US3347675A - Solid homogeneous compositions containing silver halide processing agents - Google Patents

Solid homogeneous compositions containing silver halide processing agents Download PDF

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US3347675A
US3347675A US465081A US46508165A US3347675A US 3347675 A US3347675 A US 3347675A US 465081 A US465081 A US 465081A US 46508165 A US46508165 A US 46508165A US 3347675 A US3347675 A US 3347675A
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silver halide
processing
grams
emulsion
carrier
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Richard W Henn
David W Miller
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US465081A priority Critical patent/US3347675A/en
Priority to FR64967A priority patent/FR1482773A/fr
Priority to BE682412D priority patent/BE682412A/xx
Priority to DE19661547704 priority patent/DE1547704A1/de
Priority to GB27545/66A priority patent/GB1155948A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D9/00—Diffusion development apparatus
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/261—Non-bath processes, e.g. using pastes, webs, viscous compositions
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/383—Developing-fixing, i.e. mono-baths
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4006—Development by heat ; Photo-thermographic processes using materials covered by the groups G03C8/04 - G03C8/06

Definitions

  • This invention concerns a dry photographic processing method, more particularly, the use of a solid homogeneous composition containing a processing agent to develop or otherwise process an exposed light-sensitive silver halide emulsion.
  • Photographic materials normally require processing with a developing agent after which the light-sensitive element must then be treated to render it insensitive to light.
  • Most of the processing systems involve the use of liquid baths such as aqueous alkaline solutions of a reducing agent as a developer followed by a fixing bath using a silver halide complexing agent.
  • liquid baths such as aqueous alkaline solutions of a reducing agent as a developer followed by a fixing bath using a silver halide complexing agent.
  • Land U.S. 2,616,804 describes viscous developers which contain suflicient moisture for processing.
  • the viscous method is essentially a liquid method and requires a pod or similar method when applying the liquid material to the exposed element.
  • the heat is merely used to evaporate the moisture from the surface of the photographic element.
  • German patent application 1,003,578 uses moisture released from water of crystallization.
  • the use of moisture released from water of crystallization results in unavoidably leaving a crystal pattern in the photographic element.
  • the process is difficult to control since crystal hydrates tend to decompose when exposed to air.
  • a further disadvantage of crystalline hydrates is that when stored under cyclic temperature conditions in the presence of excess moisture, as in a gelatin layer, solution and recrystallization tend to occur, resulting in the formation of very coarse crystal patterns.
  • the same deficiencies apply to heterogeneous mixtures of crystalline material.
  • One object of this invention is to provide solid processing components having a high degree of storage stability and ease in processing exposed photographic mate rial. Another object is to provide a method of dry processing exposed photographic materials. A further object is to provide a homogeneous material containing a fixed amount of moisture uniformly dispersed in the solid material which may contain a processing agent such as a silver halide developer, a fixing agent, etc. A still further object is to provide a solid block processing method which can be used with the employment of heat. Another object is to provide a processing web containing solid material having dispersed therein processing agents. Still another object is to provide a dry processing method which is subject to use with automated equipment.
  • the above objects are obtained by utilizing a fusible carrier material forming a composition solid at room temperature (about 20 C.) and melting below about C., having incorporated therein water and one or more processing agents such as a developer, stabilizer, activator, fixing agent, etc.
  • the carrier materials useful in our invention are chosen on the basis of their forming homogeneous compositions with the silver halide processing agents to be incorporated therein.
  • these compositions melt between 20 C. and 115 C.
  • the composition formed from the carrier materials and the processing agents must be fusible, that is, must melt without decomposing such that a homogeneous layer of solution will be formed on the surface of such solid compositions when they are subjected to heat, as by contact with an externally heated surface, or heat generated at the surface by friction as in rubbing, twisting, etc. Further the carrier materials must be miscible with water, such that sufficient ionization of the processing agents may occur.
  • the carrier materials most useful in our invention are alkylene oxide polymers known also as polyglycols.
  • a polyethylene glycol having an average molecular weight of about 4,000 is sold as Carbowax 4000 by Union Carbide Company.
  • Other alkylene oxide polymers having molecular weights from 1,500 to 20,000 or greater can also be used.
  • the alkylene oxide polymers may be modified without destroying their usefulness for this process, provided that the modified material is compatible with useful proportions of water and of the processing chemicals.
  • mixed ethylene oxides and propylene oxide polymers may be employed, or derivatives such as esters, ethers, amides, etc. may also be used.
  • a partial list of such derivatives is as follows:
  • Oleic ester polyethylene oxide-1000 Oleic ester polyethylene oxide-1000
  • Pluronic F38 (a polypropylene oxide-polyethylene oxide block polymer) sold by Wyandotte Chem. Corp.
  • Polyethoxyethyl-bis-carboglutamic acid (Na salt)
  • Other materials which are solid at room temperature and will form processing compositions having melting points below 115 C. include specific compounds, complexes, eutectics or mixtures of two or more compounds.
  • the preferred carrier materials are compatible with the processing chemicals and Water present to give a homogeneous mixture, and do not interfere with the reaction.
  • Beeswax. and monostearin have been successfully employed as carriers. Or-
  • ganic acids melting in the correct range may be used as carriers for stop baths, fixing and stabilizing baths, etc.
  • Particularly useful carrier materials are polar compounds having high dielectric constants containing the electron withdrawing groups -SO:- and -CO- and may be represented by the following formulas:
  • the carrier material may be used to form a complex with hydroquinone by heating the carrier material with hydroquinone and using the complex wherever the carrier material is used by itself.
  • This is a particularly advantageous method of incorporating the material, since materials which are liquid at room temperature but which form complexes which are solid at room temperature can be used.
  • Liquids which can be used include N-methyl-pyrrolidinone, acetylrnorpholine, etc.
  • the complex releases hydroquinone upon heating sufl'iciently to develop an exposed emulsion.
  • the solid material is coated in a thin layer of about 0.001 to 0.003-inch thickness on a support which is to be contacted against the silver halide emulsion.
  • a preferred coverage for the carrier material is about 1-2 g./ft. but a larger amount may be used with a binder, provided the carrier material to hinder ratio is from about 2:1 to 8:1.
  • this layer is coated over a nucleated receiving support, whereas, when used in the colloid transfer process, it is coated over an untreated receiver sheet or one which has thereon a fogging agent to increase the density of the transferred image.
  • the exposed silver halide emulsion is contacted against a nucleated receiving sheet having the overcoat of this invention and containing therein a silver halide developer and a silver'halide solvent.
  • This sandwich is then heated to a temperature sufficient to melt the carrier material for a sufficient time for the emulsion to develop and the positive image to form in the nucleated layer.
  • Supercooling occurs, so that the carrier material remains liquid for some time after the melted layer has been cooled back to room temperature, facilitating removal of the recceiving sheet from the emulsion layer.
  • the receiving sheet is separated from the emulsion revealing a positive image.
  • the tanning silver halide developer is hardened emulsion on the receiving support. Successive copies can then be made.
  • the colloidal material which may be used in the diffusion transfer process as a vehicle for the light sensitive silver halide may be any of those capable of swelling, which can be used in photographic emusions such as gelatin, polyvinyl alcohol, methyl cellulose, polyacrylamide, copolymer of ethylacrylate and acrylic acid, cellulose ether phthalate, albumin, collodion, etc.
  • the vehicle used in the colloid transfer process is a colloid which can be hardened by a tanning silver halide developer.
  • the carrier material is preferably coated together on the support with a suitable film-forming binder to provide suitable adhesion to the support.
  • binders such as for example, a copolymer of ethylene and maleic acid, cellulose ethers such as ethyl cellulose, cellulose esters such as cellulose acetate butyrate and cellulose acetate containing approximately 33% acetyl, poly-N,N-diethylacrylamide, a copolymer of vinyl pyrrolidone and vinyl acetate, a copolymer of styrene and butadiene, proteins, such as casein and the like, etc., providing the binders are water permeable.
  • silver halide processing agents we means to include those chemicals commonly used for developing, activating, acidifying, fixing, stabilizing, toning, etc. of silverhalide emulsions.
  • the particular developing agents used are not critical, but include those commonly known as silver halide reducing agents such as, for example, N-methyl-p-aminophenol sulfate, ascorbic acid, hydroquinones, B-pyrazolidones, including '1- phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl 3 pyrazolidone, etc., p-phenylene diamine, catechol, stannous octoate, dextrin, 3,5-diaminophenol, etc.
  • the silver halide solvents or silver complexing agents which are useful include, for example, thioureas, thiocyanates, thiosulfates, mercapto-containing compounds such as mercapto acetic acid, quaternary ammonium salts, polyamines such as tetraethylene pentamine, etc.
  • the silver halide emulsion is preferably silver chloride, but other conventional developing out emulsions may be used such as silver bromide, iodide, bromochloride, bromoiodide, chloroiodide, chlorobromoiodide, etc,
  • a paper receiving sheet it is preferable to use a paper receiving sheet but other supports may be used such as cellulose acetate, glass, wood, metal, polymeric materials, such as polyesters, polyolefins, and the like.
  • a solution is preferably made above the melting temperature of the carrier material and can be stored in a solid condition upon cooling.
  • the solution may be used in the molten condition at a temperature above the melting point of the solution. It will be appreciated that various components used on conventional silver halide developing solutions can be incorporated.
  • the carrier material containing the developing solution When used as an overcoat on silver halide emulsions, it may be used in a manner similar to that used With the colloid and/ or the diffusion transfer silver halide emulsions.
  • a barrier coat may be used if desired, to prevent migration of the developer from the carrier material layer into the silver halide emulsion prior to thermal processing of the exposed emulsion.
  • the carrier material and/or developer may be incorporated in the silver halide emulsion for some purposes.
  • the carrier material is advantageously used in amounts sufficient to provide a homogeneous mixture of the developer and other materials present.
  • the carrier material When incorporated in a silver halide emulsion, the carrier material should be present at a concentration of at least 0.1 g. per millimole of silver halide.
  • concentration of at least 0.1 g. per millimole of silver halide When used in a layer over or under a silver halide emulsion, it is necessary to have a higher concentration of at least 0.4 g. per millimole of silver halide.
  • the temperatures at which development takes place are above the melting point of the carrier material. However, in some instances the temperature may be considerably higher depending upon the speed of development desired, hardness of the emulsion, type of developer used, etc. The upper limit is dependent upon these same factors.
  • a solution of the processing chemical is prepared and stirred until homogeneous after which it is added to the molten carrier at a temperature above its melting point.
  • the developer-to-carrier ratio is 1:5.
  • the proportions can differ widely depending upon the processing agents, the silver halide emulsion, the form used, etc.
  • the liquid carrier material containing the processing material can be cast into blocks and then pressed in contact with the exposed photographic emulsion and heated. Polyglycols are particularly useful in this embodiment.
  • the carrier melts, releasing the processing agent to react with the photographic material.
  • the absence of processing fluid obviates the necessity of drying the processed photographic material.
  • the waxy surface results in an attractive product when this process is used with prints.
  • this processing method is rapid and does not require a drying step, it can be used in data processing systems where the photographic result is required shortly after the exposure has been made.
  • the particular processing materials which may be incorporated in the carrier material depend upon the desired results. For instance, a 3-stage process might be used wherein a first block of carrier material containing developer is contacted against the exposed photographic elements with the application of heat. The next block might contain an acid stabilizer, whereas the third block could contain a neutral stabilizer. As an alternative, the block might contain the components of a monobath so that the hotographic element would be developed and stabilized by contacting against a single wax block.
  • a Carbowax block melts at about 60 C. but is solid at room temperature (about 20 0).
  • the temperature of the exposed lightsensitive element may range from about 60 C. to about C.
  • Development may be accomplished in as little as two seconds, but stabilization may require a longer time, possibly five to ten seconds.
  • the use of two stabilizing blocks may facilitate the time balance so that the photographic element can pass through the process in a given length of time.
  • the processing chemicals which may be used for incorporation into the carrier material are not critical and may be a matter of choice. It will be appreciated, of course, that those which are incompatible with the carrier material so that a homogeneous mixture cannot be obtained are not Within the scope of this invention. It will also be appreciated that wherein a polyglycol is an especially useful material, certain other polymeric materials which are capable of holding a given amount of moisture in a homogeneous material which is solid at room temperature may also be used. For instance, hydroxy ethyl cellulose, carboxymethyl cellulose, etc., may be used for certain purposes.
  • Moisture is preferred in the mixture of the carrier and processing agent and is included along with the processing agent in the molten mixture to disperse the processing agent in the polyglycol or similar carrier material. In our preferred embodiment about 10% moisture based on the total weight of the mixture is used, but a range of 2% to 30% is useful.
  • Polyglycol solid blocks are prepared with a wax block 1 containing developer, wax block 2 containing an acid stabilizer, and wax block 3 containing a neutral developer.
  • the exposed silver halide emulsion on a support 4 is passed past a heating element 5 having a surface temperature about 200 F., each block is biased against the exposed silver halide emulsion on a support by means of spring 6.
  • the scrapers 7 remove excess carrier material from the exposed emulsion.
  • EXAMPLE 1 Kodak Developer D72 was dissolved in water to make a concentrated developer. This was thickened by the addition of hydroxyethyl cellulose and a thin layer was allowed to dry. Development of a silver halide contact paper was accomplished by applying heat to the hydroxyethyl cellulose layer by means of a fiat iron set at low heat, about 65 C. A sharp image was obtained.
  • EXAMPLE 2 A hydroxyethyl cellulose layer was prepared asin Example 1, but using a hydroquinone-thiosulfate monobath containing 1-phenyl-3-pyrazolidone, in place of the solution.
  • the paper used was a silver chloride emulsion of low silver content. Processing was accomplished by the application of heat as in Example 1. Development took about 1 minute and produced a stable image of good maximum density and fairly low minimum density.
  • Imino-diethanol-SO adduct 19% S grams 60.5 Imino-diethanol, grams 2.5 2-aminoethanol, grams 8.0 Sodium erythrobate, grams 10.0 4-methy1-1-phenyl-3-pyrazolidone, gram 1.0 Potassium bromide, grams 2.0 Sodium thiosulfate, pentahydrate, grams 10.0 Water to make, cc. 100.0
  • EXAMPLE 4 The monobath in this .case was the same as that in Example 3, except that the stabilizing agent was an amine thiosulfate rather than sodium thiosulfate.
  • the amine thiosulfate was prepared according to US. 3,169,992 by substituting 2 grams of sulfur for the sodium thiosulfate in the above formula. Processing procedures were exactly the same as those above.
  • the resulting image showed the same high quality and stability as that in Example 3.
  • the image in Examples 3 and 4 was clearly visible through the cellulose acetate support, and it was not necessary to separate it from the support for viewing.
  • EXAMPLE 1 An amine developer, similar to the monobath of Example 3 but containing 2.0 grams sodium erythrobate, no sodium thiosulfate and no methyl phenyl pyrazolidone, was incorporated in Carbowax 4000 and coated over a sheet of the unexposed photographic paper of Example 2. The paper was exposed through the wax layer and was then heated with a fiatiron. A low-contrast image was obtained. The image required fixation.
  • EXAMPLE 8 The amine developer in the Carbowax carrier of Ex ample 6 was cast into a block.
  • the hard waxy block was uesd to develop an exposed photographic enlarging paper by placing the paper, emulsion side up, on an aluminum plate heated to F., and rubbing the emulsion with the developer block. After development was completed (approximately 30 seconds were required), the paper was stabilized by treating it in the same manner with a block containing a thiourea stabilizer similar to that of Exam-' ple 6 but containing twice as much Carbowax. 4000. This resulted in a light-stable image with a hard, smooth, glossy surface.
  • EXAMPLE 9 EXAMPLE 10 Developing blocks were prepared using 5.0 grams of urea as the suspending medium. Various amounts of the following developer solution were incorporated into the melted urea.
  • Iminodiethanol-SO adduct 19% S0 grams 60.5 Iminodiethanol, grams 2.5 2-aminoethanol, grams 8.0 Hydroquinone, grams 4.0 Phenidone, gram 1.0 Potassiumbromide, grams 2.0 Water to make, cc. 100.0
  • Developing blocks were prepared by adding various amounts of developer solution to grams of acetamide.
  • the solid blocks were used to develop a recording paper containing a fine grain silver chloride gelatin emulsion as in Example 10, using a heated block at 200 F.
  • Example 12 The procedure of Example 12 was followed using 10 grams of acrylamide in place of the succinimide. The following results were obtained:
  • Dimethylurea and p-toluene sulfonamide we're also used successfully as the suspending media.
  • the p-toluene sulfonamide produced complete dense images in periods of 15 seconds at 200 F.
  • Other solid materials which have been used are 2,2-diethy1-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and 2-butyne-1,4-diol.
  • Phenylmercaptotetrazole, benzotriazole, nitroindazole, sodium antraquinone sulfonate, potassium bromide and various antifoggants may be incorporated into the processing blocks.
  • the incorporation of a small amount of diethylaminoethanethiol is effective in keeping fog levels low.
  • EXAMPLE 16 A silver halide enlarging paper having a low silver emulsion was used for all of the tests.-
  • Blocks were of Carbowax 4000 containing 10% added water plus chemical agent.
  • the developer block contained:
  • the stop block contained:
  • the stabilizer block comprised Carbowax and the different chemicals under test. Concentrations were between 2.520.0 grams per grams Carbowax.
  • Processing was at 200 with 15 seconds for development, 10-second stop and 30-second stabilizer.
  • the processed strips were tested for stability by exposing to strong light. If stable, they were further tested at 94% RH. for 3 days at 100 F.
  • T hz'oglyceroL-A promising stabilizer imparting light stability and fairly good moisture stability.
  • Quaternary salts which effected stabilization included 1 1 a-picolinium-B-phenylethyl bromide, tetrapropyl, tetraethyl, and tetramethyl bromides, preference in this order. These compounds give clear whites of good light stability.
  • EXAMPLE 17 Activation and stabilization of emulsions containing developing agents was accomplished with blocks containing 100 grams of Carbowax4000, 20 grams of methylamino ethanol (as an alkali), cc. of water and:
  • EXAMPLE 21 The following developer was prepared: To 100-gram quantities of molten Carbowax 4000, 20, 30, 40, and 50 This developer, while in the molten state, was coated upon receiver sheets containing Carey Lea silver. A finegrain positive photographic film was exposed to a suitable object and contacted with the coated receiver sheet on a plate heated to 95 C. The developerlayer melted causing development of a negative image in the film and transfer of a positive image to the receiver sheets. Particularly good transfer was obtained in the receiver coated with the mixture containing 40 cc. of Solution A per 100 grams of Carbowax. Similar results were achieved using receiver sheets nucleated with nickel sulfide nuclei. Other nucleation agents might also be used.
  • a homogeneous composition comprising a watermiscible organic compound carrier comprising an alkylene oxide polymer; a silver halide developing agent; and about 2% to about 30%, by weight of said carrier, of water, said composition being solid at about 20 C. and melting at a temperature below about 115 C.
  • a homogeneous composition comprising a watermiscible organic compound carrier comprising an alkylene oxide polymer; a silver halide stabilizing agent; and about 2% to about 30%, by weight of said carrier, of water, said composition being solid at about 20 C. and melting at a temperature below about 115 C.
  • a light-sensitive photographic element comprising a support having thereon at least one silver halide emulsion layer and having integral therewith a homogeneous material consisting essentially of a fusible mixture of a water-miscible organic compound carrier selected from the group consisting of alkylene oxide polymers, hydroxyethyl cellulose, carboxymethyl cellulose, monostearin, beeswax, mixtures of alkylene oxide polymers with propylene oxide and mixtures of alkylene oxide polymers with ethylene oxide, organic acids, and polar compounds having high dielectric constant containing the electron withdrawing groups -SO and CO- represented by the formulas:
  • X is selected from the group consisting of H and alkyl groups of 1 to 4 carbon atoms, R'NH, RO and (CH CONRR' and radicals forming a diradical with R; a is 2 to 3 and b is 3 to 5; n is 1 to 4; R is selected from the group consisting of H, CH and HOCH CH R is selected from the group consisting of H, CH and radicals forming a heterocyclic ring with R; R is selected from the group consisting of H and CH R is selected from the group consisting of lower alkyl radicals and radicals forming a heterocyclic ring with X; and Y is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, NH RO and aryl radicals; a silver halide photographic processing agent; and about 2% to about 30%, by weight of said carrier, of water, said composition being solid at
  • a photographic element comprising a support having thereon a solid homogeneous fusible processing layer containing a water-miscible organic compound carrier selected from the group consisting of alkylene oxide polymers, hydroxyethyl cellulose, carboxymethyl cellulose, monostearin, beeswax, mixtures of alkylene oxide polymers with propylene oxide and mixtures of alkylene oixde polymers with ethylene oxide, organic acids, and polar compounds having high dielectric constant containing the electron withdrawing groups s0 and -C0 represented by the formulas:
  • R CH0 0 2 and o (I) KC ONRR CHzO (II) YSOzNHz w H, CH, and HOCH CH R is selected from the group consisting of H, -CH and radicals forming a heterocyclic ring with R; R is selected from the group consisting of H and CH R" is selected from the group consisting of lower alkyl radicals and radicals forming a heterocyclic ring with X; and Y is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, NH RO and aryl radicals; a silver halide photographic processing agent; and about 2% to about 30%, by weight of said carrier, of water, said composition being solid at about 20 C. and melting at a temperature below about C.
  • a photographic element comprising a support having thereon a solid homogeneous fusible processing layer containing a silver halide developing agent and an alkylene oxide polymer carrier containing about 2% to about 30%, by weight of said carrrier, of water, said processing layer being solid at about 20 C. and melting at a temperature below about 115 C.
  • a method of processing an exposed silver halide emulsion comprising contacting said emulsion with a homogeneous composition comprising a water-miscible organic compound carrier selected from the group consisting of alkylene oxide polymers, hydroxyethyl cellulose, monostearin, beeswax, mixtures of alkylene oxide polymers with propylene oxide and mixtures of alkylene oxide polymers with ethylene oxide, organic acids, and polar compounds having high dielectric constants containing the electron withdrawing groups -SO and CO represented by the formulas:
  • X is selected from the group consisting of H and alkyl groups of 1 to 4 carbon atoms, RNH--, R"O and (CH ),,CONRR' and radicals forming a diradical with R; a is 2 to 3 and b is 3 to 5; n is 1 to 4; R is selected from the group consisting of H, -CH and HOCH CH R is selected from the group consisting of H, CH and radicals forming a heterocyclic ring with R; R is selected from the group consisting of H and CH R" is selected from the group consisting of lower alkyl radicals and radicals forming a heterocyclic ring with X; and Y is selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms, NH R"O-- and aryl radicals; a silver halide photographic processing agent; and about 2% to about 30% by weight
  • a method of developing an exposed silver halide emulsion comprising contacting said emulsion with a homogeneous composition which is solid at about 20 C. and melts at below about 115 C. comprising a silver halide developing agent and an alkylene oxide polymer carrier 15 16 containing about 2% to about 30%, by Weight of said Y References Cited cirlreiggs (zi lt as tle gilngrature at which said homo- UNITED STATES PATENTS 1 11 n 1 1 16.
  • Amethod of stabilizing an exposed silver halide 3252 emulsion comprising contacting said emulsion with a 5 homogeneous composition which is solid at about 20 C.
  • FOREIGN PATENTS and melts at below about 115 C. comprising a silver halide stabilizing agent and an alkylene oxide polymer 1,282,479 12/1961 France carrier containing about 2% to about 30%, by weight of said carrier, of Water, at a temperature at which said 10 NORMAN TORCmNP'lma'y Examme" homogeneous composition is liquid.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US465081A 1965-06-18 1965-06-18 Solid homogeneous compositions containing silver halide processing agents Expired - Lifetime US3347675A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US465081A US3347675A (en) 1965-06-18 1965-06-18 Solid homogeneous compositions containing silver halide processing agents
FR64967A FR1482773A (fr) 1965-06-18 1966-06-10 Procédé à sec et nouveaux produits de traitement photographique et nouveaux produits photographiques contenant des agents de traitement
BE682412D BE682412A (enExample) 1965-06-18 1966-06-10
DE19661547704 DE1547704A1 (de) 1965-06-18 1966-06-14 Verfahren zum Entwickeln belichteter photographischer Silberhalogenidschichten auf trockenem Wege
GB27545/66A GB1155948A (en) 1965-06-18 1966-06-20 Solid, Fusible Photographic Processing Compositions and use thereof

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Cited By (27)

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US3961958A (en) * 1973-10-18 1976-06-08 Ciba-Geigy Ag Process for fixing photographic material
US4168169A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4168170A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4232113A (en) * 1979-03-14 1980-11-04 Minnesota Mining And Manufacturing Company Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0224214A2 (en) 1985-11-21 1987-06-03 Fuji Photo Film Co., Ltd. Light-sensitive microcapsule containing polymerizable compound and silver halide, and light-sensitive material employing the same
US5252423A (en) * 1989-10-11 1993-10-12 Fuji Photo Film Co., Ltd. Light-sensitive material containing silver halide reducing agent, polymerizable compound, color image forming substance, base precursor and polar compound
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5352561A (en) * 1991-12-06 1994-10-04 Eastman Kodak Company Thermal solvents for heat image separation processes
US5468587A (en) * 1993-06-08 1995-11-21 Eastman Kodak Company Hydrogen bond accepting groups on thermal solvents for image separation systems
EP0687572A1 (en) 1994-06-15 1995-12-20 Agfa-Gevaert N.V. Thermosensitive recording method
US5480761A (en) * 1993-06-08 1996-01-02 Eastman Kodak Company Aliphatic hydroxyl hydrogen bond donating groups on thermal solvents for image separation systems
US5480760A (en) * 1993-06-08 1996-01-02 Eastman Kodak Company Sulfamoyl hydrogen bond donating groups on thermal solvents for image separation systems
EP0692391A1 (en) 1994-07-13 1996-01-17 Agfa-Gevaert N.V. Heat-sensitive recording material
EP0692732A1 (en) 1994-07-13 1996-01-17 Polaroid Corporation Thermally processable image-recording material including reductone developing agent
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
EP0775595A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermographic recording material with phosphoric acid and derivative as lubricant
EP0775592A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermal image-forming process
EP0782043A1 (en) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Thermographic recording material which improved tone reproduction
EP0845709A1 (en) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
US6730470B2 (en) 2000-09-19 2004-05-04 Fuji Photo Film Co., Ltd. Photothermographic material
US20060240366A1 (en) * 2005-04-21 2006-10-26 Eastman Kodak Company Thermally developable materials containing thermal solvents
US20110172094A1 (en) * 2010-01-11 2011-07-14 Lan Deng Recording material
US8536087B2 (en) 2010-04-08 2013-09-17 International Imaging Materials, Inc. Thermographic imaging element
US9193208B2 (en) 2011-04-20 2015-11-24 Rohm And Haas Company Recording material
WO2022271595A1 (en) 2021-06-23 2022-12-29 International Imaging Materials, Inc. Thermographic imaging element

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US4786583A (en) * 1987-06-22 1988-11-22 Eastman Kodak Company Stabilizing bath for use in photographic processing
GB0014422D0 (en) * 2000-06-13 2000-08-09 Eastman Kodak Co Method and material for photographic processing
US6309810B1 (en) * 2000-06-13 2001-10-30 Eastman Kodak Company Photochemical delivery article and method of use
GB0113023D0 (en) 2001-05-30 2001-07-18 Eastman Kodak Co Method and material for photographic processing

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US2423549A (en) * 1945-01-10 1947-07-08 Du Pont Silver halide photographic emulsions sensitized by polyalkylene glycols
US2531832A (en) * 1947-06-12 1950-11-28 Du Pont Silver halide developers containing polyethylene glycols
FR1282479A (fr) * 1960-03-17 1962-01-19 Lumoprint Zindler Kg Procédé de révélation d'émulsions photographiques et dispositif et matériau pour la mise en oeuvre du procédé

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US2423549A (en) * 1945-01-10 1947-07-08 Du Pont Silver halide photographic emulsions sensitized by polyalkylene glycols
US2531832A (en) * 1947-06-12 1950-11-28 Du Pont Silver halide developers containing polyethylene glycols
FR1282479A (fr) * 1960-03-17 1962-01-19 Lumoprint Zindler Kg Procédé de révélation d'émulsions photographiques et dispositif et matériau pour la mise en oeuvre du procédé

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961958A (en) * 1973-10-18 1976-06-08 Ciba-Geigy Ag Process for fixing photographic material
US4168169A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4168170A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
US4232113A (en) * 1979-03-14 1980-11-04 Minnesota Mining And Manufacturing Company Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0224214A2 (en) 1985-11-21 1987-06-03 Fuji Photo Film Co., Ltd. Light-sensitive microcapsule containing polymerizable compound and silver halide, and light-sensitive material employing the same
US5252423A (en) * 1989-10-11 1993-10-12 Fuji Photo Film Co., Ltd. Light-sensitive material containing silver halide reducing agent, polymerizable compound, color image forming substance, base precursor and polar compound
US6277537B1 (en) 1991-12-06 2001-08-21 Eastman Kodak Company Dye diffusion image separation systems with thermal solvents
US5843618A (en) * 1991-12-06 1998-12-01 Eastman Kodak Company Hydrogen bond donating/accepting thermal solvents for image separation systems
US5352561A (en) * 1991-12-06 1994-10-04 Eastman Kodak Company Thermal solvents for heat image separation processes
US5436109A (en) * 1991-12-06 1995-07-25 Eastman Kodak Company Hydroxy benzamide thermal solvents
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5480761A (en) * 1993-06-08 1996-01-02 Eastman Kodak Company Aliphatic hydroxyl hydrogen bond donating groups on thermal solvents for image separation systems
US5480760A (en) * 1993-06-08 1996-01-02 Eastman Kodak Company Sulfamoyl hydrogen bond donating groups on thermal solvents for image separation systems
US5468587A (en) * 1993-06-08 1995-11-21 Eastman Kodak Company Hydrogen bond accepting groups on thermal solvents for image separation systems
EP0687572A1 (en) 1994-06-15 1995-12-20 Agfa-Gevaert N.V. Thermosensitive recording method
EP0692732A1 (en) 1994-07-13 1996-01-17 Polaroid Corporation Thermally processable image-recording material including reductone developing agent
EP0692391A1 (en) 1994-07-13 1996-01-17 Agfa-Gevaert N.V. Heat-sensitive recording material
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
EP0775595A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermographic recording material with phosphoric acid and derivative as lubricant
EP0775592A1 (en) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Thermal image-forming process
EP0782043A1 (en) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Thermographic recording material which improved tone reproduction
EP0845709A1 (en) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. A heat sensitive imaging element and a method for producing lithographic plates therewith
US6730470B2 (en) 2000-09-19 2004-05-04 Fuji Photo Film Co., Ltd. Photothermographic material
US20060240366A1 (en) * 2005-04-21 2006-10-26 Eastman Kodak Company Thermally developable materials containing thermal solvents
US7169544B2 (en) 2005-04-21 2007-01-30 Eastman Kodak Company Thermally developable materials containing thermal solvents
US20110172094A1 (en) * 2010-01-11 2011-07-14 Lan Deng Recording material
US11845879B2 (en) 2010-01-11 2023-12-19 Rohm And Haas Company Recording material
US8536087B2 (en) 2010-04-08 2013-09-17 International Imaging Materials, Inc. Thermographic imaging element
US9193208B2 (en) 2011-04-20 2015-11-24 Rohm And Haas Company Recording material
WO2022271595A1 (en) 2021-06-23 2022-12-29 International Imaging Materials, Inc. Thermographic imaging element

Also Published As

Publication number Publication date
BE682412A (enExample) 1966-11-14
GB1155948A (en) 1969-06-25
DE1547704A1 (de) 1969-11-20

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