JPS63198055A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the amount of a waste liquor and to utilize effectively chemicals contd. in a processing solution by specifying the concentrations of a calcium and a magnesium compds. contd. in the replenishers of a washing and/or a stabilizing steps and by introducing a part or all of overflow of the washing and/or stabilizing steps into a fore step. CONSTITUTION:The concentrations of the calcium and the magnesium compds. contd. in the replenishers of the washing step and/or the stabilizing step are reduced to <=5mg/l based on the calcium and the magnesium respectively in the developing of the titled material. The part or all of the overflow is introduced to the fore steps of the washing and/or the stabilizing steps. Thus, the effects such as a saved water and a reduced waste liquor are obtd. and the component contd. in a processing solution is effectively utilized, without reducing the quality of the titled material to be treated.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a processing method for silver halide photographic light-sensitive materials, and in particular to a processing method that can reduce the amount of waste liquid and make more effective use of chemicals in the processing liquid. . <Prior art> In recent years, it has been suggested that the amount of water used in the washing process included in the processing of silver halide photographic light-sensitive materials should be reduced due to environmental conservation, water resource, and cost issues. . For example, the Journal of the Society on Motion Picture and Television Engineers (Journal of the 5
Ociety of Motion Picture
and Television Engineers) Volume 47, Coat~Co! Page 3 (/9!J month issue) 6
Water Flow Rain in Immersion Washing on Motion Picture Film (
WaterFlow Rates in Imme
rsion-Washingof Motion P
icture Fi1m' xy, -A 7 gold in one? - (S, R, Goldwasser) proposes a method of reducing the amount of flushing water by making the flushing tank multistage and causing the water to flow countercurrently. This method is
It is used in various automatic processors as an effective means of saving water. According to this multi-stage countercurrent system, the amount of water supplied can be reduced as the number of washing tanks increases. However, increasing the number of washing tanks has the disadvantage of increasing the installation area of the automatic developing machine. The number of washing or stabilizing tanks in the countercurrent system is -~
In many cases, it is carried out in the λ~≠ tank. In addition, a method for stabilizing the image and saving water by processing this multi-stage counter-current water washing method with a multi-stage counter-current stabilizing bath that is further provided with an image stabilizing function is disclosed in JP-A-17-1).
It is described in μ3 publication. However, even if such a stable bath is used, it has the same drawback that the number of baths must be increased in order to further save water. Therefore, the effect does not necessarily satisfy the requirements of those skilled in the art. If a large amount of water is saved without increasing the number of washing or stabilizing tanks, the concentration of pre-bath components, such as fixing or bleach-fixing components, in the washing water will increase, making it easier for photographic materials to adhere to each other after processing. This causes various problems such as a marked increase in image fading. For this reason, a method of using a reverse osmosis treatment device as a means of saving water without increasing the number of washing or stabilizing tanks has been proposed in Japanese Patent Application Laid-Open No. No. O, same O-
It is disclosed in Publication No. 2≠10!3. In both of these methods, the O79-flow liquid from the washing tank or stabilization tank is directly connected to the reverse osmosis treatment equipment, the permeated liquid coming out of the reverse osmosis treatment equipment is supplied to the washing or stabilization tank, and the concentrated liquid is It is introduced into bleach-fixing baths and silver recovery equipment. However, when we actually carry out the method described above, we find that unless the device is a large device with a large reverse osmosis membrane area and a pump that can load high pressure, the clean liquid that has passed through the reverse osmosis membrane will not permeate below C. It is extremely difficult to sufficiently reduce the amount of concentrated liquid (hereinafter referred to as concentrated liquid) that is discharged without passing through the reverse osmosis membrane, compared to the amount of concentrated liquid (hereinafter referred to as concentrated liquid). Therefore, a large amount of capital investment is required. On the other hand, from the viewpoint of saving water and reducing the total amount of waste liquid in the process, there is a method in which the overflow from the stabilization process is used as a pre-bath having a fixing ability, as described in Japanese Patent Application Laid-Open No. 10-23! It is described in Publication No. t/33. This method can also contribute to reducing processing costs because the prebath components that adhere to the photosensitive material and are taken out to the stabilization process can be returned to their original state and reused. However, if this method is carried out in an automatic processor for a long period of time, significant stains and deposits will occur on the conveyor rollers, squeeze blades, etc. of the automatic processor, which belong to the fixing bath and the subsequent stabilizing bath. do. This results in problems such as scratches that contaminate the photosensitive material. Usually, the above-mentioned stabilizing baths are used to prevent the growth of bacteria and mold. A fungicide such as -chlorocomethyl≠-inthiazolin-3-one and a chelating agent such as / -hydroxyethylidene-/, /-diphosphonic acid are required. However, the use of such additives not only makes the above-mentioned troubles more likely to occur, but also may impair the performance of the prebath. On the other hand, simple water can save water and m
Implementing the pre-bath inlet pipe for overflow of the water washing process will cause even more serious problems. That is, in the various washing processes, mold and bacteria multiply and adhere to the photosensitive materials passing through, and the aforementioned dirt and deposits mix with mold and bacteria on the conveying rollers, squeeze blades, etc. However, this method is impossible to implement because it would greatly reduce the commercial value of the processed photosensitive material. In this way, the water washing step and/or the stabilization step over 7
Although it is important to introduce 0- into the pre-bath in order to conserve water, reduce the amount of waste liquid, and effectively utilize the components of the treatment liquid, it has not been realized to date due to the above-mentioned problems. <Problems to be Solved by the Invention> Therefore, the seventh object of the present invention is to provide a processing method that can save water, reduce the amount of waste liquid, and effectively utilize processing liquid components without impairing the quality of the photosensitive material being processed. Our goal is to provide the following. A third object of the present invention is to provide a treatment method that allows the introduction of overflow from a water washing step and/or stabilization step into a prebath without affecting the performance of the prebath. A third object is to provide a processing method that reduces maintenance of automatic processors. Means for Solving the Problems> The present invention is advantageous in that in the development processing of silver halide photographic materials, the concentration of calcium and magnesium compounds in the replenisher in the water washing step and/or stabilization step is lower than that of calcium and magnesium. As each! 1) 19% or less, and part or all of the overflow of the water washing step and/or the stabilization step is removed from the water washing step and/or the stabilization step.
Or, it has been achieved by a method for processing a silver halide photographic material, which is characterized in that it is introduced in a step before the stabilization step. In the present invention, washing with water is a process for ensuring post-processing performance by washing out processing liquid components that have adhered to or occluded in the color photosensitive material, as well as photosensitive material constituents that are no longer needed during the processing process. . Further, stabilization is a process of improving the storage stability of an image to a level that cannot be obtained by washing with water, and is composed of a liquid containing a component that has an image stabilizing effect. In the present invention, the carried-in amount refers to the volume of the pre-bath that is attached to and occluded in the photosensitive material and carried into the washing or stabilization process, and can be measured, for example, by the following method. How to measure the penetration amount〉 Take a 1 m sample just before entering the washing bath or stabilization bath, immediately immerse it in distilled water/lK, and keep it warm at 3°C for 7 hours.
The mixture was stirred with a magnetic stirrer for 0 minutes. Next, this solution was collected and the thiosulfate ion concentration C1 (P/A) in the solution was determined, and at the same time, the thiosulfate ion concentration C2 in the fixer solution in the previous bath was determined.
Quantify (f/l) and use the following formula to bring in the amount A(+++
j) was calculated. The quantification of thiosulfate ions was carried out by acidic iodometry after addition of formterdehyde to mask sulfite ions. Next, the water washing step and stabilization step in the present invention will be explained in detail. The amount of replenishment in the water washing or stabilization process is 7 to 7j of the amount brought in from the previous bath per unit area of the photosensitive material to be processed.
0 times the capacity, preferably 2 to 30 times, particularly preferably 3 to λO times. The inventors believe that in such a reduced replenishment amount,
The above-mentioned problem that occurs when the overflow from the washing process and/or stabilization process is introduced into the pre-bath is due to the concentration of calcium and magnesium in the replenishment solution for the washing process and/or stabilization process! ■We have found that by reducing / to below, all problems can be solved, which is an unexpected effect. In other words, by reducing the calcium and magnesium in the replenisher, the calcium and magnesium in the washing tank and stabilizing tank will inevitably decrease, and this will prevent mold and bacteria from forming without using any disinfectants or fungicides. The proliferation of
It also eliminates dirt and deposits on the conveyor rollers and squeeze blades of automatic processors. In the present invention, calcium and magnesium in the replenisher C (hereinafter referred to as the wash replenisher or stable replenisher) in the washing step and/or stabilization step are as described above. It is necessary that it is below Wet, preferably below 3/L, particularly preferably below /Da/. Various known methods can be used to adjust the concentrations of calcium and magnesium in the water wash or stable replenisher to the above levels, but it is preferable to use an ion exchange resin and/or a reverse osmosis device. Although various cation exchange resins can be used as the ion exchange resin, it is preferable to use a Na type cation exchange resin that replaces Ca%M g t Na. Further, an H-type cation exchange resin can also be used, but in this case, the pH of the treated water becomes acidic, so it is preferable to use it together with an OH-type anion exchange resin. The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include Mitsubishi Kasei's product name Diaion SK-/B or Diaion PK-2/
6 etc. can be mentioned. These ion exchange resin substrates preferably contain divinylbenzene in an amount of μ to /j% based on the total amount of monomers used during production. The anion exchange resin that can be used in combination with the H-type cation exchange resin is preferably a strongly basic anion exchange resin that has a styrene-divinylbenzene copolymer as a base and has a tertiary amine or quaternary ammonium group as an exchange group. . Examples of such anion exchange resins include Diaion 5A-10A and Diaion PA-μ/r, both manufactured by Mitsubishi Kasei Corporation. As the reverse osmosis treatment device used in the present invention, any known device can be used without limitation, but if the area of the reverse osmosis membrane is jm
It is desirable to use an ultra-compact device with a working pressure of J OKf/m2 or less, particularly preferably 2 m2 or less, and 20 K97 m2 or less. When such a type of device is used, the workability is good and a sufficient water saving effect can be obtained. Furthermore, it is also possible to pass activated carbon or a magnetic field. The reverse osmosis membranes included in the reverse osmosis treatment equipment include cellulose acetate membranes, ethylcellulose polyacrylic acid membranes,
A polyacrylonitrile film, a polyvinylene carbonate film, a polyethersulfone film, etc. can be used. In addition, the liquid feeding pressure is usually t~60 Kti/cm2, but in order to achieve the purpose of the present invention, JOKti/cm2 is used.
An2 or less is sufficient, and a so-called low-pressure reverse osmosis device with an IO odor/cwt2 or less can also be used. The structures of reverse osmosis membranes are Snoural type and Tubular type.
A type, hollow fiber type, pleated type, or rod type can be used. In the present invention, it is further preferable to irradiate the liquid in at least seven tanks selected from the washing tank or stabilization tank and its replenishment tank with ultraviolet rays, and in this way, the growth of mold can be further suppressed. The ultraviolet lamp used in the present invention has a wavelength of jJ, 7
A low pressure mercury vapor discharge tube is used which emits a line spectrum of mm. In the present invention, especially the sterilizing radiation output O, ZW~7
．． ! W is preferably used. The ultraviolet lamp may be installed outside the liquid and irradiated with it, or it may be installed inside the liquid and irradiated from within the liquid. According to the present invention, bactericidal agents and antifungal agents may not be present in the washing and/or stable replenishment solution, but they can be used as desired if their use does not affect the performance of the pre-bath. Examples of such antibacterial agents and antibacterial agents include: - isothiazolone antibacterial agents such as chlorocomethyl-μm isothiazolin-3-one, comethyl≠-isothiazolin-3-one, /, nobenziisothiazoline-
Benziisothiazolone antibacterial agents represented by 3-one,
Triazole derivatives such as incitriazole, sulfamide antibacterial agents such as sulfanilamide, active halogen releasing compounds such as sodium hypochlorite, sodium isocyanurate dichloride, phenolic string trimmers such as ortho-phenylphenol, 10,10' -Organic arsenic thread trimming agents such as oxybisphenoxyarsine can be mentioned. In addition, as water softeners, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid, phosphonic acids and aminophosphonic acids such as l-hydroxyethylidene-/,/-diphosphonic acid, ethylenediaminenishimethylenesulfonic acid, etc. Acids can also be added. These chelating agents can be used as sodium salts, potassium salts, or ammonium salts. In the stabilization step, in addition to the compounds used in the water washing step, a compound that has a stabilizing effect is added. A typical example is formaldehyde (C formalin)
and aldehyde compounds such as geltaraldehyde. However, for a color photosensitive material using a 2-equivalent magenta coupler, an aldehyde compound such as formalin may not be used. In addition, various buffers (e.g. borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are used in combination), and other fluorescent brighteners are added depending on the purpose. Alternatively, various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, ammonium thiosulfate, etc. can be added. The pH of the water washing or stabilizing solution is usually between μ and 2, but preferably! ~r. However, depending on the use and purpose, an acidic (pH 4C or less) stabilizing liquid to which acetic acid or the like is added may be used. Next, the time for water washing or stabilization treatment will be described. The time of water washing or stabilization treatment in the present invention is 70 seconds to 1
The process is performed within 0 minutes, but from the viewpoint of speeding up the processing, it is preferable to use a shorter time, specifically 20 minutes.
The range is from seconds to minutes, particularly preferably from seconds to minutes. It is preferable to combine various cleaning promotion means in the water washing or stabilization step. As such a promoting means, ultrasonic oscillation in the liquid, air foaming, jet impingement on the surface of the photosensitive material, compression using a roller, etc. can be used. Also, the temperature of the water washing or stabilization process is very low! 0°C range, preferably CO! ~gt'C, preferably 30-4A
It is o0c. In the present invention, the washing and/or stabilization step may be carried out in a single tank or in multiple tanks, but from the viewpoint of saving water, it is preferable that the water washing and/or stabilization process be comprised of a plurality of tanks, preferably a tank or more, and particularly preferably a tank from λ to μ. . In a plurality of tanks, replenishment is preferably carried out in a multi-stage countercurrent system in which the last tank is supplied and the last tank is then transferred to the front tank. The overflow of the water washing and/or stabilization process refers to the liquid that overflows outside the facility due to replenishment, and various methods can be adopted to introduce this overflow into the prebath. for example,
Any method may be used, such as making a slit in the barrier between the pre-bath and the automatic developing machine and allowing the overflow to flow in, or storing it outside the automatic developing machine and then supplying it using a pump. In this way, by introducing the overflow into the pre-bath, the components in the bath can be maintained at the required concentration by adding a small volume of a more concentrated replenisher to the pre-bath, and as a result, the pre-bath The volume of waste liquid can be reduced by the concentration of the replenisher. Of course, the same effect can also be obtained by storing the over 70- in a liquid preparation tank, adding replenisher components to it, and using it as a replenisher. In addition, the overflow contains pre-bath components brought in, so by using this, the absolute amount of components to be replenished into the pre-bath can be reduced, reducing the pollution load and processing costs. Can be done. The amount of over 70- introduced into the pre-bath can be arbitrarily set to suit the control of the pre-bath concentration, but usually it is set to 0.0 as the ratio of the amount of replenishment to the washing or stabilizing bath to the amount of replenishment of the pre-bath. 2~! is set, preferably 0.3 to 3,
Particularly preferably, it is set to 0°3 to -. The present invention can be applied to any case where a pre-washing bath or a stabilizing bath is used, but a bath having a fixing ability is preferable. The bath having fixing ability may be a simple fixing solution or a bleach-fixing solution. Next, specific surface treatment steps of the present invention are shown below, but the steps of the present invention are not limited thereto. /0 Color development - bleaching - C washing with water) constant fixing - C washing with water) - C stable) 2. Color development - bleaching - fixing - (washing with water) -

[Stable) J1 Color development - Bleach - Bleach-fix - (Water wash 1 - (Stable) ≠0 Color development - Bleach - Bleach-fix constant - C Wash) - C Stable)! 6. Color development - Bleach constant fixing - Bleach fixing - C washing with water) - C stable) 6. Black and white development - Washing with water - C reversal) - Color development - (v4 adjustment)
- Bleach-fixing (washing with water) - (stable) 7, black and white development - washing with water - C reversal) - color development - (adjustment) - bleach-fixing - washing with water)
- ζ stable) t, black and white development - water washing - (reversal) - color development -
(1) - Bleaching, white fixing - C washing), black and white development, constant fixing - water washing, black and white development, constant fixing - stable (>t) - Processes marked with are the type of photosensitive material, purpose and use. However, water washing and stabilization cannot be omitted at the same time.The above processing bath will be explained below.Color developmentThe color developer used in the development of the light-sensitive material of the present invention is preferably an aromatic primary amine. This is an alkaline aqueous solution containing a color developing agent as a main component.As this color developing agent, amine phenol compounds are also useful, but p-7
Unilene diamine compounds are preferably used, typical examples of which are 3-methyl-≠-amino-N, N-diethylaniline, 3-methyl-≠-amino-N-ethyl-N-
β-hydroxylethylamine s J), F 3≠Methyl-Hiro-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methylder-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates, p-)luenesulfonates, tetraphenylborates, p-(t-octyl)benzenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state;
Preferably used. Examples of the amine phenol derivatives include 0-aminophenol, p-aminophenol, μm amino-corlotylphenol, rhoamin-3-methylphenol, 3-oxy-3-amino-/, μm dimethylbenzene, and the like. In addition, "Photographic Processing Chemistry" by F. A. Meson, 7 Ocal Press (1946) (L. F. Mass... "Photographic Processing C")
hemistry', Focal Press) J
Jj~Kokota page, US patent λ, /P7,0/! No., same co. ! It is also possible to use those described in No. 2.3t Da, Japanese Patent Application Laid-open No. I-j4133, and the like. If necessary, more than one color developing agent may be used in combination. The color developer may contain pH buffers such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Agents; hydroxylamine, triethanolamine, compounds described in West German Patent Application (OLD) No. 2, Bucoco, No. 210,
Preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates 1. t-
Development accelerators such as diols; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as l-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid , cyclohexanediaminetetraacetic acid, iminodiacetic acid,
N-Hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and JP-A-Sho! Aminopolycarboxylic acid, l-hydroxyethylidene-1,l'-diphosphonic acid, represented by the compounds described in r-/rirrtz, Research Disclosure/, r/70 (17 years! months) The organic phosphonic acids listed, aminotris (methylenephosphonic acid),
Aminophosphonic acids such as ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, JP-A-Sho! low 1
No. 027, No. 13-02730, No. 027! μ-l Kono l core issue, same zz-4Ao co 3 issue, same! ! -μ021, same! ! -lko≦kosan/issue, same! ! -Bu! Ri No. 33, same! ! -6! the law of nature! Issue, and Research Disclosure/1) No. 70 C/972! It may contain a chelating agent such as the phosphonocarbon WI described in 1). The color developing agent is generally used at a concentration of about 0.00% per color developer/1. /
2 to about 309, more preferably a color developer/1
It is used at a concentration of about /f to about izt. Further, the pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 73 to about 73. Furthermore, the amount of replenishment can be reduced by using a replenisher in which the concentration of halides, color developing agents, etc. is adjusted to the maximum extent possible. As an example of such a low replenishment process, there is a method of replenishing the bromide concentration ≠ x O-3 mol/ml or less with the following replenishing solution per 100 crn2 of the photosensitive material. The processing temperature of the color developer of the present invention is preferably 0-1000, more preferably JO-uO'c. Processing time is 20 seconds to 10 minutes, preferably 30 seconds! It's a minute. Bleach solution, bleach-fix solution, fix solution As a bleaching agent used in the bleach solution or bleach-fix solution used in the present invention, a ferrous ion complex is a combination of ferric ion and aminopolycarboxylic acid, aminopolyphosphonic acid, or the like. complexes with chelating agents such as salts of Aminopolycarboxylic acid salts or aminopolyphosphonates are salts of agnopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Alkali metals include sodium, potassium, and lithium, and water-soluble amines include methylamine,
Alkylamines such as diethylamine, triethylamine, butylamine, ring amines such as cyclohexylamine, arylamines such as aniline% m-toluidine, and heterocyclic amines such as pyridine, morpholine, and lysine. Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra[trimethylammonium] salt ethylenediamine Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid sodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
', N'-) ethylenediamine acetate-N-(β-oxyethyl)-N,N
',N'-Triacetic acid trisodium salt ethylenediamine-N-(β-oxyethyl)-N,N
',N'-) diaminopronone tetraacetic acid salt l, -diaminoprononetetraacetic acid/, cordiaminopronone tetraacetic acid disodium salt/, J-diaminopronone tetraacetic acid/,! -diaminopronone tetraacetic acid diammonium salt nitrilotriacetic acid nitrilotriacetic acid trisodium salt cyclohexanediamine tetraacetic acid cyclohexanediamine tetraacetic acid disodium salt iminodiacetic acid dihydroxyethyl glycine ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid ethylene diamine tetrapropionic acid phenylene diamine tetraacetic acid /, J-diaminozolopanol-N, N, N'. N'-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid/, J-propylenediamine-N,N,N'. N'-tetramethylenephosphonic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds. The ferric ion complex salt may be used in the form of a complex salt, or
Iron salts, such as ferric sulfate, ferric chloride, ferrous nitrate, ferric ammonium sulfate, ferrous phosphate, etc., and chelating agents, such as Amitsubo, ricarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. may be used to form a ferrous ion complex salt in solution. When used in the form of a complex salt, 1
On the other hand, when forming a complex salt in a solution using a ferrous salt and a chelating agent, seven types of ferrous salts may be used. Alternatively, two or more types may be used.・Additionally one or two chelating agents
More than one type may be used. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is θ, /~ in bleaching solutions for color photographic materials such as color negative films.
1 mole/1. Preferably Oo, 2 to O0≠mol/l, and in the bleach-fix solution, θ, or to o, rmol/1. Preferably it is 0.7 to 0.3 mol/L. In addition, the color range is 0.03 to 0.0.
3 mol/1. Preferably it is 0.03 to O, cosol/L. Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. Koku o, riJ issue, same co, orri, ri rr issue,
Tokukai Akira! ! -32736 issue, 13-1713/ issue, same! ! -37 da/r issue, same J-J-Jj7 JJ issue, same! 3
-72t23, same ta 3-ta rtso, same! 3-2j
Bu 31, 13-10 Hiro 23-, same! 3-/λ Tadahiro J1, same! J-/14/123, J-J-, 2t
μm2A issue, Research Disclosure A/712
Compounds having a mercapto group or a disulfide group as described in No. 9 (July 7J), etc.; JP-A-Sho! 0-/4A
Thiazolidine derivatives as described in No. O/-ta;
Special public Akira ≠ r-riot issue, Special public Akira! Cor xorsx,
Same J-3-3273! No., U.S. Pat. No. J, 704. ! t
Thiourea derivatives described in No. I; West German Patent No. 1. /27,
7/! No., Tokukai Akira! Iodide described in lr-/lco No. 3j; West German Patent No. ri At, 4A10;
Polyethylene oxides described in JP-A No. 4t30; polyamine compounds described in JP-A-KOKAI Akihiro t-reJt No.; and other JP-A No. 2-Hiro λ4t34A, JP-A No. 64A≠ from TA, J3-TAH 9 core No. same! Hiro-37727, same J
rter No. 26106 and the same! Examples include the compounds described in No. lr-/4JRgo, iodine, bromine ions, and the like. Compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat.
, 1) No. 2, JP-A Showa 3-ta! The compounds described in No. t3θ are preferred. In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
Rehalogenating agents such as potassium bromide, sodium bromide, ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, as required
one or more inorganic acids having pH buffering capacity such as tartaric acid;
Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, i.e. thiosulfates) Thiosulfates such as IJium and ammonium thiosulfate; Thiocyanates such as sodium thiocyanate and ammonium thiocyanate:
Ethylene bisthioglycolic acid, J, A-dithia-i,
thioether compounds such as r-octanediol and thioureas) which are water-soluble silver halide solubilizers,
These can be used alone or in combination of λ or more. Also, Tokukai Akira! /-1) 1J! It is also possible to use a special bleach-fixing solution consisting of a combination of the fixing agents listed in the above article and a large amount of chloride such as potassium iodide. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. 1) The amount of the fixing agent is preferably 0.3 to 2 mol. r~
1. In the processing of color photographic materials for printing, 0. It is in the range of J- to 1 mol. The p)T region of the bleach-fix solution or fix solution in the present invention is 3
-10 is preferable, and t-1 is especially preferable. pH
If it is lower than this, the desilvering performance will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if J)H is too high, desilvering will be delayed and staining will occur more easily. In order to adjust pHtl, hydrochloric acid, a-acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary. The bleach-fix solution may also contain other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and fixing solution of the present invention contain sulfite C (e.g., sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (e.g., ammonium bisulfite, bisulfite, etc.) as a preservative. potassium bisulfite, etc.), metabisulfite C such as potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, carbonate), etc.). These compounds are approximately 0.02 in terms of sulfite ion.
The content is preferably 0.1 to 0.10 mol/L, more preferably 0.0 to 4 comol/L. As a preservative, nitrite is commonly added, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, even if carbonyl compounds etc. are added, they will still erode. Furthermore, an Fi buffer, a fluorescent whitening agent, a chelating agent, a fungicide, etc. may be added as necessary. The silver halide photographic light-sensitive material used in the present invention may be a monochromatic color photographic light-sensitive material having one light-sensitive silver halide emulsion layer on a support, or a multilayer color light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. It can also be applied to photographic light-sensitive materials (for example, color negative films, color reversal films, color one-no-cure-1 direct positive color light-sensitive materials, color reversal films, etc.). It can also be applied to black and white photosensitive materials such as medical photosensitive materials and photosensitive materials for plate making. Multilayer color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which are naphthol-based phenolics, pyrazolones or pyrazoloazoles and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers used in the present invention can be found in Research Disclosure.
isclosure)/ritμj (/ri7r year l-month)
It is described in Section 2-D and the patent cited in 17/7/1999. The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. Compared to double-stroke color couplers in which the coupling active position is a hydrogen atom, double-stroke color couplers in which the coupling active position is substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a current inhibitor or release a current promoter upon coupling reaction can also be used. Typical examples of yellow couplers that can be used in combination with the present invention include oil-protected acylacetamide couplers. A specific example is U.S. Patent No. 1, No. 7. -1O, -, 17z, 017 and 3
．． 41, 10 is written in the issue. As a dual-strength yellow coupler, US Patent No. 3. Da Or, 194
No. 4, No. J, $17. ? At No. 3. ri JJ, 1
0j issue and the same IK4c, o coco, buko θ issue, and other oxygen atom separation type yellow couplers or Tokko Sho! No. t-10739, U.S. Patent No. ≠, 4A01.7/
Ko issue, Dodai Hiro, J Koro, 02μ issue, RD/10! J(/
(Registered in 2007), British patent No. 1゜＄4! , No. 0λO, West German Application Publication No. 2,2/r. No. 77, No. 2. Koti, sti, No. 2゜3λ, 1) No. 7 and No. 2. A typical example is the nitrogen atom separation type yellow coupler described in U JJ, r/co issue, etc. α-pivaloylacetanilide couplers are excellent in color development properties, especially light fastness, while α-inzoylacetanilide couplers provide high color density. The magenta coupler that can be used in combination with the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! - As for the pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and coloring density of the coloring dye, and typical examples thereof are U.S. Patent No. 1, J//, 01) No. 2゜3
4AJ, No. 703, No. 2,600, 71), Il.
l, 901. ! No. 7J, @J, 062,613, No. J, IJ-2, lribu and No. 3゜5P36,0
1j- issue etc. Two drawings! - As a leaving group for pyrazolone couplers, U.S. Patent No. 3j1,
It is particularly preferable to use a coupler having an arylthio group as described in No. 197. Also, European Patent No. 73. It has a pallast group as described in No. 74! - Pyrazolone couplers provide high color density. As pyrazoloazole couplers, US Pat.
Jtf, 172, preferably the pyrazolobenzimidazoles described in US Pat. No. 3,7! , pyrazolo (j, /-c) (/, co, 4C)) lyazoles described in No. 067, Research Disclosure Co4t Co20 (
/91μ91j) Pyrazolotetrazoles described in K and Research Disclosure 24cλ30(/rir
Examples include the pyrazolopyrazoles described in ≠June 2013). The imidazo(/, 2-b:l pyrazoles described in European Patent No. 1/1, 744/-%i are preferred in terms of the low yellow rigid absorption of coloring dyes and light fastness; European Patent No. 1) Pyrazolo [/. j-b) (/, 2. Reference) Triazoles are preferable.Cyan couplers that can be used in combination with the present invention include oil-protected naphthol-based and phenol-based couplers. 7-tall couplers described in J-jjK, preferably U.S. Pat.
! 2. Colco No. 4゜/μ4. J Riwo No., same No. Hiroshi,
Typical examples include the oxygen atom separation type two-stroke naphthol couplers described in Kokot, No. 2JJ and No. 2JJ, No. 200. Further, specific examples of phenolic couplers are given in US Patent No. 2. Jtf, P, No. 22, No. 2, 10/, No. 171, No. 2, 77, No. 742, No. 2, No. 2. It is written in ryz, zko≦ issue, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat.
．． 772,002, a phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus, US Pat. r, No. 301, same No. p, /24. JPj issue, same issue ≠, 33μ, 0/1 issue, same issue da, 3 cores. No. 773, West German Patent Publication Nos. r-≠Jt<2,! described in No. 77 etc.
- Diacylamino-substituted phenolic couplers and U.S. Pat. No. 3.1, No. 4.22, No. ! ! ,ri99
Aoi, the same number, ≠ -1,! ! No. t and g, 4
CX7,767, etc., and has a phenylureido group at the 9-position and! These include phenolic couplers having an acylamino group at the - position. of naphthol described in European Patent No. 1)/1λ4A! Cyan couplers substituted with a sulfonamide group, carmineamide group, etc. at the - position also have excellent fastness of colored images and can be preferably used in the present invention. In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No. ≠, /63,670 and Special Publication Sho J7-
Yellow-colored magenta couplers such as those described in US Pat.
, isr, JJt and British Patent No. 1. /≠4. Jt
Typical examples include magenta-colored cyan couplers described in No. R and the like. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 370 and West German Application No. 3. Ko J4L, 133
Specific examples of yellow, magenta or cyan couplers are described in the issue. The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. three! /, Iko No. 0 and Iko No. 0, oro. ! It is described in the // issue. Specific examples of polymerized magenta couplers are described in British Patent No. 2. ioco, No. 773 and U.S. Pat. No. 3, No. 7.1r-. These couplers may be either 1-weight or 2-equivalent to silver ions. It may also be a colored coupler having a color correction effect or a coupler C (so-called DIR coupler) that releases a development inhibitor during development. In addition to DIR couplers, there are also colorless DIs in which the coupling-reactive product is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. In the present invention, the gelatin may be lime-treated or acid-treated. For details on how to make gelatin, see Arthur Vuis.
Weiss1, The Macromolecule Chemistry on Gelatin
ar Chemistry of Gelatin)
, C Academic Press
ss), published in 19614). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is silver iodobromide containing silver iodide with a molar coefficient of /j or less. Particularly preferred is silver iodobromide containing from 1 mole to 1 comol of silver iodide. Average grain size C of silver halide grains in a photographic emulsion The grain size is defined as the grain diameter in the case of spherical or approximately spherical grains, and the grain size in the case of cubic grains, and is expressed as an average based on the projected area. ) is not particularly important, but it is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubes and octahedrons, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It may be a composite form of crystal forms such as these.It may also consist of a mixture of grains of various crystal forms.Furthermore, immediately after the grain, an ultra-tabular silver halide grain whose thickness is three times or more than that of the grain has a jO width of the total projected area. Silver halide grains may have different phases in their interior and surface layers.Also, they may be grains in which the latent image is mainly formed on the surface, or in the interior of the grain. The photographic emulsion used in the present invention may be used to prevent fogging during storage or photographic processing, or to stabilize photographic performance. and can contain compounds of rice, i.e. azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles. , mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially Vc/-phenyl!-mercaptotetrazole), etc.; mercaptopyrimidines: mercaptotriazines; for example, oxadrine Thioketo compounds such as thione; azaindenes, such as triazaindenes, tetraazaindenes (especially μm hydroxy-substituted (/, J, Ja, 7) tetraazaindenes), interazaindenes, etc.; benzenethiosulfone A number of compounds known as antifoggants or stabilizers can be added, such as acids, inzenesulfinic acid, benzenesulfonic acid amides, etc. The photographic emulsion layer of the light-sensitive material made using the present invention or Other hydrophilic colloid layers include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement C.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester C, such as vinyl acetate 1, acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid , meccrylic acid, α, β
- Polymers containing combinations of unsaturated dicarboxylic acids, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, sulfoalkyl acrylates, sulfoalkyl methacrylates, styrene sulfonic acids, etc. as monomer components can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benz Oxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a corchioxazolidine nucleus, a ≠-dione nucleus, a thiazolidine-2, a hiro-dione nucleus, a rhodanine nucleus, and a thiono-dione nucleus, which have a ketomethylene structure. J to 6-membered heterozygotes such as ζ-rubituric acid nuclei can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds C substituted with nitrogen-containing heterocyclic groups, for example, U.S. Pat. ,7
2/), aromatic organic acid formaldehyde condensates (e.g., those described in US Patent J, 74c3.!10), cadmium salts, azaindene compounds, and the like. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salt C chromium alum, chromium acetate, etc.)
, aldehydes C formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane n-conductors (2,J-dihydroxydioxane, etc.), activated vinyl compounds (/, 3. Yo-triacryloyl-hexahydro-5-triazine, /, 3-
(vinyl sulfo; lucopropanol, etc.), active halogen compound Cλ, Hiro-dichloro-6-hydroxy-8-
) IJ Azin n,! ``1, mucohalogen [1 (mucochloric acid, mucophenoxychloroic acid, etc.)], etc. can be used alone or in combination. In the photosensitive material produced using the present invention, dyes or When ultraviolet absorbers and the like are contained, they may be mordanted with cationic polymers, etc. The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, gallic acid, etc. as color anticaprilants. It may contain an acid derivative, an ascorbic acid derivative, etc. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group. (e.g., those described in U.S. Pat. 1, for example, those described in JP-A No. 2-27r≠), cinnamate ester compounds (for example, those described in U.S. Pat. No. 3.7
or, rot, J, 707.37r), butadiene compounds 1, eg, US Pat. 0 hiro! , Co., Ltd.), or benzoxazole compounds C, such as those described in US Pat. No. 3,700.4L!
Ji issue) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted and incorporated into specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for irradiation prevention or other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. No. 343, West German Patent No. 3 II (OLS), j≠l. J74c and same@, 2. J-41/, No. 230, etc. Example: A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating liquid preparation Yellow coupler (ExY)/9. /g and color image stabilizer (Cpd-/)g, 4tg and ethyl acetate 27.2cc
and 7.7 cc of solvent (Solv-/) were added and dissolved, and this solution was emulsified and dispersed in 10 tizelatin aqueous solution/IjCC containing 10% sodium dodecylbenzenesulfonate/CC. On the other hand, the following blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (containing 717 g/kg of zo, o mole of silver bromide) per mole of silver (1)! , θ×/θ−4 moles were added. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, /-oxy-3,yo-dichloroS-) riazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. Blue sensitive emulsion layer (ft-ps per 7 moles of silver halide, θ×/θ−4 moles), green sensitive emulsion layer (ft-ps per 7 moles of silver halide, θ×/θ−4 moles) and (ft-ps per 7 moles of silver halide) Red Sensitive Emulsion Layer The following compound was added to the red sensitive emulsion layer in an amount of λ, txio-s mole per mole of 7 silver halide. In addition, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(1-methylureidophenyl)-y-mercaptotetrazole was added at 0.0 x 10-6 mol and 3°oxio per mol of silver halide, respectively. -s mol, /, 0X
10-5 mol was added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, g-hydroxy-6-methyl-/, 3.3&, 7-titrazaindene was added per mole of silver halide/, co×10-
2 mol, /, /×10 −2 mol was added. The following dyes were added to the emulsion layer to prevent irradiation. HoOH and (Layer Structure) The composition of each layer is shown below. The numbers indicate the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene 2-laminated paper [the polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine)] First layer (blue-sensitive layer) Silver halide emulsion (Br2♂θ%) o, , 2 Otsu gelatin /, /3 Yellow coupler (ExY) 0. ♂3゛Color image stabilizer (C
pd-/) 0. / Solvent (Solv-/)
0. ! j Second layer (color mixture prevention layer) Gelatin 0.9 Color mixture prevention agent (Cpd-, 2) 0.0jr Third layer (green sensitive layer) Silver halide emulsion (Br: /1%) 0. /l gelatin 7.79 maze 7p coupler (ExM) 0.32 color image stabilizer (Cpd
-j) 0.20 color image stabilizer (Cpd-da)
0.0/color image stabilizer (cpa-♂)
o, o 3 color image stabilizer (cpa-9)
0.0! Solvent (Solv-2') 0.
6j Fourth layer (ultraviolet absorbing layer) Gelatin /, j♂ultraviolet absorber (UV-/) o, t, 2 color mixture prevention agent (
Cpd-j) o, or solvent (Solv-j)
) 0.2ath! Layer (red-sensitive layer) Silver halide emulsion (Br: 2θ%) o, 23 gelatin / 39 cyan coupler (ExC) θ, 3G color image stabilizer (Cpd
-j) θ, /2 polymer (Cpd-7)
0.4tθ solvent (Solv-g)
o,,23 Sixth layer (ultraviolet absorbing layer) Gelatin θ,j3 Ultraviolet absorber (UV-/) o,,z/solvent (SO1
'l/-j) 0. Or 7th layer (protective layer) Gelatin 7.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 77%) I! 7. /7 fluidity, rough-in 0.03 The following emulsions were used for each layer. (ExY) Yellow coupler (Ex M) Magenta coupler 81'1) 7 (t=) (ExC) Cyan coupler α (Cpd -/) Color image stabilizer (cpct-co) Color mixing inhibitor (Cpd-j) Color image stabilizer (Cpd-4t1 Color image stabilizer OH ti (Cpd-r) Color mixture inhibitor OH (Cpd-a1 Color image stabilizer CH2CH2COOC8) (17 mixture (weight ratio)) (Cpd-7 ) Polymer average molecular weight to, oo. (Cpd-/) Color image stabilizer I (Cpd-ta) Color image stabilizer (UV-/) 2:?:/Mixture (weight ratio) of ultraviolet absorber (SOIV- /) Solvent (Solv-Co) Solvent 2:/Mixture (Volume Ratio) (SolV-J') Solvent (Solv-4t) Solvent After imagewise exposure of the above sample, each washing water was treated separately in the following processing steps. Running processing was performed.The processing was 7 times each.
70.6m2 a day/! I was out for days. The amount of photosensitive material carried into the washing water is 3 per m2 of photosensitive material.
It was 0m1. Color development 3tr0c/min<to seconds 300
m1 bleach fixing 33°C 7 minutes 00 seconds 170ml water washing ■ 33°Cso seconds - water washing ■ 33°C 20 seconds - water washing ■ jj'c 20 seconds j j Oml drying 7σ~to'c to seconds (washing ■→■ A three-tank countercurrent system was used.) The composition of each treatment liquid is as follows. Color developer mother solution Replenisher water 200ml 100m
1 diethylenetriaminepentaacetic acid /, Og /, Og/-hydroxyethylidene-/, /- diphosphonic acid <tOS) Co, og Co, Og nitrilotriacetic acid Co, Og Co, Og The following compounds
g, og da, rg the above sample,
! After cutting into microorganisms and exposing them to imagewise light using an automatic printer,
In the following treatment process, using different types of washing water, each treatment was carried out for 7 days and 60 m each (actual operation for 2 μ days). In addition, the amount of bleach-fix solution brought into the washing machine is t! It was simple and easy to use. rlrlrlrl) Town) Town Town bThe various capacities are 4 At each for color development/7t% bleach-fix lot and water wash. Further, for the above processing, a minilab 23S processor pp-too manufactured by Fuji Photo Film ■ was used. All of the overflow from tatami washing with water was introduced into the bleach-fixing bath.The composition of each treatment solution is as follows. water tooyxt
roornt diethylenetriaminepentaacetic acid t, or i, oil-hydroxyethylidene-/,/-diphosphonic acid (but 041 2.Of 2.0 nitrilotriacetic acid co, Of co, oy the following compound)
france, ot4t, rt potassium bromide
0.21 - potassium carbonate
JO9319N-ethyl-N-(β-methanesulfonamidoethyl 1-3-methyl 1 μm aminoaniline sulfate!, J-97.!f diethylhydrocytyl-onda, ota, zt fluorescent brightener (UVITEX-CK Add water 1oood toooom
pH12j'c) to, xz 10.
BuO water 4cood
good ammonium thiosulfate (70) 200m μgood sodium sulfite 209 4AOf ethylenediaminetetraacetic acid iron toy 12otrI [) Add ammonium ethylenediaminetetraacetic acid water 10001d 1000d
pH (J-'C) Adjust with acetic acid and ammonia 7.00 t, 70 ml of washing water
Mother liquor and replenisher common washing water I [: 1 ttttcz-chlorocomethyl-≠-inthiazolin-3-one 0.2 t was added to the same tap water as the washing water system. C Tokukai Akibu 0-1! ! (Same as described in No. 1JJ, Example 1) Electrical conductivity JIOμS washing water ■: Tap water was mixed with H-type strongly acidic cation exchange resin (o-
Water was passed through a hotbed column filled with Amberlite IR-/20B1 manufactured by Mund Haas Co., Ltd. and OH type anion exchange resin C Amberlite IR-≠001 to obtain the following water quality. Washing water (■): To the above washing water (■), 20 (20)/It of sodium incyanurate dichloride and 19 (1301)/It of anhydrous sodium sulfate were added. The water quality was as follows. At the end of each week's treatment, bacteria and mold growth in each washing tank, stains on the treatment cleaner, stains on the conveyor roller, deposits, and yellow stain were checked, and the results are listed in Table 4. In addition, for yellow stain, unexposed is -/(- processed,
The yellow density C (reflection density) was measured using a Magbeth densitometer. As shown in Table-1 Table-1, 1. According to the present invention, bacteria and mold are generated in the washing tank. It can be seen that both of these results are satisfactory, and that the purpose of the invention has been achieved. Example: On a subbed cellulose triacetate film support,
Sample 10/, which is a multilayer color light-sensitive material having the composition shown below, was prepared in which each layer was arranged in a similar manner. (Composition of photosensitive layer) The coating amount is the amount expressed in units of 97 m2 of silver for silver halide and colloidal silver, and the amount expressed in units of f/m2 for couplers, additives and gelatin.
Further, the amount of sensitizing dye is expressed as the number of moles per mole of silver halide in the same layer. 1st layer C antihalation layer) Black colloidal silver・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.2 gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ /, 3ExM-J
r・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・o、otUV-/
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0. /UV
-1 ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0. Ko5
olv-/ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0/5
olv-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.0/2nd
Layer (intermediate layer) Fine particle tin bromide C average particle size 0.07μ)・・・・・・・・・・・・ 0
．． 10 Gelatin・・Song・・・−−−−−・−・・
−・−・−・・−・−・・・・／ , jUV-t ・・
・・・・Between songs・songs・songs・・・・・・・songs 0.
01UV-2・・・・・・・・・・・・・・・ Song−−−−−・−−−−−・−−−−−0,03ExC−
one························
・・・・・・・・・・・・ o, okoExF-/・・・
・・・・・・・Song・・Song・・・・・・・・・・・・・・
・・0.00≠5olv−/・・・River・・River・
...Song/river...0. /5olv-
2. River・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0.09 3rd layer C 1st red-sensitive emulsion layer] Silver iodobromide emulsion (12 mol of Ag, internal high kgl type, equivalent sphere diameter 0.3 μ, equivalent sphere diameter Coefficient of variation λ, normal crystal, mixed twin grain, diameter/thickness ratio, j) Coated silver amount/use □, μ gelatin ・・・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ o、buExt-/
...... Song... Song...
/, O×/'0 'ExS−λ ・・・・・・・・・
・・・・・・・・・・・・In the song...J, O x 10"-4
ExS-j ・Yu・・・・・・・・・Song・・・・
・Songs・ /X1O-5ExC-j・・Songs・Songs between songs・Songs between songs. , o6ExC-μ ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・ 0.01ExC-7・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
o, 04! ExC-2・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.03Solv-t・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0. 0JSolv-j ・・・・・・・・・・・・
・・・φ・・・・・・・・・・・・・・・・・・0
．． 0/2 μth layer CWc red-sensitive emulsion layer) Silver iodobromide emulsion (kgl Jmol), internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 2!, normal crystal, Twinned mixed particles, diameter/thickness ratio 4t) Coated silver amount・・・・・・・・・・・・・・・
・・・ 0.7Ext-/ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
/X10=ExS-2・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・3×10
-'ExS-J・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／×1O-5E
xC-J・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.2≠ExC−μ
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ O、μExC-7・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0.0μExC-2・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・ O0Oμ5olv-／・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0. /! 5olv-J・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0.
02nd layer C 3rd red-sensitive emulsion layer) Silver iodobromide emulsion (kg1) 0 molar ratio, internal height AgJ type, equivalent sphere diameter o, r μ, coefficient of variation of equivalent sphere diameter /64, normal crystal, twin Crystal mixed particles, diameter/thickness ratio/, 3) Coated silver amount...
・i,. Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 1.
0Ext-/ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・Ixl
o-'ExS-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・E×1
0-'ExS-j ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／×l
0-5ExC-1 ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・θ,
01ExC-6・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0. /
5olv-/ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0/
5olv-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・o, or 6th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 1.
0Cpd-/・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
3Solv-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.02
7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 12 molar ratio, internal high AgAl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 2rs, normal crystal, twin mixed grains, Diameter/thickness ratio j, j) Coated silver amount・・・・・・・・・・・・・・・
・0. JOExS−≠・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・J-×1
0 'ExS-Otsu ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.3×10-'ExS
-1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・λ×10' gelatin ・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ /, OExM-ta
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0. koExY-/μ
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.03ExM-Jr ・・
・・・・・・・・・・・・・・・・・・・・・・・・
...River...0.0JSolv-/ ...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0. ! 1st N (second green-sensitive emulsion layer) Silver iodobromide emulsion (kgl μmolar ratio, internal high kgl type, equivalent sphere diameter O0μ, coefficient of variation of equivalent sphere diameter 5rqb, normal crystal, mixed twin grains, diameter / Thickness ratio ≠) Coated silver amount・・・・・・・・・・・・・・・
・・・・・・ O,aExS−≠ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・J×10−'ExS−1・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・Co ×
io-″4ExS-6・・・・・・Song・・・・・・・・・
...River...0.3×10-'ExM-5'・
...Song, song...Song concave song...Song o, JjE x
M = I・・・・・・・・・・・・・・・4・
・Song・・・・Song □、OJExM-10・Song・Song・・Song・・Song・・Song・0.0/J-ExY-/J・
Song・Song・・・Song・・・Song・・ 0.0/
5o1v-/...Curved surface...Song...Song/Curved surface
. , -th layer (fgs green-sensitive emulsion layer) Silver iodobromide emulsion (Aglt moltimol part high Agl type, equivalent sphere diameter to 〇μ, coefficient of variation of equivalent sphere diameter toIIJ. Normal crystal, twin mixed grain, diameter / Thickness ratio/, c) Coated silver amount, concave, o, rr Seratin...
・・・・・・Song・・Song・・Song・Song・・・・・
/,0ExS-7・・・・・・Concave song・Song・
...J,! ×10-'ExS-1r・・River・
...Song...Listen/Kawa.../, 4AX10-'
ExM-//・Concave curved surface curved curve □, 0/ExM-
/J・Concave curved curved curve. , OJExM −/J・Concave curved surface curved curve □, Ko□ExM− is curved concave curved curved curved curve □, 02ExY-tz curved curved curve/four-phase curved concave curved surface 2Solv−/ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・O0
λ08olv-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・o, o
r70th layer (yellow filter single layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／、
Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o、orCpd−λ ・
・・・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0. /5olv-/ ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.3 1st/Layer C 1st blue-sensitive emulsion layer) Silver iodobromide emulsion (kgl molar ratio, high Agl type, equivalent sphere diameter O0!μ, Coefficient of variation of equivalent sphere diameter/! Unfortunately, r-hedral particles) Coated silver amount・・・・・・・・・・・・・・・
・・・O,4L gelatin・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ /, 0ExS-ta ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・ko×io"−'ExY−/6・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・ OooriExY−／φ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・0.07Solv-／・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・ O, C 1st layer C 2nd blue-sensitive emulsion layer) Silver iodobromide emulsion (kg1) 0 mol, internal high Agl type, equivalent sphere diameter/63 μ, variation in equivalent sphere diameter Coefficient! Unfortunately, normal crystals, twinned mixed particles, diameter/thickness ratio, 3) Coated silver amount... Curve... o
, r gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0. ≦Ext-?・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／X
/ 0-'ExY-/bu ・−・−・・−・−・−・
−・−・−−−−・−・−・0 + 2!5olv−/
−・・・・・・Fist・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o, o77/J layer C 1st
Protective layer) Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ o, 1
UV-／・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0. /
UV-,z・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ 0
．． 2Solv-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
/5olv-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・o, oi
(2nd protective layer) Fine grain silver bromide (average grain size 0.07μ)
・Oh,! Gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0. Hiro! Polymethyl methacrylate particles f diameter 1. Yo μ)・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0. JH-／・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
Song...Song... o, HiroCpd-j...
・・・・・・－・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. 2Cpd-da...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0. ! In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared by K as described above was designated as sample 10/. Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below. UV-co08oly-/tricresyl phosphate osolv-co 7-dibutyl talate08olv-j bis(J-ethylhexyl) phthalate xM-1 α ExF-/ xC-2 (b)C5H13 ExY-/gExY-ip H3 xC -1 CH2 C(CH3)5 xC-4 OCH*CH*SCH*C0OH xC-7 CH2 Summer ExY-2 mo70wi, about ko o, oo. ExY-10 α ExY-tt Ex M −/ J α ExM-/J ExY-/ Bucpct-i Cpd-CoExt-
/ ExS-CoExS-J ExS-μ ExS-1 C2H. ExS-7 ExS-1 (CH2) 4803 Na ExS-ta CH2=CH802CH2C0NHCH2CH2=CH
802-CH2C0NHCH2cpct-μ The sample prepared as above was designated as 10/. The above sample was cut to a width of 31 m, and after being photographed, the following treatment was carried out using the same washing machine ~■ as in Example-1.
For each, 30 tubes were processed per day (during the actual operation period). Further, regarding the treatment using the washing water (2), a treatment was also carried out in which the mother liquor of the bleach-fixing solution used and the replenisher were prepared using the washing water (2). ``-'' All the overflow from water washing (1) was introduced into the bleach-fixing bath.The processor was a negative processor FP-J for Champion 2JS manufactured by Fuji Photo Film Co., Ltd. with an improved version of 0. In this processor, the amount of bleach-fix solution carried into water washing was -d per width im. Next, the composition of the processing solution is described. /, l-diphosphonic acid!, OJ, sodium cosulfite da, 0!,!potassium carbonate
SO, O Hiro, O Potassium Bromide
1. ≠ - Potassium iodide!
■ Hydroxylamine W acid [J, 4LJ, 0≠-(N-ethyl-N-β-hydroxyethylamino)-11 methylaniline sulfate ゛ Hiroshi, z 7. ! Add water /, OL /, 0L pH 10,
Oj 10.20 (bleach-fix solution) -solution (f) Replenisher (?) Ethylenediaminetetraacetic acid ferric ammonium dihydrate to, o ito,. Ethylenediaminetetraacetic acid disodium salt z, 0 10.0 Sodium sulfite /J, θ μ, O ammonium thiosulfate aqueous solution (7041 coz, o zoo,. Acetic acid (Pry) 2.Oxl j, 0w
t1 Bleach accelerator o, oi mol 0.01 mol Add water /, OL /, 0L pH
J, t bu, da [Stabilizing solution 1 mother liquor and replenishing solution: a (unit: t) Formalin (
37) 2. Oyl polyoxyethylene-p-monononyl phenyl ether C average degree of polymerization to) o, J ethylenediaminetetraacetic acid disodium salt 0.02 Add water /, 0L pHz, ov,. K at the end of processing during the daytime, bacteria and mold growth in each washing tank, dirt on the processed film, dirt and deposits on the transport roller, and ≠r 00 ”K, 10oCMS
The amount of residual silver after processing of Sample 101, which had been exposed to light, was examined, and the results are shown in Table 1. As shown in Table 1, as in Example 7, the present invention has excellent efficiency, and the desilvering performance of the bleach-fix solution is also maintained well. Example-3 1 on a subbed cellulose triacetate film support
A multilayer color photosensitive material 20/ was prepared by coating each layer having the composition shown below. (Photosensitive layer composition) The numbers corresponding to each component are expressed in units of f7m2. IL is shown, and for silver halogenide, the coating amount is shown in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of the same amount of halogenated trowel. 7th #C antihalation layer) Black colloidal silver O, cogelatin 2.6 cpct-J
(7,2Solv-/
0.02 First layer C intermediate layer) Fine grain silver bromide (average grain size 0.07μ) 0. Gelatin i, to I. 3rd layer C low-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide!,! Molarity, average grain size 0.3μ, coefficient of variation related to grain size c or less, simply abbreviated as coefficient of variation 1/ P) 1. ! gelatin
3゜0ExS-/
J, 0X10-'ExS-2t, o
xto-' ExS-J o, 3xto-'
ExC-10,7 ExC-20,/ExC-jO,02 cpct-70,0/5olv-10,r Solv-20,co5olv-uO,/μth layer C high-sensitivity red-sensitive emulsion layer) Monodispersed iodine Silver Bromide Emulsion C Silver Iodide 3. ! Molar size, average particle size 0.7μ, coefficient of variation/14) l, cogelatin
Ko,jExS-/
5xto-'ExS-a
t,zxto-'ExS-J
O, IIJ-×10"-'Ex
C-go, tz ExC-ro, or ExC-20,03 ExC-so, ol Solv-/o, orS
olv-”2 0.jth! Layer C intermediate layer) Gelatin 00tCpd-
10,0jSolv-J
O, 0/th ≦ layer C low-sensitivity green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide! molar ratio, average grain size 0.03 μ, coefficient of variation l) O, da monodisperse iodobromide emulsion Silver emulsion C silver iodide 7 mol, average grain size 0. jμ) 0. r Gelatin 3.0ExS -4
/×/f' ExS-r uxlo-4
ExS-+ /x10-'
ExM-A O,2Ex
M-7o, μ ExM-to, tbuExC-ta 0.01Sol
v-2/, J Solv-g O, 0!5o
lv-t o,ot 7th layer C
High-sensitivity green-sensitive emulsion layer) Polydispersed silver iodobromide emulsion C silver iodide J, j molar size, average grain size o, rμ, coefficient of variation 7! Sorry) 0.2 Gelatin /, BuExS
-40,7×10-'ExS-7J,tXlo-' ExS-+ 0.7×10-
'ExM-7o, or ExM-10,044 ExC-ta 0.0/5o
lv-/0.0
rSolv-xO, JSolv-4co
, 1) > 3rd r layer C yellow filter layer) Yellow colloidal silver 0.2 gelatin O-ta Cpd-20,
5 olv-20, / Second layer C low-sensitivity blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion C silver iodide t moles, average grain size 0. Jμ, coefficient of variation Ko04). , 4c Monodisperse silver iodobromide emulsion C Silver iodide t moles, Average grain size o, tμ, Coefficient of variation/741 0.41 Gelatin Co, Ri ExS-7/x10
-' ExS-r 1xto-'E
xY-10/, 2 ExC-so, or Solv-J
O,4tSolv-II
O,/IO layer c High-sensitivity blue-sensitive emulsion layer 1 Monodispersed silver iodobromide emulsion (silver iodide t mol, average grain size i, zμ, coefficient of variation l d) 0.2 gelatin -7! X
1O-5 ExS-r! X1O-5
ExY-100. $ ExC-30,04 8o1v-20, / 1st/layer (1st protective layer) Gelatin /, 0cpct
-30,/Cpd-see 〇,/cpct
-tO,/Cpd-6o,/5olv-10,/5olv-! 0. / 1st co-layer (2nd protective layer) Fine grain silver bromide emulsion C average grain size 0.07μ) 0.25 gelatin
/・O polymethyl methacrylate particles (diameter /, jμ) o, Cpd-za θ,! In addition, a surfactant Cpd-7 and a hardening agent H-/ were added. Ex S-koExS-s ExS-HiroExS-j ExS-buExS-7 ExS-r ExC-≠ ExC-! ExC-2 ExY-6 XM-7 α ExY-r ExY-/. ExC-j ExC-? OH pa-1 cpct-kocpct-J Cpd-dapd-1 c4H9 cpct-a CH3 Solv-/ 2Hs SOIV-ko 5olv-jSolv-HiroshiSolv-7 Cpd-7 Cpd-1 CHz-CH-802-CH2 CH2 -CH-S O2-CH2 All procedures were carried out in the same manner as in Example-C, except that the sample (C) was used and the treatment in Example-C was changed as follows. In the treatment with Stabilizing Solution I of the present invention, the stability of the comparative example was improved with respect to all of the growth of mold and bacteria in the stabilizing solution tank, stains on the conveyor roller, adhesion of precipitates, stains on the processed film, and amount of residual silver. Better results were obtained than the treatment with liquid ①. h ＼, , き米ゝ( ■ Diethylenetriaminepentaacetic acid z, o t,. Sodium sulfite ≠, O≠, potassium carbonate
! 0.0 J7.0 catabolic potassium
/, J o, potassium taiodide
1. I■ -Hydroxylamine sulfate co, 0 2. r(N)
-ethyl-N -β-hydroxyethylamino)-2- methylaniline sulfate φ, 7 j,! Add water 1. Dr, /, 0LpH
10,0010,0J- (Bleach solution) Mother liquor (f) Replenisher solution (f) Ethylenediaminetetraacetic acid ferric ammonium dihydrate /20.0 /! 0.0 ethylenediaminetetraacetic acid μ, o
js. Ammonium bromide ioo, otto,. Ammonium nitrate 30.0! 0.0 ammonia water (section 27) 0.0ytl 3. O-
Acetic acid (9r91y) 9. OjE/
/j, add 0ml water /, OL
/,0LpHz,z da,! Ethylenediaminetetraacetic acid disodium salt 0. j /, 0 Sodium sulfite 7.0 l, 0 Sodium bisulfite j, 0 //, 0 Ammonium thiosulfate aqueous solution (70%) / 70.0 rttl 1400.
Add water /, OL /,
0L pH ≦, 7 t, BuC stable solution) Mother solution, replenisher common stable solution I; tap water" Troortt Formalin (37) /, 21) 1
)! -Chloro-1-methyl-isothiazolin-3-one 1.0 ■ Comethyl-isothiazolin-3-one 3.0 ■ Surfactant O, diethylene glycol
i. Add tap water /, 0
LpH7.0-7.0 The water quality of the tap water was the same as in the example and the flushing water treatment. Stabilizer ■; Stabilizer tap water, washing water I from Example-7
[(Ion-exchanged water) Prepared in the same manner as Stable Solution I except that K was changed. Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Letter Date: Hirotsuki, Showa t3

Claims (5)

[Claims] (1) In the development process of silver halide photographic light-sensitive materials,
The concentration of calcium and magnesium compounds in the replenishment solution of the water washing step and/or the stabilization step is reduced to 5 mg/l or less as calcium and magnesium, respectively, and a portion of the overflow of the water washing step and/or the stabilization step A method for processing a silver halide photographic material, characterized in that the entire silver halide photographic material is introduced into the water washing step and/or the stabilization step. (2) The process according to claim (1), wherein the amount of replenishment to the washing step and/or stabilization step is 1 to 50 times the amount brought in from the previous step per unit area of the photosensitive material to be processed. Method. (3) The treatment method according to claims (1) and (2), wherein the water washing step and/or the stabilization step comprises a plurality of tanks, and the replenishment is performed in a multistage countercurrent system. (4) The processing method according to claims (1) to (3), wherein the water washing step and/or the stabilization step is a step subsequent to a treatment step having fixing ability. (5) The concentration of calcium and magnesium compounds in the replenisher in at least the immediately preceding process of the water washing process and/or stabilization process is reduced to 5 mg/l or less as calcium and magnesium. 1
Processing method described in ).