁇ m, preferably 3 to 7 ⁇ m.
  • a particularly useful overcoat layer thickness is also typically within the range of 1 to 10 ⁇ m, preferably 1 to 3 ⁇ m.
  • a particularly useful adhesive interlayer thickness for the polymers having pyrrolidone or epoxy functionality is typically within the range of 0.008 to 0.05 ⁇ m, preferably 0.01 to 0.02 ⁇ m.
  • a particularly useful adhesive interlayer thickness for use of the polyalkoxysilane is typically within the range of 0.05 to 1.0 ⁇ m, preferably 0.10 to 0.40 ⁇ m.
  • Useful overcoat compositions are typically transparent and colorless. If the overcoat is not transparent and colorless, then it is necessary, if the element is a photothermographic element, that it be at least transparent to the wavelength of radiation employed to provide and view the image. The overcoat does not significantly adversely affect the imaging properties of the element, such as the sensitometric properties in the case of a photothermographic element, such as minimum density, maximum density, or photographic speed.
  • the overcoat composition preferably comprises 50 to 90% by weight of the overcoat of poly(silicic acid) and comprises a water-soluble hydroxyl-containing polymer or monomer that is compatible with the poly(silicic acid).
  • water soluble hydroxyl-containing polymers are acrylamide polymers, water-soluble cellulose derivatives, hydroxy ethyl cellulose, water-soluble cellulose acetate, and poly(vinyl alcohol). Partially hydrolyzed poly(vinyl alcohols) are preferred.
  • Thermally processable imaging elements as described can contain multiple polymer-containing layers, such as multiple overcoat layers.
  • the thermally processable imaging element can contain a first overcoat layer comprising a polymer other than poly(silicic acid), such as a cellulose derivative, and a second overcoat layer comprising poly(silicic acid) and poly(vinyl alcohol).
  • the overcoat comprises 50 to 90% by weight of poly(silicic acid) represented by the formula: wherein x is an integer within the range of at least 3 to 600 and wherein the overcoat also comprises 10 to 50% poly(vinyl alcohol).
  • the photothermographic element comprises a photosensitive component that consists essentially of photographic silver halide.
  • the latent image silver from the silver halide acts as a catalyst for the described image-forming combination upon processing.
  • a preferred concentration of photographic silver halide is within the range of 0.01 to 10 moles of photographic silver halide per mole of silver behenate in the photothermographic material.
  • Other photosensitive silver salts are useful in combination with the photographic silver halide if desired.
  • Preferred photographic silver halides are silver chloride, silver bromide, silver bromochloride, silver bromoiodide, silver chlorobromoiodide, and mixtures of these silver halides. Very fine grain photographic silver halide is especially useful.
  • the photographic silver halide can be prepared by any of the known procedures in the photographic art. Such procedures for forming photographic silver halides and forms of photographic silver halides are described in, for example, Research Disclosure , December 1978, Item No. 17029 and Research Disclosure , June 1978, Item No. 17643. Tabular grain photosensitive silver halide is also useful, as described in, for example, U.S. Patent No. 4,435,499.
  • the photographic silver halide can be unwashed or washed, chemically sensitized, protected against the formation of fog, and stabilized against the loss of sensitivity during keeping as described in the above Research Disclosure publications.
  • the silver halides can be prepared in situ as described in, for example, U.S. Patent No. 4,457,075, or prepared ex situ by methods known in the photographic art.
  • the photothermographic element typically comprises an oxidation-reduction image forming combination that contains an organic silver salt oxidizing agent, preferably a silver salt of a long chain fatty acid.
  • organic silver salts are resistant to darkening upon illumination.
  • Preferred organic silver salt oxidizing agents are silver salts of long chain fatty acids containing 10 to 30 carbon atoms. Examples of useful organic silver salt oxidizing agents are silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate, silver caprate, silver myristate, and silver palmitate. Combinations of organic silver salt oxidizing agents are also useful. Examples of useful organic silver salt oxidizing agents that are not organic silver salts of fatty acids are silver benzoate and silver benzotriazole.
  • the optimum concentration of organic silver salt oxidizing agent in the photothermographic element will vary depending upon the desired image, particular organic silver salt oxidizing agent, particular reducing agent and particular photothermographic element.
  • a preferred concentration of organic silver salt oxidizing agent is within the range of 0.1 to 100 moles of organic silver salt oxidizing agent per mole of silver in the element.
  • the total concentration of organic silver salt oxidizing agents is preferably within the described concentration range.
  • reducing agents are useful in the photothermographic element.
  • useful reducing agents in the image-forming combination include substituted phenols and naphthols, such as bis-beta-naphthols; polyhydroxybenzenes, such as hydroquinones, pyrogallols and catechols; aminophenols, such as 2,4-diaminophenols and methylaminophenols; ascorbic acid reducing agents, such as ascorbic acid, ascorbic acid ketals and other ascorbic acid derivatives; hydroxylamine reducing agents; 3-pyrazolidone reducing agents, such as 1-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone; and sulfonamidophenols and other organic reducing agents known to be useful in photothermographic elements, such as described in U.S. Patent 3,933,508, U.S. Patent 3,801,321 and Research Disclosure , June 1978, Item No. 17029. Combinations of organic acids and
  • Preferred organic reducing agents in the photothermographic element are sulfonamidophenol reducing agents, such as described in U.S. Patent 3,801,381.
  • useful sulfonamidophenol reducing agents are 2,6-dichloro-4-benzenesulfonamidophenol; benzenesulfonamidophenol; and 2,6-dibromo-4-benzenesulfonamidophenol, and combinations thereof.
  • An optimum concentration of organic reducing agent in the photothermographic element varies depending upon such factors as the particular photothermographic element, desired image, processing conditions, the particular organic silver salt oxidizing agent, and the particular polyalkoxysilane.
  • Post-processing image stabilizers and latent image keeping stabilizers are useful in the photothermographic element. Any of the stabilizers known in the photothermographic art are useful for the described photothermographic element. Illustrative examples of useful stabilizers include photolytically active stabilizers and stabilizer precursors as described in, for example, U.S. Patent 4,459,350. Other examples of useful stabilizers include azole thioethers and blocked azolinethione stabilizer precursors and carbamoyl stabilizer precursors, such as described in U.S. Patent 3,877,940.
  • the thermally processable elements as described preferably contain various colloids and polymers alone or in combination as vehicles and binders and in various layers.
  • Useful materials are hydrophilic or hydrophobic,. They are transparent or translucent and include both naturally occurring substances, such as gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, such as dextran, gum arabic and the like; and synthetic polymeric substances, such as water-soluble polyvinyl compounds like poly(vinylpyrrolidone) and acrylamide polymers.
  • Other synthetic polymeric compounds that are useful include dispersed vinyl compounds such as in latex form and particularly those that increase dimensional stability of photographic elements.
  • Effective polymers include water insoluble polymers of acrylates, such as alkylacrylates and methacrylates, acrylic acid, sulfoacrylates, and those that have cross-linking sites.
  • Preferred high molecular weight materials and resins include poly(vinyl butyral), cellulose acetate butyrate, poly(methylmethacrylate), poly(vinylpyrrolidone), ethyl cellulose, polystyrene, poly(vinylchloride), chlorinated rubbers, polyisobutylene, butadiene-styrene copolymers, copolymers of vinyl chloride and vinyl acetate, copolymers of vinylidene chloride and vinyl acetate, poly(vinyl alcohol) and polycarbonates.
  • Photothermographic elements and thermographic elements as described can contain addenda that are known to aid in formation of a useful image.
  • the photothermographic element can contain development modifiers that function as speed increasing compounds, sensitizing dyes, hardeners, antistatic agents, plasticizers and lubricants, coating aids, brighteners, absorbing and filter dyes, such as described in Research Disclosure , December 1978, Item No. 17643 and Research Disclosure , June 1978, Item No. 17029.
  • the thermally processable element can comprise a variety of supports.
  • useful supports are poly(vinylacetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film, and related films and resinous materials, as well as paper, glass, metal, and other supports that withstand the thermal processing temperatures.
  • the layers of the thermally processable element are coated on a support by coating procedures known in the photographic art, including dip coating, air knife coating, curtain coating or extrusion coating using hoppers. If desired, two or more layers are coated simultaneously.
  • Spectral sensitizing dyes are useful in the photothermographic element to confer added sensitivity to the element.
  • Useful sensitizing dyes are described in, for example, Research Disclosure , June 1978, Item No. 17029 and Research Disclosure , December 1978, Item No. 17643.
  • a photothermographic element as described preferably comprises a thermal stabilizer to help stabilize the photothermographic element prior to exposure and processing.
  • a thermal stabilizer provides improved stability of the photothermographic element during storage.
  • Preferred thermal stabilizers are 2-bromo-2-arylsulfonylacetamides, such as 2-bromo-2-p-tolysulfonylacetamide; 2-(tribromomethyl sulfonyl)benzothiazole; and 6-substituted-2,4-bis(tribromomethyl)-s-triazines, such as 6-methyl or 6-phenyl-2,4-bis(tribromomethyl)-s-triazine.
  • the thermally processable elements are exposed by means of various forms of energy.
  • forms of energy include those to which the photographic silver halides are sensitive and include ultraviolet, visible and infrared regions of the electromagnetic spectrum as well as electron beam and beta radiation, gamma ray, x-ray, alpha particle, neutron radiation and other forms of corpuscular wave-like radiant energy in either non-coherent (random phase) or coherent (in phase) forms produced by lasers.
  • Exposures are monochromatic, orthochromatic, or panchromatic depending upon the spectral sensitization of the photographic silver halide. Imagewise exposure is preferably for a time and intensity sufficient to produce a developable latent image in the photothermographic element.
  • the resulting latent image is developed merely by overall heating the element to thermal processing temperature.
  • This overall heating merely involves heating the photothermographic element to a temperature within the range of about 90°C. to 180°C. until a developed image is formed, such as within 0.5 to 60 s.
  • a preferred thermal processing temperature is within the range of 100°C. to 130°C.
  • thermographic imaging means can be, for example, an infrared heating means, laser, microwave heating means or the like.
  • Heating means known in the photothermographic and thermographic imaging arts are useful for providing the desired processing temperature for the exposed photothermographic element.
  • the heating means is, for example, a simple hot plate, iron, roller, heated drum, microwave heating means, heated air or the like.
  • Thermal processing is preferably carried out under ambient conditions of pressure and humidity. Conditions outside of normal atmospheric pressure and humidity are useful.
  • the components of the thermally processable element can be in any location in the element that provides the desired image. If desired, one or more of the components can be in more than one layer of the element. For example, in some cases, it is desirable to include certain percentages of the reducing agent, toner, stabilizer and/or other addenda in the overcoat layer over the photothermographic imaging layer of the element. This, in some cases, reduces migration of certain addenda in the layers of the element.
  • the components of the imaging combination be "in association" with each other in order to produce the desired image.
  • association herein means that in the photothermographic element the photographic silver halide and the image forming combination are in a location with respect to each other that enables the desired processing and forms a useful image.
  • the thermally processable imaging element of this invention preferably includes a backing layer.
  • the backing layer utilized in this invention is an outermost layer and is located on the side of the support opposite to the imaging layer. It is typically comprised of a binder and a matting agent which is dispersed in the binder in an amount sufficient to provide the desired surface roughness.
  • a wide variety of materials can be used to prepare a backing layer that is compatible with the requirements of thermally processable imaging elements.
  • the backing layer should be transparent and colorless and should not adversely affect sensitometric characteristics of the photothermographic element such as minimum density, maximum density and photographic speed.
  • Preferred backing layers are those comprised of poly(silicic acid) and a water-soluble hydroxyl containing monomer or polymer that is compatible with poly(silicic acid) as described in U.S. Patent 4,828,971.
  • a combination of poly(silicic acid) and poly(vinyl alcohol) is particularly useful.
  • Other useful backing layers include those formed from polymethylmethacrylate, cellulose acetate, crosslinked polyvinyl alcohol, terpolymers of acrylonitrile, vinylidene chloride, and 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, crosslinked gelatin, polyesters and polyurethanes.
  • organic or inorganic matting agents can be used.
  • organic matting agents are particles, often in the form of beads, of polymers such as polymeric esters of acrylic and methacrylic acid, e.g., poly(methylmethacrylate), styrene polymers and copolymers, and the like.
  • inorganic matting agents are particles of glass, silicon dioxide, titanium dioxide, magnesium oxide, aluminum oxide, barium sulfate, calcium carbonate, and the like. Matting agents and the way they are used are further described in U.S. Patent Nos. 3,411,907 and 3,754,924.
  • the backing layer preferably has a glass transition temperature (Tg) of greater than 50°C, more preferably greater than 100°C, and a surface roughness such that the Roughness Average (Ra) value is greater than 0.8, more preferably greater than 1.2, and most preferably greater than 1.5.
  • Tg glass transition temperature
  • Ra Roughness Average
  • the Roughness Average is the arithmetic average of all departures of the roughness profile from the mean line.
  • the concentration of matting agent required to give the desired roughness depends on the mean diameter of the particles and the amount of binder.
  • Preferred particles are those with a mean diameter of from 1 to 15 ⁇ m, preferably from 2 to 8 ⁇ m.
  • the matte particles can be usefully employed at a concentration of 1 to 100 milligrams per square meter.
  • a small amount of a colorant can be added to the overcoat layer and/or adhesive interlayer.
  • Blue colorants such as Victoria Pure Blue BO, Victoria Brilliant Blue G, Serva Blue WS, Aniline Blue, Page Blue G-90 and Methylene Blue, are especially useful for this purpose.
  • the thermally processable imaging element also includes an electroconductive layer to serve as an antistatic layer.
  • the electroconductive layer should have an internal resistivity of less than 5 X 10 10 ohms/square. Such electroconductive layers are described in United States Patent No. 5,310,640, issued May 10, 1994.
  • the electroconductive layer utilized in this invention in accordance with the teachings of the aforesaid United States Patent No. 5,310,640 is an "inner layer", i.e., a layer located under one or more overlying layers. It can be disposed on either side of the support. As indicated hereinabove, it has an internal resistivity of less than 5 X 10 10 ohms/square. Preferably, the internal resistivity of the electroconductive layer is less than 1 X 10 10 ohms/square.
  • the electroconductive layer can be composed of any of a very wide variety of compositions which are capable of forming a layer with suitable physical and electrical properties to be compatible with the requirements of thermally processable imaging elements. Included among the useful electroconductive layers are:
  • a colloidal gel of vanadium pentoxide is especially useful for forming the electroconductive layer.
  • vanadium pentoxide it is desirable to interpose a barrier layer between the electroconductive layer and the imaging layer so as to inhibit migration of vanadium pentoxide from the electroconductive layer into the imaging layer with resulting adverse sensitometric affects.
  • Suitable barrier layers include those having the same composition as the backing layer of U.S. Patent 4,828,971, namely, a mixture of poly(silicic acid) and a water-soluble hydroxyl-containing monomer or polymer.
  • the colloidal vanadium pentoxide gel typically consists of entangled, high aspect ratio, flat ribbons 5-10 nm (50-100 angstroms) wide, 1 nm (10 angstrom) thick and 100-1000 nm (1000-10000 angstroms) long.
  • the ribbons stack flat in the direction parallel to the surface when the gel is coated to form a conductive layer.
  • the result is very high electrical conductivities which are typically three orders of magnitude greater than is observed for layers of similar thickness containing crystalline vanadium pentoxide particles.
  • Low surface resistivities can be obtained with very low vanadium pentoxide coverages. This results in low optical absorption and scattering losses.
  • the coating containing the colloidal vanadium pentoxide gel is highly adherent to underlying support materials.
  • the improved thermally processable imaging element of this invention includes an adhesive interlayer, interposed between the imaging layer and the overcoat layer, which comprises at least one of (1) a polymer having pyrrolidone functionality, (2) a polymer having epoxy functionality and (3) a polyalkoxysilane.
  • the purpose of the adhesive interlayer is to strongly bond the overcoat layer to the imaging layer so that it cannot be easily removed.
  • pyrrolidone functionality is meant the presence of one or more pendant pyrrolidone rings.
  • the polymer is comprised of recurring units of which at least 50 mole percent comprise a pendant pyrrolidone ring.
  • epoxy functionality is meant the presence of one or more pendant oxirane rings.
  • the polymer is comprised of recurring units of which at least 50 mole percent comprise a pendant oxirane ring.
  • the polymer having pyrrolidone functionality can be a homopolymer of N-vinyl-2-pyrrolidone or a copolymer of N-vinyl-2-pyrrolidone with one or more ethylenically-unsaturated copolymerizable monomers.
  • the copolymer is one which contains at least 60 weight percent of N-vinyl-2-pyrrolidone.
  • the pendant pyrrolidone rings of the polymer can be substituted or unsubstituted. For example, they can be substituted with alkyl groups.
  • the homopolymer of N-vinyl-2-pyrrolidone i.e., poly(N-vinyl-2-pyrrolidone)
  • n represents a whole number, e.g., a number sufficiently high to provide a molecular weight of from several hundred to several hundred thousand.
  • These polymers are well known and can be prepared, for example, by processes of polymerization of N-vinyl-2-pyrrolidone, disclosed in U.S. Patent No. 2,265,540, issued December 9, 1941, and U.S. Patent 2,335,454, issued November 30, 1943.
  • Ethylenically unsaturated monomers that are copolymerizable with N-vinyl-2-pyrrolidone include:
  • polymers having pyrrolidone functionality that are preferred for use in this invention include:
  • the polymer having pyrrolidone functionality is comprised of recurring units represented by the formula: wherein
  • Polymers having epoxy functionality which are preferred for use in this invention are comprised of recurring units represented by the formula: wherein:
  • polymers having epoxy functionality are readily prepared by reacting a polymerizable epoxy compound with one or more polymerizable acrylic monomers.
  • Suitable polymerizable acrylic monomers include:
  • Suitable polymerizable epoxy monomers include:
  • polymers having epoxy functionality that are preferred for use in this invention include:
  • the overcoat layer comprises polysilicic acid and polyvinylalcohol
  • the imaging layer comprises polyvinylbutyral
  • the adhesive interlayer is comprised of poly(N-vinyl-2-pyrrolidone).
  • the overcoat layer comprises polysilicic acid and polyvinylalcohol
  • the imaging layer comprisies polyvinylbutyral
  • the adhesive interlayer is comprised of poly(butyl acrylate-co-allyl methacrylate-co-glycidyl methacrylate).
  • the overcoat layer comprises polysilicic acid and polyvinylalcohol
  • the imaging layer comprises polyvinylbutyral
  • the adhesive interlayer is comprised of glycidoxypropyltrimethoxysilane.
  • U.S. Patent 4,942,115 describes the use of an adhesive interlayer comprising a terpolymer such as poly(2-propenenitrile-co-1,1-dichloroethene-co-2-propenoic acid) or poly(2-propenoic acid methyl ester-co-1,1-dichloroethene-co-itaconic acid).
  • terpolymers are very effective in providing good adhesion but are costly, difficult to handle and environmentally disadvantageous and can cause adverse sensitometric effects such as an undesirably high D min .
  • a thermally processable imaging element was prepared by coating a poly(ethylene terephthalate) film support, having a thickness of 0.114 millimeters, with a photothermographic imaging layer, an adhesive interlayer and a protective overcoat layer.
  • the photothermographic imaging composition was coated from a solvent mixture containing 90 parts by weight methyl isobutyl ketone and 10 parts by weight acetone to form an imaging layer of the following composition.
  • the adhesive interlayer consisted of poly(N-vinyl-2-pyrrolidone), having a molecular weight of 360,000, coated at a coverage of 0.11 g/m 2 .
  • polysilicic acid was prepared by mixing 29.4 weight % water, 1.2 weight % one normal p-toluene sulfonic acid, 34 weight % methanol and 35.4 weight % tetraethoxysilane to form a 16.3 weight % polysilicic acid solution.
  • the polysilic acid was mixed with polyvinyl alcohol, a surfactant, matte beads and water to form a protective overcoat layer of the following composition.
  • Component Coverage (g/m 2 ) Polyvinyl alcohol 1.1 Polysilicic acid 1.65 Surfactant 0.044 Polymethylmethacrylate beads 0.055
  • a second thermally processable imaging element identified as Control A, was prepared in the same manner as the element described above except that the adhesive interlayer was omitted.
  • a third thermally processable imaging element identified as Control B, was prepared in the same manner as the element described above except that the poly(N-vinyl-2-pyrrolidone) in the adhesive interlayer was replaced with poly(butylacrylate-co-2-sulfo-1,1-dimethylethyl acrylamide-co-methyl-2-acrylamido-2-methoxyacetate).
  • adhesion of the overcoat layer to the imaging layer was evaluated using a tape adhesion test.
  • a 35-mm wide sample was prepared and laid flat on a table and a section of SCOTCH Magic Tape #811, available from Minnesota Mining and Manufacturing Company, was placed across the width of the sample and smoothed out by hand to assure uniform adhesion.
  • the percent of the overcoat layer removed was estimated and related to adhesion. Ideally, the extent of removal would be zero.
  • the test was performed up to ten times for each sample. Measurements were made for fresh samples, for samples aged two weeks at ambient conditions, and for samples aged two weeks at 49°C/15% relative humidity.
  • composition of the imaging layer was as follows: Component Coverage (g/m 2 ) Silver behenate 1.008 AgBr 0.400 Succinimide 0.352 Surfactant 0.019 2-Bromo-2-p-tolylsulfonyl acetamide 0.072 2,4-Bis(trichloromethyl)-6-(1-naphtho)-S-triazine 0.017 Sensitizing dye 0.005 Palmitic acid 0.110 4-Benzenesulfonamidophenol 1.166 Binder 3.092
  • the imaging layer was of the same composition as described in Example 2.
  • a 1.25 X 4.0 cm piece of SCOTCH Magic Tape #811 was firmly pressed by hand onto the overcoated sample and then manually removed. The test was conducted on a fresh sample and on a sample that had been dried for one hour at 60°C. The amount of the overcoat layer removed was determined and the sample was rated in accordance with the following scale:
  • both the homopolymer of N-vinyl-2-pyrrolidone and copolymers of N-vinyl-2-pyrrolidone with ethylenically unsaturated copolymerizable monomers are capable of providing good adhesion in the test performed after one hour of drying at 60°C.
  • the use of a 50/50 wt% copolymer of N-vinyl-2-pyrrolidone and vinyl acetate provided poor results in both tests.
  • the use of a 30/70 wt% copolymer of N-vinyl-2-pyrrolidone and vinyl acetate provided poor results in both tests.
  • the polymer must have a sufficient level of pyrrolidone functionality to perform well.
  • the amount of N-vinyl-2-pyrrolidone should be at least about 60 weight percent.
  • Example 1 To evaluate the effect of variation in molecular weight, three samples were prepared in which poly(N-vinyl-2-pyrrolidones) of different molecular weight were employed. In these tests, the same support, photothermographic imaging layer and protective overcoat layer as described in Example 1 were employed. The layers were coated simultaneously using multiple-layer slide hopper coating techniques. In each of Examples 7 to 9, the poly(N-vinyl-2-pyrrolidone) was coated at a coverage of 0.22 g/m 2 . Tape adhesion test measurements were made for fresh samples in the manner described in Example 1 and D min values were determined in the manner described in Example 1.
  • the support, photothermographic imaging layer and protective overcoat layer were the same as described in Example 1.
  • the adhesive interlayer consisted of poly(butyl acrylate-co-allyl methacrylate-co-glycidyl methacrylate) coated at a coverage of 0.11 g/m 2 .
  • a thermally processable imaging element was prepared in the same manner as described in Example 11 except that the glycidoxypropyltrimethoxysilane in the adhesive interlayer was replaced with tetraethoxysilane.
  • the results obtained were similar to Example 11 with the percentage removal being 10 percent for the fresh sample, zero for the two-week ambient sample and zero for the 2-week 49°C/15% RH sample and the D min being 0.21.
  • tetraethoxysilane behaves in a similar manner to glycidoxypropyltrimethoxysilane in providing effective improvement in adhesion without adverse effects on sensitometry.
  • Glycidoxypropyltrimethoxysilane coated at a dry coverage of 0.11 g/m 2 was evaluated as an adhesive interlayer using a modified adhesion test.
  • the imaging layer was of the same composition as described in Example 2.
  • a 1.25 X 4.0 cm piece of SCOTCH Magic Tape #811 was firmly pressed by hand onto the overcoated sample and then manually removed. The test was conducted on a fresh sample and on a sample that had been dried for one hour at 60°C. The amount of the overcoat layer removed was determined and the sample was rated in accordance with the following scale:
  • the present invention provides an important improvement in thermally processable imaging elements.
  • a hydrophilic overcoat layer such as a layer containing poly(silicic acid) and poly(vinyl alcohol), provides excellent protection for such elements.
  • the degree of adhesion of such an overcoat layer to hydrophobic imaging layers such as those that contain poly(vinyl butyral) is inadequate as a consequence of the general lack of compatability of hydrophiic and hydrophobic layers.
  • the adhesive interlayer of this invention overcomes the problem of inadequate adhesion and does so with low cost readily-available materials which are easy to coat and handle, are environmentally advantageous and do not cause adverse sensitometric effects.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (10)

  1. Elément formateur d'image pouvant être traité par la chaleur, ledit élément comprenant :
    (1) un support ;
    (2) une couche formatrice d'image thermographique ou photothermographique ;
    (3) une surcouche recouvrant ladite couche formatrice d'image ; et
    (4) une intercouche entre ladite couche formatrice d'image et ladite surcouche ;
    caractérisé en ce que :
    ladite surcouche comprend de 50 à 90 % en poids d'acide polysilicique représenté par la formule : où X est un entier compris entre au moins 3 et 600 et de 10 à 50 % en poids d'un polymère ou d'un monomère contenant un groupe hydroxyle soluble dans l'eau compatible avec l'acide polysilicique ; et ladite intercouche est une couche adhésive qui lie ladite surcouche à ladite couche formatrice d'image, ladite intercouche adhésive comprenant au moins un composant choisi parmi (1) un polymère ayant une fonctionnalité pyrrolidone, (2) un polymère ayant une fonctionnalité époxy et (3) un polyalcoxysilane, à la condition que la couche formatrice d'image ne contienne pas de polyalcoxysilane.
  2. Elément formateur d'image pouvant être traité par la chaleur selon la revendication 1 comprenant en outre une couche dorsale sur le côté du support opposé à ladite couche formatrice d'image.
  3. Elément formateur d'image pouvant être traité par la chaleur selon la revendication 1 ou 2 comprenant en outre une couche électroconductrice qui est une couche interne placée sur l'une ou l'autre face dudit support ; ladite couche électroconductrice ayant une résistivité interne inférieure à 5 x 1010 ohms/carré.
  4. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient un polymère comprenant des motifs récurrents représentés par la formule : où :
    R1 est l'hydrogène ou un groupe méthyle,
    D est un groupe alkylène de 1 à 6 atomes de carbone,
    L est
    x = 30 - 100 % en moles,
    y = 0 -70 % en moles.
  5. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient de la poly(N-vinyl-2-pyrrolidone).
  6. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient un polymère constitué de motifs récurrents représentés par la formule : où :
    R1 est l'hydrogène ou un groupe méthyle,
    R2 est un groupe alkyle de 1 à 8 atomes de carbone ou un groupe cycloalkyle de 3 à 8 atomes de carbone,
    D est un groupe alkylène de 1 à 6 atomes de carbone,
    L est
    a = 30 - 70 % en moles,
    b = 0 - 10 % en moles,
    c = 20 - 70 % en moles.
  7. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient un terpolymère d'acrylate de butyle, de méthacrylate d'allyle et de méthacrylate de glycidyle.
  8. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient un polyalcoxysilane représenté par les formules I ou II suivantes : Si(OR1)4 R2-Si(OR3)3 où R1 et R3 sont individuellement un groupe alkyle substitué ou non de 1 à 4 atomes de carbone et R2 est un groupe alkyle ou phényle substitué ou non.
  9. Elément formateur d'image pouvant être traité par la chaleur selon l'une quelconque des revendications 1 à 3, dans lequel ladite intercouche adhésive contient :
    Si(OC2H5)4
    Si(OCH3)4
    CH3Si(OC2H5)3
    CH3Si(OCH3)3
    C6H5Si(OC2H5)3
    C6H5Si(OCH3)3
    NH2CH2CH2CH2Si(OC2H5)3
    NH2CH2CH2CH2Si(OCH3)3
    CH3(CH2)17Si(OC2H5)3.
  10. Elément formateur d'image pouvant être traité par la chaleur, ledit élément comprenant :
    (1) un support ;
    (2) une couche formatrice d'image thermographique ou photothermographique ;
    (3) une surcouche recouvrant ladite couche formatrice d'image ; et
    (4) une intercouche adhésive liant ladite surcouche à ladite couche formatrice d'image ; caractérisé en ce que ladite intercouche adhésive contient un polymère comprenant des motifs récurrents représentés par la formule : où :
    R1 est l'hydrogène ou un groupe méthyle,
    D est un groupe alkylène de 1 à 6 atomes de carbone,
    L est
    x = 30 - 100 % en moles,
    y = 0 - 70 % en moles.
EP95200593A 1994-03-16 1995-03-10 Elément d'enregistrement thermosensible avec couche intermédiaire adhésive Expired - Lifetime EP0672544B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US08/213,784 US5393649A (en) 1994-03-16 1994-03-16 Thermally processable imaging element including an adhesive interlayer comprising a polymer having pyrrolidone functionality
US08/213,778 US5418120A (en) 1994-03-16 1994-03-16 Thermally processable imaging element including an adhesive interlayer comprising a polyalkoxysilane
US213778 1994-03-16
US08/213,496 US5422234A (en) 1994-03-16 1994-03-16 Thermally processable imaging element including an adhesive interlayer comprising a polymer having epoxy functionality
US213496 1994-03-16
US213784 1994-03-16

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Publication Number Publication Date
EP0672544A1 EP0672544A1 (fr) 1995-09-20
EP0672544B1 true EP0672544B1 (fr) 1998-05-06

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JP3995830B2 (ja) * 1999-01-13 2007-10-24 富士フイルム株式会社 熱現像画像記録材料
JP4048684B2 (ja) * 2000-03-21 2008-02-20 コニカミノルタホールディングス株式会社 熱現像感光材料とその製造方法
US6458511B1 (en) 2000-06-07 2002-10-01 Kodak Polychrome Graphics Llc Thermally imageable positive-working lithographic printing plate precursor and method for imaging
US6864040B2 (en) 2001-04-11 2005-03-08 Kodak Polychrome Graphics Llc Thermal initiator system using leuco dyes and polyhalogene compounds
US6350561B1 (en) * 2000-12-01 2002-02-26 Eastman Kodak Company Thermally developable imaging materials containing surface barrier layer
US6596460B2 (en) 2000-12-29 2003-07-22 Kodak Polychrome Graphics Llc Polyvinyl acetals having azido groups and use thereof in radiation-sensitive compositions
US6899994B2 (en) 2001-04-04 2005-05-31 Kodak Polychrome Graphics Llc On-press developable IR sensitive printing plates using binder resins having polyethylene oxide segments
US7592128B2 (en) 2001-04-04 2009-09-22 Eastman Kodak Company On-press developable negative-working imageable elements
US6846614B2 (en) 2002-02-04 2005-01-25 Kodak Polychrome Graphics Llc On-press developable IR sensitive printing plates
US6893797B2 (en) 2001-11-09 2005-05-17 Kodak Polychrome Graphics Llc High speed negative-working thermal printing plates
US7056639B2 (en) 2001-08-21 2006-06-06 Eastman Kodak Company Imageable composition containing an infrared absorber with counter anion derived from a non-volatile acid

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US4833116A (en) * 1986-10-16 1989-05-23 Kanzaki Paper Mfg. Co., Ltd. Heat-sensitive recording material
US4886739A (en) * 1988-08-10 1989-12-12 Eastman Kodak Company Thermally processable imaging element and process
EP0568023B1 (fr) * 1992-04-30 1997-01-22 Canon Kabushiki Kaisha Matériau photosensible développable à la chaleur

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DE69502323D1 (de) 1998-06-10
JPH07319106A (ja) 1995-12-08
EP0672544A1 (fr) 1995-09-20

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