EP0497053A1 - "Dry-silver"-Konstruktionen - Google Patents

"Dry-silver"-Konstruktionen Download PDF

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Publication number
EP0497053A1
EP0497053A1 EP91311801A EP91311801A EP0497053A1 EP 0497053 A1 EP0497053 A1 EP 0497053A1 EP 91311801 A EP91311801 A EP 91311801A EP 91311801 A EP91311801 A EP 91311801A EP 0497053 A1 EP0497053 A1 EP 0497053A1
Authority
EP
European Patent Office
Prior art keywords
silver
photographic material
material according
image forming
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91311801A
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English (en)
French (fr)
Inventor
David C. c/o Minnesota Mining and Weigel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0497053A1 publication Critical patent/EP0497053A1/de
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers

Definitions

  • the present invention relates to dry silver photothermographic imaging materials and to certain anti-foggants used therein.
  • Silver halide photothermographic imaging materials often referred to as "dry silver" compositions because no liquid development is necessary to produce the final image, have been known in the art for several years. See, for example, U.S. Pat. Nos. 3,457,075 and 3,839,049. These imaging materials typically contain a light insensitive material, a light sensitive material which generates silver when irradiated, and a reducing agent for silver ion.
  • the light sensitive material is generally photographic silver halide which must be in catalytic proximity to the light insensitive silver source.
  • catalytic proximity can be defined as an intimate physical association of these two materials, so that where silver nuclei or specks are generated by the irradiation or light exposure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent.
  • silver is a catalyst for the reduction of silver ions and the silver-generating light sensitive halide catalyst progenitor may be placed into catalytic proximity with the silver source in a number of different fashions, such as partial metathesis of the silver source with a halogen-containing source (e.g., see U.S. Pat. No. 3,457,075); coprecipitation of the silver halide and silver source material (e.g., see U.S. Pat. No. 3,839,049), and any other method which intimately associates the silver halide and the silver source.
  • a halogen-containing source e.g., see U.S. Pat. No. 3,457,075
  • coprecipitation of the silver halide and silver source material e.g., see U.S. Pat. No. 3,839,049
  • the light insensitive, reducible silver source used in this area of technology is a material which contains silver ions.
  • the earliest and still preferred source comprises silver salts of long chain carboxylic acids, usually of from 10 to 30 carbon atoms.
  • the silver salt of behenic acid or mixtures of acids of like molecular weight have been primarily used. Salts of other organic acids or other organic materials such as silver imidazolates have been proposed and U.S. Patent No. 4,260,677 discloses the use of complexes of inorganic or organic silver salts as image source materials.
  • the latent image In both photographic and photothermographic emulsions, exposure of the silver halide to light produces small clusters of silver atoms. The imagewise distribution of these clusters is known in the art as the latent image. This latent image generally is not visible by ordinary means and the light sensitive article must be further processed in order to produce a visual image. The visual image is produced by the catalytic reduction of silver ions which are in catalytic proximity to the specks of the latent image.
  • one or both of the foregoing compounds are employed in an amount of from about 1-10 wt%, and most preferably in an amount of from about 5 wt% based upon the total weight of the image forming system.
  • the heat-developable dry silver construction will also comprise a light insensitive silver source material; a light sensitive silver halide; a reducing agent for silver ion; and a binder.
  • the light insensitive silver source material ordinarily may be any material which contains a reducible source of silver ions.
  • Silver salts of organic acids, particularly long chain (10 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred in the practice of the present invention.
  • Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also useful in the present invention.
  • the silver source material should constitute from about 20 to 70 percent by weight of the image forming system. Preferably, it is present as 30 to 55 percent by weight.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc., and may be added to the article in any fashion which places it in catalytic proximity to the silver source.
  • the silver halide is generally present as 0.75 to 15 percent by weight of the image forming system, although larger amounts are useful. It is preferred to use from 1 to 10 percent by weight silver halide in the image forming system and most preferred to use from 1.5 to 7.0 percent.
  • the silver halide may be provided by in situ halidization or by the use of preformed silver halide.
  • sensitizing dyes for the silver halide is particularly desirable. These dyes can be used to match the spectral response of the emulsions to the spectral emissions of intensifier screens. It is particularly useful to use J-banding dyes to sensitive the emulsion as disclosed in U.S. Patent No. 4,476,220.
  • the reducing agent for silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver.
  • Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful, but hindered phenol reducing agents are preferred.
  • the reducing agent should be present as 1 to 20 percent by weight of the image forming system. In a two-layer construction, if the reducing agent is in the second layer, slightly higher proportions of from about 2 to 20 percent tend to be more desirable.
  • the binder may be selected from any of the well-known natural and synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are, of course, included in these definitions.
  • the polyvinyl acetals, such as polyvinyl butyral and polyvinyl formal, and vinyl copolymers, such as polyvinyl acetate/chloride are particularly desirable.
  • the binders are generally used in a range of from 20 to 75 percent of the image forming system.
  • Toners such as phthalazinone, phthalazine and phthalic acid are not essential to the construction, but are highly desirable. These materials may be present, for example, in amounts of from 0.2 to 5 percent by weight of the image forming system.
  • the above-disclosed light sensitive composition can be coated on a support chosen from various kinds of materials in the form of a single layer or a multilayer to complete it as a heat-developable photographic material.
  • a support chosen from various kinds of materials in the form of a single layer or a multilayer to complete it as a heat-developable photographic material.
  • Specific examples of such a support include various kinds of polymer materials, glass, wool cloth, cotton cloth, paper, metals (e.g. aluminum) and so on.
  • materials capable of being worked upon a flexible sheet or roll are particularly preferable for the application to information recording materials from the handling point of view.
  • Most suitable examples of the support in this invention include plastic films (e.g.
  • a cellulose acetate film a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, a triacetate film, and a polycarbonate film
  • papers e.g., plain paper, photographic raw paper, printing raw papers such as coated paper and art paper, baryta paper, resin-coated paper, pigment paper containing pigment like titanium dioxide, and paper sized with polyvinyl alcohol).
  • auxiliary layers e.g., a metal evaporated layer described in U.S. Pat. No. 3,748,137; a backing layer described in British Pat. No. 1,507,991 or Japanese Patent Application (OPI) Nos. 43130/76 or 129220/76; a backing layer containing a magnetic material described in Japanese Patent Application (OPI) No. 136099/75; an antistatic layer; and a subbing layer described in Japanese Patent Application (OPI) No. 87721/78 can be coated. Further, it is of great advantage to provide an overcoating polymer layer, as described in U.S. Pat. Nos.
  • a suitable thickness of the overcoating polymer layer ranges from about 1 micron to about 20 microns.
  • Suitable examples of the polymer for the overcoating layer include those described in each specification cited above as the polymers for the overcoating polymer layer.
  • polyvinyl chloride polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polystyrene, methyl cellulose, ethyl cellulose, cellulose acetate butyrate, vinyl chloride-vinylidene chloride copolymer, carboxylic acid esters, cellulose diacetate, polyvinylidene chloride polycarbonate, gelatin, and polyvinyl alcohol are particularly preferable.
  • additives known in the art of heat-developable photographic materials for example, a plasticizer, a matting agent, a surface active agent, a sensitizer, a brightening agent, a light absorbing agent, a filter dye, an antihalation dye, color couplers, a hardener, a lubricant, a development accelerating agent, and a stabilizer can be incorporated.
  • a plasticizer for example, a plasticizer, a matting agent, a surface active agent, a sensitizer, a brightening agent, a light absorbing agent, a filter dye, an antihalation dye, color couplers, a hardener, a lubricant, a development accelerating agent, and a stabilizer
  • OPI Japanese Patent Application
  • An organic silver salt prepared using one of the known methods is optionally washed with water, an alcohol or the like and then mixed with a light sensitive silver halide to make a mixture in which both are present in a close contact state.
  • a silver halide and an organic silver salt may be produced at the same time.
  • a part of an organic silver salt is converted into silver halide using a silver halide forming component.
  • sensitizing dyes it is preferable to add the sensitizing dyes in the form of a solution after the above-described mixing step to the resulting mixture.
  • the mixture of the organic silver salt and silver halide is desirably prepared in the form of a polymer dispersion in a solution of a polymer which can function as the binder afterward.
  • This polymer can be added in any of the steps, such as the step of preparing the organic silver salt, the step of mixing with the silver halide or the step of preparing the silver halide.
  • the polymer dispersion of the organic silver salt and the silver halide is molded in a film or coated in a layer on a support, and other components of this invention may be incorporated into that film or a layer provided on that layer.
  • a reducing agent and binder are added to the above-described polymer dispersion of the organic silver salt and the silver halide to prepare a heat-developable photographic composition, and the resulting composition is poured and spread into a film or coated in a layer on a support using a known method.
  • various kinds of coating methods for example, a dip coating method, an air knife coating, a curtain coating method, and a hopper coating method can be employed.
  • auxiliary layers for example, a subbing layer, an overcoating layer, etc.
  • auxiliary layers for example, a subbing layer, an overcoating layer, etc.
  • auxiliary layers can be optionally coated on prior to, simultaneously with or subsequently to the coating of the heat-developable photographic composition using a similar method to one of the above-described methods.
  • Solvents to be used for the coating solutions may be arbitrarily selected. For instance, noncombustible solvents as described in British Pat. No. 1,422,145 can be used.
  • printing can be carried out on the surface or the back of the support, or on a layer provided on the support. Therefore, the materials of this invention on which prescribed patterns are printed can be applied to a (season) ticket, a postcard and other correspondence.
  • the thus prepared heat-developable photographic material is cut in a size suitable for use and subjected to imagewise exposure.
  • Preheating up to 80°C-140°C
  • Suitable light sources for imagewise exposure include a tungsten lamp, a fluorescent lamp for a copier as used mainly for exposure of diazo type light-sensitive materials, a mercury lamp, an iodine lamp, a xenon lamp, a cathode ray tube (CRT) light source, a laser light source, etc.
  • CTR cathode ray tube
  • Printing may be carried out using a contact printing method as an original is superposed directly on the photographic material, or using a reflection printing method or an enlarging printing method.
  • a suitable exposure is determined depending upon the sensitivity of the photographic material used. It is about 1 lux. sec. in the case of high-speed photographic materials, and about 103 lux. sec. in the case of low-speed ones.
  • the thus imagewise exposed photographic material can be developed only by heating (at a temperature higher than about 80°C, and most preferably ranging from about 100°C to about 150°C).
  • the printing time is adjusted to a value within the range of 1 sec. to 60 sec. It is preferably determined depending upon the heating temperature adopted. Usually, about 5 sec. to about 40 sec. are suitable for 120°C; about 2 sec.
  • Heating may be carried out using various means.
  • the photographic material may be simply made to come into contact with a hot plate or drum, or may be made to pass through a heated space as circumstances require.
  • a high frequency wave-induced heating means, or a laser beam-induced heating means may be adopted.
  • a dispersion of silver behenate half soap was prepared at 15% solids in ethanol by homogenization. This dispersion was then prepared for coating by the addition of more solvent, halide, resin and sensitizing dye.
  • the following silver soap dispersion was used: 165 grams of the 15% silver soap dispersion was mixed with 0.1 grams of ButvarTM B-72 (Monsanto) polyvinyl butyral. 325 grams of ethyl alcohol was added and mixed until homogeneous. 6 ml. of 0.1 mole zinc bromide dissolved in 20 ml of methyl alcohol was added. An additional 26 g of ButvarTM B-72 was added with mixing and 1.0 g of 3M fluorochemical FC431 (3M) was added as a coating aid.
  • Example 1 was repeated except that to 20 g of the dispersion, 0.15 grams of a magenta developer dye, 0.2 g of phthalazinone, and 0.3g of 1,2,3-benzotriazin-4(3H)-one along with a green merocyanine sensitizing dye were added. A magenta image having a Dmin of 0.11 and a Dmax of 1.58 to the green filter of the MacBeth densitometer was produced.
  • Example 1 was repeated except that to the 20 g of silver dispersion, was added 0.3 g of 3'5'-ditertbutyl-4'-hydroxybenzoyl-3,7-di(n,n-diethylamino)-oxazine (a cyan dye developer), 0.2 g of 4-methyl-phthalic acid, and 0.05 grams of 1,2,3-benzotriazin-4(3H)-one along with a red merocyanine sensitizing dye. This produced a cyan imaging giving a Dmin of 0.18 and a Dmax of 2.04 to the red filter of the MacBeth densitometer when processed as in Example 1.
  • a cyan dye developer 3'5'-ditertbutyl-4'-hydroxybenzoyl-3,7-di(n,n-diethylamino)-oxazine
  • 4-methyl-phthalic acid 0.2 g
  • 1,2,3-benzotriazin-4(3H)-one along with a red merocyan
  • Example 1 was repeated except that to 20 grams of the silver dispersion a black and white developer, 0.3 grams Nonox W50, 0.2 grams phthalazinone, and 0.07 grams of 1,2,3-benzotriazin-4(3H)-one were added. When coated and processed the same as in Example 1, a black image with a Dmin of 0.13 and a Dmax of 1.5 to the neutral density filter of a MacBethTM densitometer was produced.
  • Example 1 was repeated except that to 20 grams of the silver dispersion was added 0.15 gram of 3',5'-dimethoxy-4'-hydroxy-propiophenone yellow developer, 0.5 gram of phthalazinone and 0.05 gram of 1-hydroxy-benzotriazole hydrate (Aldrich Chemical). After coating and processing as in Example 1, a blue filter on the MacBethTM densitometer produced a Dmin of 0.28 and a Dmax of 1.24. A sample made the same way as Example 5, except that no 1-hydroxy-benzotriazole hydrate was used, fogged upon processing giving no image.

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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)
EP91311801A 1991-01-28 1991-12-19 "Dry-silver"-Konstruktionen Withdrawn EP0497053A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64637091A 1991-01-28 1991-01-28
US646370 1991-01-28

Publications (1)

Publication Number Publication Date
EP0497053A1 true EP0497053A1 (de) 1992-08-05

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EP91311801A Withdrawn EP0497053A1 (de) 1991-01-28 1991-12-19 "Dry-silver"-Konstruktionen

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EP (1) EP0497053A1 (de)
JP (1) JPH04310945A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0654703A1 (de) * 1993-11-19 1995-05-24 Minnesota Mining And Manufacturing Company Thiosulfonatester als Antischleiermitter, Haltbarkeitsstabilisatoren und Nachbehandlungsstabilisatoren für photothermographische Elemente
EP0741319A1 (de) * 1995-05-04 1996-11-06 Du Pont De Nemours (Deutschland) Gmbh Photothermographisches lichtempfindliches Aufzeichnungsmaterial mit verminderten Schleier

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS554060A (en) * 1978-06-27 1980-01-12 Asahi Chem Ind Co Ltd Dry type image forming material
EP0194025A1 (de) * 1985-02-01 1986-09-10 Minnesota Mining And Manufacturing Company Photothermographische Toner
EP0204197A2 (de) * 1985-05-17 1986-12-10 Fuji Photo Film Co., Ltd. Verfahren zur Behandlung eines farbphotographischen Silberhalogenidmaterials
US4728600A (en) * 1985-04-17 1988-03-01 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS554060A (en) * 1978-06-27 1980-01-12 Asahi Chem Ind Co Ltd Dry type image forming material
EP0194025A1 (de) * 1985-02-01 1986-09-10 Minnesota Mining And Manufacturing Company Photothermographische Toner
US4728600A (en) * 1985-04-17 1988-03-01 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive material
EP0204197A2 (de) * 1985-05-17 1986-12-10 Fuji Photo Film Co., Ltd. Verfahren zur Behandlung eines farbphotographischen Silberhalogenidmaterials

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 4, no. 31 (P-2)(513) 18 March 1980 & JP-A-55 004 060 ( ASAHI KASEI KOGYO K.K. ) 12 January 1980 *
STURGE,WALWORTH,SHEPP (EDS.) 'Imaging Processes and Materials, Rev. 8th Ed. of Neblette's Handbook of Photography and Reprography' 1989 , VAN NOSTRAND REINHOLD , NEW YORK, US *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0654703A1 (de) * 1993-11-19 1995-05-24 Minnesota Mining And Manufacturing Company Thiosulfonatester als Antischleiermitter, Haltbarkeitsstabilisatoren und Nachbehandlungsstabilisatoren für photothermographische Elemente
EP0741319A1 (de) * 1995-05-04 1996-11-06 Du Pont De Nemours (Deutschland) Gmbh Photothermographisches lichtempfindliches Aufzeichnungsmaterial mit verminderten Schleier

Also Published As

Publication number Publication date
JPH04310945A (ja) 1992-11-02

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