EP0589460A1 - Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial - Google Patents

Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial Download PDF

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Publication number
EP0589460A1
EP0589460A1 EP93115377A EP93115377A EP0589460A1 EP 0589460 A1 EP0589460 A1 EP 0589460A1 EP 93115377 A EP93115377 A EP 93115377A EP 93115377 A EP93115377 A EP 93115377A EP 0589460 A1 EP0589460 A1 EP 0589460A1
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Prior art keywords
mole
solution
liter
fixing
sensitive material
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Granted
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EP93115377A
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English (en)
French (fr)
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EP0589460B1 (de
Inventor
Kouta c/o Fuji Photo Film Co. Ltd. Kukui
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP25456492A external-priority patent/JPH06102632A/ja
Priority claimed from JP5085196A external-priority patent/JPH06273899A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0589460A1 publication Critical patent/EP0589460A1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D15/00—Apparatus for treating processed material
    • G03D15/02—Drying; Glazing
    • G03D15/022—Drying of filmstrips
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor

Definitions

  • the present invention relates to a method for processing a black & white silver halide light-sensitive material with an automatic developing machine, specifically to a processing method in which the replenishing amount of the fixing solution and the amount of the waste solution thereof can be reduced, the impact of washing water on environmental pollution can be lowered, and the impact on the environment generally is small.
  • a black and white silver halide light-sensitive material is processed by the steps of developing-fixing-washing-drying, after exposing. Most such materials are processed with an automatic developing machine in the fields of photographic plate making and X-ray photography. In these fields, attention has been given to reduction of the waste solution amount and lowering environmental pollution caused by washing water from the viewpoint of environmental protection in recent years.
  • the nitrogen content in washing water is regulated from the viewpoint of the eutrophication of rivers.
  • Ammonium thiosulfate is used as a fixing agent for a conventional fixing solution.
  • Ammonium thiosulfate contains an elementary nitrogen and therefore the carrying over of the fixing solution in to the washing water increases the nitrogen content in the washing water. Accordingly, it is desired to replace ammonium thiosulfate with the other fixing agents.
  • the method in which sodium thiosulfate is used as the fixing agent is described in JP-A-4-11250 (the term "JP-A" as used herein means an unexamined published Japanese patent application) and JP-A-4-11251.
  • JP-A the term "JP-A" as used herein means an unexamined published Japanese patent application
  • JP-A-4-11251 the fixing solution to which amine is added is used in these inventions and therefore the nitrogen content in the washing water can not be lowered.
  • One object of the present invention is to provide a processing method for a silver halide light-sensitive material, in which a nitrogen-containing compound is not contained in the fixing solution in order to reduce the nitrogen content in a washing water and in which fixing speed is fast even where the replenishing amount is decreased in order to reduce the amount of waste solution to provide a processing method compatible with the environment.
  • Fig. 1 shows a schematic view of an automatic developing machine used in the present invention.
  • Fig. 2 shows a schematic view of a drying unit used in the present invention.
  • Ammonium thiosulfate has so far been used as a fixing agent for a fixing solution.
  • Sodium thiosulfate is inferior in fixing speed to ammonium thiosulfate in the case of a fresh solution.
  • the fixing speed of sodium thiosulfate is close to that of ammonium thiosulfate in the case of a fatigued solution after continuous processing with a low replenishing amount, and in the case of an even lower replenishing amount, the fixing speeds are reversed.
  • sodium thiosulfate is used as the fixing agent, nitrogen content in a washing water is sharply decreased.
  • the developing solution In order to decrease the replenishing amount of the fixing solution, it is necessary to accelerate the fixing speed of the fatigued fixing solution.
  • the developing solution In processing with an automatic developing machine, the developing solution is carried over to the fixing solution with the light-sensitive material.
  • the fixing speed of the fatigued fixing solution can be accelerated by lowering the potassium ion concentration in the developing solution.
  • the developing solution used for a development processing in the present invention is described.
  • the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones, or the combination of dihydroxybenzenes and p-aminophenols, is used as a developing agent for the developing solution, to readily obtain good performance.
  • the dihydroxybenzene developing agent used in the invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone. Of them, hydroquinone is particularly preferred.
  • Ascorbic acids may be used in place of hydroquinones.
  • the p-aminophenol developing agent used in the present invention includes N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol. Among them, N-methyl-p-aminophenol is preferred.
  • the 3-pyrazolidone series developing agent used in the invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
  • the developing agent is used preferably in the amount of 0.001 to 1.2 mole/liter.
  • the sulfites used as the preservative for the developing solution in a development step in the present invention include sodium sulfite, lithium sulfite, ammonium sulfite, and sodium bisulfite. Sulfites are added preferably in the amount of 0.2 mole/liter or more, particularly preferably 0.4 mole/liter or more. The upper limit thereof is preferably 2.5 mole/liter.
  • the pH value of the developing solution used for the development step in the present invention falls preferably within the range of 8.5 to 13, more preferably 9 to 12.
  • An alkali agent used for setting pH includes a pH controlling agent such as sodium hydroxide, sodium carbonate, and sodium tertiary phosphate.
  • buffer agents described in JP-A-62-186259 (borate) and JP-A-60-93433 (for example, sucrose, acetoxime, 5-sulfosalicylic acid, phosphate, and carbonate).
  • a hardener may be used in the above developing solution.
  • a disaldehyde series hardener or the bisulfite adduct thereof is preferably used as the hardener. To enumerate the concrete example thereof, it is glutaraldehyde or the bisulfite adduct thereof.
  • a development inhibitor such as sodium bromide, potassium bromide, sodium iodide, and potassium iodide
  • an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol
  • an anti-fogging agent such as a mercapto series compound including 1-phenyl-5-mercaptotetrazole and sodium 2-mercaptobenzimidazole-5-sulfonate, an indazole series compound including 5-nitroindazole, and a benzotriazole series compound including 5-methylbenzotriazole.
  • An anti-silver stain agent (for example, the compounds described in JP-A-56-24347) can be used in the developing solution.
  • an amino compound such as the alkanolamines described in JP-A-56-106244 and European Patent Publication 0136582.
  • the fixing solution contains thiosulfate as the fixing agent, and sodium thiosulfate is mainly used as thiosulfuric acid salts.
  • the use amount thereof in the form of a use solution is 0.5 to 2.5 mole/liter, preferably 0.8 to 1.8 mole/liter, and more preferably 1.0 to 1.5 mole/liter. Further, ammonium thiosulfate may be used.
  • the use amount thereof in the form of the use solution does not exceed 0.1 mole/liter, preferably 0.01 mole/liter, in terms of an ammonium ion concentration.
  • a water soluble aluminum salt may be used in the fixing solution.
  • the use amount thereof in the form of a use solution does not exceed 0.01 mole/liter, preferably 0.005 mole/liter.
  • the water soluble aluminum salt is used as a hardener in many cases. It generates a precipitate of aluminum hydroxide in the fixing solution and results in a white precipitate in the washing water. Therefore it is preferably not used for an automatic developing machine having a sufficient drying performance and transporting performance.
  • the fixing solution can contain a preservative (for example, sulfite and bisulfite), a pH buffer agent (for example, acetic acid and boric acid), a pH controlling agent (for example, sulfuric acid), a chelating agent having a softening ability, and the compounds described in JP-A-62-78551 according to necessity.
  • a preservative for example, sulfite and bisulfite
  • a pH buffer agent for example, acetic acid and boric acid
  • a pH controlling agent for example, sulfuric acid
  • tartaric acid, citric acid, gluconic acid, malic acid, glycolic acid, and the derivatives thereof can be used in the fixing solution singly or in combination of two or more. It is particularly effective to use these compounds in the amount of 0.01 to 0.3 mole/liter in the fixing solution in the form of a use solution.
  • the temperature and time in the developing and fixing steps individually are preferably about 20 to 50°C and 5 seconds to 1 minute, more preferably about 30 to 40°C and 8 to 40 seconds.
  • the replenishing amount of the developing solution is preferably 250 ml/m2 or less, particularly preferably 170 ml/m2 or less.
  • the replenishing amount of the fixing solution is preferably 250 ml/m2 or less, particularly preferably 200 ml/m2 or less.
  • the light-sensitive material after the developing and fixing steps have been finished is then subjected to a washing or stabilizing step.
  • the washing or stabilizing step can be carried out at a replenishing amount of 3 liter or less (including zero, that is, washing without replenishing) per m2 of the silver halide light-sensitive material. That is, not only does a water saving processing become possible, but also piping for settling an automatic developing machine is not necessitated.
  • washing bath with a squeeze roller and a crossover roller described in JP-A-63-18350 and JP-A-62-287252.
  • the addition of various oxidizing agents and filtration with a filter may be combined in order to reduce the effect of environmental pollution which is a problem in washng with the small amount of water.
  • a part or all of the overflow solution effluent from the washing or stabilizing bath which is generated by the replenishing water provided with an anti-mold treatment to the washing or stabilizing bath of the present invention, can also be utilized for a processing solution having a fixing function, which is the preceding bath thereof, as described in JP-A-60-255133.
  • a water soluble surface active agent and a defoaming agent may be added.
  • a dye-adsorbing agent described in JP-A-63-163456 may be provided in the washing bath.
  • a stabilization step is carried out following the above washing step in some cases, and as an example thereof, there may be used for a final bath, the bath containing the compounds described in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446.
  • an ammonium compound a metal compound of Bi and Al, a fluorescent whitening agent, various chelating agents, a membrane pH controlling agent, a hardener, a fungicide, an anti-mold agent, alkanolamine, and a surface active agent.
  • water used in a washing or stabilizing step are water subjected to a deionization processing and water sterilized with a UV bactericidal lamp and various oxidizing agents (ozone, hydrogen peroxide, and perchlorate) as well as tap water.
  • a washing water containing the compounds described in JP-A-2-147076 there may be used as a washing water containing the compounds described in JP-A-2-147076.
  • a photographic light-sensitive material subjected to developing, fixing and washing (or stabilizing) is squeezed to remove washing water therefrom, that is, it is dried through a squeeze roller. Drying is carried out at about 40 to about 100°C and a drying time is suitably changed according to the surrounding conditions.
  • the automatic developing machine used in the present invention is equipped with at least a developing unit, a fixing unit, a washing unit, and a drying unit.
  • a rinsing unit may be provided between the developing unit and the fixing unit and/or between the fixing unit and the washing unit.
  • the transporting means for a light-sensitive material in the automatic developing machine is preferably a roller transporting system.
  • the transporting speed (the line speed) of the light-sensitive material can arbitrarily be set. It is preferably set at 1000 mm/minute or more, particularly preferably 1500 mm/minute or more for rapid processing.
  • the drying unit in the automatic developing machine used in the present invention is a unit for drying the light-sensitive material which is transported along a transporting path. It is characterized by the fact that the surface and back face of the light-sensitive material are each alternatively rolled on a plurality of heat rollers which are heated on the circumferences thereof with a heat source.
  • the light-sensitive material is heated with a quantity of heat based on the temperature of the circumference of the heat roller and a contact time with the heat roller to evaporate water from the light-sensitive material face while it does not contact the heat roller.
  • a dry wind can be blown on the light-sensitive material face which does not contact the heat roller to accelerate the evaporation of water.
  • the circumferential temperature of the above heat roller is 80°C or lower and the contact time of the heat roller to the light-sensitive material is 1.5 to 5 seconds.
  • the drying unit in the present invention is a light-sensitive material drying equipment for drying the light-sensitive material which is transported along a transporting path. It comprises, (i) first heat roller and second heat roller which have built-in heat source respectively and on which the above light-sensitive material is rolled so that one face thereof contacts a part of the circumference of the heat rollers, (ii) a chamber which has a built-in heat source and in which there are formed slits disposed along the lateral direction of the above light-sensitive material opposite to one face or another of the light-sensitive material which is transported while it is rolled on a part of the circumference of the above first heat roller and a second heat roller, and (iii) a dry wind supplying means for supplying a dry wind to the inside of the above chamber.
  • the temperature of the heat roller in the drying unit of the present invention and/or the temperature of a dry wind blown on the face which does not contact the heat roller can be set based on the temperature and humidity conditions of the place where the automatic developing machine is installed to carry out the drying at the necessary minimum temperatures of the heat roller and/or the dry wind blown on the face of the material which does not contact the heat roller.
  • the amount of heat provided to a light-sensitive material with the heat roller is based on the temperature of the circumference of this heat roller and the contact time of the light-sensitive material to the heat roller. That is, the drying ability is determined by the product of the surface temperature of the heat roller and the contact time. Therefore, an increase in the rolling amount on the heat roller can extend the contact time without delaying the transporting speed and carry out a good drying even with a lowered temperature of the circumference of the heat roller. This can prevent superheating because of the lowered temperature on the circumference of the heat roller, even if paper clogging and film clogging occur and the light-sensitive material is stagnated in the vicinity of the heat roller.
  • the contact time of the light-sensitive material to the heat roller is as short as 1.5 to 5 seconds and therefore drying can be carried out in a total drying time of 6 to 20 seconds. Further, because the surface temperature of the heat roller is controlled to 80°C or lower, drying with a good dimensional stability can be carried out without damaging image quality.
  • the emulsion face of the light-sensitive material is heated with the first heat roller. This initiates evaporation on the back face, and the evaporation is accelerated by a dry wind supplied to a chamber with a dry wind supplying means.
  • heating the back face of the light-sensitive material with the second heat roller initiates evaporation on the emulsion face and the evaporation is accelerated by the dry wind.
  • the light-sensitive material is rolled on the first heat roller and the second heat roller, and it is therefore heated for a time corresponding to this rolling amount. Accordingly, the lowered temperatures of the first heat roller and the second heat roller can be compensated for by extension of the time when the light-sensitive material contacts the first and second heat rollers, to carry out an optimum heating processing.
  • the temperature of the drying unit of the present invention is quite low compared with that (100 to 150°C) of the heat roller of a conventional linear transport nipping type drying unit, and therefore its maintenance operating performance can be improved without impairing the safety of the operator during maintenance.
  • Fig. 1 is a schematic diagram of the automatic developing machine which is used in one embodiment of the present invention.
  • Film A with the size of 51 ⁇ 61 cm was subjected to a development processing with the automatic developing machine shown in above mentioned Fig. 1 under the environmental conditions of 27°C and 70% RH to determine the shortest drying time during which the sample immediately after the processing becomes dry.
  • the shortest drying time was checked. Washing was carried out with stocked water and the nitrogen content of the washing water after the processing was checked. The generating degree of a sulfur dioxide gas was checked in a fixing tank with a gas detecting tube during the processing.
  • FG-680A (a drying temperature: 50°C, manufactured by Fuji Photo Film Co., Ltd.) in which there was used a hot wind blowing method in which a heat roller was not used. Both automatic developing machines were remodeled so that the trans-porting speed could be changed.
  • FIG. 1 The schematic structural diagram of the automatic developing machine 10 which is a light-sensitive material processing equipment is shown in Fig. 1.
  • the inserting port 16 through which the light-sensitive material 14 is inserted is provided at the left side (i.e., the up stream end) of the casing 12 in Fig. 1.
  • a pair of rollers 18 was installed at the inside of the inserting port 16 and designed to rotate with a driving means which is not illustrated. This allows the light-sensitive material 14 which is inserted through the inserting port 16 to be guided to the processing unit 20 installed in the automatic developing machine 10 with the driving power of a pair of the rollers 18.
  • the developing bath 24, the rinsing bath 26, the fixing bath 28, the rinsing bath 30, and the washing bath 32 are disposed in this order from the left side of Fig. 1 in the processing unit 20.
  • a developing solution, a fixing solution and a washing water are stored in the developing bath 24, the fixing bath 26 and the washing bath 32 (hereinafter generically referred to as "the processing bath"), respectively.
  • the processing bath There are supplied a rinsing water (for example, water or an acetic acid aqueous solution) to the rinsing bath 26 and a rinsing water (for example, water) to the rinsing bath from respective stock tanks not illustrated through duct lines via pumps.
  • rinsing water Surplus rinsing water is designed to overflow from the rinsing baths 26, 30 to an overflowing bath which is not illustrated.
  • the duct lines may be provided directly to the rinsing baths 26 and 30 from a water supply via a solenoid valve without using a stock tank to supply tap water to the rinsing baths 26, 30, respectively.
  • the racks 34 are installed in the processing baths 24, 28 and 32, respectively and there are provided a plurality of pairs of rollers 36 with which the light-sensitive material 14 is nipped and transported along a prescribed transporting path.
  • the crossover racks 46 equipped with the rinsing racks are disposed over the respective processing baths.
  • the rollers 38, 40 are disposed over the rinsing baths 26, 30 to nip the light-sensitive material 14 and remove any processing solution stuck on the light-sensitive material 14 as well as quiding it to an adjacent processing bath.
  • the heaters 60, 62 are installed in the developing bath 24 and the fixing bath 28, respectively. These heaters 60, 62 are composed of a cylinder made of a stainless steel (for example, SUS 316) and a coil type heater body (not illustrated) built in this cylinder as a heat source and are inserted in the processing baths 24, 28 from the side walls of the respective processing baths 24, 28 for installation. The developing solution and the fixing solution are heated with these heaters 60, 62. In starting up the operation of the automatic developing machine 10, the temperatures are set at those at which the light-sensitive material can be processed and after starting up, the temperatures are maintained at those at which the light-sensitive material can be processed.
  • the light-sensitive material 14 washed in the washing bath 32 is transported to the drying unit 45 adjacent to the processing unit 20 with a pair of the transporting rollers 42.
  • this drying unit 45 the light-sensitive material 14 after having been subjected to a washing processing with a washing water is subjected to a drying processing.
  • the light-sensitive material 14 is inserted into the drying room 45A of the drying unit 45 from the drying room inserting port 44.
  • the squeezing rollers 48, the two heat rollers 50, 50, and the discharging rollers 52 are installed in the drying room 45A along the transporting path for the light-sensitive material 14 and are fixed between a pair of side panels at the axes.
  • These squeezing rollers 48, heat rollers 50 and discharging rollers 52 are designed so that the driving power of a driving means, not illustrated, is transmitted to them and the light-sensitive material 14 is transported at a fixed speed.
  • the two heat rollers 50 are almost vertically disposed and roll the light-sensitive material 14 on the circumference thereof to transport it.
  • Fig. 2 is the schematic diagram of the drying unit which shows an embodiment of the apparatus of the present invention.
  • This angle ⁇ is set so that a prescribed contact time to the heat roller 50 can be obtained based on the major diameter of the heat roller 50 and the transporting speed of the light-sensitive material.
  • the value based on this contact time and the peripheral temperature of the heat roller 50 is the quantity of heat given to the light-sensitive material 14. Accordingly, as shown in Fig. 2, setting the angle ⁇ at not much more than 90° as is the case with the example of the present invention and setting the circumferential temperature of the heat roller 50 at 70°C can provide an optimum heating processing.
  • These heat rollers 50 are cylidrical and the heat source 56 composed of a halogen lamp heating the circumference of the heat roller 50 is coaxially disposed at each of the axis center portions. The circumference of the heat roller 50 is heated by this heat source 56.
  • a plurality of the nipping rollers 58 are disposed at the surroundins of the heat roller 50 and are designed to nip the light-sensitive material 14 rolled on the heat roller 50 with the circumferential face of the heat roller 50.
  • the light-sensitive material 14 contacts the circumferential face of the heat roller 50 heated by the heat source 56 and is heated by a heat conduction from the heat roller 50.
  • the separating guide 66 one edge of which contacts the circumferential face of the heat roller 50 and the other edge of which is fixed at the side panel 64, is disposed in the transporting direction of the light-sensitive material 14 at the downstream side of the heat roller 50 and is designed to separate the light-sensitive material 14 rolled on the heat roller 50 from the circumferential face of the heat roller 50 at a prescribed position.
  • the intermediate portion of the separating guide is projected toward the downstream side in the transporting direction of the light-sensitive material 14 and guides the light-sensitive material 14 separated from the heat roller 50 to the downstream side in the transporting direction.
  • the guides 72 are disposed at the downstream side of each of the heat rollers 50, 50 and between the discharging rollers 52.
  • the light-sensitive material 14 sent via the squeezing roller 48, the heat roller 50 and the discharging roller 52 is guided to each of the downstream sides thereof by the guide 72.
  • the guide body 86 of the guide 72 is a cylinder with an almost rectangular section, in which one edge in a longitudinal direction is opened to form an aperture and the another edge is closed, the inside thereof being hollow. It constitutes the chamber.
  • the guide 72 is disposed so that the longitudinal direction of the guide body 86 becomes the lateral direction of the light-sensitive material 14 (a perpendicular direction to a paper face in Fig. 2) and is fixed at the side panel of the drying room (not illustrated).
  • the dry winds supplied to the blowing pipes 68 and the guides 72 are blown toward the surface of the light-sensitive material 14 from the slits 70, 74. Air containing a lot of water in the vicinity of the surface of the light-sensitive material 14 heated with the heat roller 50 is removed by these dry winds.
  • the environmental temperature and humidity-detecting sensor is provided at the outside of the automatic developing machine 10 to detect the environmental temperature and humidity at the place where the automatic developing machine is set and to control the temperature of the heat roller based on the conditions thereof.
  • the light-sensitive material 14 subjected to a drying processing in the drying room 45A is discharged from the exhaust port 78 to the external of the automatic developing machine.
  • the silver halide emulsion is prepared by mixing a water soluble silver salt, a water soluble halide and water in the presence of a hydrophilic colloid by the methods well known in the art (for example, a single jet process, a double jet process, and a controlled double jet process) and subjecting it to physical ripening and chemical ripening such as a gold sensitization and/or a sulfur sensitization.
  • the grain form of silver halide used in the present invention is not specifically limited, and there can be used cube, octahedron, sphere, of tabular silver halide grains with a high aspect ratio described in Research Disclosure 22534 (January 1983).
  • a tabular silver halide emulsion is preferably used.
  • silver bromide or silver bromoiodide is preferred and the silver iodide content is preferably 10 mole% or less, particularly preferably 0 to 5 mole%. This emulsion can provide a high sensitivity and is suited to rapid processing.
  • the preferred grain form of the tabular silver halide grains has an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of the grain is preferably 0.3 ⁇ m or less, particularly preferably 0.2 ⁇ m or less.
  • the aspect ratio of the tabular silver halide grains is given by the ratio of the average value of the diameters of the circles each having the same area as the projected area of each of the tabular grains to the average value of the grain thicknesses of the respective tabular grains.
  • the tabular grains are present preferably in the proportion of 80 weight % or more, more preferably 90 weight % or more, based on all the grains contained in the tabular silver halide emulsion.
  • the use of a tabular silver halide emulsion can further increase the stability of photographic performance in the running processing according to the present invention. Further, because the coated silver amount can be reduced, the load particularly in a fixing process and a drying process can be decreased and a rapid processing becomes possible as well from this point.
  • the tabular silver halide emulsion can be obtained by forming seed crystals in which the tabular grains are present in an amount of 40% or more by weight in an atmosphere of as relatively low a pBr value as 1.3 or less and growing the seed crystals by simultaneously adding a silver salt aqueous solution and a halide aqueous solution while maintaining the pBr value at the same level as that described above.
  • the silver salt aqueous solution and the halide aqueous solution are added desirably so that a new crystal nucleus is not generated.
  • the size of the silver halide grains can be controlled by adjusting the temperature, selecting the kind and amount of the solvent and controlling the silver salt used in growing the grains and the adding speed of halide.
  • the silver halide emulsion used in the present invention may be either a polydispersed emulsion or a monodispersed emulsion having a uniform grain size distribution.
  • the monodispersed emulsion in which the fluctuation coefficient showing the grain distribution is 20% or less.
  • the silver halide grains may be either of a composition in which the inside and the surface are even or a composition in which they are different. There may be used a silver halide emulsion prepared by mixing two or more kinds of silver halide emulsions separately prepared.
  • the silver halide emulsion used in the present invention may be an emulsion containing at least one of an iron compound, a rhenium compound, and an osmium compound.
  • the addition amount thereof is 10 ⁇ 3 mole or less, preferably 10 ⁇ 6 to 10 ⁇ 4 mole, per mole of silver.
  • the silver halide emulsion used in the present invention may or may not be chemically sensitized.
  • the known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used as the chemical sensitiza-tion. They can be used singly or in combination thereof.
  • the preferred chemical sensitizing method is the sulfur sensitization.
  • the gold sensitizing process is a typical one and a gold compound, mainly a gold complex salt, is used.
  • a gold compound mainly a gold complex salt
  • the noble metals other than gold for example, the complex salts of platinum, palladium, and iridium. Concrete examples thereof are described in U.S Patent 2,448,060 and British Patent 618,061.
  • the silver halide grains used in the present invention are preferably subjected to a spectral sensitization with a sensitizing dye.
  • a cyanine dye there may be included with the dye used, a cyanine dye, a merocycnine dye, a composite cyanine dye, a composite merocyanine dye, a holopolarcyanine dye, a hemicyanine dye, a styryl dye, or a hemioxonol dye.
  • the particularly useful dyes are a cyanine dye, a merocynine dye, and a composite merocyanine dye. Any of the nuclei usually utilized for the cyanine dyes as a base heterocyclic nucleus can be applied to these dyes.
  • a polymer and an emulsion such as an alkyl acrylate latex and a surfactant such as polyols including trimethylolpropane can be incorporated into the emulsion layer of the light-sensitive material of the present invention in order to improve its pressure characteristic.
  • the photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material prepared according to the present invention may contain various surface active agents for various purposes such as aiding coating, the prevention of electrification, the improvement in a sliding performance, the promotion of emulsification-dispersion, the prevention of sticking, and the improvement of the photographic characteristics (for example, development acceleration, harder gradation and sensitization).
  • the nonionic surface active agents such as saponin (a steroid series), an alkylene oxide derivative (for example, polyethylene glycol, a polyethylene glycol/polypropylene glycol condensation product (polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, and polyethylene oxide adducts of silicon), a glycidol derivative (for example, alkenylsuccinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohol, and alkyl esters of sucrose; the anionic surface active agents having acid groups including a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group and a phosphoric acid ester group, such as an alkylcarbonic acid salt, an alkyl
  • the light-sensitive material according to the present invention can have an intermediate layer, a filter layer, and an anti-halation layer according to necessity.
  • the coated silver amount in the light-sensitive material used in the present invention is preferably 0.5 to 5 g/m2 (one side), more preferably 1 to 4 g/m2 (one side).
  • It preferably does not exceed 5 g/m2 for rapid processing suitability. It is preferably 0.5 g/m2 or more, in order to obtain a constant image density and contrast.
  • Gelatin is advantageously used as a binder or protective colloid for a photographic emulsion.
  • the other hydrophilic colloids can be used as well.
  • proteins such as a gelatin derivative, a graft polymer of gelatin and the other polymers, albumin, and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfuric acid esters; sucrose derivatives such as sodium alginate and a starch derivative; and various synthetic hydrophilic high molecular materials such as homopolymers or copolymers of vinyl alcohol, partially-acetalized vinyl alcohol, N-vinyl-pyrrolidone, acrylic acid, methacrylic acid, acrylamide, vinylimidazole, and vinylpyrazole.
  • acid-treated gelatin may be used as gelatin, and a gelatin hydrolysis product and a gelatin enzyme-decomposed product can be used as well.
  • An organic material which will be effluent in a development processing process is preferably incorporated into an emulsion layer or the other hydrophilic colloid layers particularly in an X-ray sensitive material.
  • the effluent material is gelatin
  • a gelatin of the kind which is not subject to a crosslinking reaction of gelatin with a hardener is preferred.
  • acetalized gelatin and phthalized gelatin correspond to this. Those having a small molecular weight are preferred.
  • a hydrophilic polymer such as polyacrylamide described in U.S. Patent 3,271,158, polyvinyl alcohol, and polyvinyl-pyrrolidone, and sugars such as dextran, sucrose, and pulran are effective as well.
  • polyacrylamide and dextran are preferred and polyacrylamide is the particularly preferred material.
  • the average molecular weight of these materials is preferably 20,000 or less, more preferably 10,000 or less.
  • the effluent amount thereof during a processing is effectively 10% or more and 50% or less, preferably 15% or more and 30% or less, based on the total weight of the coated organic materials excluding the silver halide grains.
  • the layer containing the organic material which is effluent in the processing according to the present invention may be either an emulsion layer or a surface protective layer.
  • the total coated amount of the organic material is fixed, it is incorporated preferably into both of the surface protective layer and the emulsion layer, rather than only into the emulsion layer. Further, it is more preferably incorporated only into the surface protective layer.
  • a greater amount of the organic material is incorporated preferably into the emulsion layer closer to the surface protective layer in the case where the total coated amount of the organic material is fixed.
  • a matting agent there can be used as a matting agent, the fine particles of an organic compound such as a homopolymer of polymethyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid as described in U.S. Patents 2,992,101, 2,701,245, 4,142,894, and 4,396,706, and starch, and an inorganic compound such as silica, titanium dioxide, strontium sulfate, and barium sulfate.
  • the particle size thereof is preferably 1.0 to 10 ⁇ m, particularly preferably 2 to 5 ⁇ m.
  • a photographic emulsion layer or the other layers may be colored with a dye for the purpose of absorbing rays with a specific wavelength, that is, for the purposes of preventing halation and irradiation and providing a filter layer to control the spectral composition of the rays incident upon the photographic emulsion layer.
  • the layer which is aimed at crossover cutting may be provided under the emulsion layer.
  • an oxonol dye having a pyrazolone nucleus and a barbituric acid nucleus an azo dye, an azomethine dye, an anthraquinone dye, an allylidene dye, a styryl dye, a triarylmethane dye, a merocyanine dye, and a cyanine dye.
  • the dye which is irreversibly decolored in the developing-fixing-washing processes is preferably applied.
  • the layer to which the dye is mordanted with the polymer having the cationic site may be an emulsion layer, a surface protective layer, or the opposite side of the emulsion layer on a support. It is preferably between the emulsion layer and the support.
  • the dye is mordanted ideally to a subbing layer for the purpose of the crossover cutting of an X-ray duplicated film for medical use.
  • a nonionic surface active agent of an ethylene oxide series can be used as a coating aid for the subbing layer preferably in combination with a polymer having a cationic site.
  • the various known quaternary ammonium salt (or a phosphonium salt) polymers can be used as the anion-converted polymer.
  • the quaternary ammonium salt (or a phosphonium salt) polymers are widely known as a mordant polymer and an antistatic polymer in the publications mentioned below.
  • an aqueous polymer latex prepared by copolymerizing a monomer having at least two or more (preferably 2 to 4) ethylenically unsaturated groups and crosslinking the copolymer is particularly preferably used.
  • the solid matter dispersing method described in JP-A-55-155350 and WO88/0479 is also effective as a fixing method for a dye.
  • the light-sensitive material used in the present invention may be designed so that a super hard gradation photographic characteristic is shown with a hydrazine nucleus-forming agent.
  • This system and the hydrazine nucleus-forming agent to be used are described in the following literature references. In particular, this system is suitably used for in graphic arts: Research Disclosure Item 23516 (November 1983, p. 346) and the publications cited therein, and in addition, U.S.
  • the hydrazine nucleus-forming agent When the hydrazine nucleus-forming agent is incorporated into a photographic light-sensitive material, it is incorporated preferably into a silver halide emulsion layer, but it may be incorporated into a different non-light-sensitive hydrophilic colloid layer (for example, a protective layer, an intermediate layer, a filter layer, and an anti-halation layer).
  • the addition amount of the hydrazine nucleus-forming agent falls preferably within the range of 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 2 mole, particularly preferably 1 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 2 mole, per mole of silver halide.
  • accelerators are different with respect to their optimum addition amount according to the kind of compound. They are used desirably in the range of 1.0 ⁇ 10 ⁇ 3 to 0.5 g/m2, preferably 5.0 ⁇ 10 ⁇ 3 to 0.1 g/m2.
  • a redox compound releasing a development inhibitor can be used in combination.
  • this redox compound there can be used as this redox compound, the compounds described in JP-A-2-293736, JP-A-2-308239, JP-A-1-154060, and JP-A-1-205885.
  • the use amount thereof falls preferably within the range of 1 ⁇ 10 ⁇ 6 to 5 ⁇ 10 ⁇ 2 mole, particularly preferably 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 mole, per mole of silver halide.
  • Various compounds can be incorporated into the light-sensitive material according to the present invention for the purpose of preventing fog during manufacturing, during the storage or during the photographic processing of the light-sensitive material, or for stabilizing a photographic performance. That is, there can be added many compounds known as an anti-fogging agent and a stabilizer, such as azoles, for example, a benzothiazolium salt, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, and nitrobenzotriazoles; mercaptotriazines; a thioketo compound such as, for example, oxazolinethione; azaindenes, for example, triazaindenes, tetraazaindenes (paricularly 4-hydroxysubstituted (1,3,3a,
  • benzotriazoles for example, 5-methylbenzotriazole
  • nitroindazoles for example, 5-nitroindazole
  • a developing agent such as a hydroquinone derivative and a phenidone derivative can be incorporated into the light-sensitive material according to the present invention to function as a stabilizer or an accelerator.
  • An inorganic or organic hardener may be incorporated into a photographic emulsion layer and the other hydrophilic colloid layers in the light-sensitive material according to the present invention.
  • a chromium salt chromium alum and chromium acetate
  • aldehydes formaldehyde and glutaraldehyde
  • an N-methylol compound dimethylolurea
  • a dioxane derivative an active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine and 1,3-vinylsulfonyl-2-propanol
  • an active halogen compound (2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids mucochloric acid
  • hydroquinone derivative a so-called DIR-hydroquinone
  • a development inhibitor to a photographic emulsion layer and the other hydrophilic colloid layers according to the density of the image during developing.
  • Concrete examples thereof include, the compounds described in U.S. Patents 3,379,529, 3,620,746, 4,377,634, and 4,332,878, and JP-A-49-129536, JP-A-54-67419, JP-A-56-153336, JP-A-56-153342, JP-A-59-278853, JP-A-59-90435, JP-A-59-90436, and JP-A-59-138808.
  • a dispersion of a water insoluble or slightly soluble synthetic polymer can be incorporated into the light-sensitive material according to the present invention for the purpose of dimensional stability.
  • a compound having an acid group is preferably incorporated into the silver halide emulsion layer and the other layers of the light-sensitive material according to the present invention.
  • an organic acid such as salicylic acid, acetic acid, and ascorbic acid
  • a polymer or a copolymer having an acid monomer such as acrylic acid, maleic acid and phthalic acid as a repetitive unit.
  • ascorbic acid as a low molecular compound
  • aqueous dispersible latex of the copolymer consisting of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene as a high molecular compound.
  • the silver halide emulsion thus prepared is coated on the support of a cellulose acetate film and a polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, and a duplex coating method.
  • Solution 1 Water 1.0 liter Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 8 mg
  • Solution 2 Water 400 ml Silver nitrate 100 g
  • Solution 3 Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexachloroiridate (III) (0.001% aqueous solution) 15 ml Potassium hexabromorhodate (III) (0.001% aqueous solution) 1.5 ml
  • Solution 2 and Solution 3 were simultaneously added to Solution 1 maintained at 38°C and pH 4.5 over a period of 10 minutes while stirring to form a nuclear grain of 0.16 ⁇ m. Subsequently, the following Solution 4 and Solution 5 were added over a period of 10 minutes. Further, potassium iodide 0.15 g was added to finish the grain formation.
  • Solution 4 Water 400 ml Silver nitrate 100 g
  • Solution 5 Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexacyanoferrate (III) (0.1% aqueous solution) 5 ml
  • the emulsion thus prepared was washed by a conventional flocculation method and gelatin 30 g was added.
  • the emulsion was adjusted to pH 5.3 and to pAg 7.5, and sodium thiosulfate (2.6 mg), triphenylphosphine selenide (1.0 mg), and chlorauric acid (6.2 mg) were added thereto. Further, sodium benzenethiosulfonate (4 mg) and sodium benzenethiosulfinate (1 mg) were added, whereby the emulsion was subjected to chemical sensitization so that an optimum sensitivity could be obtained at 55°C.
  • An ortho sensitizing dye (the following compound) was added to the above emulsion in the amount of 5 ⁇ 10 ⁇ 4 mole/mole Ag to subject it to ortho sensitization.
  • hydroquinone and 1-phenyl-5-mercaptotetrazole as an anti-fogging agent in the amounts of 2.5 g and 50 mg per mole of Ag, respectively, a polyethyl acrylate latex as a plasticizer in the ratio of 25% based on the amount of gelatin binder, 2-bis(vinylsulfonylacetoamide)ethane as a hardener, and further colloidal silica in the ratio of 40% based on the amount of gelatin binder.
  • the coating solution thus prepared was applied on a polyester support to Ag 3.0 g/m2 and gelatin 1.0 g/m2.
  • a lower protective layer and an upper protective layer each having the following composition were coated thereon.
  • Lower protective layer Gelatin 0.25 g/m2 Sodium benzenethiosulfonate 4 mg/m2 1,5-Dihydroxy-2-benzaldoxime 25 mg/m2 Polyethyl acrylate latex 125 mg/m2
  • Upper protective layer Gelatin 0.25 g/m2 Silica matting agent with the average particle size of 2.5 ⁇ m 50 mg/m2 Compound (1) (gelatin dispersion) Colloidal silica with a particle size of 10 to 20 ⁇ m 30 mg/m2 Compound (2) 5 mg/m2 Sodium dodecylbenzenesulfonate 22 mg/m2
  • the support used in the present examples had a back layer and a back protective layer each having the following composition:
  • Back layer Sodium dodecylbenzenesulfonate 80 mg/m2 Compound (3) 70 mg/m2 Compound (4) 85 mg/m2 Compound (5) 90 mg/m2 1,3-Divinylsulfonyl-2-propanol 60 mg/m2
  • Step Temparature Time Developing 38°C 20 seconds Fixing 37°C 18.9 seconds Washing 26°C 18.3 seconds Drying 55°C 24.0 seconds Total 85.4 seconds
  • the fixing time was changed while passing the sample of the above size.
  • the fixing time was determined by the time when a fixing drop failure was generated (the partial generation was judged as the fixing drop failure).
  • the status of the fixing solution was checked observing the precipitate in the rack after the running was finished.
  • the nitrogen content in a washing water was determined by analyzing the washing water after the running was finished.
  • an aqueous solution (500 ml) containing silver nitrate (100 g) and an aqueous solution (500 ml) containing potassium bromide (40 g), sodium chloride (14 g) and potassium hexachloroiridate (III) (10 ⁇ 7 mole/mole silver) were added by a double jet method to form a shell portion containing 40 mole% silver chloride, whereby so-called core/shell type cubic monodispersed silver bromochloride grains having an average grain size of 0.35 ⁇ m were prepared.
  • gelatin 40 g was added, and pH and pAg were adjusted to 6.0 and 8.5, respectively, followed by adding triethyl thiourea (2 mg), chlorauric acid (4 mg), and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (0.2 g) to thereby provide a chemical sensitization at 60°C.
  • the vessel in which the emulsion (850 g) was put and weighed was heated to 40°C and the additives were added in the manner shown below to prepare the emulsion layer coating solution.
  • Composition of the emulsion layer coating Solution A Emulsion 850 g Spectral Sensitizing Dye [II] 1.2 ⁇ 10 ⁇ 4 mole Supersensitizer [III] 0.8 ⁇ 10 ⁇ 3 mole Preservativity Improver [IV] 1 ⁇ 10 ⁇ 3 mole Polyacrylamide (molecular weight: 40,000) 7.5 g Trimethylolpropane 1.6 g Poly(sodium styrenesulfonate) 2.4 g Poly(ethyl acrylate/methacrylic acid) latex 16 g N,N'-ethylenebis-(vinylsulfonacetoamide) 1.2 g
  • composition of the surface protective layer coating solution for the emulsion layer Gelatin 100 g Polyacrylamide (molecular weight: 40,000) 10 g Poly(sodium styrenesulfonate) (molecular weight: 600,000) 0.6 g N,N'-ethylenenebis-(vinylsulfonacetoamide) 1.5 g Polymethyl methacrylate fine grains (average grain size: 2.0 ⁇ m) 2.2 g Sodium t-octylphenoxyethoxyethanesulfonate 1.2 g C16H33O-(CH2CH2O)10-H 2.7 g Poly(sodium acrylate) 4 g C8F17SO3K 70 mg C8F17SO2N(C3H7)(CH2CH2O)4(CH2)4-SO3Na 70 mg NaOH (1N) 4 ml Methanol 60 ml
  • composition of the back layer coating solution Gelatin 80 g Dye [V] 3.1 g Poly(sodium styrenesulfonate) 0.6 g Poly(ethyl acrylate/methacrylic acid) latex 15 g N,N'-ethylenenebis-(vinylsulfonacetoamide) 4.3 g
  • composition of the surface protective layer coating solution for the back layer Gelatin 80 g Poly(sodium styrenesulfonate) 0.3 g N,N'-ethylenebis-(vinyl-sulfonacetoamide) 1.7 g Polymethyl methacrylate fine grains (average grain size: 4.0 ⁇ m) 4 g Sodium t-octylphenoxyethoxyethanesulfonate 3.6 g NaOH (1N) 6 ml Poly(sodium acrylate) 2 g C16H33O-(CH2CH2O)10-H 3.6 g C8F17SO3K 50 mg C8F17SO2N(C3H7)(CH2CH2O)4(CH2)4-SO3Na 50 mg Methanol 130 ml
  • the above mentioned back layer coating solution was coated on a polyethylene terephthalate support together with the surface protective layer coating solution for the back layer so that the total gelatin coating amount was 3 g/m2. Subsequently, the above mentioned emulsion layer coating solution and surface protective layer coating solution were applied on the opposite side of the support so that the coated Ag amount and the gelatin coating amount of the surface protective layer were 2.5 g/m2 and 1 g/m2, respectively
  • the fixing time was determined by the time when a fixing drop failure was generated (the partial generation was judged as the fixing drop failure).
  • the status of the fixing solution was checked observing the precipitate in the rack after the running was finished.
  • the nitrogen content in the washing water was determined by analyzing the washing water after the running was finished.
  • Example 2 the results show that the replenishing amount of the fixing solution is small in the present invention and that the present invention provides a processing method in which the environmental pollution in the washing water is low.
  • a 0.05% aqueous solution (110 ml) of Sensitizing Dye (I) was added to the emulsion (1 kg) thus obtained and then there were added hydroquinone (100 mg/m2), a polyethyl acrylate latex as a plasticizer in the ratio of 25% based on the amount of gelatin binder, and 2-bis(vinylsulfonylacetoamide)ethane (85 mg/m2) as a hardener.
  • the coating solution thus prepared was applied on a polyester support to Ag 3.7 g/m2.
  • the coated amount of gelatin was 2.0 g/m2.
  • gelatin 0.8 g/m2
  • polymethyl methacrylate having an average particle size of 2.5 ⁇ m (40 mg/m2) as a matting agent
  • colloidal silica having an average particle size of 4 ⁇ m (30 mg/m2)
  • silicon oil 80 mg/m2
  • sodium benzenesulfonate 80 mg/m2
  • Surface Active Agent (1) having the following structural formula in back protective layer, a polyethyl acrylate latex (150 mg/m2), and potassium 1,1'-disulfobutyl-3,3,3',3'-tetramethyl-5,5'-disulfoindo-tri-carbocyanine (6 mg/m2).
  • a back layer and a back protective layer each having the following composition are provided on the opposite side of a polyester support in these samples:
  • Back layer Gelatin 2.4 g/m2 Sodium dodecylbenzenesulfonate 60 mg/m2 Dye (2) 80 mg/m2 Dye (3) 30 mg/m2 Potassium 1,1'-disulfobutyl-3,3,3',3'-tetramethyl-5,5'-disulfoindotricarbocyanine 80 mg/m2 1,3-Divinylsulfonyl-2-propanol 60 mg/m2 Poly(sodium vinylbenzenesulfonate) 30 mg/m2
  • Back protective layer Gelatin 0.75 g/m2 Polymethyl methacrylate (average particle size: 3.5 ⁇ m) 40 mg/m2 Sodium dodecylbenzenesulfonate 20 mg/m2 Surface Active Agent C8F17SO2N(C3H7)-CH2COOK 2 mg/m
  • Emulsions A and B were prepared by the following method.
  • a 0.5 M silver nitrate aqueous solution and a halide aqueous solution containing 0.1 M potassium bromide, 0.44 M sodium chloride, potassium hexachloroiridate (III), and ammonium hexabromorhodate (III) were added to a gelatin aqueous solution containing sodium chloride, 1,3-dimethylimidazolidine-2-thione and benzenethiosulfonic acid and having its pH adjusted to 4.0 by a double jet method at 38°C for 10 minutes while stirring, whereby the silver bromochloride grains having an average grain size of 0.16 ⁇ m and a silver chloride content of 70 mole% were obtained to thereby form the nuclei.
  • a 0.5 M silver nitrate aqueous solution and a halide aqueous solution containing 0.1 M potassium bromide, 0.44 M sodium chloride, and potassium ferrocyanide were similarly added by a double jet method for 10 minutes to finish the grain formation.
  • the grains thus obtained were silver bromochloride cubic grains having an average grain size of 0.2 ⁇ m and a silver chloride content of 70 mole% and containing Ir of 3.8 ⁇ 10 ⁇ 7 mole per mole of silver, Rh of 6.1 ⁇ 10 ⁇ 8 mole per mole of silver and Fe of 2.3 ⁇ 10 ⁇ 5 mole per mole of silver (fluctuation coefficient: 10%).
  • the emulsion was washed by a conventional flocculation method and gelatin (30 g) was added thereto. This emulsion was divided to two equal parts to prepare Emulsions A and B in the following manner.
  • a pigment (4.2 mg/m2) having the following structure was added to Emulsions A and B thus obtained. Further, there were added disodium 4,4'-bis(4,6-dinaphthoxypyrimidine-2-ylamino)stilbenedisulfonate (234 mg) and 1-phenyl-5-mercaptotetrazole (25 mg) each per mole of silver.
  • hydroquinone 150 mg/m2
  • a polyethyl acrylate latex in the ratio of 30% based on the amount of gelatin binder
  • colloidal silica 0.01 ⁇ m in the ratio of 30% based on the amount of gelatin binder
  • 2-bis(vinylsulfonyl-acetoamide)ethane 70 mg/m2
  • the coating solution thus prepared was applied on a polyester support to Ag 3.2 g/m2 and a coated gelatin amount 1.4 g/m2.
  • a protective layer coating solution was prepared by adding gelatin (0.5 g/m2), the dye having the following structure (70 mg/m2), polymethyl methacrylate having a particle size of 2.5 ⁇ m (60 mg/m2) as a matting agent, colloidal silica having a particle size of 10 ⁇ m (70 mg/m2), sodium dodecylbenzenesulfonate as a coating aid and a fluorine-containing surface active agent having the following structure (1.5 mg/m2) as a coating aid, and the following chelating agent (20 mg/m2).
  • the coating solution was adjusted to pH 5.5 and then coated on an emulsion layer simultaneously with the emulsion layer.
  • Example 3 The sample thus obtained was exposed by half of the film to a xenon flash light at an emitting time of 10 ⁇ 5 second via an interference filter having a peak at 633 nm.
  • the same running test as in Example 3 was carried out.
  • the results of the running test were the same as those in Example 1, and it was found that even a low replenishing does not generate a fixing drop failure in the processing method of the present invention.
  • Solution 1' Water 1.0 liter Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 8 mg
  • Solution 2' Water 400 ml Silver nitrate 100 g
  • Solution 3' Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexachloroiridate (III) (0.001% aqueous solution) 15 ml Potassium hexabromorhodate (III) (0.001% aqueous solution) 1.5 ml
  • Solution 2' and Solution 3' were simultaneously added to Solution 1' maintained at 38°C and pH 4.5 over a period of 10 minutes while stirring to form nuclear grains of 0.16 ⁇ m. Subsequently, the following Solution 4' and Solution 5' were added over a period of 10 minutes. Further, potassium iodide (0.15 g) was added to finish grain formation.
  • Solution 4' Water 400 ml Silver nitrate 100 g
  • Solution 5' Water 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexacyanoferrate (III) (0.1% aqueous solution) 5 ml
  • the emulsion was adjusted pH 5.3 and pAg 7.5, and sodium thiosulfate (2.6 mg), triphenylphosphine selenide (1.0 mg), and chlorauric acid (6.2 mg) were added thereto. Further, sodium benzenethiosulfonate (4 mg) and sodium benzenethiosulfinate (1 mg) were added, whereby the emulsion was subjected to chemical sensitization so that an optimum sensitivity could be obtained at 55°C.
  • An ortho sensitizing dye (the compound used in coated sample in Example 1) was added to the above emulsion in the amount of 5 ⁇ 10 ⁇ 4 mole/mole Ag to subject it to an ortho sensitization.
  • hydroquinone and 1-phenyl-5-mercaptotetrazole as an anti-fogging agent in the amounts of 2.5 g and 50 mg per mole of Ag, respectively, a polyethyl acrylate latex as a plasticizer in the ratio of 25% based on the amount of gelatin binder, 2-bis(vinylsulfonylacetoamide)ethane as a hardener, and further colloidal silica in the ratio of 40% based on the amount of gelatin binder.
  • the coating solution thus prepared was applied on a polyester support to Ag 3.0 g/m2.
  • a lower protective layer and an upper protective layer each having the following composition were coated thereon.
  • Lower protective layer Gelatin 0.25 g/m2 Sodium benzenethiosulfonate 4 mg/m2 1,5-Dihydroxy-2-benzaldoxime 25 mg/m2 Polyethyl acrylate latex 125 mg/m2
  • Upper protective layer Gelatin 0.25 g/m2 Silica matting agent with an average particle size of 2.5 ⁇ m 50 mg/m2 Compound (1) used in Example 1 (gelatin dispersion) 30 mg/m2 Colloidal silica with the particle size of 10 to 20 ⁇ m Compound (2) used in Example 1 5 mg/m2 Sodium dodecylbenzenesulfonate 22 mg/m2
  • the support used in the present examples had a back layer and a back protective layer each having the following composition:
  • Back layer Sodium dodecylbenzenesulfonate 80 mg/m2 Compound (3) used in Example 1 70 mg/m2 Compound (4) " 85 mg/m2 Compound (5) " 90 mg/m2 1,3-Divinylsulfonyl-2-propanol 60 mg/m2
  • Back protective layer Gelatin 0.5 g/m2 Polymethyl methacrylate (grain size: 4.7 ⁇ m) 30 mg/m2 Sodium dodecylbenzenesulfonate 20 mg/m2 Compound (2) 2 mg/m2 Compound (1) (gelatin dispersion) 100 mg/m2
  • the coated sample thus prepared was designated as Film A and the sample which was prepared in the same manner except that triphenylphosphine selenide was replaced with triphenylphosphine telluride was 4 designated as Film B.
  • compositions of the fixing solutions are described in Table 3. The experiments were carried out for five kinds of fixing solutions.
  • a 0.37 M silver nitrate aqueous solution and a halide aqueous solution containing (NH4)3RhCl6 corresponding to 5 ⁇ 10 ⁇ 7 mole and K3IrCl6 5 ⁇ 10 ⁇ 7 mole each per mole of silver, 0.11 M potassium bromide, and 0.27 M sodium chloride were added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method at 45°C for 12 minutes while stirring, whereby silver bromochloride grains having an average grain size of 0.02 ⁇ m and a silver chloride content of 70 mole% were obtained to thereby form nuclei.
  • a 0.63 M silver nitrate aqueous solution and a halide aqueous solution containing 0.19 M potassium bromide and 0.47 M sodium chloride were similarly added by a double jet method over a period of 20 minutes.
  • a KI solution of 1 ⁇ 10 ⁇ 3 mole was added to carry out a conversion and washing was carried out by a flocculation method according to a conventional method, followed by adding gelatin (40 g) and adjusting pH and pAg to 6.5 and 7.5, respectively.
  • a short wave cyanine dye of Compound (a) represented by the following structural formula and a polymer of Compound (b) (200 mg/m2), hydroquinone (50 mg/m2), a dispersion of polyethyl acrylate (200 mg/m2), 1,3-bis(vinylsulfonyl)-2-propanol (200 mg/m2), and the following Hydrazine Compound (c).
  • the coating solution thus prepared was applied to a coated silver amount of 3.6 g/m2 and a gelatin amount of 2.0 g/m2.
  • a 1.0 M silver nitrate aqueous solution and a halide aqueous solution containing (NH4)3RhCl6 of 3 ⁇ 10 ⁇ 7 mole per mole of silver, 0.3 M potassium bromide, and 0.74 M sodium chloride were added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method at 45°C for 30 minutes while stirring, whereby silver bromochloride grains having an average grain size of 0.28 ⁇ m and a silver chloride content of 70 mole% were obtained.
  • the emulsion was washed by a flocculation method according to a conventional method and gelatin (40 g) was added, followed by adjusting pH and pAg to 6.5 and 7.5, respectively. Further added were sodium thiosulfate (5 mg) and chlorauric acid (8 mg) each per mole of silver and heating was applied at 60°C for 60 minutes to provide a chemical sensitization, followed by adding 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (150 mg) as a stabilizer, Proxel and phenoxyethanol.
  • the grains thus obtained were silver bromochloride cubic grains having an average grain size of 0.28 ⁇ m and a silver chloride content of 70 mole% (fluctuation coefficient: 10%).
  • Light-sensitive Emulsion B was dissolved once again and there were added 1 ⁇ 10 ⁇ 3 mole of potassium 5-[3-(4-sulfobutyl)-5-chloro-2-benzoxazolidilidene]-1-hydroxy ethoxyethyl-3-(2-pylidyl)2-thiohydantoin as a sensitizing dye, and 1.0 ⁇ 10 ⁇ 3 mole of a KI solution each per mole of silver.
  • gelatin 1.0 g/m2
  • polymethyl methacrylate grains average grain size: 2.5 ⁇ m
  • surface active agents 1.0 g/m2 and the polymethyl methacrylate grains (average grain size: 2.5 ⁇ m) (0.3 g/m2) by means of the following surface active agents.
  • a back layer and a back protective layer each having the following composition were coated.
  • composition of the back protective layer is Composition of the back protective layer :
  • the composition of the developing solution is shown below.
  • Developing solution Hydroquinone 50 g N-methyl-p-aminophenol 0.3 g Sodium hydroxide 18 g 5-Sulfosalicylic acid 45 g Boric acid 10 g Potassium sulfite 110 g Disodium ethylenediaminetetraacete 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.3 g 3-(5-Mercaptotetrazole)benzenesulfonic acid 0.2 g Sodium p-toluenesulfonate 8.0 g N-n-butyldiethanolamine 15.0 g Water was added to 1 liter pH was adjusted to (by adding potassium hydroxide) 11.6
  • GR-Fl and SR-Fl (each manufactured by Fuji Photo film Co., Ltd.) were used as a fixing solution.
  • GR-Fl contains aluminum sulfate of 0.01 mole/liter or more and SR-Fl contains aluminum sulfate of 0.01 mole/liter or less.
  • Film C with a size of 51 ⁇ 61 cm was subjected to a development processing with the same automatic developing machine of Fig. 1 as that used in Example 5 under the environmental conditions of 27°C and 70% RH to determine the shortest drying time when the sample was completely dried immediately after the processing. In the experiments, the shortest drying time was found after continuously passing 20 sheets of the sample having the above size.
  • the aqueous solution (500 ml) containing silver nitrate (100 g) and the aqueous solution (500 ml) containing potassium bromide (40 g), sodium chloride (14 g) and potassium chloroiridate (III) (10 ⁇ 7 mole/mole silver) were added by a double jet method to form a shell portion containing 40 mole% of silver chloride, whereby so-called core/shell type cubic monodispersed silver bromochloride grains having an average grain size of 0.35 ⁇ m were prepared.
  • gelatin 40 g was added and pH and pAg were adjusted to 6.0 and 8.5, respectively, followed by adding triethylthiourea (2 mg), chlorauric acid (4 mg) and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (0.2 g) to thereby provide a chemical sensitization at 60°C.
  • the vessel in which the emulsion (850 g) was put and weiged was heated to 40°C and additives were added in the manner shown below to prepare the emulsion layer coating solution.
  • Composition of the emulsion layer coating solution A Emulsion 850 g Spectral Sensitizing Dye [II] (used in Example 2) 1.2 ⁇ 10 ⁇ 4 mole Supersensitizer [III] (used in Example 2) 0.8 ⁇ 10 ⁇ 3 mole Preservativity Improver [IV] (used in Example 2) 1 ⁇ 10 ⁇ 3 mole Polyacrylamide (molecular weight: 40,000) 7.5 g Trimethylolpropane 1.6 g Poly(sodium styrenesulfonate) 2.4 g Poly(ethyl acrylate/methacrylic acid) latex 16 g N,N'-ethylenebis-(vinylsulfonacetoamide) 1.2 g
  • a vessel was heated to 40°C and the additives were added in the manner shown below to prepare the coating solution.
  • composition of the back layer coating solution Gelatin 80 g Dye [V] (used in Example 2) 3.1 g Poly(sodium styrenesulfonate) 0.6 g Poly(ethyl acrylate/metacrylic acid) latex 15 g N,N'-ethylenebis-(vinylsulfonacetoamide) 4.3 g
  • a vessel was heated to 40°C and the additives were added in the manner shown below to prepare the coating solution.
  • the above mentioned back layer coating solution was applied on a polyethylene terephthalate support together with the surface protective layer coating solution for the back layer so that the total gelatin coating amount was 3 g/m2. Subsequently, the above mentioned emulsion layer coating solution and the surface protective layer coating solution were applied on the opposite side of the support so that the coated Ag amount and the gelatin coating amount of the surface protective layer were 2.5 g/m2 and 1 g/m2, respectively
  • the composition of the developing solution is shown below: Developing solution Potassium hydroxide 17 g Sodium sulfite 40 g Potassium sulfite 50.4 g Diethylenetriaminepentaacetic acid 2 g Boric acid 8 g Hydroquinone 34 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 6 g Diethylene glycol 12 g 5-Methylbenzotriazole 0.08 g Potassium bromide 4 g Water was added to make the total quantity 1 liter (pH was adjusted to 10.35)
  • RF-10 (manufactured by Fuji Photo Film Co., Ltd.) was used as a fixing solution.
  • RF-10 is the fixing solution containing no aluminum hydroxide and having a pH of 5. While the shortest drying time during which the sample was completely dried after processing was 18 seconds when the roller transporting type automatic developimg machine FPM-2000 (manufactured by Fuji Photo Film Co., Ltd.), the use of the automatic developing machine shown in Fig. 1 provided the shortest drying time of 12 seconds.
  • the use of a non-hardening fixing solution could provide a good drying performance and gave a processing method having a good rapid processing suitability.
  • Sample A prepared in Example 5 was used.
  • Developing solution Developing Solution-A Developing Solution-B Diethylenetrriaminepentacetic acid 2.0 g 2.0 g Sodium carbonate 5.0 g 5.0 g Boric acid 10.0 g 10.0 g 2,3,5,6,7,8-hexahydro-2-thioxo-4-(1H)-quinazolinone 0.1 g 0.1 g Potassium sulfite 85.0 g - Sodium sulfite - 67.7 g Sodium bromide 6.0 g 6.0 g Diethylene glycol 40.0 g 40.0 g 5-Methylbenzotriazole 0.2 g 0.2 g g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.3 g 0.3 g Hydroquinone 30.0 g 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 1.6 g Water was added to (after adjusting
  • the drying time and the nitrogen content in the washing water were measured in the same manner as in Example 5. Further, the running test was carried out at a developing temperature of 38°C, a fixing temperature of 37°C and a developing time of 20 seconds. In the running test, a film with a size of 50.8 cm ⁇ 61.0 cm was processed by 450 sheets per day and the running was carried out for 2 days. After the running was finished, a fixing time was changed while passing the above non-developed sample of the above size and the fixing time was determined by the time when a fixing drop failure was generated after the processing (the partial generation was judged as the fixing drop failure). Washing water flowed in the amount of 2 liter per minute during the running test. The experimental results and the compositions of the fixing solutions are shown in Table 6.
  • Film B in Example 5 was used to carry out the same experiments.
  • the results of the running test were the same as those with Film A and it could be confirmed that the processing method having a good drying performance and a short fixing time could be provided.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP93115377A 1992-09-24 1993-09-23 Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial Expired - Lifetime EP0589460B1 (de)

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JP25456492A JPH06102632A (ja) 1992-09-24 1992-09-24 黒白ハロゲン化銀写真感光材料の処理方法
JP254564/92 1992-09-24
JP25456492 1992-09-24
JP5085196A JPH06273899A (ja) 1993-03-22 1993-03-22 ハロゲン化銀黒白写真感光材料の現像処理方法
JP8519693 1993-03-22
JP85196/93 1993-03-22

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Cited By (2)

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EP0704756A1 (de) * 1994-09-09 1996-04-03 Konica Corporation Photographisches Verarbeitungsverfahren zur Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials
GB2303220A (en) * 1995-07-06 1997-02-12 Kodak Ltd Photographic developing and fixing process

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