Patent Publication Number: US-6670108-B1

Title: Method of processing silver halide color photographic materials

Description:
FIELD OF THE INVENTION 
     This invention relates to a method of processing a silver halide photographic element. It particularly relates to the rapid processing of a photographic element in a single processing chamber. 
     BACKGROUND OF THE INVENTION 
     Conventional processing of photographic material requires the use of large tanks of processing solutions. Each tank contains a processing solution such as developer, bleach, fixing solution, or washing solution. The material is transported through each tank in turn, typically in a sinusoidal manner. There is a tendency for the solutions to carry over from one tank to another leading to pollution of the solutions. Conventional processing has several other drawbacks. The temperatures which can be utilized are limited and, therefore, the process is slow. The composition of the solutions must be stable over long time periods in the processing tanks. Replenishment of the solutions is difficult to control. The processing apparatus is also very large due to the number of processing tanks. 
     In color negative film processing carried out in small continuous processors or “minilabs” the film passes through each stage of the process and from one tank of processing solution to the next tank of processing solution in a sinusoidal manner. The processing tanks used in a “minilab” processor are usually within the range of 3 to 20 litres volume for each tank depending on the individual design. In Process C-41SM the developer stage has one tank, the bleach stage has one tank, the fixer stage consists of two tanks, and the stabilizer stage consists of three tanks. This gives the total number of tanks as seven. It can be seen that each processing solution is in at least one separate tank, and the film passes sequentially through these tanks. The amounts of processing solution used in a minilab vary with the type of solution and processor, but a developer replenishment rate is generally about 375-500 mL/m 2 , a bleach replenishment rate is about 130 mL/m 2 , a fixer replenishment rate is about 200-900 mL/m 2 , and a rinse or stabilizer replenishment rate is about 775-1000 mL/m 2 . 
     A method of processing photographic material in a single processing chamber is described in U.S. application Ser. No. 09/920,495 of Twist et al filed Aug. 1, 2001. One of the advantages of the process is that small volumes of processing solutions are used per unit surface area of the photographic material that is processed (9.4 to 1900 mL/m 2 ). Examples of the process include the sequential application and removal of developer+stop, bleach, fixer, and rinse solutions from the processing chamber. A rapid process example applies developer solution at 280 mL/m 2  and stop, bleach, and fixer solutions each at 375 ml/m 2 . 
     A compact processing method that comprises the sequential addition to a processing chamber of a first processing solution (for example, a developer, fixer, or bleach solution) to process the material and then a second processing solution (for example, a stop, fixer, bleach, or bleach-fixer solution) to process the material further without removing the first processing solution has been disclosed in U.S. application Ser. No. 10/012673 of Twist filed Oct. 30, 2001. Such a process is referred to hereafter as a merged process. In a preferred version of the method a developer solution is first added to the chamber to develop the material. Then, a fixer solution is added to the developer solution within the chamber for the purpose of stopping development and initiating fixing. Subsequent to this, a bleaching agent solution is added to the developer/fixer mixture within the chamber to bleach developed silver and complete the fixing of the material. Again, low volumes of processing solutions are applied. For color negative film processing, the first processing solution of the method is applied at 50 to 2850 mL/m 2 , and the second and subsequent processing solutions are applied at 6 to 2000 mL/m 2 . Highly concentrated processing solutions can be used. 
     Useful concentrations of fixing agents and bleaching agents in rapid versions of such a merged processing method for color negative films have been disclosed, for example, in U.S. application Ser. No.10/012,673 of Twist filed Oct. 30, 2001 and U.S. application Ser. No. 10/051,074 of Hall et al filed Jan. 30, 2002. Fixing agent concentrations (thiosulfate is preferred, and ammonium thiosulfate is more preferred as a fixing agent for rapid fixing) above 0.5 mol/L are useful in processing solution mixtures of the method. The fixing agents should be preferably at a total concentration from about 0.75 mol/L to about 2.0 mol/L in processing solution mixtures of the method in order to process rapidly without costly, wasteful use of fixer. The preferred Fe(III)chelate bleaching agents should be at a total concentration from about 0.09 equivalents/L to about 0.6 equivalents/L in the processing solution mixtures of the method in order to process rapidly without costly, wasteful use of bleaching agent. A more preferred Fe(III)chelate bleaching agent concentration is from about 0.12 equivalents/L to about 0.6 equivalents/L. This concentration of Fe(III)chelate bleaching agent is that concentration resulting after the oxidation of any developing agent in the mixture has taken place. Such oxidation results in the reduction of an equivalent of Fe(III)chelate to Fe(II)chelate for each equivalent of developing agent that is oxidized and results in a lower concentration of Fe(III)chelate bleaching agent in the mixture that is available for bleaching silver. The more preferred Fe(III)chelate bleaching agents are Fe(III) complexes of ethylenediaminetetraacetic acid, 1,3-propanediamine-N,N,N′,N′-tetraacetic acid, ethylenediamine-N-(2-carboxyphenyl)-N,N′,N′-triacetic acid, ethylenediaminedisuccinic acid (particularly the S,S-isomer), ethylenediaminemonosuccinic acid, N-(2-carboxyethyl)aspartic acid, and N-methyliminodiacetic acid, which may be used alone or in combination. 
     When processing solutions are added to the processing chamber to form a bleach-fixing solution mixture, the pH of the bleach-fixing solution mixture should be from about 4 to about 8, preferably from about 4.5 to 7, and more preferably from about 4.5 to 6.5. At pH&#39;s lower than about 4.5, bleaching occurs quite rapidly, but the formation of colorless (leuco) forms of cyan image dyes may occur which degrades image quality. At pH&#39;s higher than about 6.5, bleaching takes place more slowly. Also, the non-imagewise formation of image dye from bleach-induced dye formation (bleach stain) can occur at higher bleach-fixer pH&#39;s, causing.densities of the photographic material to be unacceptably high. 
     These desired concentrations of fixing agents and bleaching agents can be achieved with low applied volumes of stop, fixer, bleach, or bleach-fixer solutions added to the developer solution when the volume of applied developer solution is also kept low. This is because the volume of each solution—developer, stop, fixer, bleach, or bleach-fixer—dilutes the constituents of each solution comprising the merged mixture. In addition, the developing agent reduces some of the bleaching agent in the mixture making less available to accomplish bleaching of developed silver. Lower volumes of solutions can be used to achieve the necessary processing concentrations if they are more concentrated in fixing and bleaching agents, but even so, there is a limit to the solubility of processing agents in aqueous solution. The pH parameters can also be easily met when the volume of applied developer solution is kept low. This is because with less applied developer solution, there is less alkalinity present that must be neutralized to stop development and to adjust the pH into the range for rapid and effective desilvering by the merged mixture. This alkalinity is neutralized by providing the stop, fixer, bleach, or bleach-fixer solutions with a suitably low pH and a quantity of one or more acid-providing buffers. Applied processing solutions are measured in terms of the volume added per unit area of material to be processed, for example, in milliliters of solution per square meter of photographic material. 
     For example, in the merged process method the applied volume of various processing solutions can be as shown below. 
     
       
         
           
               
               
             
               
                   
                   
               
               
                   
                 Applied Volume 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 Add developer to processing chamber and develop 
                 566 mL/m 2   
               
               
                 Add fixer solution to processing chamber to stop 
                 377 mL/m 2   
               
               
                 development 
               
               
                 Add bleach solution to processing chamber to bleach 
                 377 mL/m 2   
               
               
                 and fix the material 
               
               
                   
               
            
           
         
       
     
     Often, however, a larger volume of developer is desirable or necessary in order to develop the material more rapidly or with improved uniformity. However, if a larger volume of developer is applied, then a larger volume of fixer (or a more concentrated fixer solution), a larger volume of bleach solution (or a more concentrated solution of bleaching agent), or a larger volume of a bleach-fixer solution (or a more concentrated bleach-fixer solution) must be applied to achieve the desired concentrations of fixing and bleaching agent in the resulting mixture in order to process sufficiently rapidly. Larger amounts of acid-providing buffers must be used to neutralize the alkalinity of the developer solution. The larger volumes of processing solution, or the use of more concentrated processing solutions, increase the cost of running the process. In particular, larger volumes of bleach or bleach-fixer solutions or more concentrated bleach or bleach-fixer solutions contribute significantly to the cost of the processing chemistry for the process. 
     A method of processing is needed which reduces the amount of bleaching agent, provided by a bleach solution or bleach/fix solution, which must be utilized in a merged process utilizing a single chamber processor. This is particularly needed when larger volumes of developer solution are required. 
     SUMMARY OF THE INVENTION 
     A method for processing a silver halide color photographic material comprising the steps of loading the material into a chamber adapted to hold the material therein; introducing a measured amount of a developer solution into the chamber; developing the photographic material with the developer solution; introducing into the chamber a measured amount of a processing solution which arrests development, without removing th e developer solution, to form a developer/stop solution mixture; processing the photographic material with the developer/stop solution mixture, substantially removing all of the developer/stop mixture solution from the chamber; then providing in the chamber a bleach/fixer solution mixture comprising a bleaching agent and a fixing agent; and processing the photographic material with the bleach/fixer solution mixture; wherein the color developer solution is utilized in the amount of greater than or equal to 375 ml/m 2  of the photographic material that is processed; and wherein the total volume of solution or solution mixture for each processing stage is spread over the whole area of the photographic material in a repetitive manner to enable uniform processing. In one embodiment the ratio of the bleaching agent equivalents utilized in the process to the volume of color developer solution utilized in the process, in liters, is less than or equal to 0.48. 
     This invention provides a more cost effective method for processing silver halide elements in a single chamber processor by reducing the amount of bleaching agent, provided by a bleach solution or bleach/fix solution, which must be utilized. The inventive process also uses less total processing solution volume. The advantages of the invention become greater if the applied developer volume must be increased further in order to process satisfactorily, such as with greater rapidity or uniformity. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIGS. 1A and 1B show a schematic side view and section view, respectively, of apparatus in which the method of the present invention can be performed. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the method of the invention the silver halide color photographic material is loaded into a chamber adapted to hold the material therein; a measured amount of a developer solution is introduced into the chamber, and the photographic material is developed with the developer solution. Next a measured amount of a processing solution which arrests development is introduced into the chamber without removing the developer solution, to form a developer/stop solution mixture in the chamber. The photographic material is processed with the developer/stop solution mixture to stop development, and substantially all of the developer/stop mixture solution is removed from the chamber prior to the introduction of the next solution. In this aspect the invention differs from a preferred merged process as described above. At that point there is provided in the chamber a bleach/fixer solution mixture comprising a bleaching agent and a fixing agent, and the photographic material is processed with the bleach/fixer solution mixture. In this method the total volume of solution or solution mixture for each processing stage is spread over the whole area of the photographic material in a repetitive manner to enable uniform processing. The method of merged processing whereby a second solution is introduced into a processing chamber prior to removal of a first processing solution is described in detail in U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001, the entire specification of which is incorporated herein by reference. Although this inventive process sequence requires the additional time to remove the mixture of developer and stop solution, the overall time required for the process sequence can be just as short as the time required for the developer/fixer/bleach mixture process. In addition, the total volume of processing solutions used per square meter of photographic material processed is similar to that of the more costly developer/fixer/bleach mixture process and can be significantly less. The processing steps of the inventive method of processing may be conducted independently at a temperature of 20 to 80° C., preferably from 35 to 60° C. by independently heating and applying the solutions at prescribed temperatures. 
     This invention is suitable for use when the color developer solution is utilized in the amount of greater than or equal to 375 ml/m 2  of the photographic material that is processed. It is more suitable when the color developer solution is utilized in the amount of greater than or equal to 470 ml/m 2  of photographic material that is processed, even more suitable when the color developer solution is utilized in the amount of greater than or equal to 850 ml/m 2  of photographic material that is processed, and most suitable when the color developer solution is utilized in the amount of greater than or equal to 1200 ml/m 2  of photographic material that is processed. Preferably the developer is applied in the inventive process in an amount less than 2000 mL/m 2  of photographic material processed. 
     Preferably the ratio of the bleaching agent equivalents utilized in the process to the volume of color developer solution utilized in the process, in liters, is less than or equal to 0.48, preferably less than or equal to 0.4 equivalents, more preferably less than or equal to 0.33, and most preferably less than or equal to 0.25. By “bleaching agent equivalents” is meant the following. A bleaching agent is an oxidizing agent. The quantity of oxidizing agent involved in an oxidation/reduction reaction, or redox reaction, can be expressed in terms of equivalents of oxidizing agent. An equivalent of an oxidizing agent is the amount of oxidizing agent that accepts one mole of electrons from reducing agents in an oxidation/reduction chemical reaction. Similarly, an equivalent of a reducing agent gives up one mole of electrons to oxidizing agents in a redox reaction. This invention is concerned with the amount of bleaching agent used in the process, in equivalents, relative to the volume of developer solution used in the process, in liters. When this ratio is less than or equal to certain amounts and when the applied developer solution volume is above certain amounts, then the method of processing of this invention is advantageous in terms of cost and the total volume of processing solutions required for the method of processing. 
     The development step may be carried out for a period from 15 to 195 seconds, preferably less than 100 seconds, and most preferably from 30 to 100 seconds for rapid processing. Photographic color developing compositions used in the invention typically include one or more color developing agents and various other conventional addenda including preservatives or antioxidants (including sulfites, and hydroxylamine and its derivatives), sulfites, metal ion sequestering agents, corrosion inhibitors, and buffers. These materials can be present in conventional amounts. For example, the color developing agent is generally present in an amount of at least 0.001 mol/l (preferably at least 0.01 mol/l), and an antioxidant or preservative for the color developing agent is generally present in an amount of at least 0.0001 mol/l (preferably at least 0.001 mol/l). The pH of the composition is generally from about 9 to about 13, and preferably from about 10 to about 12.5. 
     Exemplary color developing compositions and components (except the sensitizing dye stain reducing agents described herein) are described, for example, in EP-A-0 530 921 (Buongiorne et al), U.S. Pat. No. 5,037,725 (Cullinan et al), U.S. Pat. No. 5,552,264 (Cullinan et al), U.S. Pat. No. 5,508,155 (Marrese et al), U.S. Pat. No. 4,892,804 (Vincent et al), U.S. Pat. No. 4,482,626 (Twist et al), U.S. Pat. No. 4,414,307 (Kapecki et al), in U.S. Pat. No. 4,876,174 (Ishikawa et al), U.S. Pat. No. 5,354,646 (Kobayashi et al) and U.S. Pat. No. 4,264,716 (Vincent et al), all incorporated herein for their teaching about color developing compositions. 
     Useful preservatives in the color developing compositions include sulfites (such as sodium sulfite, potassium sulfite, sodium bisulfite and potassium metabisulfite), hydroxylamine and its derivatives, especially those derivatives having substituted or unsubstituted alkyl or aryl groups, hydrazines, hydrazides, amino acids, ascorbic acid (and derivatives thereof), hydroxamic acids, aminoketones, mono- and polysaccharides, mono- and polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, and oximes. More particularly useful hydroxylamine derivatives include substituted and unsubstituted monoalkyl- and dialkylhydroxylamines (especially those substituted with sulfo, carboxy, phospho, hydroxy, carbonamido, sulfonamido or other solubilizing groups). Mixtures of compounds from the same or different classes of antioxidants can also be used if desired. 
     Examples of useful antioxidants are described, for example, in U.S. Pat. No. 4,892,804 (noted above), U.S. Pat. No. 4,876,174 (noted above), U.S. Pat. No. 5,354,646 (noted above), U.S. Pat. No. 5,660,974 (Marrese et al), and U.S. Pat. No. 5,646,327 (Bums et al), the disclosures of which are all incorporated herein by reference for description of useful antioxidants. Many of these antioxidants are mono- and dialkylhydroxylamines having one or more substituents on one or both alkyl groups. Particularly useful alkyl substituents include sulfo, carboxy, amino, sulfonamido, carbonamido, hydroxy, and other solubilizing substituents. 
     Most preferably, the noted hydroxylamine derivatives can be mono- or dialkylhydroxylamines having one or more hydroxy substituents on the one or more alkyl groups. Representative compounds of this type are described for example in U.S. Pat. No. 5,709,982 (Marrese et al), incorporated herein by reference. Specific di-substituted hydroxylamine antioxidants include, but are not limited to: N,N-bis(2,3-dihydroxypropyl)hydroxylamine, N,N-bis(2-methyl-2,3-dihydroxypropyl)hydroxylamine and N,N-bis(1-hydroxymethyl-2-hydroxy-3-phenylpropyl)hydroxylamine. The first compound is preferred. 
     Particularly useful color developing agents include aminophenols, p-phenylenediamines (especially N,N-dialkyl-p-phenylenediamines) and others which are well known in the art, such as EP 0 434 097 Al (published Jun. 26, 1991) and EP 0 530 921 Al (published Mar. 10, 1993). Preferred color developing agents include, but are not limited to, N,N-diethyl p-phenylenediamine sulfate (KODAK Color Developing Agent CD-2), 4-amino-3-methyl-N-(2-methane sulfonamidoethyl )aniline sulfate, 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate (KODAK Color Developing Agent CD-4), p-hydroxyethylethylaminoaniline sulfate, 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine sesquisulfate (KODAK Color Developing Agent CD-3), 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine sesquisulfate, and others readily apparent to one skilled in the art. 
     Development may be arrested by adding a stop solution, a fixer solution, a bleach solution, or a bleach-fixer solution to the processing chamber containing the developer solution, thoroughly mixing the solutions together to form a developer/stop solution, and bringing the mixture into contact with the photographic material. This processing step is performed for a period from 5 to 60 seconds, preferably for a period of less than 30 seconds, and most preferably for a period from 10 to 30 seconds. Preferably an acidic stop solution or a fixer solution is used. More preferably a fixer solution is used. This fixer solution can be the same composition as the one used to form the bleach-fixer mixture subsequently in the processing chamber. A stop solution stops development by rapidly lowering the pH of the mixture below that at which development occurs. A bleach solution also stops development by rapidly lowering the pH of the mixture. A fixer when added to the developer solution can stop development by fixing or dissolving some of the silver halide. A stop/fix solution is simply a low pH fix solution that stops development by lowering pH and as well as by fixing silver halide. The pH of the mixture may be lowered also by one or more acid-providing buffer compounds in the solution that arrests development. Such buffers include carboxylic acids such as acetic acid, succinic acid, maleic acid, and sulfosuccinic acid, and amine salts such as imidazolium salts. The developer/stop solution is then substantially removed from the chamber. There may be some developer/stop solution remaining in the chamber since the chamber is not normally rinsed before the next step. 
     The bleach/fixer solution mixture comprising a bleaching agent and a fixing agent may be provided to the chamber in many fashions, and the term “provided” may include any of the following. The bleach/fixer solution mixture may be provided by combining a measured amount of a bleach solution and a measured amount of a fixer solution prior to introducing them into the chamber, or the bleach/fixer solution mixture may be provided by introducing separately into the chamber a measured amount of a fixer solution and a measured amount of a bleach solution. The bleach solution may be introduced into the chamber before the fixer solution, the fixer solution may be introduced into the chamber before the bleach solution or the fixer solution, and the bleach solution may be introduced into the chamber simultaneously. There may also be utilized a pre-prepared bleach/fixer solution, such as KODAK EKTACOLOR RA Bleach-Fix which is marketed by Eastman Kodak Company, Rochester, New York wherein a measured amount of the pre-prepared bleach/fixer solution is introduced into the chamber. The pre-prepared bleach/fixer solution and a measured amount of a bleach solution may be introduced into the chamber, with either solution being introduced first or both solutions may be introduced into the chamber simultaneously. They may also be mixed before introduction to the chamber. The pre-prepared bleach/fixer solution may also be introduced with a measured amount of a fixer solution, again with either solution being introduced first or both solutions introduced into the chamber simultaneously. Again, the solutions may be mixed before introduction into the chamber. A preferred method of providing the bleach/fixer solution mixture within the processing chamber is to add a measured amount of a concentrated fixer solution and a measured amount of a concentrated bleach solution to the processing chamber, or to form a mixture of the fixer and bleach solutions just prior to introducing the mixture to the chamber. 
     The bleaching and fixing may be independently or simultaneously conducted for a period from 10 to 240 seconds, preferably less than 120 seconds, and. most preferably from 15 to 120 seconds for rapid processing. For example, the fixer solution may be introduced first into the processing chamber to fix the photographic material, and after a time a bleach or a bleach-fixer solution can be added to the chamber to bleach the material. Alternatively, a bleach solution may be introduced first into the processing chamber to begin bleaching the photographic material, and after a time a fixer or a bleach-fixer solution can be added to the chamber to fix the material. 
     In this inventive process, the concentration of fixing agents in the bleach-fixing mixture within the processing chamber should be at least about 0.75 mol/L, preferably at least about 1 mol/L up to about 2 mol/L. The concentration of bleaching agents in the bleach-fixing mixture within the processing chamber should be at least about 0.2 equivalents/L, preferably at least about 0.25 equivalents/L up to about 0.6 equivalents/L. 
     When processing solutions are added to the processing chamber to form a bleach-fixing solution mixture, the pH of the bleach-fixing solution mixture should be from about 4 to about 8, preferably from about 4.5 to 7, and more preferably from about 4.5 to 6.5. At pH&#39;s lower than about 4.5, bleaching occurs quite rapidly, but the formation of colorless (leuco) forms of cyan image dyes may occur which degrades image quality. At pH&#39;s higher than about 6.5, bleaching takes place more slowly. Also, the non-imagewise formation of image dye from bleach-induced dye formation (bleach stain) can occur at higher bleach-fixer pH&#39;s, causing densities of the photographic material to be unacceptably high. 
     The concentration of fixing agents in the fixer solution should be from about 1.3-5 mol/L, preferably from about 2-5 mol/L, and more preferably from about 2-4 mol/L. The pH of the fixer solution should be from about 4.5-8, preferably from about 5 to 7.5, and more preferably from about 5.25 to 7 for the best overall chemical stability. The concentration of bleaching agents in the bleach solution should be at least about 0.25 equivalents/L, preferably at least 0.3 equivalents/L, and more preferably at least 0.375 equivalents/L. The concentration of bleaching agents in the bleach solution can be as high as 1.7 equivalents/L. More concentrated fixer solutions allow the process to be run more economically with lower volumes of fixer solution having to be applied and with lower amounts of bleaching agents in the bleaching or bleach-fixing solutions having to be applied. Likewise, more concentrated bleach or bleach-fixing solutions allow the process to be run more economically with lower volumes of bleach or bleach-fixing solutions having to be applied and with lower amounts of fixing agents in the fixer solution having to be applied. 
     Photographic bleaching compositions which may be used in this invention generally include one or more high metal valent ion bleaching agents, such as iron(III) complexes with simple anions (such as nitrate, sulfate, and acetate), or with carboxylic acid or phosphonic acid ligands. Particularly useful bleaching agents include iron complexes of one or more aminocarboxylic acids, aminopolycarboxylic acids, polyaminocarboxylic acids or polyaminopolycarboxylic acids, or salts thereof. Particularly useful chelating ligands include conventional polyaminopolycarboxylic acids including ethylenediaminetetraacetic acid and others described in  Research Disclosure , noted above, U.S. Pat. No. 5,582,958 (Buchanan et al) and U.S. Pat. No. 5,753,423 (Buongiorne et al). Biodegradable chelating ligands are also desirable because the impact on the environment is reduced. Useful biodegradable chelating ligands include, but are not limited to, iminodiacetic acid or an alkyliminodiacetic acid (such as methyliminodiacetic acid), ethylenediaminedisuccinic acid and similar com rpounds as described in EP-A- 0 532,003, and ethylenediamine monosuccinic acid and similar compounds as described in U.S. Pat. No. 5,691,120 (Wilson et al), all of which are incorporated herein by reference in relation to their description of bleaching agents. 
     These and many other such complexing ligands known in the art including those described in U.S. Pat. No. 4,839,262 (Schwartz), U.S. Pat. No. 4,921,779 (Cullinan et al), U.S. Pat. No. 5,037,725 (noted above), U.S. Pat. No. 5,061,608 (Foster et al), U.S. Pat. No. 5,334,491 (Foster et al), U.S. Pat. No. 5,523,195 (Darnon et al), U.S. Pat. No. 5,582,958 (Buchanan et al), U.S. Pat. No. 5,552,264 (noted above), U.S. Pat. No. 5,652,087 (Craver et al), U.S. Pat. No. 5,928,844 (Feeney et al) U.S. Pat. No. 5,652,085 (Wilson et al), U.S. Pat. No. 5,693,456 (Foster et al), U.S. Pat. No. 5,834,170 (Craver et al), and U.S. Pat. No. 5,585,226 (Strickland et al), all incorporated herein by reference for their teaching of bleaching compositions. 
     Other components of the bleaching solution include buffers, halides, corrosion inhibiting agents, and metal ion sequestering agents. These and other components and conventional amounts are described in the references in the preceding paragraph. The pH of the bleaching composition is generally from about 3.5 to about 6.5. 
     The more preferred Fe(III)chelate bleaching agents are Fe(III) complexes of ethylenediaminetetraacetic acid (EDTA), 1 ,3-propanediamine-N,N,N′,N′-tetraacetic acid (PDTA), ethylenediamine-N-(2-carboxyphenyl)-N,N′,N′-triacetic acid, ethylenediaminedisuccinic acid (particularly the S,S-isomer), ethylenediaminemonosuccinic acid, N-(2-carboxyethyl) aspartic acid, and N-methyliminodiacetic acid, which may be used alone or in combination. The most preferred bleaching agent is a ferric ion complex of PDTA for processing color reversal and color negative materials rapidly. For processing color paper materials a ferric complex of EDTA is preferred. Multiple bleaching agents can be present if desired. 
     Fixing solutions which may be used in the invention contain a photographic fixing agent. Examples of photographic fixing agents include, but are not limited to, thiosulfates (for example, sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate), thiocyanates (for example, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate), thioethers (such as ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol), imides, and thiourea. Thiosulfates and thiocyanates are preferred, and thiosulfates are more preferred. Ammonium thiosulfate is most preferred. 
     It is also known to use fixing accelerators in fixing compositions. Representative fixing accelerators include, but are not limited to, ammonium salts, guanidine, ethylenediamine and other amines, quaternary ammonium salts and other amine salts, thiourea, thioethers, thiols and thiolates. Examples of useful thioether fixing.accelerators are described in U.S. Pat. No. 5,633,124 (Schmittou et al), incorporated herein for the teaching of fixing compositions. 
     Fixing compositions generally contain one or more monovalent or divalent cations supplied by various salts used for various purposes (for example, salts of fixing agents). It is preferred that the cations be predominantly ammonium cations, that is at least 50 % of the total cations are ammonium ions. Such fixing compositions are generally known as “high ammonium” fixing compositions. 
     Fixing compositions can also include one or more of various addenda optionally but commonly used in such compositions for various purposes, including hardening agents, preservatives (such as sulfites or bisulfites), metal sequestering agents (such as polycarboxylic acids and organophosphonic acids), buffers, and fixing accelerators. The amounts of such addenda in the working strength compositions would be readily known to one skilled in the art. 
     Other details of fixing compositions not explicitly described herein are considered well known in the art and are described, for example, in  Research Disclosure  publication 38957 (noted below), and publications noted therein in paragraph XX(B), U.S. Pat. No. 5,424,176 (Schmittou et al), U.S. Pat. No. 4,839,262 (noted above), U.S. Pat. No. 4,921,779 (noted above), U.S. Pat. No. 5,037,725 (noted above), U.S. Pat. No. 5,523,195 (noted above), U.S. Pat. No. 5,552,264 (noted above), all incorporated herein by reference for their teaching of fixing compositions. 
     Following bleaching and fixing one or more washing or rinsing steps may be carried out either within or externally to the processing chamber. These steps may be performed for a period of 5 to 120 seconds, preferably from 10 to 30 seconds if within the processing chamber. Each washing or rinsing solution within the processing chamber is substantially removed from the chamber before any subsequent washing or rinsing solution is added to the chamber. The washed or rinsed photographic material may then be dried within or externally to the processing chamber. 
     The used processing solutions from the inventive process can be delivered to one or more waste containers for silver recovery, developer oxidation, and control of corrosivity as described in U.S. application Ser. No. 10/021,703 of Schmittou filed Oct. 30, 2001. For example, silver-bearing fixer-containing or bleach-fixer-containing wastes and subsequent wash or rinse solutions can be added to a container containing a silver precipitating agent such as trisodium trimercapto-s-triazine (TMT). This lowers the soluble silver concentration so that the waste may be safely transported, and the precipitated silver can be easily recovered. The waste bleaching or bleach-fixing solution can be added to a container containing waste developer so that the developer may be oxidized by the bleaching agent. A single waste container may contain all of the processing solution waste liquid from the process. The pH and buffer content of the processing solutions and the alkaline nature of the TMT silver precipitating agent can be selected so that the waste mixture or mixtures have a pH greater than or equal to about 7.0, rendering the waste non-corrosive to low-carbon steel. 
     The inventive process can be very effectively applied to the system and method of processing photographic film images that is described in U.S. application Ser. No. 10/051,074 of Hall et al filed Jan. 18, 2002. The individual steps of development, stoppage of development, and bleach-fixing can be individually adjusted and programmed for processing time, processing solution temperature, and processing solution composition based on the type of photographic material being processed. If a separate fixer or separate bleach solution is used in the formation of the bleach-fixer mixture within the processing chamber, then these solutions can be individually measured and delivered to the chamber to control the amounts of fixing agents and bleaching agents in the mixture for each photographic material. Such control of processing conditions can help optimize a process for processing speed, processing ecology, or processing economy, or energy usage. 
     The method of the invention may be performed in a single use wave processor of the type disclosed in co-pending application no GB 0023091.2, filed on Sep. 20 2000, also incorporated herein by reference. The processor comprises an apparatus for processing a photographic material, comprising a chamber adapted to hold the material therein, means. for introducing a measured amount of solution into the chamber, means for removing the solution from the chamber, means for rotating the chamber and means for sweeping the surface of the material at each rotation of the chamber, thereby to form a wave in the solution through which the material may pass. FIGS. 1A and 1B show a single use wave processor. 
     The wave processor comprises a cylinder  1  having at least one open end. The cylinder may be made of stainless steel, plastics, or any other suitable material. A transparent material, such as polycarbonate, may be used if it is desired to scan the material while it is within the cylinder. The cylinder defines a processing chamber. An arm  3  is provided on the outer side of the cylinder for holding a film cassette  4 . A slot  6  with a water tight cover (not shown) is provided through the wall of the cylinder to allow the strip of film  5  from the film cassette to enter the processing chamber. The watertight cover may be in the form of a hinged door having a rubber wedge. However, any suitable means may be used. A circular slot is defined around the inner circumference of the chamber for holding the strip of film  5  by the edges. 
     A second arm  21  is located within the chamber. This arm  21  grabs the tongue of the film and holds it against the inner circumference of the chamber. A close fitting cover (not shown) may be provided around the inner circumference of the chamber which sits above the film surface by at least 0.5 mm. This cover provides at least three functions to improve the performance of the apparatus. Firstly, it lowers water evaporation which can cause a temperature drop and can concentrate the processing solution as processing is occurring. Secondly, it can itself provide agitation by maintaining a puddle of solution in the gap between the cover and the film surface at the lowest point of the chamber. Thirdly, it provides a film retaining means making edge guides unnecessary, although edge guides can be also be provided to prevent the film sticking to the cover. It allows both 35 mm film and APS film (24 mm) to be loaded in the same apparatus, and it also allows any length of film to be loaded. The material of the cover can be impervious to processing solution and as such is provided with a break or gap in its circumference so that the two extreme ends of the cover do not meet and through which processing solution is added to the film surface. In this embodiment the cover is fixed and rotates with the chamber as the chamber rotates. In another embodiment the cover is not fixed and rests on rails on each side which allow the cover to slide and remain stationary as the chamber rotates. In this embodiment the cover is again provided with a break or gap in its circumference so that processing solutions can be added to the film surface. In this embodiment a roller can also be provided which sits in the gap in the circumference of the cover and which remains essentially at the lowest point of the chamber. The roller provides additional agitation. In another embodiment the cover can be made of a material which is porous to processing solution such as a mesh material or a material punctured with holes. The cover can be made of plastic, metal, or any suitable material. However, the cover is not an essential feature of the invention. 
     A drive shaft  2  is provided at the closed end of the cylinder for rotation thereof. The open end of the cylinder  1  is provided with a flange  7 . The flange retains solution within the chamber. In the embodiment shown in FIG. 1B the processing solutions are introduced into and removed from the chamber by means of syringes  8 . However any suitable means may be used, for example, metering pumps. The solutions may be introduced from a reservoir  9 . Alternatively the solutions may be held in a cartridge prior to use. The cartridge can consist of part or all the processing solutions required to complete the process and is easily placed or “plugged in” the processor without the need to open or pour solutions. The cartridge can consist of an assembly of containers for each of the solutions required for the process. When required, merged solutions may be removed by suction or any other means. Residue of solutions therefore do not build up within the processing chamber. This results in the processing chamber being essentially self cleaning. The crossover times from one solution to another are very short. It is possible to mount an infrared sensor outside of the chamber. The sensor monitors the silver density of the material during development thereof. 
     A wave forming mechanism is provided within the processing chamber. This wave forming mechanism sweeps the film surface and forms a wave of solution, primarily at the lowest point in the chamber. In the embodiment shown in FIG. 1 the mechanism is a freestanding roller  10 . It is possible that this roller may be held on a loose spindle (not shown) which would allow the roller to be steered and also to be raised and lowered into position. The position of the roller can be changed with this mechanism so that it is to the left or right of bottom dead center which can be advantageous for the smooth running of the roller. It is also desirable to raise or lower the roller which might facilitate film loading. 
     In operation a film cassette  4  is located in the arm  3  and held on the outside of the cylinder  1 . The end of the film  5  is withdrawn from the cassette and entered into the processing chamber by means of the slot  6 . The arm  21  holds the film against the inner circumference of the cylinder and the cylinder  1  is rotated so that the film  5  is unwound from the cassette and loaded into the processing chamber. The film is held in a circular configuration within the processing chamber. This loading is carried out while the processing chamber is dry although it is also possible to load the film if the chamber is wet. The film is held with the emulsion side facing inwards with respect to the chamber. It is also possible to load the film with the emulsion side facing outwards provided a gap is present between the film surface and the inner circumference of the chamber. Once loaded, the film is held by the edges thereof within the circular slot around the circumference of the chamber. 
     The processing chamber is heated. The chamber can be heated electrically or by hot air. Alternatively the chamber may be heated by passing the lower end thereof through a heated water bath. The chamber is then rotated. When the desired temperature is reached, a given volume of a first processing solution is introduced into the chamber. The processing solution may be heated prior to being introduced into the chamber. Alternatively the solution may be unheated or cooled. As the chamber rotates, the film is continuously re-wetted with the given volume of solution. 
     Processing solution is added onto the roller  10  which is contacted across the whole width thereof by a spreader  52 . This can be seen in more detail in FIG.  2 . The spreader may be made of flexible soft plastic, rigid plastic, or any other suitable material. The roller  10  rotates in contact with the spreader  52 . Processing solution is delivered, via a supply pipe, down the spreader to the region of contact between the roller and the spreader. This method forms a uniform bead of solution over the region of contact between the roller and the spreader that extends across the width of the roller  10 . This allows uniform spreading of the processing solution onto the film  5  as it passes under the roller  10 . It is also possible to add solutions very quickly by “dumping” a given volume into the chamber while it is rotating so that it immediately forms a “puddle” or wave in front of the roller. Yet another method is to add the processing solutions when the chamber is stationary to a region where there is no film or to a region where there is no image such as the fogged end of the film. The rotation of the chamber is then started after the solution has been added. The time interval between adding the solution and starting the rotation can be from zero to any desired hold time. 
     The roller  10  acts as a wave forming mechanism. This wave forming mechanism, in combination with the rotation of the chamber, provides very high agitation which gives uniform processing even with very active processing solutions. High agitation and mixing are required when only small volumes of solution are being used. If a large volume of solution is added to the chamber in the absence of a wave forming mechanism, a “puddle” of solution is formed, and spreading and agitation is achieved. However if a small volume of solution is added to the chamber in the absence of a wave forming mechanism, then solution adheres to the film as the chamber rotates. There is no “puddle” formed, and there is consequently no agitation or mixing and processing is slow and non-uniform. The agitation and mixing mechanism of the present invention, i.e., the wave forming mechanism, is sufficient to minimize density differences from the front to the back of the film. 
     Once the first stage of the processing is completed, a given volume of the next processing solution or solid is then introduced into the chamber after the desired time and so on. When merged solution processing is complete, the merged solutions are removed. Finally, the wash solutions are added and removed. The normal mode of operation of the method of the invention is to perform the complete process cycle within the single processing space of the rotating chamber. The process cycle may be develop, stop, bleach, fix, and wash. The processing solution for each stage is added to the chamber and left for the required time. The film  5  may be dried in-situ with hot air. The whole process cycle may thus be carried out within a single processing space 
     Representative sequences for processing various color photographic materials are described, for example, in  Research Disclosure  publication 308119, December 1989; publication 17643, December 1978; and publication 38957, September 1996. 
     Silver halide photographic elements which are processed include color negative photographic films, color reversal photographic films, and color photographic papers. Color negative element and particularly color negative films are most preferred. The general sequence of steps and conditions (times and temperatures) for processing are well known as Process C-41 and Process ECN-2 for color negative films, Process E-6 and Process K-14 for color reversal films, Process ECP for color prints, and Process RA-4 for color papers. 
     For example, color negative films that can be processed using the compositions described herein include, but are not limited to, KODAK MAX™πfilms, KODAK ROYAL GOLD™ films, KODAK GOLD™ films, KODAK PRO GOLD™ films, KODAK FUNTIME™, KODAK EKTAPRESS PLUS™ films, EASTMAN EXR™ films, KODAK ADVANTIX™ films, FERRANIA SOLARIS films, FUJI SUPER G Plus films, FUJI SMARTFILM™ products, FUJICOLOR NEXIA™ films, FUJICOLOR SUPERIA™ films, FUJICOLOR REALA™ films, KONICA DX films, KONICA VX films, KONICA CENTURIA™ films, KONICA SR-G films, KONICA SUPER XG films, KONICA SUPER SR films, KONICA SUPER DD films, 3M SCOTCH™ ATG films, SCOTCHCOLOR™ films, AGFA VISTA films, AGFA FUTURA films, AGFA ULTRA films, and AGFA HDC and XRS films. Films processed can also be those incorporated into what are known as “single-use cameras”. 
     In addition, color papers that can be processed include, but are not limited, KODAK EKTACOLOR EDGE V, VII and VIII Color Papers (Eastman Kodak Company), KODAK ROYAL VII Color Papers (Eastman Kodak Company), KODAK PORTRA III, IIIM Color Papers (Eastman Kodak Company), KODAK SUPRA III and IIIM Color Papers (Eastman Kodak Company), KODAK ULTRA III Color Papers (Eastman Kodak Company), FUJI SUPER Color Papers (Fuji Photo Co., FA5, FA7, and FA9), FUJI CRYSTAL ARCHIVE and Type C Color Papers (Fuji Photo Co.), KONICA COLOR QA Color Papers (Konica, Type QA6E and QA7), and AGFA TYPE II and PRESTIGE Color Papers (AGFA). The compositions and constructions of such commercial color photographic elements would be readily determined by one skilled in the art. KODAK DURATRANS, KODAK DURACLEAR, KODAK EKTAMAX RAL and KODAK DURAFLEX photographic materials, and KODAK Digital Paper Type 2976 are also typically processed as described above. 
     As noted the method of the invention is preferably used to provide a color image in an exposed color negative silver bromoiodide film element. The color negative film element may comprise a support and one or more silver halide emulsion layers (or color records) containing an imagewise distribution of developable silver halide emulsion grains, and has one or more color forming couplers associated therewith. 
     Generally, the iodide content of such silver bromoiodide emulsions is less than about 40 mol % (based on total silver), preferably from about 0.05 to about 10 mol %, and more preferably from about 0.5 to about 6 mol %. The emulsions can be of any crystal morphology (such as cubic, octahedral, cubooctahedral, or tabular as are known in the art), or irregular morphology (such as multiple twinning or rounded). Especially useful in this invention are tabular grain silver halide emulsions. Tabular grains are those having two parallel major crystal faces and having an aspect ratio of at least 2. The term “aspect ratio” is the ratio of the equivalent circular diameter (ECD) of a grain major face divided by its thickness (t). Tabular grain emulsions are those in which the tabular grains account for at least 50 percent (preferably at least 70 percent and optimally at least 90 percent) of the total grain projected area. Preferred tabular grain emulsions are those in which the average thickness of the tabular grains is less than 0.3 micrometer (preferably thin—that is, less than 0.2 micrometer and most preferably ultrathin—that is, less than 0.07 micrometer). The major faces of the tabular grains can lie in either {111} or {100} crystal planes. The mean ECD of tabular grain emulsions rarely exceeds 10 micrometers and more typically is less than 5 micrometers. 
     In their most widely used form tabular grain emulsions are high bromide {111} tabular grain emulsions. Such emulsions are illustrated by Kofron et al U.S. Pat. No. 4,439,520; Wilgus et al U.S. Pat. No. 4,434,226; Solberg et al U.S. Pat. No. 4,433,048; Maskasky U.S. Pat. Nos. 4,435,501; 4,463,087; and 4,173,320; Daubendiek et al U.S. Pat. Nos. 4,414,310 and 4,914,0.14; Sowinski et al U.S. Pat. No. 4,656,122; Piggin et al U.S. Pat. Nos. 5,061,616 and 5,061,609; Tsaur et al U.S. Pat. Nos. 5,147,771; &#39;772; &#39;773; 5,171,659; and 5,252,453; Black et al U.S. Pat. Nos. 5,219,720 and 5,334,495; Delton U.S. Pat. Nos. 5,310,644; 5,372,927 and 5,460,934, Wen U.S. Pat. NO. 5,470,698; Fenton et al U.S. Pat. No. 5,476,760; Eshelman et al U.S. Pat. Nos. 5,612,175 and 5,614,359; and Irving et al U.S. Pat. No. 5,667,954. 
     Ultrathin high bromide { 111 } tabular grain emulsions are illustrated by Daubendiek et al U.S. Pat. Nos. 4,672,027; 4,693,964; 5,494,789; 5,503,971 and 5,576,168; Antoniades et al U.S. Pat. No. 5,250,403; Olm et al U.S. Pat. No. 5,503,970; Deaton et al U.S. Pat. No. 5,582,965; and Maskasky U.S. Pat. No. 5,667,955. High bromide {100} tabular grain emulsions are illustrated by Mignot U.S. Pat. Nos. 4,386,156 and 5,386,156. 
     Such color silver bromoiodide elements generally have a camera speed defined as an ISO speed of at least 25, preferably an ISO speed of at least 50, and more preferably an ISO speed of at least 100. The speed or sensitivity of color negative photographic materials is inversely related to the exposure required to enable the attainment of a specified density above fog after processing. Photographic speed for color negative films with a gamma of about 0.65 has been specifically defined by the American National Standards Institute (ANSI) as ANSI Standard Number PH 2.27-1979 (ASA speed) and relates to the exposure levels required to enable a density of 0.15 above fog in the green light sensitive and least sensitive recording unit of a multicolor negative film. This definition conforms to the International Standards Organization (ISO) film speed rating. 
     The photographic elements processed in the practice of this invention can be single or multilayer color elements. Preferably, the elements have at least two separate light sensitive emulsion layers, and each layer contains a silver bromoiodide emulsion as defined above. Preferably the elements are multilayer color elements typically containing dye image-forming units (or color records) sensitive to each of the three primary regions of the visible spectrum. Each unit can be comprised of a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element can be arranged in any of the various orders known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer. The elements can also contain other conventional layers such as filter layers, interlayers, subbing layers, overcoats, and other layers readily apparent to one skilled in the art. A magnetic backing can be used as well as conventional supports. 
     The photographic element may also comprise a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support, as described in  Research Disclosure , November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND. Typically, the element will have a total thickness (excluding the support) of from about 5 to about 30 microns. Further, the photographic elements may have an annealed polyethylene naphthalate film base such as described in Hatsumei Kyoukai Koukai Gihou No. 94-6023, published Mar. 15, 1994 (Patent Office of Japan and Library of Congress of Japan) and may be utilized in a small format system, such as described in  Research Disclosure , June 1994, Item 36230 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND, and such as the Advanced Photo System, particularly the Kodak ADVANTIX films or cameras. 
     In the following Table, reference will be made to (1)  Research Disclosure , December 1978, Item 17643, (2)  Research Disclosure , December 1989, Item 308119, (3)  Research Disclosure , September 1994, Item 36544, and (4)  Research Disclosure , September 1996, Item 38957, all published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND, the disclosures of which are incorporated herein by reference. The Table and the references cited in the Table are to be read as describing particular components suitable for use in the elements of the invention. The Table and its cited references also describe suitable ways of preparing, exposing, processing and manipulating the elements, and the images contained therein. Photographic elements and methods of processing such elements particularly suitable for use with this invention are described in  Research Disclosure , February 1995, Item 37038, and  Research Disclosure , September 1997, Item 40145, both published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND, the disclosures of which are incorporated herein by reference. 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Reference 
                 Section 
                 Subject Matter 
               
               
                   
                   
               
             
            
               
                   
                 1 
                 I, II 
                 Grain composition, 
               
               
                   
                 2 
                 I, II, IX, X, 
                 morphology and preparation. 
               
               
                   
                   
                 XI, XII, 
                 Emulsion preparation 
               
               
                   
                   
                 XIV, XV 
                 including hardeners, coating 
               
               
                   
                 3 &amp; 4 
                 I, II, III, IX 
                 aids, addenda, etc. 
               
               
                   
                   
                 A &amp; B 
               
               
                   
                 1 
                 III, IV 
                 Chemical sensitization and 
               
               
                   
                 2 
                 III, IV 
                 spectral sensitization/ 
               
               
                   
                 3 &amp; 4 
                 IV, V 
                 Desensitization 
               
               
                   
                 1 
                 V 
                 UV dyes, optical brighteners, 
               
               
                   
                 2 
                 V 
                 luminescent dyes 
               
               
                   
                 3 &amp; 4 
                 VI 
               
               
                   
                 1 
                 VI 
                 Antifoggants and stabilizers 
               
               
                   
                 2 
                 VI 
               
               
                   
                 3 &amp; 4 
                 VII 
               
               
                   
                 1 
                 VIII 
                 Absorbing and scattering 
               
               
                   
                 2 
                 VIII, XIII, 
                 materials; Antistatic layers; 
               
               
                   
                   
                 XVI 
                 matting agents 
               
               
                   
                 3 &amp; 4 
                 VIII, IX 
               
               
                   
                   
                 C &amp; D 
               
               
                   
                 1 
                 VII 
                 Image-couplers and image- 
               
               
                   
                 2 
                 VII 
                 modifying couplers; Wash-out 
               
               
                   
                 3 &amp; 4 
                 X 
                 couplers; Dye stabilizers and 
               
               
                   
                   
                   
                 hue modifiers 
               
               
                   
                 1 
                 XVII 
                 Supports 
               
               
                   
                 2 
                 XVII 
               
               
                   
                 3 &amp; 4 
                 XV 
               
               
                   
                 3 &amp; 4 
                 XI 
                 Specific layer arrangements 
               
               
                   
                 3 &amp; 4 
                 XII, XIII 
                 Negative working emulsions; 
               
               
                   
                   
                   
                 Direct positive emulsions 
               
               
                   
                 2 
                 XVIII 
                 Exposure 
               
               
                   
                 3 &amp; 4 
                 XVI 
               
               
                   
                 1 
                 XIX, XX 
                 Chemical processing; 
               
               
                   
                 2 
                 XIX, XX, 
                 Developing agents 
               
               
                   
                   
                 XXII 
               
               
                   
                 3 &amp; 4 
                 XVIII, XIX, 
               
               
                   
                   
                 XX 
               
               
                   
                 3 &amp; 4 
                 XIV 
                 Scanning and digital 
               
               
                   
                   
                   
                 processing procedures 
               
               
                   
                   
               
            
           
         
       
     
     The photographic elements can be incorporated into exposure structures intended for repeated use or exposure structures intended for limited use, variously referred to as single use cameras, lens with film, or photosensitive material package units. 
     The photographic elements may be used in association with materials that accelerate or otherwise modify the processing steps e.g. of bleaching or fixing to improve the quality of the image. Bleach accelerator releasing couplers such as those described in EP 193,389; EP 301,477; U.S. Pat. Nos. 4,163,669; U.S. Pat. Nos. 4,865,956; and U.S. Pat. Nos. 4,923,784 may be useful. Also contemplated is use of the compositions in association with nucleating agents, development accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. Pat. Nos. 4,859,578; U.S. Pat. Nos. 4,912,025); antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers. 
     The photographic elements may also be used in combination with filter dye layers comprising colloidal silver sol or yellow, cyan, and/or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with “smearing” couplers (e.g., as described in U.S. Pat. No. 4,366,237; EP 96,570; U.S. Pat. Nos. 4,420,556; and U.S. Pat. Nos. 4,543,323.) Also, the compositions may be blocked or coated in protected form as described, for example, in Japanese application 61/258,249 or U.S. Pat. No. 5,019,492. 
     The photographic elements may further be used in combination with image-modifying compounds such as “Developer Inhibitor-Releasing” compounds (DIR&#39;s). DIR&#39;s useful in conjunction with the compositions of the invention are known in the art and examples are described in U.S. Pat. No. Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications: 272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; and 401,613. 
     Such compounds are also disclosed in “Developer-Inhibitor-Releasing (DIR) Couplers for Color Photography,” C. R. Barr, J. R. Thirtle and P. W. Vittum in  Photographic Science  and  Engineering , Vol. 13, p. 174 (1969), incorporated herein by reference. Generally, the developer inhibitor-releasing (DIR) couplers include a coupler moiety and an inhibitor coupling-off moiety (IN). The inhibitor-releasing couplers may be of the time-delayed type (DIAR couplers) which also include a timing moiety or chemical switch which produces a delayed release of inhibitor. Examples of typical inhibitor moieties are: oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles. 
     The following examples illustrate the practice of this invention. They are not intended to be exhaustive of all possible variations of the invention. Parts and percentages are by weight unless otherwise indicated. 
     EXAMPLES 
     Example 1 
     To demonstrate the cost advantages of the inventive process, first consider comparative Processes A, conducted as described in Example 2 Merged Process Cycle(A) of U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001. The volume requirements to conduct this process are shown in Table I, for various applied volumes of Developer A solution. These amounts are the minimum desired to achieve satisfactory rapid fixing and bleaching of a color negative film - about 0.75 mol/L of thiosulfate for fixing, and about 0.12 equivalents/L of Fe(III)PDTA for bleaching by the mixture. 
     Next, consider the inventive Process B. The volume requirements to conduct this process are shown in Table II, for various applied volumes of Developer A solution, the same volumes used to illustrate Processes A. The concentrations of fixing agents and bleaching agents in the fixer and bleach solutions are the same as for Process A, in order to compare the two processes fairly. However, the applied volumes of fixer and bleach are significantly different. 
     For Process A, the combined volumes of Developer A, Fixer A, and Bleach A result in a thiosulfate concentration of 0.75 mol/L and a Fe(III)PDTA concentration of 0.12 equivalents/L after developer oxidation for equally rapid processing for each process. If a higher volume of developer is used in Process A, a proportionately higher volume of bleach (and fixer) is required, with a proportional increase in relative cost. The ratio of applied bleaching agent equivalents to the developer volume in liters is constant, reflecting the constant proportion of bleach solution to developer solution. Higher volumes of fixer and bleach may be used for even more rapid bleaching and fixing with a constant amount of developer, but at a higher relative solution cost. Relative costs per unit volume of Developer A, Fixer A, and Bleach A are 1.69, 1.0, and 8.17, respectively. Therefore, the amount of bleach used in the process greatly controls the overall chemical cost for the process. In particular, there is concern with the amount of bleaching agent relative to the amount of developer solution used in the process when we compare processes. 
     The inventive Process B adds a first volume of fixer to the developer to stop development, after which the combined developer/fixer solution is removed from the processing chamber. A residual solution volume of at least about 94 mL/m 2  of processed material will be retained in the chamber after solution removal. Next are added to the processing chamber a second volume of fixer and a volume of bleach to complete bleach-fixing of the material. The retained volume of the developer/fixer mixture will mix with the new bleach-fix mixture. Alternatively, the bleach-fix mixture could be formed by introducing a single bleach-fixer solution into the processing chamber with or without a separate second solution such as a fixer solution, a bleach solution, or an accelerator solution. In general, the combined volumes of the fixer solution (second amount added) and the bleach solution, or the volume of the bleach-fixer solution and any second solution if used should constitute no more than 95% of the total volume of the resulting bleach-fixer mixture in the chamber, including the volume of any residual developer/fixer mixture that was not previously able to be removed from the chamber. Preferably, the combined volumes should constitute no more than 93.3% of the total volume, and more preferably no more than 91.7% of the total volume. 
     In Table II the combined volumes of Fixer A (2 nd  volume) and Bleach B result in a thiosulfate concentration of 0.75 mol/L and a Fe(III)PDTA concentration of 0.2 equivalents/L for bleach-fix processing. The concentration of bleaching agents in the bleach-fixer mixture in the chamber may be as low as 0.2 equivalents/L. Note that this is a higher concentration of bleaching agent (and a more rapidly bleaching bleach-fixer mixture) than can be cost-effectively achieved in the comparative Process A. The concentration of fixing agents in the bleach-fixer mixture in the chamber may be as low as 0.75 mol/L. Relative costs per unit volume of Developer A, Fixer A, and Bleach B are 1.69, 1.0, and 7.47, respectively. Note that the relative cost of Bleach B is less than that of Bleach A. The inventive Process B does not require as much acid-providing buffer to form the bleach-fixer mixture, because the developer has been substantially removed from the chamber before the bleach-fixer mixture is provided to the chamber. As with Process A, the amount of bleaching agent used greatly determines the chemical cost of the process. 
     When the ratio of the number of bleaching agent equivalents used in the inventive Process B to the volume of developer solution (in liters) is approximately equal to or less than the corresponding ratio for Process A, the inventive Process B is less costly than the comparative Process A that uses the same applied developer volume (compare Process A8 with Process B8, A14 with B14, etc.). At even higher applied developer volumes, the inventive process also uses less total processing solution volume than the comparison process (compare Process A6 with Process B6, etc), an additional advantage. The advantage of Process B becomes even greater as the applied developer volume is increased further. 
     The ratio of the number of bleaching agent equivalents used in the inventive process to the volume of developer solution (in liters) should be less than or equal to about 0.48 equivalents of bleaching agent per liter of applied developer solution, preferably less than or equal to 0.4 equivalents of bleaching agent per liter of applied developer solution, more preferably less than or equal to 0.33 equivalents of bleaching agent per liter of applied developer solution, most preferably less than or equal to 0.25 equivalents of bleaching agent per liter of applied developer solution. 
     As shown in the subsequent Examples, the preferred 0.4 ratio is suitable when moderately concentrated fixer (from 2-3 mol/L fixing agent) and bleach (up to about 0.4 mol/L bleaching agent) solutions are used. The more preferred 0.33 ratio is suitable under the foregoing conditions and, in addition, when a moderately concentrated fixer (from 2-3 mol/L fixing agent) and a more concentrated bleach (from 0.4-0.5 mol/L bleaching agent) are used. The most preferred 0.25 ratio is suitable under the foregoing conditions and, in addition, when a highly concentrated fixer (more than 3 mol/L fixing agent) or a very concentrated bleach (more than 0.5 mol/L bleaching agent) are used. 
     The developer is applied in the inventive process in an amount greater than 375 mL/ 2 , preferably in an amount greater than 470 mL/ 2 , more preferably in an amount greater than 850 mL/m 2 , most preferably in an amount greater than 1200 mL/m 2  of photographic material processed. The developer is applied in the inventive process in an amount less than 2000 mL/m 2  of photographic material processed. 
     As shown in the subsequent Examples, the preferred amount of 470 mL/m 2  is suitable when a moderately concentrated fixer (from about 2-3 mol/L fixing agent) and a moderately concentrated bleach is used (up to about 0.4 mol/L bleaching agent). Also, this amount is suitable when a highly concentrated fixer (greater than about 3 mol/L fixing agent) or a very concentrated bleach is used (greater than about 0.5 mol/L bleaching agent). The more preferred amount of 850 mL/ 2  is suitable under the foregoing conditions and, in addition, when a moderately concentrated fixer (fixing agent concentration of about 2-3 mol/L) and more concentrated bleach solutions are used (bleaching agent concentration greater than 0.4 mol/L. 
     The cost of Bleach B used in Processes B is about 8% cheaper than the cost of Bleach A used in Processes A, and this contributes to a small extent to some of the cost advantage of Processes B. However, the major cost advantage for Processes B can be seen to be the significantly lower volume of Bleach B that is used compared to the volume of Bleach A required for Processes A (at the same applied developer volume). 
     
       
         
           
               
             
               
                 TABLE I 
               
             
            
               
                   
               
               
                 Example 1 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 
                 Bleach A 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                 Comparative 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes A 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 A1  
                  187 
                  179 
                  271 
                  637 
                  2710 
                 0.454 
                   
               
               
                 A2  
                  281 
                  268 
                  406 
                  956 
                  4064 
                 0.454 
               
               
                 A3  
                  375 
                  357 
                  542 
                 1274 
                  5419 
                 0.454 
               
               
                 A4  
                  469 
                  447 
                  677 
                 1593 
                  6774 
                 0.454 
                 comparison 
               
               
                 A5  
                  562 
                  536 
                  813 
                 1911 
                  8129 
                 0.454 
                 comparison 
               
               
                 A6  
                  656 
                  625 
                  948 
                 2230 
                  9484 
                 0.454 
                 comparison 
               
               
                 A7  
                  750 
                  715 
                 1084 
                 2548 
                 10839 
                 0.454 
                 comparison 
               
               
                 A8  
                  843 
                  804 
                 1219 
                 2867 
                 12193 
                 0.454 
                 comparison 
               
               
                 A9  
                  937 
                  893 
                 1355 
                 3185 
                 13548 
                 0.454 
                 comparison 
               
               
                 A10 
                 1031 
                  983 
                 1490 
                 3504 
                 14903 
                 0.454 
                 comparison 
               
               
                 A11 
                 1125 
                 1072 
                 1625 
                 3822 
                 16258 
                 0.454 
                 comparison 
               
               
                 A12 
                 1218 
                 1162 
                 1761 
                 4141 
                 17613 
                 0.454 
                 comparison 
               
               
                 A13 
                 1312 
                 1251 
                 1896 
                 4459 
                 18968 
                 0.454 
                 comparison 
               
               
                 A14 
                 1406 
                 1340 
                 2032 
                 4778 
                 20322 
                 0.454 
                 comparison 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach A is 1.69:1.0:8.17  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE II 
               
             
            
               
                   
               
               
                 Example 1 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 1 st   
                 Fixer A 2 nd   
                 Bleach B 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                   
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes B 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 B1  
                  187 
                  83 
                 315 
                 716 
                 1302 
                 6065 
                 1.200 
                   
               
               
                 B2  
                  281 
                 125 
                 315 
                 716 
                 1438 
                 6265 
                 0.800 
               
               
                 B3  
                  375 
                 167 
                 315 
                 716 
                 1573 
                 6465 
                 0.600 
               
               
                 B4  
                  469 
                 208 
                 315 
                 716 
                 1708 
                 6665 
                 0.480 
                 invention 
               
               
                 B5  
                  562 
                 250 
                 315 
                 716 
                 1844 
                 6866 
                 0.400 
                 invention 
               
               
                 B6  
                  656 
                 292 
                 315 
                 716 
                 1979 
                 7066 
                 0.343 
                 invention 
               
               
                 B7  
                  750 
                 333 
                 315 
                 716 
                 2114 
                 7266 
                 0.300 
                 invention 
               
               
                 B8  
                  843 
                 375 
                 315 
                 716 
                 2250 
                 7466 
                 0.267 
                 invention 
               
               
                 B9  
                  937 
                 417 
                 315 
                 716 
                 2385 
                 7666 
                 0.240 
                 invention 
               
               
                 B10 
                 1031 
                 458 
                 315 
                 716 
                 2521 
                 7866 
                 0.218 
                 invention 
               
               
                 B11 
                 1125 
                 500 
                 315 
                 716 
                 2656 
                 8066 
                 0.200 
                 invention 
               
               
                 B12 
                 1218 
                 541 
                 315 
                 716 
                 2791 
                 8266 
                 0.185 
                 invention 
               
               
                 B13 
                 1312 
                 583 
                 315 
                 716 
                 2927 
                 8466 
                 0.171 
                 invention 
               
               
                 B14 
                 1406 
                 625 
                 315 
                 716 
                 3062 
                 8666 
                 0.160 
                 invention 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach B is 1.69:1.0:7.47  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     Example 2 
     A more preferred concentration of fixing agents in the bleach-fixing mixture of the inventive process is greater than or equal to about 1 mol/L for more rapid bleach-fixing. A more preferred concentration of bleaching agents in the bleach-fixing mixture of the inventive process is greater than or equal to about 0.25 mol/L for more rapid bleach-fixing. Illustrative inventive processes under these more preferred conditions are Processes D in Table IV. To achieve these concentrations, it is convenient to use a more concentrated bleaching agent solution (Bleach D, 0.465 mol/L bleaching agent) than used for inventive Processes B (0.314 mol/L bleaching agent). A corresponding more concentrated bleaching solution for use in a comparative set of merged Processes C, as described in U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001, is Bleach C. These comparative processes are described in Table III. 
     As with Processes A, the combined volumes of developer A, fixer A, and bleach C result in a fixing agent (thiosulfate) concentration of 0.75 mol/L and a bleaching agent (Fe(III)PDTA) concentration of 0.12 equivalents/L after developer oxidation for equally rapid processing for each Process C. Higher volumes of fixer and bleach may be used for even more rapid bleaching and fixing with a constant amount of developer, but at a higher relative solution cost. Relative costs per unit volume of developer A, fixer A, and bleach C are 1.69, 1.0 and 11.68, respectively, for Processes C. Relative costs per unit volume of developer A, fixer A and bleach D are 1.69, 1.0 and 10.98, respectively, for Processes D. 
     The cost of Bleach D used in Processes D is about 6% cheaper than the cost of Bleach C used in Processes C, and this contributes to a small extent to some of the cost advantage of Processes D. This is because Processes D do not require Bleach D to contain an acid-providing buffer in order to control the bleach-fixer solution pH. However, the major cost advantage for Processes D can be seen to be the significantly lower volume of Bleach D that is used compared to the volume of Bleach C required for Processes C (at the same applied developer volume). 
     When the ratio of the number of bleaching agent equivalents used in the inventive Process D to the volume of developer solution (in liters) is approximately equal to or less than the corresponding ratio for comparative Process C, the inventive Process D is less costly than the comparative Process C that uses the same applied developer volume (compare Process C4 with Process D4, C6 with D6, etc). Under these more preferred process conditions, this occurs when the ratio of the number of bleaching agent equivalents used in the inventive Process D to the volume of developer solution (in liters) is less than or equal to about 0.33 equivalents of bleaching agent per liter of applied developer solution. At even higher applied developer volumes, the inventive process also uses less total processing solution volume than the comparison process (compare Process C7 with Process D7, etc.) an additional advantage. The advantage of Process D becomes even greater as the applied developer volume is increased further. 
     
       
         
           
               
             
               
                 TABLE III 
               
             
            
               
                   
               
               
                 Example 2 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 
                 Bleach C 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                 Comparative 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes C 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 C1  
                  562 
                 375 
                  401 
                 1338 
                  6010 
                 0.332 
                   
               
               
                 C2  
                  656 
                 438 
                  468 
                 1561 
                  7009 
                 0.332 
               
               
                 C3  
                  750 
                 500 
                  535 
                 1784 
                  8017 
                 0.332 
               
               
                 C4  
                  843 
                 562 
                  602 
                 2007 
                  9016 
                 0.332 
                 comparison 
               
               
                 C5  
                  937 
                 625 
                  668 
                 2231 
                 10014 
                 0.332 
                 comparison 
               
               
                 C6  
                 1031 
                 687 
                  736 
                 2454 
                 11022 
                 0.332 
                 comparison 
               
               
                 C7  
                 1125 
                 750 
                  802 
                 2677 
                 12021 
                 0.332 
                 comparison 
               
               
                 C8  
                 1218 
                 813 
                  869 
                 2900 
                 13019 
                 0.332 
                 comparison 
               
               
                 C9  
                 1312 
                 874 
                  936 
                 3123 
                 14027 
                 0.332 
                 comparison 
               
               
                 C10 
                 1406 
                 937 
                 1003 
                 3346 
                 15026 
                 0.332 
                 comparison 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach C is 1.69:1.0:11.68  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE IV 
               
             
            
               
                   
               
               
                 Example 2 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 1 st   
                 Fixer A 2 nd   
                 Bleach D 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                   
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes D 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 D1  
                  562 
                 250 
                 420 
                 605 
                 1837 
                  8260 
                 0.500 
                   
               
               
                 D2  
                  656 
                 292 
                 420 
                 605 
                 1973 
                  8460 
                 0.429 
               
               
                 D3  
                  750 
                 333 
                 420 
                 605 
                 2108 
                  8660 
                 0.375 
               
               
                 D4  
                  843 
                 375 
                 420 
                 605 
                 2243 
                  8860 
                 0.333 
                 invention 
               
               
                 D5  
                  937 
                 417 
                 420 
                 605 
                 2379 
                  9060 
                 0.300 
                 invention 
               
               
                 D6  
                 1031 
                 458 
                 420 
                 605 
                 2514 
                  9260 
                 0.273 
                 invention 
               
               
                 D7  
                 1125 
                 500 
                 420 
                 605 
                 2649 
                  9460 
                 0.250 
                 invention 
               
               
                 D8  
                 1218 
                 541 
                 420 
                 605 
                 2785 
                  9660 
                 0.231 
                 invention 
               
               
                 D9  
                 1312 
                 583 
                 420 
                 605 
                 2920 
                  9860 
                 0.214 
                 invention 
               
               
                 D10 
                 1406 
                 625 
                 420 
                 605 
                 3056 
                 10060 
                 0.200 
                 invention 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach D is 1.69:1.0:10.98  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     Processing solutions can be used in even smaller volumes if they are more concentrated. For example, a more concentrated fixer solution, Fixer B, can be used in the inventive process, as can a more concentrated bleach solution, Bleach F. 
     Example 3 
     Using Fixer B (3.565 mol/L fixing agent) and Bleach C, the solution requirements for a series of comparative Processes E are shown in Table V. These are merged processes, conducted as described in U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001. Relative costs per unit volume of developer A, fixer B, and bleach C are 1.69, 1.41, and 11.68, respectively, for Processes E. The combined volumes of developer A, fixer B,. and bleach C result in a fixing agent (thiosulfate) concentration of 0.75 mol/L and a bleaching agent (Fe(III)PDTA) concentration of 0.12 equivalents/L after developer oxidation for equally rapid processing for each Process E compared to previously described Processes A and C. 
     Using Fixer B and Bleach D, the solution requirements for a series of inventive Processes F are shown in Table VI. Relative costs per unit volume of developer A, fixer B, and bleach D are 1.69, 1.41, and 10.98, respectively, for Processes F. The combined volumes of fixer B and bleach D result in a preferred fixing agent (thiosulfate) concentration of at least 1.0 mol/L and a preferred bleaching agent (Fe(III)PDTA) concentration of at least 0.25 equivalents/L after mixing with about 94 mL/m 2  of residual developer/fixer mixture retained in the chamber after solution removal. 
     When the ratio of the number of bleaching agent equivalents used in the inventive Process F to the volume of developer solution (in liters) is approximately equal to or less than the corresponding ratio for comparative Process E, the inventive Process F is less costly than the comparative Process E that uses the same applied developer volume (compare Process E4 with Process F4, E6 with F6, etc.). Under these more preferred process conditions, this occurs when the ratio of the number of bleaching agent equivalents used in the inventive Process F to the volume of developer solution (in liters) is less than or equal to about 0.25 equivalents of bleaching agent per liter of applied developer solution. The inventive process also uses less total processing solution volume than the comparison process (compare Process E7 with Process F7, etc.), an additional advantage. The advantage of Process F becomes even greater as the applied developer volume is increased further. 
     
       
         
           
               
             
               
                 TABLE V 
               
             
            
               
                   
               
               
                 Example 3 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer B 
                 Bleach C 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                 Comparative 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes E 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 E1  
                  187 
                  82 
                 119 
                  388 
                  1818 
                 0.294 
                   
               
               
                 E2  
                  281 
                 122 
                 178 
                  582 
                  2728 
                 0.294 
               
               
                 E3  
                  375 
                 163 
                 237 
                  776 
                  3637 
                 0.294 
               
               
                 E4  
                  469 
                 204 
                 297 
                  969 
                  4546 
                 0.294 
                 comparison 
               
               
                 E5  
                  562 
                 245 
                 356 
                 1163 
                  5455 
                 0.294 
                 comparison 
               
               
                 E6  
                  656 
                 286 
                 415 
                 1357 
                  6364 
                 0.294 
                 comparison 
               
               
                 E7  
                  750 
                 326 
                 475 
                 1551 
                  7274 
                 0.294 
                 comparison 
               
               
                 E8  
                  843 
                 367 
                 534 
                 1745 
                  8183 
                 0.294 
                 comparison 
               
               
                 E9  
                  937 
                 408 
                 594 
                 1939 
                  9092 
                 0.294 
                 comparison 
               
               
                 E10 
                 1031 
                 449 
                 653 
                 2133 
                 10001 
                 0.294 
                 comparison 
               
               
                 E11 
                 1125 
                 490 
                 712 
                 2327 
                 10910 
                 0.294 
                 comparison 
               
               
                 E12 
                 1218 
                 530 
                 772 
                 2520 
                 11820 
                 0.294 
                 comparison 
               
               
                 E13 
                 1312 
                 571 
                 831 
                 2714 
                 12729 
                 0.294 
                 comparison 
               
               
                 E14 
                 1406 
                 612 
                 890 
                 2908 
                 13638 
                 0.294 
                 comparison 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer B:Bleach C is 1.69:1.41:11.68  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE VI 
               
             
            
               
                   
               
               
                 Example 3 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer B 1 st   
                 Fixer B 2 nd   
                 Bleach D 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                   
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes F 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 F1  
                  187 
                  56 
                 145 
                 278 
                  666 
                 3649 
                 0.689 
                   
               
               
                 F2  
                  281 
                  84 
                 145 
                 278 
                  788 
                 3847 
                 0.459 
               
               
                 F3  
                  375 
                 112 
                 145 
                 278 
                  910 
                 4045 
                 0.344 
               
               
                 F4  
                  469 
                 141 
                 145 
                 278 
                 1032 
                 4243 
                 0.276 
                 invention 
               
               
                 F5  
                  562 
                 169 
                 145 
                 278 
                 1154 
                 4441 
                 0.230 
                 invention 
               
               
                 F6  
                  656 
                 197 
                 145 
                 278 
                 1275 
                 4639 
                 0.197 
                 invention 
               
               
                 F7  
                  750 
                 225 
                 145 
                 278 
                 1397 
                 4837 
                 0.172 
                 invention 
               
               
                 F8  
                  843 
                 253 
                 145 
                 278 
                 1519 
                 5035 
                 0.153 
                 invention 
               
               
                 F9  
                  937 
                 281 
                 145 
                 278 
                 1641 
                 5233 
                 0.138 
                 invention 
               
               
                 F10 
                 1031 
                 309 
                 145 
                 278 
                 1763 
                 5431 
                 0.125 
                 invention 
               
               
                 F11 
                 1125 
                 337 
                 145 
                 278 
                 1885 
                 5629 
                 0.115 
                 invention 
               
               
                 F12 
                 1218 
                 366 
                 145 
                 278 
                 2006 
                 5827 
                 0.106 
                 invention 
               
               
                 F13 
                 1312 
                 394 
                 145 
                 278 
                 2128 
                 6025 
                 0.098 
                 invention 
               
               
                 F14 
                 1406 
                 422 
                 145 
                 278 
                 2250 
                 6223 
                 0.092 
                 invention 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer B:Bleach D is 1.69:1.41:10.98  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     Example 4 
     Using Fixer A and Bleach E (0.6 mol/L bleaching agent), the solution requirements for a series of comparative Processes G are shown in Table VII. These are merged processes, conducted as described in U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001. Relative costs per unit volume of developer A, fixer A, and bleach E are 1.69, 1.0, and 14.8, respectively, for Processes G. The combined volumes of developer A, fixer A, and bleach E result in a fixing agent (thiosulfate) concentration of 0.75 mol/L and a bleaching agent (Fe(III)PDTA) concentration of 0.12 equivalents/L after developer oxidation for equally rapid processing for each Process G compared to previously described Processes A, C, and E. 
     Using Fixer A and Bleach F, the solution requirements for a series of inventive Processes H are shown in Table VIII. Relative costs per unit volume of developer A, fixer A, and bleach F are 1.69, 1.0, and 14.1, respectively, for Processes H. The cost of Bleach F used in Processes H is cheaper than the cost of Bleach E used in Processes G, and this contributes to a small extent to some of the cost advantage of Processes H. This is because Processes H do not require Bleach F to contain an acid-providing buffer in order to control the bleach-fixer solution pH. The combined volumes of fixer A and bleach F result in a preferred fixing agent (thiosulfate) concentration of at least 1.0 mol/L and a preferred bleaching agent (Fe(III)PDTA) concentration of at least 0.25 equivalents/L after mixing with about 94 mL/m 2  of residual developer/fixer mixture retained in the chamber after solution removal. 
     When the ratio of the number of bleaching agent equivalents used in the inventive Process H to the volume of developer solution (in liters) is approximately equal to or less than the corresponding ratio for comparative Process G, the inventive Process H is less costly than the comparative Process G that uses the same applied developer volume (compare Process G4 with Process H4, G6 with H6, etc.). Under these more preferred process conditions, this occurs when the ratio of the number of bleaching agent equivalents used in the inventive Process H to the volume of developer solution (in liters). is less than or equal to about 0.25 equivalents of bleaching agent per liter of applied developer solution. The inventive process also uses less total processing solution volume than the comparison process (compare Process G7 with Process H7, etc.), an additional advantage. The advantage of Process H becomes even greater as the applied developer volume is increased further. 
     
       
         
           
               
             
               
                 TABLE VII 
               
             
            
               
                   
               
               
                 Example 4 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 
                 Bleach E 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                 Comparative 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes G 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 G1  
                  187 
                 109 
                  92 
                  388 
                  1787 
                 0.294 
                   
               
               
                 G2  
                  281 
                 163 
                 138 
                  582 
                  2680 
                 0.294 
               
               
                 G3  
                  375 
                 217 
                 184 
                  776 
                  3573 
                 0.294 
               
               
                 G4  
                  469 
                 272 
                 230 
                  970 
                  4467 
                 0.294 
                 comparison 
               
               
                 G5  
                  562 
                 326 
                 276 
                 1164 
                  5360 
                 0.294 
                 comparison 
               
               
                 G6  
                  656 
                 381 
                 322 
                 1358 
                  6253 
                 0.294 
                 comparison 
               
               
                 G7  
                  750 
                 435 
                 368 
                 1553 
                  7147 
                 0.294 
                 comparison 
               
               
                 G8  
                  843 
                 489 
                 414 
                 1747 
                  8040 
                 0.294 
                 comparison 
               
               
                 G9  
                  937 
                 544 
                 460 
                 1941 
                  8933 
                 0.294 
                 comparison 
               
               
                 G10 
                 1031 
                 598 
                 506 
                 2135 
                  9827 
                 0.294 
                 comparison 
               
               
                 G11 
                 1125 
                 652 
                 552 
                 2329 
                 10720 
                 0.294 
                 comparison 
               
               
                 G12 
                 1218 
                 707 
                 598 
                 2523 
                 11613 
                 0.294 
                 comparison 
               
               
                 G13 
                 1312 
                 761 
                 644 
                 2717 
                 12507 
                 0.294 
                 comparison 
               
               
                 G14 
                 1406 
                 815 
                 690 
                 2911 
                 13400 
                 0.294 
                 comparison 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach E is 1.69:1.0:14.8  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE VIII 
               
             
            
               
                   
               
               
                 Example 4 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer A 1 st   
                 Fixer A 2 nd   
                 Bleach F 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                   
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes H 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 H1  
                  187 
                  83 
                 167 
                 186 
                  624 
                 3192 
                 0.596 
                   
               
               
                 H2  
                  281 
                 125 
                 167 
                 186 
                  759 
                 3392 
                 0.398 
               
               
                 F3  
                  375 
                 167 
                 167 
                 186 
                  895 
                 3592 
                 0.298 
               
               
                 H4  
                  469 
                 208 
                 167 
                 186 
                 1030 
                 3792 
                 0.239 
                 invention 
               
               
                 H5  
                  562 
                 250 
                 167 
                 186 
                 1166 
                 3992 
                 0.199 
                 invention 
               
               
                 H6  
                  656 
                 292 
                 167 
                 186 
                 1301 
                 4192 
                 0.170 
                 invention 
               
               
                 H7  
                  750 
                 333 
                 167 
                 186 
                 1436 
                 4392 
                 0.149 
                 invention 
               
               
                 H8  
                  843 
                 375 
                 167 
                 186 
                 1572 
                 4592 
                 0.133 
                 invention 
               
               
                 H9  
                  937 
                 417 
                 167 
                 186 
                 1707 
                 4792 
                 0.119 
                 invention 
               
               
                 H10 
                 1031 
                 458 
                 167 
                 186 
                 1842 
                 4992 
                 0.108 
                 invention 
               
               
                 H11 
                 1125 
                 500 
                 167 
                 186 
                 1978 
                 5192 
                 0.099 
                 invention 
               
               
                 H12 
                 1218 
                 541 
                 167 
                 186 
                 2113 
                 5392 
                 0.092 
                 invention 
               
               
                 H13 
                 1312 
                 583 
                 167 
                 186 
                 2249 
                 5592 
                 0.085 
                 invention 
               
               
                 H14 
                 1406 
                 625 
                 167 
                 186 
                 2384 
                 5792 
                 0.080 
                 invention 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer A:Bleach F is 1.69:1.0:14.1  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     Example 5 
     Using both of the more concentrated Fixer B and Bleach E, the solution requirements for a series of comparative Processes I are shown in Table IX. These are merged processes, conducted as described in U.S. application Ser. No. 10/012,673 of Twist filed Oct. 30, 2001. Relative costs per unit volume of developer A, fixer B, and bleach E are 1.69, 1.41, and 14.8, respectively, for Processes I. The combined volumes of developer A, fixer B, and bleach E result in a fixing agent (thiosulfate) concentration of 0.75 mol/L and a bleaching agent (Fe(III)PDTA) concentration of 0.12 equivalents/L after developer oxidation for equally rapid processing for each Process I compared to the previously described Processes A, C, E, and G. 
     Using both of the more concentrated Fixer B and Bleach F, the solution requirements for a series of inventive Processes J are shown in Table X. Relative costs per unit volume of developer A, fixer B, and bleach F are 1.69, 1.41, and 14.1, respectively, for Processes J. The combined volumes of fixer B and bleach F result in a preferred fixing agent (thiosulfate) concentration of at least 1.0 mol/L and a preferred bleaching agent (Fe(III)PDTA) concentration of at least 0.25 equivalents/L after mixing with about 94 mL/m 2  of residual developer/fixer mixture retained in the chamber after solution removal. 
     When the ratio of the number of bleaching agent equivalents used in the inventive Process J to the volume of developer solution (in liters) is approximately equal to or less than the corresponding ratio for comparative Process I, the inventive Process J is less costly than the comparative Process I that uses the same applied developer volume (compare Process 14 with Process J4, 16 with J6, etc.). Under these more preferred process conditions, this occurs when the ratio of the number of bleaching agent equivalents used in the inventive Process J to the volume of developer solution (in liters) is less than or equal to about 0.25 equivalents of bleaching agent per liter of applied developer solution. The inventive process also uses less total processing solution volume than the comparison process (compare Process 17 with Process J7, etc.), an additional advantage. The advantage of Process J becomes even greater as the applied developer volume is increased further. 
     
       
         
           
               
             
               
                 TABLE IX 
               
             
            
               
                   
               
               
                 Example 5 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer B 
                 Bleach E 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                 Comparative 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes I 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 I1  
                  187 
                  72 
                  83 
                  342 
                  1644 
                 0.265 
                   
               
               
                 I2  
                  281 
                 108 
                 124 
                  513 
                  2466 
                 0.265 
               
               
                 I3  
                  375 
                 144 
                 166 
                  684 
                  3289 
                 0.265 
                 comparison 
               
               
                 I4  
                  469 
                 180 
                 207 
                  855 
                  4111 
                 0.265 
                 comparison 
               
               
                 I5  
                  562 
                 216 
                 249 
                 1026 
                  4933 
                 0.265 
                 comparison 
               
               
                 I6  
                  656 
                 251 
                 290 
                 1197 
                  5755 
                 0.265 
                 comparison 
               
               
                 I7  
                  750 
                 287 
                 331 
                 1369 
                  6577 
                 0.265 
                 comparison 
               
               
                 I8  
                  843 
                 323 
                 373 
                 1540 
                  7399 
                 0.265 
                 comparison 
               
               
                 I9  
                  937 
                 359 
                 414 
                 1711 
                  8221 
                 0.265 
                 comparison 
               
               
                 I10 
                 1031 
                 395 
                 456 
                 1882 
                  9043 
                 0.265 
                 comparison 
               
               
                 I11 
                 1125 
                 431 
                 497 
                 2053 
                  9866 
                 0.265 
                 comparison 
               
               
                 I12 
                 1218 
                 467 
                 539 
                 2224 
                 10688 
                 0.265 
                 comparison 
               
               
                 I13 
                 1312 
                 503 
                 580 
                 2395 
                 11510 
                 0.265 
                 comparison 
               
               
                 I14 
                 1406 
                 539 
                 621 
                 2566 
                 12332 
                 0.265 
                 comparison 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer B:Bleach E is 1.69:1.41:14.8  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE X 
               
             
            
               
                   
               
               
                 Example 5 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Total 
                 Bleach 
                   
               
               
                   
                 Developer A 
                 Fixer B 1 st   
                 Fixer B 2 nd   
                 Bleach F 
                 Total 
                 Relative 
                 Equivalents/ 
               
               
                   
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Volume, 
                 Solution 
                 Developer 
               
               
                 Processes J 
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 mL/m 2   
                 Cost a   
                 Volume (L) 
                 Comments 
               
               
                   
               
               
                 J1  
                  187 
                  56 
                 87 
                 129 
                  459 
                 2336 
                 0.413 
                   
               
               
                 J2  
                  281 
                  84 
                 87 
                 129 
                  581 
                 2534 
                 0.275 
               
               
                 J3  
                  375 
                 112 
                 87 
                 129 
                  703 
                 2732 
                 0.206 
                 invention 
               
               
                 J4  
                  469 
                 141 
                 87 
                 129 
                  825 
                 2930 
                 0.165 
                 invention 
               
               
                 J5  
                  562 
                 169 
                 87 
                 129 
                  947 
                 3128 
                 0.138 
                 invention 
               
               
                 J6  
                  656 
                 197 
                 87 
                 129 
                 1069 
                 3326 
                 0.118 
                 invention 
               
               
                 J7  
                  750 
                 225 
                 87 
                 129 
                 1190 
                 3524 
                 0.103 
                 invention 
               
               
                 J8  
                  843 
                 253 
                 87 
                 129 
                 1312 
                 3722 
                 0.092 
                 invention 
               
               
                 J9  
                  937 
                 281 
                 87 
                 129 
                 1434 
                 3920 
                 0.083 
                 invention 
               
               
                 J10 
                 1031 
                 309 
                 87 
                 129 
                 1556 
                 4118 
                 0.075 
                 invention 
               
               
                 J11 
                 1125 
                 337 
                 87 
                 129 
                 1678 
                 4316 
                 0.069 
                 invention 
               
               
                 J12 
                 1218 
                 366 
                 87 
                 129 
                 1800 
                 4514 
                 0.064 
                 invention 
               
               
                 J13 
                 1312 
                 394 
                 87 
                 129 
                 1921 
                 4712 
                 0.059 
                 invention 
               
               
                 J14 
                 1406 
                 422 
                 87 
                 129 
                 2043 
                 4910 
                 0.055 
                 invention 
               
               
                   
               
               
                 Relative Cost per Volume: Developer A:Fixer B:Bleach F is 1.69:1.41:14.1  
               
               
                   a Total Relative Solution Cost = (Developer Volume * Relative Developer Cost) + (Fixer Volume * Relative Fixer Cost) + (Bleach Volume * Relative Bleach Cost).  
               
            
           
         
       
     
     EXAMPLE 6 
     Example 6 of the Inventive Process 
     One 36-exposure roll each of KODAK Max 800 Zoom 35mm film and Konica Centuria 800 35mm film was suitably exposed to light through a variable density test object and then loaded and processed singly in the processing chamber of a processor as described in U.S. application Ser. No. 09/920,495 of Twist et al filed Aug. 1, 2001. The chamber and its environment were heated to 54.40C before the films were loaded and processed. Processing of each of the films was conducted as follows: 
     Developer A at 54.4°C. was added all at once to the stationary chamber in the amount of 1406 mL/m 2  of film. Film was not present in the region of the processing chamber to which the developer was added. Rotation of the chamber at 30 rpm was then begun in order to apply the developer to the entire surface of the film. After developing for 60 seconds, Fixer A at 54.4°C. was added to the processing chamber containing the film and developer. The fixer was added all at once in the amount of 562 mL/m 2  of film while continuing to rotate the chamber at 30 rpm. This stopped development and initiated fixing. After 10 seconds, rotation of the chamber was stopped and the mixture of Developer A and Fixer A was removed from the processing chamber by suction. 
     Then, another volume of Fixer A at 54.4° C. was added all at once to the stationary processing chamber in the amount of 375 mL/m 2  of film to continue fixing of the film. Immediately thereafter, Bleach D at 54.4°C. was added all at once to the stationary processing chamber in the amount of 544 mL/m of film to bleach the developed silver. The chamber was then rotated at 30 rpm, and bleach-fixing was conducted for 70 seconds after which the rotation of the processing chamber was stopped and the mixture of Fixer A and Bleach D was removed from the chamber by suction. The film was then rinsed four times with water at 54.4° C. Each application of water was in the amount of 1125 mL/m 2  of film. Each rinse stage consisted of adding the water volume to the stationary processing chamber, rotating the processing chamber at 30 rpm for 10 seconds, stopping the rotation of the chamber, and removing the solution by suction. The film was then dried in warm air. A useful image was obtained as shown below and silver was satisfactorily removed from the film. Red, green, and blue Status M image densities were measured for each exposure level (step number) of the film and these densities are tabulated below for each film. 
     
       
         
           
               
            
               
                   
               
               
                 KODAK Max 800 Zoom Film 
               
            
           
           
               
               
            
               
                   
                 Status M Density 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Step Number 
                 Red 
                 Green 
                 Blue 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 1 (D-max) 
                 1.54 
                 2.65 
                 3.13 
               
               
                   
                 2 
                 1.46 
                 2.53 
                 2.97 
               
               
                   
                 3 
                 1.4 
                 2.41 
                 2.86 
               
               
                   
                 4 
                 1.32 
                 2.26 
                 2.7 
               
               
                   
                 5 
                 1.24 
                 2.13 
                 2.52 
               
               
                   
                 6 
                 1.16 
                 1.98 
                 2.31 
               
               
                   
                 7 
                 1.05 
                 1.83 
                 2.13 
               
               
                   
                 8 
                 0.97 
                 1.7 
                 1.98 
               
               
                   
                 9 
                 0.87 
                 1.56 
                 1.83 
               
               
                   
                 10 
                 0.77 
                 1.4 
                 1.68 
               
               
                   
                 11 
                 0.67 
                 1.26 
                 1.54 
               
               
                   
                 12 
                 0.58 
                 1.14 
                 1.41 
               
               
                   
                 13 
                 0.5 
                 1.02 
                 1.3 
               
               
                   
                 14 
                 0.45 
                 0.93 
                 1.21 
               
               
                   
                 15 
                 0.42 
                 0.87 
                 1.16 
               
               
                   
                 16 
                 0.4 
                 0.84 
                 1.13 
               
               
                   
                 17 
                 0.39 
                 0.82 
                 1.11 
               
               
                   
                 18 
                 0.39 
                 0.81 
                 1.1 
               
               
                   
                 19 
                 0.39 
                 0.81 
                 1.1 
               
               
                   
                 20 
                 0.4 
                 0.82 
                 1.12 
               
               
                   
                 21 (D-min) 
                 0.39 
                 0.81 
                 1.11 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
            
               
                   
               
               
                 KONICA Centuria 800 Film 
               
            
           
           
               
               
            
               
                   
                 Status M Density 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Step Number 
                 Red 
                 Green 
                 Blue 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 1 (D-max) 
                 1.7 
                 2.3 
                 2.89 
               
               
                   
                 2 
                 1.6 
                 2.19 
                 2.73 
               
               
                   
                 3 
                 1.5 
                 2.08 
                 2.56 
               
               
                   
                 4 
                 1.37 
                 1.95 
                 2.38 
               
               
                   
                 5 
                 1.25 
                 1.83 
                 2.24 
               
               
                   
                 6 
                 1.12 
                 1.7 
                 2.09 
               
               
                   
                 7 
                 0.99 
                 1.58 
                 1.95 
               
               
                   
                 8 
                 0.89 
                 1.48 
                 1.84 
               
               
                   
                 9 
                 0.79 
                 1.38 
                 1.73 
               
               
                   
                 10 
                 0.69 
                 1.29 
                 1.6 
               
               
                   
                 11 
                 0.59 
                 1.19 
                 1.47 
               
               
                   
                 12 
                 0.49 
                 1.1 
                 1.34 
               
               
                   
                 13 
                 0.41 
                 0.99 
                 1.23 
               
               
                   
                 14 
                 0.37 
                 0.92 
                 1.16 
               
               
                   
                 15 
                 0.35 
                 0.9 
                 1.14 
               
               
                   
                 16 
                 0.34 
                 0.88 
                 1.12 
               
               
                   
                 17 
                 0.33 
                 0.88 
                 1.11 
               
               
                   
                 18 
                 0.33 
                 0.88 
                 1.11 
               
               
                   
                 19 
                 0.33 
                 0.88 
                 1.11 
               
               
                   
                 20 
                 0.33 
                 0.88 
                 1.11 
               
               
                   
                 21 (D-min) 
                 0.33 
                 0.88 
                 1.11 
               
               
                   
                   
               
            
           
         
       
     
     The solution volumes used in this process were slightly less than those for Process Dl0 in Table IV. A slightly smaller 1 St  volume of Fixer A, a smaller 2 nd  volume of Fixer A, and a smaller volume of Bleach D were used. So this process consumed less processing solution at less cost than Process D10, which is inventive. The ratio of the number of bleaching agent equivalents used in the inventive Process D10 to the volume of developer solution (in liters) was equal to 0.18 equivalents of bleaching agent per liter of applied developer solution 
     
       
         
           
               
             
               
                   
               
               
                 Component 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 Developer A Formulation 
               
            
           
           
               
               
            
               
                 Sodium Sulfite 
                 6.0 g/L 
               
               
                 Sodium Bromide 
                 2.1 g/L 
               
               
                 Hydroxylamine Sulfate 
                 1.0 g/L 
               
               
                 Diethylenetriaminepentaacetic acid, pentasodium salt 
                 3.6 g/L 
               
               
                 (40% w/w solution) 
               
               
                 Sodium Carbonate, monohydrate 
                 26.9 g/L 
               
               
                 Polyvinylpyrrolidinone K-15 
                 2.4 g/L 
               
               
                 4-(N-ethyl-N-(β-hydroxyethyl)-amino)-2-methylaniline 
                 6.75 g/L 
               
               
                 sulfate 
               
               
                 pH (adj with NaOH or H 2 SO 4 ) 
                 10.1 
               
            
           
           
               
            
               
                 Fixer A Formulation 
               
            
           
           
               
               
            
               
                 Ammonium Thiosulfate Solution (56% w/w 
                 525 mL/L 
               
               
                 ammonium thiosulfate, 4% w/w ammonium sulfite) 
               
               
                 Sodium Metabisulfite 
                 7.8 g/L 
               
               
                 Succinic acid 
                 12 g/L 
               
               
                 pH (adjust with succinic acid and ammonium 
                 5.75 
               
               
                 hydroxide) 
               
            
           
           
               
            
               
                 Fixer B Formulation 
               
            
           
           
               
               
            
               
                 Ammonium Thiosulfate Solution (56% w/w 
                 700 mL/L 
               
               
                 ammonium thiosulfate, 4% w/w ammonium sulfite) 
               
               
                 Sodium Metabisulfite 
                 16.4 g/L 
               
               
                 Succinic acid 
                 18.4 g/L 
               
               
                 pH (adjust with succinic acid and ammonium 
                 5.75 
               
               
                 hydroxide) 
               
            
           
           
               
            
               
                 Bleach A Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 105.9 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 127 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx. 101 mL/L 
               
               
                 ingredients 
               
               
                 Succinic Acid 
                 30 g/L 
               
               
                 Sulfuric acid and Water to give a volume of 1 L and 
               
               
                 pH of 
               
               
                 pH 
                 4.1 
               
            
           
           
               
            
               
                 Bleach B Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 105.9 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 127 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx. 101 mL/L 
               
               
                 ingredients 
               
               
                 Sulfuric acid and Water to give a volume of 1 L and 
               
               
                 pH of 
               
               
                 pH 
                 5.9 
               
            
           
           
               
            
               
                 Bleach C Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 156.8 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 188 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx. 150 mL/L 
               
               
                 ingredients 
               
               
                 Succinic Acid 
                 30 g/L 
               
               
                 Sulfuric acid and Water to give a volume of 1 L and 
               
               
                 pH of 
               
               
                 pH 
                 4.1 
               
            
           
           
               
            
               
                 Bleach D Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 156.8 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 188 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx.  150 mL/L 
               
            
           
           
               
            
               
                 Bleach E Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 202 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 242.6 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx. 194 mL/L 
               
               
                 ingredients 
               
               
                 Succinic Acid 
                 30 g/L 
               
               
                 Sulfuric acid and Water to give a volume of 1 L and 
               
               
                 pH of 
               
               
                 pH 
                 4.1 
               
            
           
           
               
            
               
                 Bleach F Formulation 
               
            
           
           
               
               
            
               
                 1,3-Diaminopropanetetraacetic acid 
                 202 g/L 
               
               
                 Ferric Nitrate, 9 Hydrate 
                 242.6 g/L 
               
               
                 Ammonium hydroxide (28%) to dissolve the above 
                 approx. 194 mL/L 
               
               
                 ingredients 
               
               
                 Sulfuric acid and Water to give a volume of 1 L and 
               
               
                 pH of 
               
               
                 pH 
                 5.9 
               
               
                   
               
            
           
         
       
     
     The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.