US3765891A - Process for developing photographic elements - Google Patents

Process for developing photographic elements Download PDF

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US3765891A
US3765891A US00256071A US3765891DA US3765891A US 3765891 A US3765891 A US 3765891A US 00256071 A US00256071 A US 00256071A US 3765891D A US3765891D A US 3765891DA US 3765891 A US3765891 A US 3765891A
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process according
silver halide
color
silver
photographic element
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W Travis
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/42—Reducing; Intensifying
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • 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
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/137—Cobalt complex containing

Definitions

  • This invention relates to a process for developing photographic elements which comprise layer units containing imagewise-exposed silver halide having associated therewith a photographic color coupler.
  • this invention relates to a process for developing a visible image record in photographic elements which comprise color-providing layer units containing a low silver coverage.
  • this invention relates to a continuous process for developing imagewiseexposed photographic elements which comprise at least two color-providing layer units wherein, if desired, at least a portion of the image dye can be produced under roomlight conditions.
  • New processes for developing and amplifying an image record recorded in a light-sensitive metal salt are disclosed in Bissonette, U.S. Ser. No. 189,289, entitled Image-Forming Processes and Compositions filed Oct. 14, 1971, and incorporated herein by reference.
  • the process disclosed relates to image formation in photographic elements comprising color-providing layer units containing a silver halide emulsion having associated therewith a color coupler.
  • the photographic element is contacted with a photographic color-developing agent and a metal complex, such as a cobalt(lII) complex having a coordination number of 6, until the desired dye density is obtained.
  • cobalt complex is apparently reduced to cobalt (ll), which isnot a catalyst for further redox reaction, in the presence of silver, and the color developer is oxidized whereby it can react with the color coupler in each respective layer unit to form the desired image dye.
  • this process comprises the improvement in forming a visible image record in a photographic element wherein the photographic element comprising both silver halide and an imagewise distribution of metallic silver (i.e., a photographic element which has not been fixed to remove the undeveloped silver halide) is contacted in the presence of a color-developing agent with an amplifier composition which represses substantially additional net silver development and which contains a cobalt (lIl) complex having a coordination number of 6, wherein said contact is maintained under conditions which reduce cobalt(Ill) to cobalt(ll) and in turn oxidize said color-developing agent, whereby image dye is formed from the color coupler in said photographic element and said oxidized color-developing agent.
  • the metallic silver in the photographic element can be latent image silver and is preferably metallic silver formed in a reaction with a silver halide reducing agent such as by development of a latent image with a silver halide developer. While latent image silver can be used as a catalyst in the amplification, dye production can generally be expedited by providing larger catalytic surfaces as produced in silver halide development.
  • the color-developing agent can be present in the amplification bath but is preferably imbibed into the element prior to contact with the amplifier composition.
  • the metallic silver is provided, when larger than latent image quantities are desired, in a bath which contains a color-developing agent, such as an aromatic primary amino compound, which can reduce silver halide to silver and in turn produce image dye through its reaction products.
  • metallic silver is produced, before-amplification, in a bath in the presence of a black-and-white developing agent and a color-developing agent wherein improved results with respect to shortened process time and matched developability of the various layers in a multilayer photographic element can be obtained.
  • this invention relates to an improved process of producing image dye in an imagewise-exposed photographic element having a support and at least one layer thereon containing a silver halide emulsion having associated therewith an image dye-providing color coupler
  • said process comprises 1) development of said imagewiseexposed photographic element with a silver halide developing agent to produce an imagewise distribution of metallic silver and imbibition of a color-developing agent in said photographic element and then 2) contacting said photographic element which contains silver halide and said imagewise distribution of metallic silver with an amplifier composition which represses substantially additional net silver development, wherein said amplifier composition contains a cobalt(lll) metal complex having a coordination number of 6 and said amplifier composition is maintained in contact with said photographic element under conditions which reduce cobalt(lIl) to cobalt(ll), which in turn oxidizes said color-developing agent whereby additional image dye is provided from said image dye-providing color coupler and said oxidized color-developing agent.
  • the elements processed, as above, can, of course, be bleached, fixed and washed, etc., in the normal manner after contact with the amplifier.
  • the improved processes of this invention reduce the necessity of fixing the silver halide out of a photographic element before amplification and also reduce the problems associated with silver halide development in an amplifier bath wherein the amount of catalytic silver formation may be very dependent on conditions, reaction byproducts, etc.
  • this process also provides highly improved stability of development compositions and amplifying compositions and is especially suited to continuous processing of color photographic elements. The process is especially advantageous in processing multicolor photographic elements since stability in processing solutions is highly improved allowing reproducible results over long periods of operating time.
  • the amplifier solution contains a sufficient quantity of a development restrainer or combination of development restrainers to repress substantially any further net silver development.
  • the color-developing agent is an aromatic primary amino compound and is preferably a phenylenediamine color-developing agent.
  • the photographic element is developed in an aqueous bath and contacted with an amplifying solution which is maintained at temperatures above 90 F. and preferably above 100 F.
  • an amplifying solution which is maintained at temperatures above 90 F. and preferably above 100 F.
  • the photographic element is developed in a liquid which is substantially free of a cobalt(lll) metal complex having a coordination number of 6.
  • the amplifier solution is substantially free of silver halide solvents or contains less than 30 percent, by weight, of the amount of silver halide solvent which would be necessary to fix the silver halide emulsion in the element being processed.
  • the photographic elements processed in accordance with this invention preferably contain a water-insoluble image dye-providing color coupler dissolved in a coupler solvent.
  • the photographic element is processed in a bath containing a coupling accelerator which is an alcohol and the amplifier solution preferably contains a coupling accelerator which is an alcohol.
  • this invention relates to an improved procedure for processing a multicolor photographic element comprising at least two color-providing layer units which each contains a silver halide emulsion and an image dye-providing color coupler in at least a 40 percent and preferably a 70 percent stoichiometric excess based on effective silver coverage in said layer.
  • the red and green recording layers are preferably in accordance with said color-providing layer units above, and. the blue recording layer can be coated in accordance with said definition, but where it is necessary to obtain differential photographic speed between the blue recording layer and other recording layers, it may be desirable to use high coverages of silver and different ratios of coupler to silver in the blue-sensitive layer.
  • the photographic elements of this invention comprise at least one and preferably two image dye-providing layer units wherein the silver halide is coated at a coverage of less than 30 mg. of silver per ft.
  • a development restrainer is used in the amplifier bath in sufficient quantities to repress substantially further development of silver halide. Improved fog levels can be obtained if development is not allowed to proceed in the amplification bath, especially in continuous processes where one may encounter ammonia buildup in the amplifier.
  • the preferred development restrainers are water-soluble bromide compounds such as KBr, etc., or heterocyclic compounds such as tetrazoles, azaindines and triazoles which are free of mercapto or ionic iodide groups.
  • Development restrainers as a class of compounds are known in the art, as mentioned in US. Pat. No. 3,458,317 issued July 19, 1969. Development restrainers which have ionic iodide groups or mercapto groups appear to retard the catalytic effect of silver.
  • Typical preferred development re strainers include high levels of KBr such as 2 to 40 g./l., methyl benzotriazole, benzotriazole, 3-methyl-l ,3- benzothiazolium bromide, S-nitrobenzimidazole, decamethylene bis(benzothiazolium bromide), and the like.
  • organic development restrainers include the sodium salt of 4-hydroxy-6-methyl-1,3,3a,7- tetrazaindene, the sodium salt of 4-hydroxy-6-methyl- 2-methylmercapto-l ,3 ,3 a,7-tetrazaindene, 4,5- dihydro-l ,4-diphenyl-3,S-phenylamino-l ,2,4-triazole and the like.
  • the heterocyclic development restrainers are generally incorporated in the amplifier at concentrations of 0.01 to 2.0 g./l.
  • the heterocyclic groups containing sulfur substitution can be used as development restrainers where the compound as used in the amplifier remains in its thione form rather than in the thiole or mercapto form.
  • a combination of an alkali metal bromide and an organic development restrainer are present in the amplifier composition.
  • the amplifying baths of this invention preferably contain only low amounts or are substantialy free of silver halide solvents. If high amounts of solvents are present, there is very little noticeable amplification effeet in the bath. Therefore, the amplifying baths generally comprise less than 30 percent by weight of the amount of a silver halide solvent which would be necessary to fix a silver halide emulsion.
  • the fixing processes are well-known in the art, for example, as disclosed in Stephen, U.S. Pat. No. 3,615,508 issued Oct. 26, 1971.
  • photographic color coupler and image dye-providing color coupler include any compound which reacts (or couples) with the oxidation products of primary aromatic amino developing agent on photographic development to form an image dye, and are nondiffusible in a hydrophilic colloid binder (e.g., gelatin) useful fo photographic silver halide, and also those couplers which provide useful image dyes when reacted with oxidized primary aromatic amino developing agents such as by a couplerrelease mechanism.
  • the couplers can form diffusible or nondiffusible dyes.
  • Typical useful color couplers include phenolic S-pyrazolone and open-chain ketomethylene couplers.
  • the useful couplers include Fischer-type incorporated couplers such as those described in Fischer, U.S. Pat. No. 1,055,155 issued Mar. 4, 1913, and particularly nondiffusible Fischer-type couplers containing branch carbon chains, e.g., those referred to in the references cited in Frohlich et al, U.S. Pat. No. 2,376,679 issued May 22, 1945, column 2, lines 50-60.
  • Particularly useful in the practice of this invention are the nondiffusible color couplers which form nondiffusible dyes.
  • the incorporated couplers in the layer units of this invention are waterinsoluble color couplers which are incorporated in a coupler solvent which is preferably a moderately polar solvent.
  • Typical useful solvents include tri-o-cresyl phosphate, di-n-butyl phthalate, diethyl lauramide, 2,4- diarylphenol, liquid dye stabilizers as described in an article entitled Improved Photographic Dye Image Stabilizer-Solvent, Product Licensing Index, Vol. 83, March, 1971, and the like.
  • the coupler solvents in the elements appear to aid the imbibition of color developer where it is carried into an amplifier bath via the element.
  • the photographicelements processed in accordance with this invention generally comprise a light-sensitive silver halide emulsion wherein the halide is generally less than 6 mole percent iodide and preferably less than 3 percent iodide and, in some highly preferred embodiments, is less than 0.25 percent iodide. If iodide is near the surface of the emulsion grains, it can build up in the solutions at a high level during development and amplification and affect dye production in the amplification step. Therefore, high amounts of iodide in the emulsion are generally avoided, especially when the element is to be processed in a continuous-process apparatus.
  • nondiffusible used herein as applied to couplers and products derived from couplers has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through photographic hydrophilic colloid layers, such as gelatin, particularly during processing in aqueous alkaline solutions. The same meaning is attached to the term immobile.”
  • diffusible and mobile have the converse meaning.
  • the photographic elements of this invention comprise a support having thereon image dye-providing layer units.
  • a multicolor photographic element comprises at least two of said image dyeproviding layer units which each records light primarily in different regions of the light spectrum.
  • the layer unit comprises a light-sensitive silver salt, which is generally spectrally sensitized to a specific region of the light spectrum, and has associated therewith a photographic color coupler.
  • the colorproviding layer units are effectively isolated from other layer units by barrier layers, spacer layers, layers containing scavengers for oxidized developer and the like to prevent any substantial color contamination between the image dye-providing layer units.
  • the effective isolation of the layer units is known in the art and is utilized to prevent color contamination in many commercial color products.
  • the photographic elements of this invention preferably comprise a support having thereon at least one image dye-providing layer units and preferably at least two image dye-providing layer units containing a lightsensitive silver salt, preferably silver halide, having associated therewith a stoichiometric excess of coupler of at least 40 percent and at least preferably percent.
  • a lightsensitive silver salt preferably silver halide
  • the equivalency of color couplers is known in the art, for example, the 4 equivalent couplers require 4 moles of oxidized color developer, which in turn requires development of 4 moles of silver, to produce 1 mole of dye. Thus, for a stoichiometric reaction with silver halide one equivalent weight of this coupler will be 0.25 mole.
  • the color image-providing unit comprises at least a 40 percent excess of the equivalent weight of image dye-providing color coupler required to react with the silver and preferably a 70 percent excess of said coupler based on effective silver.
  • the photographic color couplers are employed in the image dye-providing layer units at a concentration of at least three times, such as from three to 20 times, the weight of the silver in the silver halide emulsion, or at a stoichiometric excess of at least 1 10 percent based on effective silver in said layer unit.
  • the coupler is present in an amount sufficient to give a density of at least 1.7 and preferably at least 2.0 when coated on a paper support and preferably at least 3.0 when coated on a transparent film support.
  • the coupler is present in said layer units in at least 1 X 10 moles/ftF.
  • the difference between the maximum density and the minimum density (which can comprise unbleached silver) is at least 0.6 and preferably at least 1.0.
  • the photographic elements prepared in accordance with this invention are those described in Bissonette, U.S. Ser. No. 256,072, entitled Photographic Elements, filed on even data herewith and incorporated herein by reference.
  • the photographic color couplers utilized are selected so that they will give a good neutral.
  • the cyan dye formed has its major absorption between about 600 and 700 nm.
  • the magenta dye has its major absorption between about 500 and 600 nm.
  • the yellow dye has its major absorption between about 400 and 500 nm.
  • each of the color-providing layer units of the photographic elements contains a light-sensitive silver halide.
  • the colorproviding layer units comprise a silver salt at a concentration of up to 30 mg. of silver per square foot.
  • the silver halide is preferably present at concentrations based on silver of less than 30 mg./ft. it is possible to coat emulsions at higher silver coverages within this embodiment, as long as no more than 30 mg./ft.
  • Such emulsions may contain silver halide grains which are relatively light-insensitive or may contain developer restrainers such as development inhibitor-releasing coupiers, and still provide a photographic element which isadvantageously used in the various processes as described herein to produce improved image records.
  • relatively light-insensitive silver halide grains or development restrainers are desirable to enable one to obtain more uniform coating coverage with less precise coating equipment, as well as for other reasons.
  • highly preferred photographic elements processed according to this invention contain at least two color-providing layer units, each containing a silver halide emulsion, defined in terms of effective coverage and developability, as one which, when it is fully exposed and processed for about 1 minute at 100 F.
  • the fully exposed layer containing silver halide emulsion is one which is exposed to Dmax as is well-known in the art, for example, by exposue exposure a SOD-watt, 3000K lamp for about seconds (total exposure at the film plane 113 X 10 ergs./cm.
  • the photographic elements processed in accordance with this invention generally can contain negative silver halide emulsions, direct-positive silver halide emulsions, silver halide emulsions designed for processing in reversal processes, and the like. It is understood, of course, that with negative emulsions the catalytic metallic silver development will be in the exposed areas whereas with direct-positive emulsions the catalytic metallic silver will be formed in the unexposed areas.
  • the amplifiers of this invention comprise a cobalt (1!) metal complex.
  • Such complexes feature a molecule having a cobalt atom or ion. This cobalt atom or ion is surrounded by groups of atoms, ions or other molecules which are, generically referred to as ligands.
  • the cobalt atom or ion in the center of these complexes is a Lewis. acid; the ligands are Lewis bases. Werner complexes are well-known examples of such complexes.
  • the useful cobalt salts are typically capable of existing in at least two valent states.
  • the cobalt complexes are those referred to by American chemists as inert and by European chemists as robust.
  • compositions of a cobalt ion with a ligand which, when a test sample thereof is dissolved at 0.1 molar concentration at 20 C. in an inert solvent solution also containing 0.1 molar concentration of a tagged ligand of the same species which is uncoordinated, exhibits essentially no exchange of uncoordinated and coordinated ligands for at least 1 minute, and preferably for at least several hours, such as up to 5 hours or more.
  • This test is advantageously conducted under the pH conditions which will be utilized in the practice of the invention. In silver halide photography, this generally will be a pH of over about 8.
  • Many cobalt metal complexes useful in this invention show essentially no exchange of uncoordinated and coordinated ligands for several days.
  • inert metal complexes and the method of measuring ligand exchange using radioactive isotopes to tag ligands are well-known in the art; see, for example, Taube, Chem. Rev., Vol. 50, p. 69 (1952) and Basolo and Pearson, Mechanisms of Inorganic Reactions, A Study of Metal Complexes and Solutions, 2nd Edition, 1967, published by John Wiley and Sons, p. 141. Further details on measurement of ligand exchange appear in articles by Adamson et al, J. Am. Chem. Soc., Vol. 73, p. 4789 (1951).
  • the inert metal complexes should be contrasted with labile complexes which, when tested by the method described above, have a reaction half-life generally less than 1 minute.
  • Metal chelates are a special type of metal complex in which the same ligand (or molecule) is attached to the central metal ion at two or more different points. The metal chelates generally exhibit somewhat slower ligand exchange than nonchelated complexes. Labiletype chelates may have a half-life of several seconds, or perhaps slightly longer. Generally, the oxidizing agents employed are not reduced to a zero valent metal during the redox reaction of the invention. 7
  • Preferred cobalt complexes in accordance with this process have coordination numbers of 6 and are known as octahedral complexes. Cobalt complexes are especially useful in the practice of this invention.
  • a wide variety of ligands can be used with a metal ion to form suitable cobalt complexes.
  • Nearly all Lewis bases i.e., substances having an unshared pair of electrons
  • Some typical useful ligands include the halides, e.g., chloride, bromide, fluoride, nitrite, water, amino, etc., as well as such common ligands as those referred to on page 44 of Basolo et al, supra.
  • the lability of a complex is influenced by the nature of the ligands selected in forming said complex.
  • cobalt complexes have a coordination number of 6 and have a ligand selected from the group consisting of ethylenediamine(en), propylenediamine(tn), diethylenetriamine(dien), triethylenetetraamine(trien), ammine(Nl-I 'nitrate, nitrite, azide, chloride, thiocyanate, isothiocyanate, water and carbonate.
  • the preferred cobalt complexes comprisel) at least two ethylenediamine ligands or 2) at least five amine ligands or 3) one triethylenetetraamine ligand.
  • cobalt hexarn mine salts e.g., the chloride, bromide, sulfite, sulfate, perchlorate, nitrite and acetate salts.
  • Some other specific highly useful cobalt complexes include those hav ing one of the following formulas: rco 1vu, ,n,o1x; [CO(NH:;)5CO3]X; 3)s l a)' CO ]X; [Co(en) 1X; cis-[Co(en) (N ]X; trans- [Co(en) Cl(NCS)]X; trans-[Co(en) (N ]X; cis- [Co(en) (NH )N ]X; cis-[Co(en) Cl ]X'; transl )2 2l )2( )2] )2( )z] )al l )2( and [Co(tn)(en) ]X; where
  • the anions selected can substantially effect the reducibility of the complex.
  • the following ions are listed in the order of those which give increasing stability to cobalt hexammine complexes: bromide, chloride, nitrite, perchlorate, acetate, carbonate, sulfite and sulfate.
  • Other ions will also effect the reducibility of the complex.
  • These ions should, therefore, be chosen to provide complexes exhibiting the desired degree of reducibility.
  • Some other useful anions include chloride, nitrate, thiocyanate, dithionate and hydroxide.
  • Neutral complexes such as [Co(dien)(SCN) OH] are useful, but positively charged complexes are generally preferred.
  • the barrier may be set up by ligands tightly bound to and surrounding the central metal atom or ion. In the presence of certain catalysts, it seems that one or more of the ligands may be bound less tightly to the central metal atom or ion, thus facilitating reaction between the central metal atom or ion and the reducing agent.
  • this invention is not limited to that theory.
  • color-developing agents can be imbibed in the photographic element in accordance with the present invention.
  • the color-developing agents utilized herein undergo redox reaction with the oxidizing agent at a catalytic surface.
  • Especially preferred colordeveloping agents are those which reduce silver halide to metallic silver, such as those which are capable of developing imagewise-exposed light-sensitive photographic silver halide.
  • Typical preferred colordeveloping agents are aromatic primary amine colordeveloping agents such as p-aminophenols (which form particularly stable redox combinations with certain complexes, e.g., [Co(en) ]Cl or pphenylenediamines.
  • Useful color-developing agents include 3-acetamido-4-amino-N,N-diethylaniline, P- amino-N-ethyl-N-B-hydroxyethylaniline sulfate, N,N- diethyl-p-phenylenediamine, 2-amino-5- diethylaminotoluene, N-ethyl-N-B- methanesulfonamidoethyl-3-methyl-4-aminoaniline, 4-amino-N-ethyl-3-methy1-N-([3-sulfoethyl)aniline, 4- amino-N-butyl-N-y-sulfobutylaniline, 4-amino-N,N- diethyl-3-n-propylaniline hydrochloride, and the like.
  • aromatic primary amino color-developing agents which provide good results in the process of this invention are 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3- methyl-N,N-diethylaniline hydrochloride, 4-amino-3- methyl-N-ethyl-N-B-(methanesulfonamido)ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-B- hydroxyethylaniline sulfate, 4-amino-3-dimethylamino- N,N-diethylaniline sulfate hydrate, 4-amino-3- methoxy-N-ethyl-N-B-hydroxyethylaniline hydrochloride, 4-amino-N-'ethyl-N-(2-methoxyethyl)-m-toluidine di-paratoluene sul
  • the black-and-white silver halide developers generally refer to those developers which do not couple with photographic color couplers to form useful image dyes.
  • the black-and-white silver halide developers can be effectively used in some instances in the formation or development of the metallic silver in the photographic element.
  • Typical useful developers of this type include hydroquinones, catechols, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, lphenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-3-pyrazolidone and the like, 1-, d or isoascorbic acid, reductones, N-methyl-p-aminophenols, and the like.
  • the amplifier bath can generally comprise any liquid as a carrier medium, but the liquid is preferably predominantly water.
  • the bath generally comprises from about 0.2 to about 20 g. per liter of the transition metal ion complex which preferably is maintained at between about 1 to about 15 g./l.
  • concentrations of cobalt complexes can be used in preferred amplifier baths of this invention without adverse sensitometric effects compared with color-developing solutions which contain the cobalt complexes which contain sufficient color-developing agent to develop substantial amounts of silver halide rapidly.
  • the amplifier bath generally contains a development restrainer and preferably contains enough development restrainer to repress any further silver formation.
  • a development restrainer preferably contains enough development restrainer to repress any further silver formation.
  • the organic development'restrainers i.e., other than the inorganic development restrainers such as the alkali metal bromides
  • the organic development restrainers can be used in the bath in combination with the inorganic development restrainers or alone, but are preferably used in combination with alkali metal bromides.
  • the organic development restrainers are used in concentrations of from 0 to 2 g. and preferably from 0.01 to l g./l.
  • the amplifier bath is generally operated in a pH range of from 6 to '14 and preferably at pH ranges of 8 to 12.
  • the amplifying baths contain only small amounts of or are substantially free of silver halide solvents such as sodium thiosulfate, thiocyanates, thioethers and the like. While bromide ions are often desirable in small amounts of about 2 to 40 g./l. of amplifying solution to repress development, high concentrations such as above 200 g./l. could function to bleach silver halide layers and, likewise, defeat the primary amplification step. In certain embodiments, it is also desirable to maintain the ammonia in the amplifier at less than 10 g./l. since high ammonia concentrations can act as a silver halide solvent, thus allowing bleaching of the silver image.
  • silver halide solvents such as sodium thiosulfate, thiocyanates, thioethers and the like. While bromide ions are often desirable in small amounts of about 2 to 40 g./l. of amplifying solution to repress development, high concentrations such as above 200 g./l.
  • silver halide solvents generally refers to compounds and concentration levels of those compounds which, when employed in an aqueous solution C.), are capable of dissolving more than ten times the amount (by weight) of silver chloride than that which can be dissolved by water at 60 C.
  • concentration of a solvent necessary to fix a silver halide layer is understood to mean that concentration of solvent in a liquid bath which will remove substantially all silver bromide from a photographic element containing a single silver bromide gelatin emulsion layer coated at 30 mg. silver per ft. in 1% minutes at 105 F. maintained at a pH range within 4.0l2.0.
  • the amplifier bath is generally maintained under conditions to repress further net metallic silver formation in the photographic element.
  • color developer can be carried into the amplifier bath in certain embodiments by imbibition in the element, buildup of color developer in the bath can occur.
  • the concentration of color developer in the amplifier solution is maintained below 3 g./l. and preferably below 1 g./l. of amplifier solution.
  • an antioxidant in the amplifier bath, such as sulfites and the like.
  • the concentration of the color developer is maintained at a constant level.
  • color-developer scavengers and the like are used in the bath to keep the amplifier bath substantially free of unoxidized effective color developer.
  • the highly preferred organic development restrainers which are useful in the amplifiers of this invention can be further characterized by the following test.
  • Preferred organic development restrainers or combinations of development restrainers with an alkali metal bromide are those which, when incorporated at about 200 mg./l. in a bath of the following composition:
  • sample is a photographic element comprising a transparent support and one emulsion layer thereon comprising a silver chlorobromide emulsion at 30 mg. of Ag/ft.
  • oxidized color developer such as oxidized 4-amino-N-ethyl-N-(2- methoxyethyl)-m-toluidine-di-paratoluene sulfonate
  • said element is first fully exposed to Dmax and developed in a black-and-white developer such as Kodak Developer D-l9 for 4 minutes at room temperature and fixed with sodium thiosulfate to remove substantially all undeveloped silver halide.
  • organic development restrainers have an additive or superadditiVe effect when used in combination with an alkali metal bromide as shown in some of the following examples.
  • the amplifier bath can be operated over a wide range of temperatures depending on the effect desired. Generally, the amplifier bath is much more stable than amplifier baths previously used and, therefore, is preferably used in processes where it is operated at temperatures above F. and more preferably above F. to decrease the residence time of a photographic element in the bath, thus speeding up the process.
  • the amplifier baths of this invention which are held for l week at F. provide substantially the same development properties as a fresh amplifier bath.
  • the developing baths and amplifier solutions of this invention preferably contain a coupling accelerator which can be an alcohol including aromatic alcohols such as benzyl alcohol, which appears to increase dye yields.
  • a coupling accelerator which can be an alcohol including aromatic alcohols such as benzyl alcohol, which appears to increase dye yields.
  • the alcohol is used in the respective baths at a concentration of up to 40 g.ll. and preferably from about 2 g. to 20 g./l.
  • Coupling accelerators are known in the art, for example, the alcohols disclosed in U.S. Pat. No. 2,304,925 by Jelley issued Dec. 15, 1942, U.S. Pat. No. 2,950,920 by Schwan et al issued Aug. 30, 1960, and the like.
  • the improved processes of this invention can be carried out in several types of processing equipment. Simple manual tray or dip tank processing can be used, as well as processes as described by Tregillus et al, U.S. Pat. No. 3,179,517 issued Apr. 20, 1965, roller transport processes as described in Russell et al, U.S. Pat. No. 3,025,779 issued Mar. 20, 1962, and the like.
  • the process is carried out in a unidirectional processing equipment where the element leaves a bath in the same relative direction with respect to the plane of the element as it enters the bath.
  • a continuous web of the photographic material is processed in unidirectional continuousprocessing equipment.
  • processing solutions can be used in image transfer processes with the developer and amplifier put in separate rupturable pods, such as in the general format as disclosed in Cole, U.S. Pat. No. 3,635,707 issued Jan. 18, 1972, and the like.
  • FIGS. 1-4 accompanying this application.
  • FIG. 1 is an H and D curve of the image records of Example 1.
  • FIG. 2 is an H and D curve of the image records of Example 3, with the curves for the respective imagerecording layers separated for clarity with the caret indicating the point of the 1 1th step on the 2l-stepwedge sensitometric exposure for each set of curves.
  • FIG. 3 is an H and D curve of the image records of Example 4.
  • FIG. 4 is an H and D curve of the image records of Example 6.
  • the designations B, G and R refer to the curves produced by the blue-sensitive layer unit, the green-sensitive layer unit and the red-sensitive layer unit respectively.
  • the improvements in amplifying the image record in the red and green recording layer of a photographic element are readily apparent when processing by first developing the element in a color developer and then inserting the element containing silver halide and an imagewise distribution of metallic silver into an amplifier bath.
  • a photographic element is prepared by coating the following layers in order on a paper support:
  • Samples of the coating are sensitometrically exposed to a graduated-density test object and then processed at a temperature of 32 C. in the following sequence:
  • Test 1A (Control) Test 18 color-develop 3.5 min. 3.5 min. amplify l min. bleach-fix 1.5 min. 1.5 min. wash 2 min. 1 min. stabilize l min. 1 min.
  • the respective baths have the following compositions:
  • Color Developer A water to 1 liter 114 pH6.8 at F.
  • Stabilizer citric acid 6.15 g acetic acid 13.1 g benzoic acid 0.34 g KOH 5 97 g water to 1 liter pH 3.60 at 80 F.
  • Test 1A is run at the optimum time of development to produce Dmax with the cyan and magenta dyes. While this amount of developed silver is more than necessary for the amplification process of Test 13, the development time is held constant to show that the amplification step will generate additional dye beyond that provided in the development step.
  • the H and D curves of the elements of Tests 1A and 1B are produced in FIG. 1.
  • the density of the dyes produced in the red-, blueand green-sensitive layers are reported as dashed lines for Test 1A and solid lines for Test 18.
  • EXAMPLE 2 Additional samples prepared and exposed as described in Example 1 are processed by the procedure of Test 1B, except the development time is 15 seconds and the amplification step is run at 1, 2 and 3 minutes in separate tests.
  • EXAMPLE 4 The imagewise-exposed element of Example 1 is processed according to procedures below to provide for better developability of the blue-sensitive layer:
  • Test 4A Test 4B develop 1 1 amplify O 3 bleach-fix 1% 1% wash 2 2 stabilize 1 1
  • the developer, bleach-fix and stabilization baths are the same as Example 1, and the amplification bath is made as follows:
  • the results are shown in FIG. 3 on an H and D curve where the solid lines represent Test 48 and the dashed lines represent the results of Test 4A.
  • the bluesensitive layer apparently produces more catalytic silver than is shown in Example 3, and as a result provides improved matched dye production in the amplification bath.
  • This amplifier is designed to give high contrast and low sensitivity to build-up effects. This includes carry-over of the color developing solution and subsequent buildup of ammonia in the amplifier. Similar results are obtained with the concentrations of 5- methylbenzotriazole of about 0.3 g./l. The 5- methylbenzotriazole prevents development and fog growth, thus stabilizing the overall process response.
  • EXAMPLE 5 A repeat of the procedures of Test 48 of Example 4 is made wherein the [Co(NH ]C1 is replaced with equimolar amounts respectively of [Co(Nl-I H O]Cl )2( )lz' 3)5( 2 4)3,
  • EXAMPLE 6 A photographic element is prepared and imagewiseexposed as described in Example 1 and processed as follows:
  • the developer is as follows:
  • the amplifier has the following composition:
  • the bleach-fix bath is as follows:
  • the element processed in Test 6A at 105 F. produces a good image record with a sensitometric H and D curve as shown in FIG. 4.
  • the H and D curve where no amplification is used is shown in FIG. 4 in dashed lines. It is apparent that good matched color production can be obtained by continuing to amplify the catalytic silver in each respective layer. Thus, one can raise the contrast and dye Dmax by controlling development and amplification.
  • the developing solution and amplifier solution are held at 105 F. for extended periods of time with periodic processing of similar elements. After 7 days there are no significant changes apparent in the records produced in this system.
  • Test 6C The elements processed in Test 6C produce a sensitometric curve very similar to Test 6A, but the total processing time is considerably reduced.
  • the bleach-fix bath is preferably maintained with a cobalt metal salt level of about 2 to 6 g./1. This can be achieved by addition or carry-over from the amplifier bath.- When 10 g./1. are presentin the amplifier bath, enough cobalt salt is apprently apparently into the bleach-fix solution to keep the level at about 3 g./1 with most multicolor photographic elements.
  • EXAMPLE '7 Test 6A is repeated with the photographic element which is prepared and imagewise-exposed as described in Example 1, with the exception that the amplifier bath is used for only 1% minutes and the [Co(NH;,) ]Cl is replaced, respectively, with equimolar amounts of [Co(NH ](C l-1 O [Co(NH 03 [CO(NHS)B]Z(SO4)3! a)s( 2 a 2)]( a)2 and a)5 2 C Good dye images are obtained in each instance which have much higher density than the control run through Test 68.
  • EXAMPLE 8 A photographic element prepared and imagewiseexposed as described in Example 1 is processed in a continuous process as follows:
  • the amplifier, bleach-fix and wash are the same as in Example 6.
  • the developer is varied in each test to the constituency as follows:
  • Test A With low amounts of color developer produces low yellow dye density but a cyan density of 2.3 and a magenta density of about 1.9.
  • Tests B, C and D all produce dye densities in the element of yellow, cyan and magenta of about 2.0-2.4.
  • concentration of the colordeveloping agent can be reduced and high dye densities can still be achieved in the amplification bath.
  • a photographic film element is prepared as follows (with all ingredients as listed in mg./ft.
  • Test 10A F. Test 1013 (105 F.)
  • the bleach-fix bath is as described in Example 6.
  • the densities for the samples processed in Tests 10A and 10B are as follows:
  • Test 10A (control) Test 10B Dmin Dmax Dmin Dmax yellow 0.15 1.7 0.15 above 3.7 cyan 0.15 1.46 0.15 above 3.2 magenta 0.15 1.64 0.15 above 3.7
  • a process of providing or intensifying a visible image record in an imagewise-exposed photographic element which comprises at least one color-providing layer unit which contains silver halide and an imagewise distribution of metallic silver having associated therewith an image dye-providing photographic color coupler, said process comprising contacting said photographic element in the presence of a color-developing agent with an amplifier composition which contains 1) a development restrainer in a concentration sufficient to repress substantially additional net silver development and 2) a cobalt (ill) complex having a coordination number of 6, wherein said contact is maintained under conditions which reduce cobalt (III) to cobalt- (II) and in turn oxidize said color-developing agent whereby image dye is formed from the color coupler in said layer unit and the oxidized color-developing agent in the areas corresponding to the imagewise distribution of metallic silver.
  • a process according to claim 5 wherein said silver halide developing agent is a primary aromatic amino compound.
  • said developer contains at least two silver halide developing agents which comprise a primary aromatic amino compound and at least one other compound which is a black-and-white silver halide developing agent.
  • said silver halide developing agent is a black-and-white silver halide developing agent.
  • said photographic element comprises at least two of said colorproviding layer units.
  • each of said color-providing layer units comprises said color coupler in at least a 40 percent stoichiometric excess based on effective silver.
  • an imagewise-exposed photographic element comprising a support and at least one image dye-providing layer unit thereon which contains a light-sensitive silver halide emulsion having associated therewith a color coupler
  • the improvement comprising development of the imagewise-exposed silver halide emulsion to provide an imagewise distribution of metallic silver and imbibition of a colordeveloping agent in said photographic element, and then contacting said photographic element with an amplifier composition which contains a development restrainer in a concentration sufficient to repress substantially additional net silver development and wherein said amplifier solution contains a cobalt(lll) metal complex having a coordination number of 6 and said amplifier solution is maintained in contact with said photographic element under conditions which reduce said cobaltflll) to cobalt(II) and in turn oxidize said color-developing agent to provide an increase in dye density with dye produced from said coupler in the areas corresponding to the imagewise distribution of said metallic silver.
  • a process according to claim 11 wherein said color-developing agent imbibed in said photographic element is an aromatic primary amino compound.
  • said color-providing layer unit in said photographic element contains a silver halide emulsion in concentrations of up to 30 mg. of silver per square foot.
  • said photographic element is a multicolor photographic element comprising at least two color-providing layer units which each contains a silver halide emulsion having associated therewith a photographic color coupler in at least a 40 percent stoichiometric excess based on silver.
  • said photographic element is a photographic element comprising at least one image dye-providing layer unit which contains a silver halide emulsion having associated therewith a water-insoluble image dye-providing coupler dissolved in a coupler solvent wherein said coupler is present in at least a 40 percent stoichiometric excess based on effective silver.
  • each of said color-providing layer units contains a silver halide emulsion at a concentration of less than 30 mg. of silver per square foot. 7
  • a process according to claim 12 wherein said development restrainer is the combination of from 0.0l to 2 g./l. of a benzotriazole and from 2 g. to 40 g./l. of an alkali metal bromide.
  • a process according to claim 11 wherein said color-developing agent is 4-amino-N-ethyl-N-( 2- methoxyethyl)-m-toluidine di-p-toluenes ulfonate.
  • a process according to claim 11 where.development of said silver halide emulsion is carried out in a bath which contains a coupling accelerator which is an alcohol.
  • a process according to claim 11 wherein the halide of the silver halide emulsion in said element is less than 0.25 mole percent iodide.
  • a process for developing an imagewise-exposed photographic element comprising a support having at least one layer unit thereon which contains a silver halide emulsion which has associated therewith at least a 40 percent stoichiometric excess of an image dyeforming color coupler based on silver, which process comprises 1) a development step wherein said photographic element is developed to form an imagewise distribution of silver and an aromatic primary amino color-developing agent is imbibed in said photographic element, and then 2) contacting said photographic element with an amplifier bath containing a) a cobalt (III) metal complex having a coordination number of 6 and b) a development restrainer for sufficient time to produce image dye in addition to any dye produced in said development step.
  • a process for providing or intensifying an image record in an imagewise-exposed photographic element comprising a support having thereon at least one image dye-providing layer unit which contains a lightsensitive silver halide emulsion and a dye imageproviding coupler in at least a 40 percent excess based on effective silver, comprising the steps of 1) developing said photographic element in the presence of an aromatic primary amino color-developing agent and 2) contacting said element with an amplifier composition which comprises a cobalt(III) metal complex, an alkali metal bromide at a concentration of from 2 g.
  • an organic development restrainer at a concentration of from 0.01 to 2 g./l., and wherein said amplifier composition contains less than 30 percent by weight of the silver halide solvent which would be necessary to fix said silver halide emulsion.
  • said image dye-providing layer unit contains said color coupler in at least a percent stoichiometric excess based on effective silver.
  • a process for providing or intensifying an image record in an imagewise-exposed photographic element comprising a support having thereon at least two image dye-providing layer units each of which contains a light-sensitive silver halide emulsion and at least a 40 percent excess of an image dye-providing color coupler based on effective silver, comprising the steps of 1 developing said photographic element in the presence of an aromatic primary amino color-developing agent and 2) contacting said element with an amplifier composition which comprises a cobalt(III) metal complex, an alkali metal bromide at a concentration of from 2 g.
  • an organic development restrainer at a concentration of from 0.01 to 2 g./l., and wherein said amplifier composition contains less than 30 percent by weight of the silver halide solvent which would be necessary to fix said silver halide emulsion.
  • one of said image dye-providing layer units comprises a cyan dye-providing coupler and another of said image dyeproviding layer units comprises a magenta dyeproviding coupler and each of said layer units comprises said silver halide emulsion at a concentration of less than 30 mg./ft.
  • each of said image dye-providing layers contain a 110 percent stoichiometric excess of said image dye-providing color coupler.

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US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US3901712A (en) * 1974-03-11 1975-08-26 Eastman Kodak Co Low concentration sensitization and development acceleration
US3923511A (en) * 1971-10-14 1975-12-02 Eastman Kodak Co Photographic process and composition employing CO(III) complexes and silver halide solvents
US3964912A (en) * 1974-09-09 1976-06-22 Eastman Kodak Company Ruthenium containing photographic developers
US3989526A (en) * 1973-11-28 1976-11-02 Eastman Kodak Company Processing compositions comprising inert transition metal complex oxidizing agents and reducing agents
US4002477A (en) * 1973-11-28 1977-01-11 Eastman Kodak Company Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents
US4022616A (en) * 1974-06-03 1977-05-10 Eastman Kodak Company Photographic process involving amplification with CO (III) complexes, silver-dye-bleaching and colorless dye formers which form bleachable dyes
US4035187A (en) * 1972-11-20 1977-07-12 Eastman Kodak Company Process for bleaching silver halide photographic elements containing anionic organic acid compounds
US4045225A (en) * 1975-07-23 1977-08-30 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4057428A (en) * 1972-11-20 1977-11-08 Eastman Kodak Company Photographic elements containing anionic organic acids
US4062684A (en) * 1975-07-23 1977-12-13 Fuji Photo Film Co., Ltd. Method for forming images by a stabilized color intensifying treatment
US4069050A (en) * 1975-08-11 1978-01-17 Fuji Photo Film Co., Ltd. Image forming process
US4084969A (en) * 1975-12-12 1978-04-18 Fuji Photo Film Co., Ltd. Color photographic process
US4097278A (en) * 1975-09-02 1978-06-27 Eastman Kodak Company Redox amplification process employing a combination of oxidizing agents
DE2803233A1 (de) * 1977-01-26 1978-07-27 Konishiroku Photo Ind Verfahren zur herstellung hochkontrastreicher silberbilder
US4113490A (en) * 1974-07-12 1978-09-12 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide photographic materials
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
DE3302741A1 (de) * 1982-01-27 1983-08-04 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbbilderzeugungsverfahren
WO1992007299A1 (en) * 1990-10-19 1992-04-30 Kodak Limited Method of forming a photographic image
US5418117A (en) * 1993-07-24 1995-05-23 Eastman Kodak Company Method of photographic processing
US5439784A (en) * 1990-04-18 1995-08-08 Eastman Kodak Company Method and apparatus for photographic processing solution replenishment
US5466562A (en) * 1993-07-30 1995-11-14 Eastman Kodak Company Method of photographic processing
US5719010A (en) * 1995-12-16 1998-02-17 Eastman Kodak Company Treatment method for treating effluents from a photographic development process
US5736306A (en) * 1994-12-24 1998-04-07 Eastman Kodak Company Photographic silver halide material having improved spectral characteristics
US5972573A (en) * 1997-04-15 1999-10-26 Konica Corporation Image forming method
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GB9024783D0 (en) * 1990-11-14 1991-01-02 Kodak Ltd Method of processing a photographic silver halide colour material
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GB9114933D0 (en) * 1991-07-11 1991-08-28 Kodak Ltd Method for forming a photographic colour image
GB9118299D0 (en) * 1991-08-24 1991-10-09 Kodak Ltd Method of photographic processing
US5702873A (en) * 1991-12-03 1997-12-30 Eastman Kodak Company Redox amplification solutions containing metal ion sequestering agents
GB9126386D0 (en) * 1991-12-12 1992-02-12 Kodak Ltd Method of making stable colour photographic prints
EP0620495A1 (de) * 1993-04-13 1994-10-19 Kodak Limited Fotografische Entwicklungsmaschine
GB9423381D0 (en) 1994-11-19 1995-01-11 Kodak Ltd Photographic developer/amplifier compositions
GB9423382D0 (en) 1994-11-19 1995-01-11 Kodak Ltd Photographic developer/amplifier compositions
GB2302596B (en) * 1995-06-22 1999-02-03 Kodak Ltd Method of photographic processing with solution replenishment
GB9516578D0 (en) 1995-08-12 1995-10-11 Kodak Ltd Method of processing photographic silver halide materials
GB9600112D0 (en) 1996-01-04 1996-03-06 Kodak Ltd Improvements in or relating to photographic processsing apparatus

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US3701660A (en) * 1970-10-21 1972-10-31 Ici Ltd Photosensitive element containing photolabile cobalt or iron complex and the use thereof in color development

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GB239875A (en) * 1924-09-12 1925-11-05 Robert Schwarz Improvements in photographic printing materials
GB777635A (en) * 1954-03-11 1957-06-26 Gevaert Photo Prod Nv Improvements in or relating to a process for simultaneously bleaching and fixing a photographic colour image
US3701660A (en) * 1970-10-21 1972-10-31 Ici Ltd Photosensitive element containing photolabile cobalt or iron complex and the use thereof in color development

Cited By (27)

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Publication number Priority date Publication date Assignee Title
US3923511A (en) * 1971-10-14 1975-12-02 Eastman Kodak Co Photographic process and composition employing CO(III) complexes and silver halide solvents
US4035187A (en) * 1972-11-20 1977-07-12 Eastman Kodak Company Process for bleaching silver halide photographic elements containing anionic organic acid compounds
US4057428A (en) * 1972-11-20 1977-11-08 Eastman Kodak Company Photographic elements containing anionic organic acids
US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US3989526A (en) * 1973-11-28 1976-11-02 Eastman Kodak Company Processing compositions comprising inert transition metal complex oxidizing agents and reducing agents
US4002477A (en) * 1973-11-28 1977-01-11 Eastman Kodak Company Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents
US3901712A (en) * 1974-03-11 1975-08-26 Eastman Kodak Co Low concentration sensitization and development acceleration
US4022616A (en) * 1974-06-03 1977-05-10 Eastman Kodak Company Photographic process involving amplification with CO (III) complexes, silver-dye-bleaching and colorless dye formers which form bleachable dyes
US4113490A (en) * 1974-07-12 1978-09-12 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide photographic materials
US3964912A (en) * 1974-09-09 1976-06-22 Eastman Kodak Company Ruthenium containing photographic developers
US4045225A (en) * 1975-07-23 1977-08-30 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4062684A (en) * 1975-07-23 1977-12-13 Fuji Photo Film Co., Ltd. Method for forming images by a stabilized color intensifying treatment
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
US4069050A (en) * 1975-08-11 1978-01-17 Fuji Photo Film Co., Ltd. Image forming process
US4097278A (en) * 1975-09-02 1978-06-27 Eastman Kodak Company Redox amplification process employing a combination of oxidizing agents
US4084969A (en) * 1975-12-12 1978-04-18 Fuji Photo Film Co., Ltd. Color photographic process
DE2803233A1 (de) * 1977-01-26 1978-07-27 Konishiroku Photo Ind Verfahren zur herstellung hochkontrastreicher silberbilder
DE3302741A1 (de) * 1982-01-27 1983-08-04 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbbilderzeugungsverfahren
US4469780A (en) * 1982-01-27 1984-09-04 Fuji Photo Film Co., Ltd. Color image forming process
US5439784A (en) * 1990-04-18 1995-08-08 Eastman Kodak Company Method and apparatus for photographic processing solution replenishment
WO1992007299A1 (en) * 1990-10-19 1992-04-30 Kodak Limited Method of forming a photographic image
US5418117A (en) * 1993-07-24 1995-05-23 Eastman Kodak Company Method of photographic processing
US5466562A (en) * 1993-07-30 1995-11-14 Eastman Kodak Company Method of photographic processing
US5736306A (en) * 1994-12-24 1998-04-07 Eastman Kodak Company Photographic silver halide material having improved spectral characteristics
US5719010A (en) * 1995-12-16 1998-02-17 Eastman Kodak Company Treatment method for treating effluents from a photographic development process
US5972573A (en) * 1997-04-15 1999-10-26 Konica Corporation Image forming method
US9895527B2 (en) * 2004-04-16 2018-02-20 Bayer Healthcare Llc Fluid delivery system, fluid path set, and pressure isolation mechanism with hemodynamic pressure dampening correction

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