Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group

Definitions

• the present invention relates to a method for processing silver halide photo-sensitive materials, in particular to a method for fast and stably processing silver halide photo-­sensitive materials capable of preventing fog from increasing.
• a silver halide color photo-sensitive material is provided with three kinds of silver halide color emulsion layer each selectively and spectrometrically sensitized so as to be sensitive to a blue light, a green light and a red light, respectively, applied on a support member.
• a color negative photo-sensitive material is generally provided with a blue light-sensitive emulsion layer, a green light­sensitive emulsion layer and a red light-sensitive layer ap­plied in this order from a side exposed.
• a bleachable yellow filter layer is disposed between the blue light-sensitive emul­sion layer and the green light-sensitive emulsion layer to absorb a blue light passing through the blue light-sensitive emulsion layer.
• each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for achieving various kinds of special object.
• a color printing paper photo-sensitive material is generally provided with a red light-sensitive emul­sion layer, a green light-sensitive emulsion layer and a blue light-sensitive emulsion layer applied in this order from a side exposed.
• the color printing paper photo-­sensitive material is provided with an intermediate layer, a protective layer and the like in addition to an ultraviolet ray-absorption layer for achieving a special object, respec­tively, in the same manner as in the color negative photo-­sensitive material.
• these emulsion layers can be arranged in a manner other than the above des­cribed. It has been known also that a sensitive emulsion layer consisting of two layers having a sensitivity in the substan­tially same wave length range to a light of each color is used as the emulsion layer.
• a sensitive emulsion layer consisting of two layers having a sensitivity in the substan­tially same wave length range to a light of each color is used as the emulsion layer.
• a sensitive emulsion layer consisting of two layers having a sensitivity in the substan­tially same wave length range to a light of each color is used as the emulsion layer.
• a sensitive emulsion layer consisting of two layers having a sensitivity in the substan­tially same wave length range to a light of each color is used as the emulsion layer.
• a sensitive emulsion layer consisting of two layers having a sensitivity in the substan­tially same wave length range to a light
• a silver halide color photo-sensitive material (hereinafter referred to as a color sensitive material), which can be fast and stably processed, giving a high image quality, and being inexpensive, has been desired.
• a fast processable silver halide color photo-sensitive material has been desired.
• a silver halide photo-sensitive material has been subjected to a running process in an automatic devel­oping machine placed in each developing shop but it has been required to develop and return the silver halide photo-sensitive material to a user within its receipt date as one of improved services for the user. Recently, it is being required even to return the silver halide photo-sensitive material to the user within several hours from its receipt. Thus, the rapid devel­opment of an increasingly fast processable silver halide color photo-sensitive material is being desired.
• the speed-up of the color developing process can be achieved also by processing a silver halide photo-sensitive material containing silver halide particles substantially com­prising silver chloride in the presence of a bromide ion in a color developer.
• hydroxyl amine derivatives having at least one substituent to the nitrogen atom are useful as a compound having a sufficient preservative capacity without extremely reducing the coloring capacity even in the event that the concentration of color de­veloper is sufficiently high and benzyl alcohol is not con­tained.
• mercapto compounds are preferably used as a fog inhibitor. Although mercapto compounds are ef­fective as a fog inhibitor, they exihibit no sufficient effect in an inhibition of such the fog that is apt to be generated in the event that the color developing process was speeded up in the above described manner.
• the present invention was achieved in view of the above described state of art.
• an object of the present invention to provide a method for processing a silver halide photo-sensitive material in which a pollution load is reduced by removing benzyl alcohol from a color developer and a dye image can be fast formed by carrying out a color developing process in the presence of a specific hydroxyl amine derivative, hereby restraining fog, with a reduced sensitivity or gradation fluctuation due to a change of pH.
• the present invention specifically relates to a method of processing a light-sensitive silver halide photo­graphic material which comprises a step of processing an image-­wise exposed light-sensitive silver halide photographic mate­rial comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are sensitized with a sensitizing dye represented by general formula [I];
• Z1 and Z2 are independently represent a group of atoms necessary to complete a heterocyclic ring consisting of a thiazole, a benzothiazole, a selenezole, a benzoselenazole, a naphthoselenazole, a benzimidazole, a naphthoimidazole, a pyridine or a quinoline ring, wherein said heterocyclic ring may have a substituent; R1 and R2 are independently selected from a group consisting of an alkyl group, an alkenyl group and an
• Heterocyclic rings expressed by Z1, Z2 in said general formula [I] preferably include a thiazole-, a benzothiazol-, a naphthothiazol-, a selenazol-, a benzoselenazol- and a naththoselenazol ring, more preferably a thiazole-, a benzo­thiasol-, a selenazol- and a benzoselenazol ring, and most pre­ferably a benzothiazol ring.
• These rings may be substituted by various kinds of substi­tuent, preferably halogen atoms, a hydroxyl group, a cyano group, aryl groups, alkyl groups, alcoxyl groups or alcoxycar­bonyl groups, more preferably halogen atoms, a cyano group, aryl groups, alkyl groups of C1 to C6 or alcoxyl groups of C1 to C6, and most preferably halogen atoms, a cyano group, a methyl group, an ethyl group, a methoxy group and an ethoxy.
• substi­tuent preferably halogen atoms, a hydroxyl group, a cyano group, aryl groups, alkyl groups, alcoxyl groups or alcoxycar­bonyl groups, more preferably halogen atoms, a cyano group, aryl groups, alkyl groups of C1 to C6 or alcoxyl groups of C1 to
• R1 and R2 are alkyl groups, alkenyl groups or aryl groups.
• alkyl groups expressed by R1 and R2 preferably include alkyl groups of C1 to C6, and most preferably an ethyl group, a propyl group and a butyl group.
• These alkyl groups may be sub­stituted by various kinds of substituent, preferably a carbo­xylic group and a sulfonic group. In this case, salts may be formed between them and alkaline metal ions and an ammonium ion.
• At least one of R1 and R2 is preferably an alkyl group substituted by a sulfonic group.
• the alkenyl groups include an allyl group while the aryl groups include a phenyl group and the like.
• R3 is a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.
• X ⁇ is an anion, preferably a chloride ion, a bromide ion, an iodide ion and a p-toluene sulfonic acid ion.
• l is an integer of 0 or 1.
• l is 0 in the event that at least one of R1 and R2 is a group having a minus electric charge itself such as a carboxylic group and a sulfo­nic group.
• Typical examples of a sensitizing dye expressed by the general formula [I] are below described but they are not re­strictive.
• the sensitizing dye expressed by said general formula [I] according to the present invention can be easily synthesized in accordance with methods disclosed in for exmaple BP 660,408 and USP 3,149,105.
• the sensitizing dye expressed by said general formula [I] according to the present invention is preferably dis­solved in organic solvents, such as methanol and ethanol, which can be optionally blended with water.
• the sensitizing dye may be added in every step of the process of manufacturing an emulsion, preferably in the chemi­cal ageing step.
• a quantity of the sensitizing dye to be added is depend upon a kind of the sensitizing dye and a kind of the silver halide emulsion but the sensitizing dye is preferably added at a ratio of 0.01 to 0.5 g based on one mol of silver halide.
• hydroxyl amine derivatives used in the pre­sent invention are preferably added to the color developer solution
• a system in which the hydroxyl amine derivative of the present invention is previously incorporated in the sensi­tive material and the hydroxyl amine derivative of the present invention is supplied in the color developer by continuously processing the sensitive material, is also possible.
• hydroxyl amine derivative represented by general for­mula [II] inculdes, as preferable and non-limitative example those compounds listed below:
• the hydroxylamine derivative of the present invention can be used in the form of acid salt such as hydrochloride, sul­fate, p-toluenesulfate, oxalate, phosphate, acetate and so forth.
• the hydroxyl amine derivative or an acid salt thereof is used at an amount of 0.5 to 50 g, preferably 1 to 20 g, based on one liter of the color developer.
• the above described hydroxylamine derivative can be used together with hydroxylamine salts as far as the effects of the present invention are not spoiled, the latter is added at a ratio of about 1 g or less, preferably 0.5 g or less, based on 1 liter of the color developer (calculated as NH2OH ⁇ 1/2H2SO4).
• the hydroxylamine derivative when the hydroxylamine derivative is incorpo­rated in the photo-sensitive material and the color developer is supplied with it by continuously processing the photo-­sensitive material, the hydroxylamine is used at a ratio of 0.05 to 5 g, preferably 0.1 to 2 g, per 1 m2 of the photo-­sensitive material.
• Heterocyclic rings in the nitrogen-containing heterocyclic mercapto compounds used in the present invention are preferably selected from a group consisting of an imidazoline ring, an imidazol ring, an imidazolone ring, a pyrazoline ring, a pyrazol ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazol ring, a thiazolone ring, a selenazoline ring, a selenazole ring, a selenazolone ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a benztriazole ring, an indazole ring, a benzoxaxole ring
• mercapto oxadiazole mercapto thiadiazole
• mercapto triazole expressed by the following general formula [III] and mercapto tetrazole are preferably used: wherein X is selected from a group consisting of a hydrogen agom, an amino group, a hydroxyl group, a hydrazino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -NHCOR1 group, a -NHSO2R1 group or a -R2S group; Y is selected from a group consisting of hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -CONHR3 group, a -COR4 group, a -NHCOR5 group or a -NHSO2R5 group; Z
• the alkyl group expressed by X and Y is preferably selected from those containing 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and a benzyl group.
• Cycloalkyl group is preferably selected from a cyclohexyl group, a cyclopentyl group and the like.
• the alkenyl group is preferably selected from those containing 2 to 18 atoms such as an allyl group and an octenyl group.
• Aryl group is selected, for example, from a phenyl group, a naphthyl group and the like.
• the alkyl group expressed by R1, R2, R3, R4 and R5 may preferably be linear or branched alkyl groups con­taining 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group.
• the cycloalkyl group is preferably selected for example, from a cyclopentyl group, a cyclohexyl group and the like.
• the alkenyl group is preferably selected from those containing 2 to 18 carbon atoms such as an allyl group, an octenyl group and an octadecenyl group.
• the aryl groups are a phenyl group, a naphthyl group and the like.
• alkyl groups, cycloalkyl groups, alkenyl groups and aryl groups expressed by said X, Y, R1, R2, R3, R4 and R5 may have a substituent.
• substituent includes an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a halogen atom, nitro group, cyano group, mercapto group, an amino group, a carboxyl group, a hydroxyl group and the like.
• the compounds expressed by the general formula [III] ac­cording to the present invention show the following isomeriza­tion.
• the present invention includes also these isomers.
• Said compounds have been generally known and disclosed in for example Japanese Patent Unexamined Publication No. 107129/­1976, Japanese Patent Unexamined Publication No. 102621/1973, Japanese Patent Unexamined Publication No. 59463/1980, Japanese Patent Unexamined Publication No. 124333/1984 and BP 1,204,623.
• heterocyclic mercapto compounds can also be mentioned as preferable examples of the present inven­tion.
• the use of the above-mentioned heterocyclic mercapto compound in a photo-sensitive material comprising a photo-sensitive silver halide emulsion containing silver halide grains which consist essentially of silver chlo­ride in combination with the sensitizing dye of formula [I] has an advantage that occurrence of fog can be restrained effec­tively even in the case where the possibility of contamination of a bleach-fixing solution with a color developer solution carried in from a previous step is increased and the pH value thereof tends to increase when a photo-sensitive material un­dergoes bleach-fixing process immediately after color develop­ment process.
• nitrogen-containing heterocyclic mercapto compounds may be added to either the color developer or the sensitive material but it is preferable to add them to the sensitive material. In the event that they are added to the color devel­oper, they are added at a ratio of 10 ⁇ 6 to 10 ⁇ 4 mol based on 1 liter of the color developer.
• the nitrogen-containing heterocyclic mercapto compounds according to the present invention can be added to a sensitive silver halide emulsion layer or a non-sensitive constituent layer of photogrpahy but it is preferable to add the nitrogen-­containing heterocyclic compound to the sensitive silver halide emulsion layer.
• nitrogen-containing heterocyclic mercapto compound according to the present invention Two or more kinds may be added and the nitrogen-containing heterocyclic mercapto com­pounds according to the present invention may be added to two or more different layers.
• These nitrogen-containing hetero­cyclic mercapto compounds are used at a ratio of 10 ⁇ 8 to 10 ⁇ 4 mol/m2, preferably 10 ⁇ 7 to 10 ⁇ 5 mol/m2.
• nitrogen-containing heterocyclic mercapto compounds according to the present invention may be added in the form of alkaline metal salts such as a sodium salt, a potassium salt and a lithium salt.
• the fog-preventing effect by the combination of said sen­sitizing dye expressed by the general formula [I] with said nitrogen-containing heterocyclic mercapto compounds in a method of forming a dye image according to the present invention can reduce not only fog of a silver halide emulsion layer contain­ing silver halide particles spectrally sensitized with said sensitizing dye but also that of other silver halide emulsion layers. This cannot be easily anticipated from the prior art.
• the silver halide particles used in the present invention are formed of silver chloride, silver bromide, silver iodide, silver chloro-bromide, silver iodo-bromide, silver chloro-­iodide and the like, preferably silver chloro-bromide, and in particular preferably silver chloro-bromide containing silver chloride at a ratio of 10% or more by mol.
• An average particle diameter of said single dispersive silver halide particles are not especially limited but it should be 1.0 ⁇ m or less, preferably 0.8 ⁇ m or less.
• the silver halide particles used in the pre­sent invention may have regular shapes, such as cubic shape and octahedral shape, and irregular shapes such as sharp shapes.
• the silver halide emulsion of the sensitive silver halide emulsion layer according to the present invention may be doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium, copper or the like.
• this silver halide emulsion can be chemically sensitized.
• it can be sensitized by sul­fur sensitizing agents, such as allylthiocarbamides, N, N-­ diphenyl thiourea, sodium thiosulfate and cystine, noble metal sensitizing agents, such as gold compounds, palladium com­pounds, platinum compounds, ruthenium compounds, rhodium com­pounds and iridium compounds, or the combinations thereof.
• reducing agents such as stannous chloride.
• the binder used in the constituent layer of the silver halide photo-sensitive material according to the present inven­tion is most generally formed of gelatine such as alkali-­treated gelatine or acid-treated gelatine. Also, a part of this gelatine can be used together with gelatine derivatives, such as phthalized gelatine and phenylcarbamoylgelatine, albumin, agar-agar, Arabian rubber, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed poly­vinyl acetate, polyacrylamide, polyvinylalcohol, polyvinyl­pyrolidone and copolymers of these vinyl compounds.
• gelatine such as alkali-­treated gelatine or acid-treated gelatine.
• gelatine derivatives such as phthalized gelatine and phenylcarbamoylgelatine, albumin, agar-agar, Arabian rubber, alginic acid, partially hydrolyzed cellulose derivative
• the silver halide photo-sensitive material according to the present invention is subjected to the color developing process after the imagewise exposure to form the dye image.
• Particularly useful color developing agents used in the color developer include N, N-diethyl-p-phenylene diamine hydrochlo­ride, N-methyl-p-phenylene diamine hydrochloride, N, N-­dimethyl-o-phenylene diamine hydrochloride, 2-amino-5-(N-ethyl-­N-dodecylamino)-toluene, N-ethyl-N- ⁇ -methane sulfonamide ethyl-­3-methyl-4-aminoanilin sulfate, N-ethyl-N- ⁇ -hydroxylethyl­ aminoanilin sulfate, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, N-ethyl-N- ⁇ -hydroxylethyl-3-
• color developing agents can be used singly or in the form of mixtures of two or more kinds thereof.
• concentration of the color developing agents can be suit­ably selected within a range of 0.01 to 0.05 mol based on 1 liter of the color developer.
• the color developer according to the present invention can comprise various kinds of additive for use in the development of photogrpahy in addition to said color developing agent and said hydroxylamine derivative as the preservative.
• alkali agents such as sodium hydroxide, potassium hydro­xide, sodium carbonate, potassium carbonate, sodium meta-borate and tertiary potassium phosfate
• pH-buffer agents such as sodium hydrogen phosfate, potassium bihydrogen phosfate, biso­dium hydrogen phosfate and potassium bicarbonate
• organic sol­vents such as methanol and ethylene glycol triethanol amine and the like can be suitable selected and used.
• benzyl alcohol as the coloring capacity-improving agent is not contained in the color developer according to the present invention. However, it can be contained in a slight amount.
• Benzyl alcohol is contained in the color developer at a ratio of 0 to 5 ml, preferably 0 to 3 ml, per 1 liter of the color developer.
• the color developer according to the present invention comprises a small amount of sulfites, such as sodium sulfite and potassium sul­fite, in combination in addition to said hydroxylamine deriva­tive.
• the sulfites are used at a ratio of 0.05 to 2 g, preferivelyably 0.1 to 0.3 g, per l liter of the color developer.
• the color developer according to the present invention can comprise known development-inhibitors.
• development-­inhibitors include bromides, such as sodium bromide and potas­sium bromide, chlorides, such as potassium chloride and sodium chloride, and organic development-inhibitors, such as benztria­zole and benzimidazole.
• the effects of the present invention is remarkable in the case where the concentration of the color developer according to the present invention is aobut 0.005 mol or more.
• the effect of the present invention that is to say the effect of inhibiting the generation of fog due to the speedy processing in the event that hydroxylamine derivative is used, is remarkably increased.
• the speedy processing means a processing in which the color development processing time is 90 seconds or less.
• the temperature of the color developer is set at 20 to 50°C, preferably 30 to 40°C.
• the bleach-fixing time is set at 90 seconds or less, pre­ferably 60 seconds or less.
• the bleach used in the bleach-fixing solution includes metal complexes of organic acids in which metallic ions, such as iron ions, cobalt ions and copper ions, are coordinated in organic acids such as polycarboxylic acids, polyaminocarboxylic acids, oxalic acid and citric acid.
• organic acids such as polycarboxylic acids, polyaminocarboxylic acids, oxalic acid and citric acid.
• the most preferable organ­ic acids of said organic acids are polycarboxylic acids and polyaminocarboxylic acids.
• These polycarboxylic acids may be used also in the form of alkali metal salt, ammonium salt or water soluble amine salt. Concrete examples of these include the following compounds:
• bleaches are used at a ratio of 5 to 450 g/liter, preferably 20 to 250 g/liter.
• the bleach-fixing solution may comprise sulfites as pre­servatives in addition to said bleaches if necessary.
• the bleach-fixing solution may comprise an ethylene dia­mine tetraacetic acid iron (III) complex salt bleach and halides such as ammonium bromide.
• Said halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like in addi­tion to ammonium bromide.
• the silver halide-fixing agents used in the bleach-fixing solution include compounds, which react upon silver halide to form water soluble complex salts, used in the usual fixing process, typically thiosulfates, such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates, such as potassium thiocyanate, sodium thiocyanate and ammonium thio­cyanate, thiourea, thioether and the like.
• thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate
• thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thio­cyanate
• thiourea thioether and the like.
• the bleach-fixing solution can comprise vari­ous kinds of pH-buffer agent, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, singly or in com­bination.
• the bleach-fixing solution can comprise verious kinds of fluorescent whitening agent, anti-foamant or surfactant.
• the bleach-fixing solution can bisulfite-­addition products of hydroxylamine, hydrazine and aldehyde com­pounds, preservatives such as N, N-dialkyl-hydroxylamine, organic chelating agents such as polyaminocarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylsulfoamide and dimethylsulfoxide and the like according to circumstances.
• preservatives such as N, N-dialkyl-hydroxylamine
• organic chelating agents such as polyaminocarboxylic acids
• stabilizers such as nitroalcohol and nitrates
• organic solvents such as methanol, dimethylsulfoamide and dimethylsulfoxide and the like according to circumstances.
• the bleach-fixing solution can comprise various kinds of bleach-accelerator disclosed in Japanese Patent Unexamined Publication No. 280/1971, Japanese Patent Examined Publication No. 8506/1970, Japanese Patent Examined Publication No. 556/­1971, Belgian Patent 770,910, Japanese Patent Examined Publica­tion No. 8836/1970, Japanese Patent Examined Publication No. 9854/1978, Japanese Patent Unexamined Publication No. 71634/­1979, Japanese Patent Unexamined Publication No. 42349/1974 and the like.
• the pH of the bleach-fixing solution is set at 5.0 to 9.0, preferably 5.5 to 8.5.
• the silver halide photo-sensitive material according to the present invention may be subjected to washing-substitute stabilizing treatments disclosed in Japanese Patent Unexamined Publication No. 14834/1983, Japanese Patent Unexamined Publica­tion No. 105145/1983, Japanese Patent Unexamined Publication No. 134634/1983, Japanese Patent Unexamined Publication No. 18631/1983, Japanese Patent Application No. 2709/1983, Japanese Patent Application No. 89288/1984 and the like.
• the following layers were coated in turn on a titanium dioxide-contained polyethylene side of a support member ob­tained by laminating polyethylene on one side of a paper sup­port member of 170 g/m2 and laminating polyethylene containing anatase type titanium dioxide a a ratio of 11% by weight on the other side of hte paper support member to form silver halide color photo-sensitive materials No. 1 to 25.
• the addition quantity was expressed in a quantity per 1 m2 so far as it was not specially mentioned otherwise.
• Silver chloro-bromie emulsion containing silver chloride at a ratio of 90% by mol was chemically ripened until the opti­mum sensitivity point to sodium thiosulfate and then spectrally sensitized by the use of sensitizing dyes as shown in Table 1 (at a ratio of 5 ⁇ 10 ⁇ 3 mol per 1 mol of silver halide).
• Each of said sensitive materials No. 1 to No. 25 was ex­posed to a white light through an optical wedge and then sub­jected to the following processes:
• compositions of the color developer and the bleach-­fixing solution are as follows:
• the reflective concentration of a blue monochromatic light was measured for each of the resulting samples.
• the sensitivi­ty was measured from the characteristic curve [B] corresponding to the yellow dyer image.
• the gradation and fog were measured. As regards fog, it was also measured by the use of green mono­chromatic light.
• the obtained results are shown in Table 1.
• the sensitivity was expressed by a relative sensitivity with the sensitivity obtained in the event that the sensitive mate­rial 1 was processed in accordance with the process [A] as 100.
• the gradation is expressed by an inclination of the characteristic curve having a reflective density of 0.5 to 1.5.
• Table 2 shows the results obtained in the cases where the samples obtained by adding the mercapto compound [III]-24, which exhibited the best effect of preventing fog in EXAMPLE 1, to the layers containing the blue light-sensitive silver chloro-bromide emulsion sensitized by the comparative sensitiz­ing dye and the sensitizing dyes [I]-3, [I]-7 and [I]-21 and the samples obtained by adding said mercapto compound [III]-19 to the layers containing the green light-sensitive emulsion were processed with the color developers [A], [B] and [C] used in EXAMPLE 1.
• Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing silver chloride at a ratio of 99.5 % by mol and having an average grain size of 0.70 ⁇ m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 5 ⁇ 10 ⁇ 3 mol per 1 mol of silver halide of a sensitizing dye given in Table 4 and 2 ⁇ 10 ⁇ 4 mol per 1mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.
• Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing silver chloride at a ratio of 99.1 % by mol and having an average grain size of 0.40 ⁇ m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 3 ⁇ 10 ⁇ 3 mol per 1 mol of silver halide of a sensitizing dye (GSD-1) given hereinbelow and 2.5 ⁇ 10 ⁇ 4 mol per 1mo
• GSD-1 sensitizing dye
• Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing si
• RSD-1 sensitizing dye
• the photo-sensitive materials thus obtained were subjected to white exposure through an optical wedge and, thereafter, to the following processes:
• compositions used of the color developera with respect to the processes are as follows:
• Example 2 The same bleach-fixing solution as used in Example 1 was used except that this solution did not contain color developer and pH was adjusted to 6.2.
• the bleach-fixing solution used for process [D] and the color developer used for [E] were mixed at a ratio of 1:1 and pH thereof was adjusted to 7.0.
• the bleach-fixing solution used for process [D] and the color developer used for [F] were mixed at a ratio of 1:1 and pH thereof was adjusted to 7.0.
• Samples 63 thru 86 were prepared respectively in the same manner as Samples 39 thru 62 in EXAMPLE 4, exept that in the samples of this EXAMPLE a half amount of mercapto compound used in layer 1 of the respective samples in EXAMPL 3 were further added to layer 2.

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• 1987
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