US3856526A - Protective layer for photothermographic elements - Google Patents

Protective layer for photothermographic elements Download PDF

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US3856526A
US3856526A US38593473A US3856526A US 3856526 A US3856526 A US 3856526A US 38593473 A US38593473 A US 38593473A US 3856526 A US3856526 A US 3856526A
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protective layer
photothermographic element
layer
photothermographic
protective
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F Hamb
G Hiller
A Wise
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US38593473 priority Critical patent/US3856526A/en
Priority to CA204,153A priority patent/CA1031617A/fr
Priority to FR7426353A priority patent/FR2240467B1/fr
Priority to GB3442774A priority patent/GB1458737A/en
Priority to BE147338A priority patent/BE818544A/fr
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic

Definitions

  • PROTECTIVE LAYER FOR PHOTOTHERMOGRAPHIC ELEMENTS [75] Inventors: Fredrick L. Hamb, Rochester;'Gary L. Hiller, Hilton; Albert W. Wise, Rochester, all of NY.
  • a protective layer comprising certain carboxylic polyesters provides improved resistance to abrasion and fingerprinting, resistance to reticulation and surface cracking without adversely affecting sensitorneric properties of the photographic element upon processing.
  • a latent image in such an element can be developed by uniformly heating the element containing the protective layer.
  • Silica particles in the protective layer can enhance resistance of the protective layer to sticking to a heated metal surface and further enable the layer to glide smoothly over the heated metal surface.
  • This invention relates to protective layers comprising certain film-forming carboxylic polyesters for photographic elements comprising at least one heatprocessable, photographic layer, said protective layers providing improved surface properties without adversely affecting sensitometric properties of the photographic element upon processing.
  • it relates to photothermographic elements Containing such improved protective layers.
  • it relates to a method of developing a latent image in a photothermographic element employing the described protective layer.
  • a commonly employed overcoat layer for photothermographic elements comprises cellulose acetate.
  • overcoat layers are described, for example, in Belgian Pat. No. 729,043 and U.S. Pat. No. 2,732,304 issued Jan. 24, 1956.
  • Photothermographic materials are also known as described, for example, in Belgian Pat. No. 765,452 issued May 28, 1971; Belgian Pat. No. 765,602 issued May 28, 1971; Belgian Pat. No. 765,601 issued May 28, 1971; Belgian Pat. No. 766,658issued June 30, 1971; Belgian Pat. No. 766,590 issued June 15, 1971; Belgian Pat. No.
  • Photosensitive elements designed for processing with heat and which lack protective layers are especially susceptible to fingerprint marks and scratches which can become visible upon exposure to room-light handling and processing.
  • Such photosensitive elements also are susceptible to abrasion marks, especially in machine processing wherein the photosensitive layer side of the element is contacted with a metal roller or the like.
  • the processing of photothermographic elements by contacting the side of the photothermographic element containing the photosensitive layer with the heating means can cause surface cracking, reticulation, and bubbling which can detract from the overall image quality desired.
  • An ethyl cellulose overcoat layer has not satisfactorily overcome these problems. It has also been proposed, as described in copending application Ser. No. 244,850 of Hiller and Hamb, filed Apr. 17, 1972, to employ certain polycarbonate polymers with silica particles in an overcoat for photographic materials. However, such polycarbonate compounds have been considered to be very expensive compared to such overcoat materials as ethyl cellulose.
  • matting agents have also been employed in photosensitive materials. Such matting agents are described, for example, in British Pat. No. 692,592 published June 10, 1953; U.S. Pat. No. 3,411,907 of Whitmore et al., issued Nov. 19, 1968; and U.S. Pat. No.
  • A is a radical selected from the group consisting of a. a radical represented by the. formula:
  • each of said bivalent polycyclic radicals having bonded to at least one of the polycyclic rings at'least one radical selected from the group consisting of hydrogen, halogen, such as chlorine, bromine or iodine; phenyl, and alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl or propyl; b. a radical represented by the formula:
  • R and R are the same or different and each is hydrogen or alkyl containing 1 to 6 carbon atoms, such as methyl, ethyl or propyl;
  • R is alkyl containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl or butyl;
  • R R R and R are the same or different and each is hydrogen; aryl containing 6 to 12 carbon atoms, such as phenyl or naphthyl; halogen, such as chlorine, bromine or iodine; nitro; cyano; amino or alkoxy containing 1 to 4 carbon atoms, such as methoxy, propoxy or butoxy;
  • R and R are the same or different and are each hydrogen or alkyl containing 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, or decyl; ii. R R R R R R and R are the same or different and are each hydrogen or or alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, pro-.
  • R and R are the same and R and R are the same and that the sum of the carbon atoms in R and R equals the sum of the carbon atoms in R and R and equals the sum of the carbon atoms in R R R and R plus 2,
  • X is a radical selected from the group consisting of designated radicals (a) through (i) and g. a radical represented by the formula:
  • R and R are the same ordifferent and each is hydrogen; aryl containing 6 to 20 carbon atoms, such as phenyl and naphthyl; halogen, such as chlorine, and bromine; nitro; amino; cyano or alkoxy containing l to 5 carbon atoms, such as methoxy or ethoxy;
  • R and R are the same or different and each is hydrogen; aryl containing 6 to 20 carbon atoms, such as phenyl or naphthyl; halogen, such as chlorine, bromine or iodine; nitro; cyano; or alkoxy containing 1 to 5 carbon atoms such as methoxy, ethoxy and propoxy;
  • R and R are the same or different and each is hydrogen; alkyl containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl or butyl; cycloalkyl containing 4 to 6 carbon atoms, such as cyclopentyl or cyclohexyl; or aryl containing 6 to 20 carbon atoms, such as phenyl or naphthyl; or R and R taken together with the carbon atoms to which they are bonded can be a bridged ring moiety, such as containing up to 12 carbon atoms, for example and GUI
  • n 100-m mole percent
  • Alkyl and aryl as employed herein include alkyl and aryl substituted with groups which do not adversely affect the properties of the described photothermographic materials.
  • alkyl includes substituted alkyl wherein the substituent group can be methyl or ethyl or phenyl.
  • Aryl for instance, includes substituted aryl wherein the substituent group can be alkyl containing 1 to 3 carbon atoms, or can be phenyl.
  • the described carboxylic polyesters preferably have a glass transition temperature above that employed for processing ofthe photographic material.
  • silica particles such as silica particles having an average particle size of 0.001 to 0.10 micron improved properties, such as enhanced resistance of the described in the protective layer to provide protective layer to sticking to a heated metal surface and further enable the layer to glide smoothly over the heated metal surface.
  • a process for developing an image in the described photographic element comprising a support having thereon at least one heat developable photographic layer and a protective overcoat layer comprising the described carboxylic polyester by uniformly heating the element, such as from about 80C. to about 250C. for a sufficient time to provide the desired developed image.
  • This process can be carried out by contacting the photographic element with a suitable heating means to provide the described temperature.
  • a range of carboxylic polyesters within the designated formula, having glass transition temperatures of at least C., are useful in protective layers according to the invention.
  • a carboxylic polyester protective layer is useful which has a glass transition temperature greater than the processing temperature of the photographic material in order to prevent distortion of the protective layer during heating.
  • the most useful carboxylic polyesters have a glass transition temperature above 200C. and preferably above 220C.
  • Useful carboxylic polyesters have an average molecular weight of at least 10,000 and preferably from about 30,000 to 100,000. The molecular weight can be determined by methods known in the polymer art.
  • the glass transition temperatures can be determined by differential thermoanalysis as described in Techniques and Methods of Polymer Evaluation, Volume 1, Marcel Dekker, Inc., New York, 1966.
  • Useful carboxylic polyesters are soluble in common organic coating solvents such as methylene chloride, chloroform, 1,1,2-trichloroethane, acetone, Z-pentanone, ethyl acetate and toluene. This is a useful property in order to facilitate application of a layer as described. Other useful properties are that the selected carboxylic polyester should be chemically and physically stable and have good flexibility.
  • Useful carboxylic polyesters are described, for example, in US. Pat. No.
  • the described carboxylic polyesters can be prepared employing procedures known in the polymer art, such as described in US. Pat. No. 3,725,070 of I-Iamb and Wilson, issued Apr. 3, 1973.
  • any of the known esterification procedures used in the polymer art are useful for making the described carboxylic polyesters. These include so-called interfacial procedures, solution procedures and ester procedures known in the art.
  • Useful carboxylic polyesters are typically completely transparent and colorless when coated on a support. It is necessary, however, if the polymer is not completely transparent that it at least be transparent to the wavelength of radiation employed to provide a latent image in the photographic element when exposure is through the protective layer.
  • moiety A being for example:
  • the described carboxylic polyesters have a glass transition temperature which is much higher than, for example, cellulose acetate. This property provides an advantage for photothermographic materials enabling the photothermographic materials to be processed at higher temperatures without formation of the described surface defects.
  • the described carboxylic polyesters do not adversely affect the sensitometric properties of photothermographic materials such as minimum density, maximum density, photographic speed and the like, whereas cellulose acetate, a commonly employed overcoat causes changes in sensitometric behavior.
  • the concentration of carboxylic polyester which is useful in the protective layer of a photographic element, especially a photothermographic element, according to the invention can vary depending upon the particular photographic element, processing conditions, components in the photographic element, particular carboxylic polyester and the like.
  • a useful concentration range, or coating coverage is about milligrams to about 400 milligrams or carboxylic polyester per 929'square centimeters of support of the photographic element.
  • An especially useful concentraion of carboxylic polyester in a protective layer of a photothermographic element is about 50 milligrams to about 200 milligrams of carboxylic polyester per 929 square centimeters of support of the photothermographic element.
  • silica particles are especially useful in the described protective layer. Silica particles typically having an average particle size range of 0.001 micron to 0.05 micron, preferably 0.005 micron to 0.10 micron are useful. Silica products for this purpose are available commercially, such as silica sold under the trade name of Cab-O-Sil which is a registered trademark of Cabot Corporation, USA.
  • a useful silica product is colloidal silica in the form of a dry powder which is mixed with the described carboxylic polyester before coating. This enables writing information on the photographic element with a pencil or ball-point pen after processing.
  • fSyloid Another useful product is fSyloid which is registered trademark of W. R. Grace Company, USA.
  • the concentration of matting agent, especially silica. which is useful in a protective layer according to the invention can vary depending upon the particular photographic element, processing conditions, particular carboxylic polyester employed, and the like.
  • a useful concentration is about 2 milligrams to about 25 milligrams of silica per 929 square centimeters of support of the photographic element.
  • an especially useful concentration is about 5 milligrams to about 15 milligrams of silica per 929 square centimeters of the photothermographic element.
  • the described protective layer according to the invention can be employed with various photographic elements. Accordingly, one embodiment of the invention is: in a photographic element comprising a support having thereon at least one heat-processable, photographic layer and a protective layer, the improvement comprising as said protective layer a carboxylic polyester having a glass transition temperature of at least 190C. having repeating units represented by the formula of the described generic structure.
  • Especially useful car boxylic polyesters in this embodiment are copolymcrs of (i) terephthalic acid, (ii) 3,3,3',3'-tetramethyl-l,l spirobi[indan]-6,6-diol and (Ill) bisphenol A. This c0- polymer is especially useful in combination with the described silica particles to provide improved resistance to reticulation.
  • bisphenol A asemployed herein refers to the compound 4,4-isopropylidene diphenol also known as 2,2-(para-hydroxyphenyl)propane and 2,2- bis(4-hydroxyphenyl) propane.
  • a useful embodiment of the invention is: in a photographic element comprising a support having thereon at least oneheat-processable, photographic layer and a protective overcoat layer, the improvement comprising as said protective, overcoat layer a carboxylic poly ester having a glass transition temperature of at least 200C. represented by the formula:
  • K is selected from the group consisting of i. 3 ,3 ,3,3'-tetrarriethyl-l l l-spirobi[indan]-6,6-
  • an oxidation-reduction image-forming combination comprising i. a silver salt oxidizing agent with ii. an organic reducing agent, 2. photosensitive silver halide,
  • activator-toning agent also known as a toner.
  • Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly- (ethylene terephthalate) film, poly(ethylene 2,6- naphthalene dicarboxylate), polyesters of 1,1,3- trimethyl-3-(p-carboxyphenyl)-5-carboxyindan and bisphenols, as described in US. Pat. No. 3,634,089 issued Jan. 1 1, 1972,- polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support such as a paper support which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer such as a polymer of an alpha-olefin containing 2 to carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • an alpha-olefin polymer such as a polymer of an alpha-olefin containing 2 to carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • the photographic elements according to the invention contain a photosensitive component.
  • the photosensitive component is typically a photosensitive silver salt or complex, such as photosensitive silver halide or a complex or silver with an organic compound such as a silver dye complex.
  • the photosensitive silver halide is especially useful as a photosensitive component because of its high photosensitivity.
  • a typical concentration of photo sensitive component in a photothermographic element according to the invention is about 0.005 to about 0.50 moles of photosensitive component per mole of oxidizing agent in the photothermographic element.
  • Especially useful photosensitive silver halides include silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof.
  • the photosensitive silver halide can be coarse or fine-grain, very fine-grain silver halide being especially useful.
  • the photosensitive silver halide can be prepared by any of the procedures known in the photographic art. Such procedures and forms of photosensitive silver halide are described, for example, in the Product Licensing Index, Volume 92, December, 1971, publication 9232, pages 107-110, paragraph-l. g
  • the photosensitive silver halide employed according to the invention can be unwashed or washed, can be chemically sensitized, can be protected against the production of fog and stabilized against loss of sensitivity during keeping, as described in the Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107-110.
  • Photographic elements according to the invention can contain development modifiers that function as speed-increasing compounds, developing agents, hardeners, antistatic layers, plasticizers and lubricants, coating aids, brighteners, spectral sensitizing dyes, absorbing and filter dyes, also as described in the Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107-110.
  • development modifiers that function as speed-increasing compounds, developing agents, hardeners, antistatic layers, plasticizers and lubricants, coating aids, brighteners, spectral sensitizing dyes, absorbing and filter dyes, also as described in the Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107-110.
  • the described photothermographie elements can comprise an oxidation-reduction image-forming combination which contains an oxidizing agent, typically a heavy metal salt oxidizing agent.
  • the heavy metal salt oxidizing agent can be a heavy metal salt of an organic acid such as a fatty acid which is resistant to darkening upon illumination.
  • An especially useful class of heavy metal salts of organic acids is represented by the water insoluble silver salts of long-chain fatty acids which are stable to light.
  • Compounds which are suitable silver salt oxidizing agents include silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxystearate. sil ver caprate, silver myristate and silver palmitate.
  • Silver salts can be employed as the silver salt oxidizing agents which are not silver salts of long-chain fatty acids.
  • Such silver salt oxidizing agents which are useful according to the invention include, for example, silver benzoate, silver benzotriazole, silver terephthalate, silver phthalate, and the like.
  • Oxidizing agents which are not silver salts can be employed if desired such as gold stearate, mercury behenate, gold behenate, and the like, but silver salts are preferred. Combinations of the described oxidizing agents can be employed if desired.
  • Reducing agents which can be employed in the described oxidation-reduction image-forming combination include, for example, substituted phenols and naphthols, for example, bis-B-naphthols.
  • Suitable bis-B- naphthols include, for example, 2,2'-dihydroxy-1,1'- binaphthyl, 6,6dibromo-2,2-dihydroxy- 1 ,1 binaphthyl, 6,6-dinitro-2,2-dihydroxy-l,1-binaphthyl and/or bis-(Z-hydroxy-l-naphthyl)methane.
  • reducing agents which can be employed in photographic elements according to the invention include polyhydroxybenzenes such as hydroquinone silver halide de veloping agents, e.g., hydroquinone, alkyl-substituted hydroquinones such as tertiary butyl hydroquinone, methyl hydroquinone, 2,5-dimethyl hydroquinone and 2,6-dimethyl hydroquinone; catechols and pyrogallols; chloro-substituted hydroquinones such as chloro'hydroquinone or dichloro hydroquinone; alkoxysubstituted hydroquinone such as methoxy hydroquinone or ethoxy hydroquinone; aminophenol developing agents, such as 2,4-diaminophenols and methylaminophenols; ascorbic acid developing agents such as ascorbic acid, ascorbic acid ketals and ascorbic acid derivatives; hydroxylamine developing agents; 3- pyrazolidone developing agents such as l-pheny
  • Reducing agents which are also useful include sulfonamidophenols as described in pending U.S.S application Ser. No. 272,832 of Evans and McLaen, filed July 18, 1972 and now US. Pat. No. 3,801,231. Combinations of the described reducing agents can be employed if desired.
  • activatortoning agent is typically useful in a range of concentration, such as a concentration of about 0.10 moles to about 1.1 moles of activator-toning. agent per mole of oxidizing agent in the photothermographic element.
  • a typical suitable activator-toning agent is a bet erocyclic activator-toning agent containing at least one nitrogen atom as described in Belgian Pat. No. 766,590 issued June 15, 1971.
  • Typical activator-toning agents include, for example, phthalimide, N- hydroxyphthalimide, N-potassium phthalimide, N- silver phthalimide, N-mercury phthalimide, succinimide, N-hydroxynaphthalimide, and/or N- hydroxysuccinimide.
  • Other activator-toning agents which can be employed include phthalazinone, 2- ace tylphthalazinone, and the like.
  • Typical image stabilizers or stabilizer precursors are described, for example, in Belgian Pat. No. 768,071 issued July 30, 1971.
  • Typical stabilizer precursors include, for example, azothioethers and blocked azole thione stabilizer precursors as de scribed in this Belgian patent and the stabilizers described in U.S. Pat. No. 3,707,377 issued Dec. 26, 1972.
  • a photographic element, especially a photothermographic element, as described according to the invention can contain various colloids alone or in combination as vehicles, binding agents and in various layers, including the described protective layer.
  • Suitable materials can be hydrophobic or hydrophilic depending on the particular means of processing employed. They are transparent or translucent and include both naturallyoccurring substances such as proteins, for example, 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(vinyl pyrrolidone), acrylamide polymers and the like.
  • Other synthetic polymeric compounds which can be employed include dispersed vinyl compounds such as in latex form and particularly those which increase dimensional stability of photographic materials.
  • Effective polymers include water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates, methacrylates and those which have cross-linking sites which facilitate hardening or curing as well as those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054.
  • Especially useful high molecular weight materials and resins include poly(vinyl butyral), cellulose acetate butyrate, poly(methyl methacrylate), poly(vinyl pyrrolidone), ethylcellulose, polystyrene, poly(vinyl chloride), chlorinated rubber, polyisobutylene, butadiene-styrene copolymers, vinyl chloridevinyl acetate copolymers, copolymers of vinyl acetate, vinyl chloride and maleic acid andpolyvinyl alcohol.
  • the photosensitive silver halide employed in the described photothermographic elements can be prepared ex situ, that is, away from other components of the photothermographic materials, and/or in situ,
  • the photosensitive silver halide can be prepared in situ such as described in U.S. Pat. No. 3,457,075 of Morgan et a1. issued July 22, 1969.
  • the photosensitive layers and other layers according to the invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. No. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as described in U.S. Pat. No. 2,761,791 of Russell issued Sept. 4, 1956 and British Pat. No. 837,095.
  • Spectral sensitizing dyes can be used in the described photographic elements and photothermographic elements of the invention to confer additional sensitivity to the elements of the inveniton.
  • Useful sensitizing dyes are described, for example, in the Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107-110, paragraph XV.
  • Photographic elements according to the invention containing the described protective layer can be processed by various methods including processing in alkaline solutions containing conventional developing agents and by processing by other means as described in the Product Licensing Index, Vol. 92, December, 1971, publication 9232, pages 107-110, paragraph XXIII.
  • the protective layers employed according to the invention can be provided in elements designed for color photography, for example, elements containing colorforming couplers or elements to be developed in solutions containing color-forming couplers; or in so-called false sensitized color materials such as described in U.S. Pat. No. 2,763,549 of Hansen issued Sept. 18, 1956.
  • the resulting latent image can be developed merely by heating the element to moderately elevated temperatures. This merely involves heating the described photothermographic element overall to about C. to about 250C. such as for about 0.5 seconds to about 60 seconds. By increasing or decreasing the length of time of heating, a higher or lower temperature within the described range can be employed depending upon the desired image.
  • a developed image is typically produced within several seconds, such as about 0.5 seconds to about 60 seconds.
  • the heating means can be, for example, a simple hot plate, iron or roller; or hot air convection heating means; or dielectric heating means.
  • the photothermographic element containing the protective layer of the invention can be contacted with the heating means with the protective layer contacting the heating means directly.
  • one or more components of the photographic element, or photothermographic element can be in one or more layers of the element.
  • a photothermographic element is prepared as follows:
  • a silver behenate dispersion designated as dispersion A, is prepared by ball-milling the following components for 72 hours:
  • a photothermographic composition is prepared by combining 639 ml. of dispersion A with the following components in the order indicated:
  • This photothermographic composition is coated at 6.0 g. of photothermographic composition per 929 square centimeters on a paper support. The coverage corresponds to 6.46 mg. of silver per dm
  • the resulting photothermographic element is overcoated with a dichloromethane-methanol solution (19:1 by volume) containing 5% by weight of a copolymer of (i) terephthalic acid, (ii) 3,3,3,3'-tetramethyll,1'-spirobi[indan] 6,6-diol and (iii) bisphenol A.
  • This copolymer has a glass transition temperature of 254C. and is represented by the formula:
  • the resulting, overcoated photothermographic element is not susceptible to fingerprint marks and abrasion, exhibits no surface cracking or reticulation, and exhibits no surface bubbling.
  • the copolymer is amorphous and is more than 5% by weight soluble in organic solvents such as methylene chloride, chloroform, 1,1,2-trichl0roethane, acetone, 2-pentanone, ethyl acetate and toluene. No adverse sensitometric effects are observed in the photothermographic element as a result of the copolymer overcoat.
  • EXAMPLE 2 This is a comparative example.
  • Example 1 The procedure set out in Example 1 is repeated with the exception that the photothermographic element is not overcoated with the described copolymer of Example l.
  • the resulting developed image is neutral (jet black) with a beige background.
  • the element is susceptible to abrasion and fingerprinting which becomes visible upon room-light exposure, such as after 1 week storage under -foot candles of light and 80% relative humidity.
  • EXAMPLE 3 The procedure set out in Example 1 is repeated except that silica particles are mixed with the described polyester before overcoating the photothermographic element to provide an overcoat containing 10 mg. of silica per 929 square centimeters of support.
  • the silica particles have an average particle size of 0.001 to 0.10 microns.
  • Example 2 The procedure set out in Example 1 is repeated except that a copolyester (Tg is 127C.) represented by the formula:
  • R 1 In a photothermographic element having a protec- 23 tive layer, the improvement comprising as said protective layer a. carboxylic polyester having a glass transi- R R tion temperature of at least 190C. represented by the R 2].
  • formulazh 10 wherein I 1. R and R are the same or different and are each- 0 A O C Q C hydrogen or alkyl containing 1 to 12 carbon u H atoms, 0 0 ii.
  • R R R R R R R, R and R are the same or different and are each alkyl having 1 to F" 6 carbon atoms;
  • A is a radical selected from the group consisting of 3 ⁇ 3 a. a radical represented by the formula: 25
  • R R R and R are the same or different and e a radlcal represented by the formu a each are hydrogen, halogen or alkyl containing 1 0 to 4 carbon' atoms, 7 ii.
  • R is a bivalent polycyclic radical selected from the group consisting of Z-norbornylidene, hexahydro-4,7-methanoindane-5-ylidene, decahydro- 3 3 l,4:5,8-dimethanonaphth-2-ylmethylene, octah- 4O ydro-4,7-methanoisobenzofuran-6-ylidene, bicyand Clo [321] ocglylidenes and tricycle f.
  • X is a radical selected from the group consisting of designated radicals (a) through (f) and g. a radical represented by the formula: I
  • I Lt i. R and R are the same or different and each are R R hydrogen or alkyl containing 1 to 6 carbon atoms; wherein ii. R is alkyl containing 1 t 6 carbon atoms; i. R and R are the same or different and each are iii. R, R, R and R are the same or different hydrogen, aryl containing 6 to 20 carbon atoms,
  • aryl containing 6 to 12 halogen, nitro, amino, cyano or alkoxy containcarbon atoms, halogen, nitro, cyano, amino or ing Ho 5 carbon atoms; alkoxy containing 1 to 4 carbon atoms; ii. R and R are the same or different and each are c. a radical represented by the formula: hydrogen, aryl containing 6 to 20 carbon atoms,
  • R and R are the same or different and each are hydrogen, alkyl containing 1 to 6 carbon atoms, cycloalkyl containing 4 to 6 carbon atoms, or aryl containing 6 to carbon atoms, or R and R taken together with the carbon atom to which they are bonded can be a monocyclic, bicyclic or heterocyclic moiety containing 4 to 7 atoms in the ring;
  • a photothermographic element having a protective overcoat layer
  • the improvement comprising as said protective, overcoat layer a carboxylic polyester having a glass transition temperature of at least. 200C. represented by the formula:
  • a photothermographic element as in claim 1 wherein said protective layer comprises about 50 mg. to about 300 mg. of said carboxylic polyester per 929 square centimeters of support.
  • a photothermographic element having thereon a protective layer wherein said photothermographic element comprises a support and a. an oxidation-reduction image-forming combination comprising i. silver behenate with ii. a sulfonamidophenol reducing agent,
  • an activator-toning agent comprising N- hydroxynaphthalimide
  • a protective layer the improvement wherein said protective layer is a copolymer of (i) terephthalic acid, (ii) 3,3,3,3-
  • a process of developing an image in a photothermographic element having thereon a protective overcoat layer comprising a carboxylic polyester as defined in claim 1 comprising heating said element from about C. to about 250C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Polyesters Or Polycarbonates (AREA)
US38593473 1973-08-06 1973-08-06 Protective layer for photothermographic elements Expired - Lifetime US3856526A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US38593473 US3856526A (en) 1973-08-06 1973-08-06 Protective layer for photothermographic elements
CA204,153A CA1031617A (fr) 1973-08-06 1974-07-05 Couche protectrice pour elements photosensibles et methode de fabrication
FR7426353A FR2240467B1 (fr) 1973-08-06 1974-07-30
GB3442774A GB1458737A (en) 1973-08-06 1974-08-05 Heat-processable photographic material
BE147338A BE818544A (fr) 1973-08-06 1974-08-06 Produit photographique thermodeveloppable comprenant une coucheprotectrice et procede pour developper a chaud ce produit

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US38593473 US3856526A (en) 1973-08-06 1973-08-06 Protective layer for photothermographic elements

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BE (1) BE818544A (fr)
CA (1) CA1031617A (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3893860A (en) * 1974-07-16 1975-07-08 Eastman Kodak Co Photothermographic element and process
US3997346A (en) * 1973-09-11 1976-12-14 Fuji Photo Film Co., Ltd. Method for stabilizing the image of a thermally developable photosensitive material
US4021245A (en) * 1974-04-30 1977-05-03 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4022622A (en) * 1972-11-22 1977-05-10 Agfa-Gevaert N.V. Dispersing polymeric particles in aqueous medium for coating silver halide emulsion layers
US4123282A (en) * 1975-09-08 1978-10-31 Minnesota Mining And Manufacturing Company Photothermographic toners
US4199615A (en) * 1974-09-18 1980-04-22 Energy Conversion Devices, Inc. Dry-process imaging film and method
US4463162A (en) * 1980-12-09 1984-07-31 Asahi-Dow Limited Polynuclear fused aromatic ring type polymer and preparation thereof
US4552949A (en) * 1983-10-21 1985-11-12 General Electric Company Polycarbonate of spiro dihydric phenol
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US6436616B1 (en) 1994-11-16 2002-08-20 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
EP1246002A3 (fr) * 2001-03-30 2003-10-22 Eastman Kodak Company Matériaux pour l'enregistrement d'images développables à la chaleur contentant une couche barrière en polyester
US20030203322A1 (en) * 1994-11-16 2003-10-30 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
US6746831B1 (en) 2003-01-27 2004-06-08 Eastman Kodak Company Thermally developable imaging materials with barrier layer containing a cellulose ether polymer
US20060004151A1 (en) * 2004-06-30 2006-01-05 General Electric Company Copolymers containing indan moieties and blends thereof

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US3079837A (en) * 1959-03-18 1963-03-05 Agfa Ag Protective coatings for photographic films
US3190197A (en) * 1960-08-11 1965-06-22 Eastman Kodak Co Protective colloidal silica lacquer for developed photographic prints
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US3656954A (en) * 1969-03-17 1972-04-18 Agfa Gevaert Nv Photographic material with improved surface properties
US3725070A (en) * 1971-05-07 1973-04-03 Eastman Kodak Co Photographic element comprising film forming polymeric support
US3769264A (en) * 1971-11-01 1973-10-30 Eastman Kodak Co Film forming condensation polymers
US3772405A (en) * 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby
US3793249A (en) * 1971-06-30 1974-02-19 Eastman Kodak Co Polyesters of 2,2'-spirobi(chroman)diols
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Publication number Priority date Publication date Assignee Title
US3079837A (en) * 1959-03-18 1963-03-05 Agfa Ag Protective coatings for photographic films
US3190197A (en) * 1960-08-11 1965-06-22 Eastman Kodak Co Protective colloidal silica lacquer for developed photographic prints
US3317466A (en) * 1961-09-14 1967-05-02 Eastman Kodak Co Three-dimensional polycyclic bisphenol polycarbonates and polyesters
US3656954A (en) * 1969-03-17 1972-04-18 Agfa Gevaert Nv Photographic material with improved surface properties
US3634089A (en) * 1969-04-04 1972-01-11 Eastman Kodak Co Film-forming polyester compositions
US3657185A (en) * 1970-04-02 1972-04-18 Minnesota Mining & Mfg Copolymers of phenylindan dicarboxylic acid and an aromatic dihydroxy compound
US3725070A (en) * 1971-05-07 1973-04-03 Eastman Kodak Co Photographic element comprising film forming polymeric support
US3793249A (en) * 1971-06-30 1974-02-19 Eastman Kodak Co Polyesters of 2,2'-spirobi(chroman)diols
US3803096A (en) * 1971-09-13 1974-04-09 Eastman Kodak Co Polyesters from hydroxymethyl-phenylindans
US3769264A (en) * 1971-11-01 1973-10-30 Eastman Kodak Co Film forming condensation polymers
US3772405A (en) * 1972-02-02 1973-11-13 Eastman Kodak Co Process for preparing aromatic diester containing copolyesters and products obtained thereby

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4022622A (en) * 1972-11-22 1977-05-10 Agfa-Gevaert N.V. Dispersing polymeric particles in aqueous medium for coating silver halide emulsion layers
US3997346A (en) * 1973-09-11 1976-12-14 Fuji Photo Film Co., Ltd. Method for stabilizing the image of a thermally developable photosensitive material
US4021245A (en) * 1974-04-30 1977-05-03 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US3893860A (en) * 1974-07-16 1975-07-08 Eastman Kodak Co Photothermographic element and process
US4199615A (en) * 1974-09-18 1980-04-22 Energy Conversion Devices, Inc. Dry-process imaging film and method
US4123282A (en) * 1975-09-08 1978-10-31 Minnesota Mining And Manufacturing Company Photothermographic toners
US4463162A (en) * 1980-12-09 1984-07-31 Asahi-Dow Limited Polynuclear fused aromatic ring type polymer and preparation thereof
US4552949A (en) * 1983-10-21 1985-11-12 General Electric Company Polycarbonate of spiro dihydric phenol
US5928857A (en) * 1994-11-16 1999-07-27 Minnesota Mining And Manufacturing Company Photothermographic element with improved adherence between layers
US6436616B1 (en) 1994-11-16 2002-08-20 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
US6599686B2 (en) 1994-11-16 2003-07-29 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
US20030203322A1 (en) * 1994-11-16 2003-10-30 Eastman Kodak Company Photothermographic element with reduced woodgrain interference patterns
EP1246002A3 (fr) * 2001-03-30 2003-10-22 Eastman Kodak Company Matériaux pour l'enregistrement d'images développables à la chaleur contentant une couche barrière en polyester
US6746831B1 (en) 2003-01-27 2004-06-08 Eastman Kodak Company Thermally developable imaging materials with barrier layer containing a cellulose ether polymer
US20060004151A1 (en) * 2004-06-30 2006-01-05 General Electric Company Copolymers containing indan moieties and blends thereof

Also Published As

Publication number Publication date
BE818544A (fr) 1975-02-06
CA1031617A (fr) 1978-05-23

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