JPH0431103B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic light-sensitive material with excellent preservability, and particularly to a silver halide color photographic light-sensitive material with good processability and excellent preservability. (Prior Art) It is well known that silver halide photographic materials, particularly multilayer color photographic materials, contain non-light-sensitive silver halide fine grain emulsions for various purposes. For example, Japanese Patent Publication No. 49-26134 describes a method for improving sharpness by simultaneously containing ultrafine silver halide grains with a diameter of 0.2 microns or less in a layer containing a photosensitive silver halide emulsion, and Japanese Patent Publication No. 50-23228. In order to prevent contamination of the developer by the leaving group of the interlayer color correction coupler, there is a method in which an adsorbing colloid layer of an organic development inhibitor consisting of fine silver halide particles which is not substantially developed by color development is provided on the upper or lower layer of the emulsion layer. , JP-A-52-143016 discloses a method of accelerating development by adding a silver chloride fine grain agent to a high-sensitivity silver halide emulsion layer or an adjacent layer. These utilize the characteristics of fine-grain silver halide emulsions that they scatter little visible light, are substantially transparent, and have a large surface area. (Problems to be Solved by the Invention) However, when these techniques are actually applied to silver halide photographic light-sensitive materials, the storage stability of the light-sensitive materials, especially at high temperatures, deteriorates significantly;
This has been an obstacle in making full use of the above technology. The present inventor conducted various experiments to solve this problem, and found that increasing the silver iodide content without changing the grain size, that is, the surface area, of a silver halide fine grain emulsion deteriorates the storage stability, especially during high temperature and low humidity storage. It was found that the increase in fog was reduced. However, when the silver iodide content is increased to a level sufficient to satisfy storage stability,
It was found that problems such as the original purpose of adding silver halide fine particles were no longer achieved, the fixing speed deteriorated, and optical sensitivity loss occurred due to increased absorption of visible light. . (Object of the Invention) Therefore, the object of the present invention is to develop a silver halide photographic light-sensitive material while maintaining the effects obtained using the above-mentioned fine-grain silver halide emulsion and without adversely affecting other photographic properties. Another purpose is to improve storage stability, and another purpose is to provide a silver halide photographic material having such characteristics. (Means for Solving the Problems) The present inventor has provided that the support has at least one photosensitive silver halide emulsion layer, and that the emulsion layer and/or other constituent layers are substantially non-photosensitive. In a silver halide photosensitive material containing silver halide fine grains, the silver iodide content on the grain surface is equal to the average silver iodide content of the grains as the substantially non-photosensitive silver halide fine grains. By using substantially non-photosensitive silver haloiodide fine grains larger than
It has been found that the above-mentioned problems are solved and the objects of the present invention are achieved. The silver haloiodide fine grains of the present invention have a feature that the silver iodide content on the grain surface is larger (particularly preferably 50% or more larger) than the average silver iodide content of the grains. It is distinguished from ordinary silver haloiodide fine grains in which the silver iodide content is uniform with the average silver iodide content of the grains. The particle surface here refers to the depth from the surface to about 100 Å to 200 Å. The silver iodide content on the grain surface of silver haloiodide fine grains can be measured using an X-ray electron spectrometer (XPS), and the average silver iodide content of the grains can be determined by After annealing for 3 hours to make the distribution of silver iodide uniform within the grains, measurement can be performed in the same manner using XPS. The silver haloiodide fine grains of the present invention may be any of silver iodochloride, silver iodobromide, and silver iodochlorobromide, and the silver iodide content is on average 0.1 to 10 mol%, preferably 0.1 to 5 mol%. and the average particle size is preferably 0.2μ or less, further 0.15μ or less, particularly 0.1μ or less. There is basically no limit to the particle size distribution, but monodispersity is more preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles are composed of particles having a size within ±40% of the average particle size. The silver haloiodide fine grain emulsion of the present invention is disclosed in, for example, US Pat. No. 2,592,250, US Pat.
It can be prepared by conventional methods such as the conversion method described in Japanese Patent No. 55-127549 and the core/shell emulsion preparation method described in British Patent No. 1027146. More specifically,
For example, silver bromide is prepared by simultaneously adding a silver nitrate aqueous solution and a potassium bromide aqueous solution to a gelatin solution kept at a constant temperature to maintain a constant pAg, and then a potassium iodide aqueous solution is added to convert the surface. A method of converting silver iodide into silver iodide by a method, a method of adding a potassium iodide aqueous solution at the same time as a potassium bromide aqueous solution immediately before the end of addition of a silver nitrate aqueous solution instead of producing silver iodide in the above method, a method of adding a silver nitrate aqueous solution in the same way There are methods such as adding fine grain silver iodide to the reaction vessel sometime from just before completion to after completion, and forming silver iodide (shell) on the surface of silver bromide grains (core) through Ostwald ripening, but this is not always the case. It is not limited to this. The particle size can be changed by changing the addition time of the silver nitrate aqueous solution and the potassium bromide aqueous solution and the temperature of the reaction vessel. The emulsion thus prepared is preferably washed with water according to a conventional method. Although chemical sensitization may be applied, it is preferable to use so-called unripened emulsions that are not subjected to chemical sensitization. The silver haloiodide fine-grain emulsion "substantially not having photosensitivity" as used in the present invention means that it is not photosensitivity relative to the light-sensitive silver halide emulsion layer. More specifically, it should be understood that when the light energy necessary to sensitize the photosensitive silver halide is applied to the light-sensitive material of the present invention, it is not substantially sensitized by that light energy. More specifically, the substantially non-photosensitive silver halide grains of the present invention generally have at most 1/10 the photosensitivity of the haloiodide grains as compared to the photosensitive silver halide grains. Preferably, they are fine particles of silver. The amount of the substantially non-photosensitive silver haloiodide fine grain emulsion used in the present invention is appropriately determined depending on the purpose of use, but is usually 0.5 in terms of silver amount per 1 m ² of support.
It is used in the range of g to 1.2 g. This fine-grain emulsion is incorporated into at least one of the photosensitive silver halide emulsion layers or other constituent layers (intermediate layer, protective layer, etc.) depending on the purpose of use. In the present invention, it is particularly preferable to provide a substantially non-photosensitive silver haloiodide fine grain emulsion layer adjacent to the photosensitive silver halide emulsion layer or via an intermediate layer. Generally, the fine-grain emulsion layer arranged in this manner has the function of occluding development-inhibiting substances such as iodide ions generated during development of the photosensitive silver halide emulsion, so that the development of the photosensitive silver halide emulsion is accelerated. By using the silver haloiodide fine grain emulsion layer of the present invention, it is possible to enjoy the effects of accelerating development and improving storage stability without deteriorating other photographic properties. This effect is particularly desired in multilayer color photographic materials. The multilayer color photographic light-sensitive material referred to herein refers to at least two light-sensitive silver halide emulsion layers containing dye-forming couplers that are sensitive to different spectral regions and develop colors of different hues on a support. It includes both those that give negative images and those that give positive images as a result of color reversal processing. The above-mentioned photosensitive silver halide emulsion layer may be composed of two or more emulsion layers having the same color sensitivity but different sensitivities. When the present invention is applied to a multilayer color photographic light-sensitive material, between the support of the silver haloiodide fine grain emulsion layer having substantially no photosensitivity and the light-sensitive silver halide emulsion layer closest to the support. It is particularly preferable to arrange. Silver haloiodide, which does not have substantially photosensitivity, is used to further improve the stability of the performance of silver haloiodide fine-grain emulsions that do not have substantially photosensitivity, and to control the solubility in developing solutions. It is also possible to use a fine grain emulsion by adsorbing sensitizing dyes and various compounds onto the grain surfaces. Sensitizing dyes useful in this case include, for example, German Patent No. 929080, US Pat.
No. 2493748, No. 2503776, No. 2519001, No.
No. 2912329, No. 3656959, No. 3672897, No.
No. 3694217, No. 4025349, No. 4046572, British Patent No. 1242588, Special Publication No. 14030, No. 52-24844
This is what is written in the issue. These sensitizing dyes may be used alone or in combination. The amount of sensitizing dye to be used is 1×10 ^-6 to 1×10 -2 mol, especially 1×10 ⁻² mol per mol of silver haloiodide fine particles.
x10 ^-5 to 5 x 10 ^-3 mol is preferred. Compounds other than sensitizing dyes include azoles,
For example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, Mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindene Many compounds known as stabilizers such as tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; benzenesulfuric acid; can be used. The use of these compounds is 1 mole of silver haloiodide fine grains.
x10 ^-6 to 0.5 mol, particularly 1 x 10 ^-5 to 0.1 mol is preferred. In particular, when the silver haloiodide fine grain emulsion having substantially no photosensitivity of the present invention is applied to a color reversal photographic light-sensitive material, a substance that acts as a so-called color mixing inhibitor (a scavenger for oxidized developing agent), For example, US Patent No. 2336327, US Patent No. 2403721
No. 2418613, No. 2675314, No. 2675314, No. 2418613, No. 2675314, No.
It is desirable to use it in combination with the hydroquinone derivatives described in No. 2704713, No. 2728659, No. 2732300, No. 2735765, and JP-A-59-28136. For example, it is added to a fine grain emulsion layer or an intermediate layer between a fine grain emulsion layer and a light-sensitive silver halide emulsion layer. During the reversal process (fogging process), silver haloiodide fine particles produce a developing solution on their surface that can be developed during the subsequent color development process, and may have the effect of converting the developing agent into an oxidized form during color development. The above-mentioned color mixture inhibitor has the effect of preventing the oxidized form of the developing agent from diffusing into the photosensitive silver halide emulsion layer and reacting with the coupler in the emulsion layer to cause excessive color development. The preferred amount of this compound used is in the range of 0.01 to 1 mole per mole of fine grain silver halide iodide. The halogen composition of the photosensitive silver halide used in the present invention may be silver chloride, silver bromide, silver iodide, or a mixed crystal thereof, but silver iodobromide is particularly preferred. The silver iodide content of this silver iodobromide is preferably 0.1 to 25 mol%, particularly 2 to 18 mol%. The shape of the grains may be spherical, octahedral, cubic, or turbular grains with a high aspect ratio, and even if the silver iodide is concentrated inside the grain,
It may be concentrated on the surface or uniformly dispersed. The grain size of the photosensitive silver halide emulsion is not particularly limited, but the volume of the largest grain contained therein is 1μ ³
The effect of the present invention is remarkable when the emulsion contains a highly sensitive emulsion with coarse grains exceeding . The particle size distribution may be narrow or wide. A photosensitive silver halide emulsion is prepared according to a conventional method. Its preparation is well known to those skilled in the art. The photosensitive silver halide emulsion used in the present invention contains cadmium salt, zinc salt, lead salt, thallium salt,
It may be made by coexisting an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron complex salt, or the like. The light-sensitive silver halide emulsion of the present invention can be produced without chemical sensitization, so-called "primitive" emulsion.
It is preferable to chemically sensitize the emulsion rather than use it as an emulsion. For chemical sensitization, see the above-mentioned book by Glafkides or Zelikman et al., or the book by H. Frieser (ed.) in Die Grundlagen der Photographischen, Prozesse mit Silberhalogeniden.
(Akademische Verlahsgesellschaft, 1968) can be used. The light-sensitive silver halide emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Useful sensitizing dyes include, for example, the German patent
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No.
No. 2503776, No. 2519001, No. 2912329, No. 2519001, No. 2912329, No.
No. 3656959, No. 3672897, No. 3694217, No.
No. 4025349, No. 4046572, British Patent No. 1242588,
Examples include various dyes described in Japanese Patent Publications Nos. 44-14030 and 52-24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. A color image-forming coupler for the photographic light-sensitive material of the present invention, that is, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) in color development processing. May contain. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule, or a polymerized coupler. The coupler may be either 4-equivalent or 2-equivalent to silver ions.
It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).
Moreover, the product of the coupling reaction is colorless,
Colorless DIR coupling compounds that release development inhibitors may also be included. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), Examples of cyan couplers include naphthol couplers and phenol couplers. Of course, two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. A coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or boiling point approx.
Organic solvent at 30°C to 150°C, such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. It is described in Publication No. 43-7561. The color image-forming couplers used are conveniently chosen to give intermediate scale images. The maximum absorption band of cyan dye formed from cyan color former is approximately
The maximum absorption band of the magenta dye formed from the magenta color former is between about 500 and 580 nm, and the maximum absorption band of the yellow dye formed from the yellow color former is about 400 to 480 nm. It is preferable that it is between. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin and "Bull.Soc.Sci.Phot.Japan" No.
16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. The light-sensitive silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. can. namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.; Compounds; azaindenes {e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.}; benzenethiosulfonic acid, benzenesulfonic acid Many compounds known as antifoggants or stabilizers can be added, such as fluoric acid, benzenesulfonic acid amides, etc. For more detailed examples of these and methods of their use, see, for example, U.S. Pat. No. 3,954,474; same
Those described in No. 3982947 and Japanese Patent Publication No. 52-28660 can be used. The photographic material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. Examples of ultraviolet absorbers include benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), and benzophenone compounds. (For example, JP-A-46-
2784), cinnamate ester compounds (e.g., those described in U.S. Pat.
4,045,229) or benzoxide compounds (eg, those described in US Pat. No. 3,700,455). Furthermore, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers. The photographic material of the present invention contains hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-
- Oxyphenol derivatives, bisphenols, ascorbic derivatives, etc. can be used. Specific examples include U.S. Patent No. 2360290 and
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, No. 2710801, No. 2816028, British Patent No. 1363921, No. 3457079, No. 3069262, British Patent No.
No. 2735765, No. 3698909, Special Publication No. 1977-20977,
No. 52-6623, U.S. Patent No. 3432300, U.S. Patent No. 3573050
No. 3574627, No. 3764337, Japanese Unexamined Patent Publication No. 1974-
No. 35633, No. 52-147434, No. 52-152225, and US Pat. No. 3,700,455. In addition, the photographic material of the present invention may contain conventional photographic additives such as brighteners, filter dyes, anti-irradiation dyes, polymer dispersions, development accelerators, surfactants, etc., if necessary. can. Details of these conventional photographic additives are described in Research Disclosure 17643 (December 1978). For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C.
Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylene diamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. In addition, LFA Meson's “Photography
"Processin Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent 2193015
No. 2,592,364, JP-A-48-64933, etc. may be used. The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates;
Development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants may be included. If necessary, water softeners, preservatives such as hydroxylamine, benzene alcohol,
Organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone. , a viscosity imparting agent, a polycarboxylic acid chelating agent as described in US Pat. No. 4,083,723, an antioxidant as described in OLS No. 2,622,950, and the like. When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process is
The fixing process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (),
Compounds of polyvalent metals such as cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-
Aminopolycarboxylic acids such as propanoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The present invention will be explained in more detail with reference to Examples below. Example 1 Various fine grain emulsions shown in Table 1 were prepared. The fine grain emulsions used in Sample B, Sample C, and Sample D were each prepared by a conventional double jet method. The fine grain emulsions used in Samples E and F were each prepared by preparing cubic silver bromide by a conventional double jet method and then adding an aqueous potassium iodide solution to convert the silver bromide surface to iodide. Each of the fine grain emulsions exhibited good monodispersity and almost no sensitivity to light. Sample A shown in Table 1 is a cellulose triacetate film coated with the following layers in sequence. (1) Emulsion layer Γ negative type silver iodobromide emulsion (silver iodide 7 mol% average grain size 0.8 μ) ...Amount of silver coated 1.2 g/m ² Γ coupler Cp-1 ... 0.8 g/m ² Γ Tricrezi rufuosphate
...0.4g/m ² Γgelatin ...0.7g/m ² (2) Protective layer Γ2,4-dichloro-6-hydroxy-s-
Sodium triazine: 0.08 g/m ² Γ gelatin: 1.5 g/m ² The structure of coupler Cp-1 is as follows. Samples B to F each had a first layer on the gelatin protective layer described above.
The fine grain emulsion shown in the table was added and coated so that the amount of coated silver was 0.1 g/m ² while keeping the amount of gelatin constant. Table 1 shows the results of sensitometry using these samples immediately after production and after performing a forced deterioration test for 3 days at 50° C. and 10% relative humidity. The treatment was carried out in the following steps. Processing step 1 Color development...3 minutes 15 seconds2 Bleaching...6 minutes 30 seconds3 Washing with water...3 minutes 15 seconds4 Fixing...4 minutes 20 seconds5 Washing with water...3 minutes 15 seconds6 Stability ...3 minutes 15 seconds The processing temperature is 38°C. The composition of the treatment liquid used in each step is as follows. Processing color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g Potassium iodide 1.5mg 4-(N-ethyl-N-β-hydroxyethylamino)-2 -Methyl-aniline sulfate 4.5g Add water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0ml Add water 1 Process (Using a tired fixer) The composition of the fixer in the process was changed as follows. Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 100ml Sodium bisulfite 4.6g Potassium iodide 1.0g Potassium bromide 15g Add water 1

[Table] As is clear from this result, sample E of the present invention,
Immediately after production, F shows the same development acceleration effect as Samples B and C, and this performance is maintained even after the forced aging test, whereas Comparative Samples B and C show marked fogging and desensitization during the forced aging test. do. In addition, in comparison sample D, although the increased fog and desensitization caused by the forced aging test were improved, the addition of fine grain emulsion did not have much of a development accelerating effect, and the fixing speed was slow, so silver remained in the film due to the tired fixer. It is clear that there are drawbacks, and the advantages of the present invention are obvious. Example 2 A color reversal photographic material was prepared by coating the first to eleventh layers on a triacetate film base in the following order. <Sample G> First layer: antihalation layer (gelatin layer containing black colloidal silver). 2nd layer: Gelatin intermediate layer A 10% gelatin solution was applied to give a dry film thickness of 2 μm. 3rd layer; low-sensitivity red-sensitive emulsion layer 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2'',4''-di-t-amylphenoxy)butyramide}-phenol
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirred at high speed with 1 kg of 10% gelatin aqueous solution. 500 g of the emulsion obtained was mixed with 1 kg of red-sensitive silver iodobromide emulsion ( Contains 70g of silver, 60g of gelatin, and the iodine content is 6 mol%), and the dry film thickness is
It was applied to a thickness of 1μ. (Amount of silver: 0.5 g/m ² ) 4th layer: Highly sensitive red-sensitive emulsion layer 2-(heptafluorobutyramide)-5-{2′-(2″,4″-di-t-amylphenoxy) which is a cyan coupler )Butyramide}-phenol 100g
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirred at high speed with 1 kg of 10% gelatin aqueous solution. 1000 g of the emulsion obtained was mixed with 1 kg of red-sensitive silver iodobromide emulsion ( 70g of silver, 60g of gelatin, iodine content is 6 mol%), and further 1-
3[3-(3-methylureido)phenyl]-5-
A methyl alcohol solution of mercaptotetrazole was added and coated to a dry film thickness of 2.5 μm.
(Amount of silver 0.8 g/m ² ) Fifth layer: Intermediate layer 2,5-di-t-octylhydroquinone,
1 kg of an emulsion obtained by dissolving 100 c.c. of dibutyl phthalate and 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of an aqueous solution in 10% gelatin is mixed with 1 kg of 10% gelatin to obtain a dry film thickness of 1 μm. It was applied like this. 6th layer; low green sensitivity emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the third layer emulsion except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
300g, green-sensitive silver iodobromide emulsion 1Kg (70g silver,
The mixture contained 60 g of gelatin (7 mol % iodine content) and was coated to a dry film thickness of 1.3 μm.
(Amount of silver: 1.1 g/m ² ) 7th layer: Highly sensitive green-sensitive emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the third layer emulsion except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
1000g of green-sensitive silver iodobromide emulsion (1kg of silver 70g,
60 g of gelatin (with an iodine content of 6 mol%) was mixed, and a methyl alcohol solution of 2-mercapto-benzothiazole was added to give a dry film thickness of 3.3μ.
It was applied so that (Amount of silver: 1.1 g/m ² ) 8th layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of 1 μm. 9th layer: Low-sensitivity blue-sensitive emulsion layer Instead of cyan coupler, yellow coupler α-(pivaloyl)-α-(1-benzyl-5-
Ethoxy-3-hydantoynyl)-2-chloro-
1000 g of an emulsion obtained in the same manner as the emulsion of the first layer except that 5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (silver
(containing 70 g of gelatin and 60 g of gelatin, 7 mol % iodine content) and coated to a dry film thickness of 1.5 μm. (Amount of silver: 0.4 g/m ² ) 10th layer: Highly sensitive blue-sensitive emulsion layer Instead of cyan coupler, yellow coupler α-(pivaloyl)-α-(1-benzyl-5-
Ethoxy-3-hydantoynyl)-2-chloro-
1000 g of an emulsion obtained in the same manner as the emulsion of the first layer except that 5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (silver
(containing 70 g of gelatin, 60 g of gelatin, and iodine content of 6 mol %) were mixed and coated to a dry film thickness of 3 μm. (Amount of silver: 0.8 g/m ² ) Eleventh layer: Protective layer A 10% gelatin solution was applied to give a dry film thickness of 2.8 μm. <Sample H> Sample C of Example 1 in the second layer (gelatin intermediate layer)
Fine grain silver iodobromide emulsion used in (average grain size
0.07 μ, average silver iodide content 2 mol %, ratio of silver iodide content on the grain surface to grain average silver iodide content = 1) was added so that the coated silver amount was 0.26 g/m ² Other than that, the same as sample G. <Sample I> The fine grain silver iodide emulsion used in Sample E of Example 1 for the second layer (average grain size 0.07μ, average silver iodide content 2 mol%, grain surface relative to grain average silver iodide content) Coating silver amount (ratio of silver iodide content = 1.5)
Same as sample G except that it was added at 0.26g/ ^m2 . <Sample J> Hydroquinone derivative of the following formula was added to the second layer at 1.72×
Sample I except that it was added at a concentration of 10 ^-4 mol/m ²
Same as. Samples G, H, I, and J at 50°C and 10% relative humidity.
The sample was aged for 3 days, exposed to white light through an optical wedge, and subjected to the following reversal process. The sensitometry results obtained by measuring the density of the cyan images of these samples using a red filter are shown in Table 2 together with the values immediately after manufacture. Reversal process Process Time Temperature First development 6 minutes 38℃ Water washing 2 minutes Inversion 2 minutes Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixing 4 minutes Process Time Temperature Water washing 4 minutes Stable at 38℃ for 1 minute Dry at room temperature The composition of the processing solution used is as follows. First developer water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Thiocyanide Potassium acid 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml (PH10.1) Inversion liquid water 700ml Nitro-N-N-N-trimethyleneoschinic acid 6Na salt 3g Stannous chloride (2 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Add water to 1000 ml Color developer water 700 ml Sodium tetrapolyphosphate 2 g Sodium sulfite 7 g Sodium tertiary phosphate (12 hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N.ethyl-N-(β-methanesulfonamidoethyl)-3.methyl-4-aminoaniline sulfate 11g Ethylenediamine 3g Add water 1000ml Adjustment water 700ml Sodium sulfite 12g Ethylenediamine, sodium tetraacetate (2
8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml Bleach solution water 800g Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ammonium ethylenediaminetetraacetate (dihydrate) 120.0g Potassium bromide 100.0g Add water 1000ml Fixer water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilizer water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water 1000ml

[Table] Table 2 shows that by using the fine grain emulsion of the present invention, the effects of promoting development and improving storage stability can be achieved without conflicting effects, and that the fine grain emulsion of the present invention and a hydroquinone derivative are used in combination. It can be seen that, as a result, excessive color development due to the development of the fine grain emulsion is prevented.

Claims (1)

[Claims] 1 In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, in the emulsion layer and/or other constituent layers, the silver iodide content on the grain surface is A silver halide photographic light-sensitive material characterized by containing substantially non-photosensitive silver haloiodide fine grains having a higher than average silver iodide content.