JPH1062885A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material having rapid processing aptitude and yet enhanced in storage stability with the lapse of time and graininess. SOLUTION: This silver halide photographic sensitive material having at least one silver halide emulsion layer on a support contains a gelatin having an iron ion content of <=5ppm and an α component having a molecular weight of about 100,000 in an amount of 40weight% and the average silver iodide content of the silver halide grains of each emulsion layer contained in the photosensitive material is <=7mol% in the average value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material which exhibits excellent graininess, is suitable for quick processing, and has excellent storage stability over time.

[0002]

2. Description of the Related Art In recent years, the environment surrounding a silver halide photographic system is rapidly changing. With the spread of personal computers to general users and the global spread of information networks such as those found on the Internet, the digitalization wave is also influencing photographs. Under such circumstances, in developing a conventional silver halide photographic light-sensitive material, it is more necessary than ever to make use of the features of the silver halide system, overcome the disadvantages, and respond to real customer needs. More specifically, for example, there is a problem of shortening the time required to obtain a photographic print while increasing the sensitivity of a silver halide photographic material to increase the characteristics of high image quality. It is also a very important subject to exhibit stable performance under various film use conditions or storage environments.

[0003] As one of the means for improving the image quality, especially for improving the graininess, the improvement of silver halide grains has been actively studied for a long time. For example, in the grains disclosed in Japanese Patent Publication No. 3-18695, a grain internal phase having a relatively high silver iodide content and a coating phase having a relatively low silver iodide content are provided outside the phase. It is stated that a clear double structure exists and that high sensitivity and high granularity are achieved by using these particles. However, in the grains having such a multiple structure, when the average silver iodide content per grain is relatively high, the speed of the development process cannot be further increased, and the average iodide content cannot be increased. When the silver halide content is relatively low, there is a drawback that the graininess is insufficiently improved and that the fog and gradation change during storage with time are increased. Recently, tabular grains having a high aspect ratio as typified by Japanese Patent Publication No. 5-60574 have been actively studied. Particles of this type are generally spherical with the same volume,
Because it has higher sensitivity than normal crystals such as cubic and octahedral,
When manufacturing the same silver amount and the same sensitivity as the conventional photosensitive material,
By increasing the number of particles per unit area while reducing the particle volume, the granularity can be improved. However, even in this type of grain, if the average silver iodide content per grain is relatively high, rapid processing suitability is insufficient, and if the average silver iodide content is relatively low, granular The deterioration was remarkable, and the performance fluctuation during storage with time was not satisfactory.

[0004] On the other hand, various means have been studied for suppressing performance fluctuations during storage of the film over time. For example, U.S. Pat. Nos. 2,403,927, 3,266,897 and 3,708,303, JP-A-55-135835,
Nos. 59-71047 and mercaptotetrazole;
It is described that a compound of a mercaptotriazole or a mercaptodiazole is contained, but it is not practically preferable because the inhibitory effect is weak, the improvement effect is small, and desensitization is caused by using a large amount.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in storage stability over time and granularity while having appropriate processing speed.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, gelatin used in the photographic material contains iron ions of 5 ppm or less and has a molecular weight of 5 ppm or less. A gelatin containing about 100,000 alpha components in an amount of 40% by weight or more, and in each emulsion layer of all silver halide emulsion layers contained in the light-sensitive material, the amount of silver halide grains contained in the emulsion layer is reduced. A silver halide photographic light-sensitive material characterized in that the average value of the average silver iodide content of each layer is 7 mol% or less when the average silver iodide content is determined.

(2) In a silver halide emulsion layer in which the average silver iodide content of at least one layer contained in the silver halide photographic light-sensitive material according to the above (1) is 7 mol% or less, it is contained in the emulsion layer. 50 of the total projected area of the silver halide grains
% Or more is occupied by grains having an aspect ratio of 3 or more.

(3) The silver halide photographic material as described in (2), wherein the coefficient of variation of the grain size of the silver halide grains contained in the emulsion layer is 20% or less.

Hereinafter, the present invention will be described in detail.

The gelatin used in the present invention will be described.

[0012] Gelatins usually used in the photographic industry include, in a process for producing collagen, alkali-treated gelatin accompanied by treatment with lime and the like and acid-treated gelatin accompanied by treatment with hydrochloric acid and the like. Manufactured using pig skin as a raw material.

For details of the production method and properties of these gelatins, see, for example, “Ther
Macromolecular Chemistry
of Gelatin ", Academic Pres
s, 187-217 (1964); H. Jam
es: The Theory of the Photo
graphical Process 4th. ed. 1
977, (Mcmilllan), p. 55, Handbook of Scientific Photography (above), pp. 72-75 (Maruzen), Basics of Photographic Engineering-Silver Salt Photography, pp. 119-124 (Corona Co., Ltd.) and the like.

Regarding the molecular weight of gelatin, see D.C. Lor
ry and M.R. Vedlines, Proceed
ings of the 4th IAG Confe
rence, Friborg, Sept. , 198
3, p. 35. As described in Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Journal of the Photographic Society of Japan, 47, 237 (1984), etc., an alpha component (molecular weight of about 100,000), which is a structural unit of collagen, and its two quantities Β component, γ
In general, these components are composed of high molecular weight components which are multimers, and low molecular weight components in which these components are irregularly cleaved. The measurement of the gelatin molecular weight distribution is based on the above literature,
JP-A Nos. 60-80838, 62-87952, 62-265645, 62-279329, and 6
As described in JP-A-4-46742 and the like, the reaction is carried out by gel permeation chromatography (hereinafter referred to as "GPC method"). The ratio of the α component of the gelatin used in the present invention can be determined by the GPC method under the following conditions.

(GPC method) a) Column: Asahipak, GS-620 (manufactured by Asahi Chemical Industry Co., Ltd.) Two columns connected in series Column temperature 50 ° C. b) Eluent: 0.1 M KH ₂ PO ₄ and 0.1 M Na ₂ HPO ₄ C) Sample: 0.2% eluent solution of gelatin Injection volume: 100 μl d) Detection: UV absorption spectrophotometer (UV wavelength 230 nm) Retention time ( Retention Time)
The chart showing the change in the absorption at 230 nm caused by the following: First, the peak of the exclusion limit appears, then the peaks due to the γ component, β component, and α component of gelatin appear in order, and further, the tails become lower as the retention time becomes longer. Becomes

The proportion of the α component in the present invention can be determined by calculating the proportion of the peak area of the α component in the above chart to the entire area. Specifically, a line b perpendicular to the horizontal axis is drawn from the minimum point on the left (in the direction of smaller retention time) of the peak a of the α component that appears at the 23rd minute of the retention time. Next, a line c perpendicular to the horizontal axis is drawn at a position of +1.5 minutes in retention time from the peak a. The ratio of the area surrounded by the measurement curves, b, c and the baseline to the total area is calculated.

The proportion of the α component determined by the above method in the gelatin used in the present invention is at least 40% by weight,
It is preferably in the range of not less than 95% by weight and not more than 95% by weight. If it is 95% by weight or more, there is a disadvantage that the production cost is high.

In the present invention, when the desired gelatin is obtained by blending gelatins having different values of the α component, even if any of the gelatin components is 40% by weight or less, the proportion of the α component in the whole colloid after blending is not limited. The proportion occupied may be 40% by weight or more.

The proportion of the high molecular weight component of the gelatin used in the present invention is preferably 3% or less. Here, the proportion of the high molecular weight component in the present invention can be determined by calculating the proportion of the area of the exclusion limit peak to the entire area. Specifically, a perpendicular line is drawn on the horizontal axis from the minimum point next to the peak appearing at the 15th minute of the retention time, and the ratio of the area of the portion (high molecular weight component) on the left side of the perpendicular line to the total area is calculated. Required by

The gelatin of the present invention may be a lime-processed gelatin or an acid-processed gelatin, or may be a gelatin derived from any of bovine bone, cow skin, pork skin and the like, but is preferably bovine bone. This is a lime-processed gelatin produced using as a raw material.

The gelatin of the present invention has a jelly strength (by the puggy method) of preferably 250 g or more.

The calcium content (according to the Paggy method) of the gelatin of the present invention is preferably 1000 ppm or less, particularly preferably 500 ppm or less. In order to reduce the calcium content in gelatin, generally, treatment with an ion exchange resin column is preferably used.

The gelatin of the present invention can be subjected to an oxidation treatment with hydrogen peroxide or the like for the purpose of reducing photographic activity.

In order to obtain the gelatin of the present invention, means for increasing the α component having a molecular weight of about 100,000 include, for example,
The following means are provided.

The conditions such as the period and temperature of the lime treatment of the raw material are adjusted.

The temperature and time for extracting gelatin from the pretreated raw material into the aqueous phase are adjusted, and extraction is performed at a relatively low temperature of 50 to 60 ° C. In general, extraction is performed in order, first extraction,
The second extraction and the third extraction are performed, and the first extract is preferable, and more preferably the extraction is performed in a short extraction time.

When the extracted gelatin solution is concentrated, gelled and dried to obtain gelatin, the temperature is preferably as low as possible (40 ° C.).
Below) to prevent decomposition by heat. Preferably, a vacuum concentration method or a concentration method by ultrafiltration is used.

A molecular weight fractionation method using an ultrafiltration membrane is used.

A molecular weight fractionation method using a coacervation method using an organic solvent such as alcohols is used.

The gelatin of the present invention can be obtained by using these means alone or in combination.

In the gelatin used in the present invention, iron ions contained in the gelatin are 5 ppm or less,
Preferably it is 5 to 3 ppm or less. If it is less than 1 ppm, there is a disadvantage that the production cost is high. Here, the method of controlling the content of iron ions to 5 ppm or less generally involves an ion exchange treatment using an ion exchange resin. However, depending on the type of the ion exchange resin, a small amount of iron ions contained in gelatin may be used. The removal is not always effective, and methods such as the use of a chelating resin, solvent extraction, and bubble separation are also used. Also, producing gelatin using a raw material having a low iron content is effective in reducing the iron content in gelatin, and further preventing or mixing iron from the production equipment in the gelatin production process. The removal of the iron powder by a magnet or the like is also effective for reducing the iron content in gelatin.

Of these, iron is removed by adding a water-soluble salt and / or water-soluble base to the gelatin extract, and then treating with an anion exchange resin to obtain a treatment solution having a pH of 9.0 or more. Is preferred.

The gelatin of the present invention is used in the step of preparing a coating for a silver halide emulsion layer, but may be used in the step of preparing a coating solution for another non-photosensitive layer.

Next, the silver halide emulsion used in the light-sensitive material of the present invention will be described.

In the silver halide emulsion used in the light-sensitive material of the present invention, the halogen composition may be silver chlorobromide, silver bromide, silver chloride, silver iodide, silver iodobromide, silver iodochloride, iodosalt. Any of silver bromide may be used, but silver iodobromide is preferred in that an emulsion having a particularly high sensitivity can be obtained.

The silver iodide content of each silver halide emulsion used in the light-sensitive material of the present invention is not particularly specified. When the average silver iodide content of the silver halide grains contained in the layer was determined, the average value of the average silver iodide content of each layer was 7 mol% or less. It is 7 mol% or less in that it has excellent rapid processing characteristics, and is more than 0 mol% in that no significant deterioration in graininess is observed. Further, 7 to 1 mol% is preferable from the viewpoint of granularity. In order to further enhance the effect of the present invention, the average silver iodide content of each emulsion layer is all 7 mol% or less, preferably more than 0 mol%, and all 5 mol% or less and more than 0 mol%. Is most preferred. Here, "determining the average silver iodide content of each emulsion layer" means specifically determining by the method shown below.

The method for measuring the average halogen composition of silver halide grains in a certain layer in the photographic material will be described.

To extract silver halide grains from the light-sensitive material, see Seiki Aoki Photographic Society, Vol. 53, No. 1, 1990, p. p.
After obtaining a flake of a desired layer by the method described in 1, the gelatin and silver halide grains may be separated by a gelatinolytic enzyme. That is, using a microtome, thin slices are successively cut from the surface of the membrane such that they are cut with a plane to obtain a slice of a desired layer. Thereafter, the flakes are placed in an aqueous gelatin-decomposing enzyme solution to decompose gelatin, and centrifuged to take out silver halide grains. Alternatively, the film may be immersed in an aqueous solution of gelatin-decomposing enzyme, gradually peeled off from the surface, and only the silver halide grains in a desired layer may be taken out by centrifugation.

From the obtained silver halide grains, an average halogen composition can be determined by a fluorescent X-ray method (WDX method) using a calibration curve prepared in advance. The number of particles to be measured is preferably at least 1000 or more.

For the measurement, for example, a fluorescent X-ray analyzer system 3080 manufactured by Rigaku Denki Kogyo KK can be used. The measurement conditions can be arbitrarily selected, but the measured fluorescent X-ray intensity Ag Br I spectral crystal LIF1 LIF1 LIF3 absorber 1/1 1/1 1/1 slit slit COARSE COARSE COARSE filter IN OUT OUT PHA conditions 10-30 10 30 15 to 30 Counting time (sec) It is desirable that the conditions be such as peak 40 40 40 background 40 40 40.

For quantitative determination, after measuring the fluorescent X-ray intensity of Ag, Br, I by WDX, AgBr and Ag were determined from the calibration curve.
I% is determined, and the average silver iodide content in that layer is calculated. Further, the whole silver halide emulsion layer means all the layers containing silver halide grains and having a function of forming a color image by a development process after exposure. In the silver halide emulsion used in the light-sensitive material of the present invention, the distribution of silver iodide in the grains may be uniform in the grains, or may be limited to so-called core / shell type silver halide grains. The layer may have a layer structure in which silver iodide is unevenly distributed in one of the core and the shell.

The silver halide emulsion used in the light-sensitive material of the present invention may have a regular crystal form such as cubic, tetradecahedral, or octahedral, or may have a spherical or plate-like form. It may have a surface or a mixture thereof. However, in at least one silver halide emulsion layer among the emulsion layers constituting the light-sensitive material of the present invention, 50% or more of the total projected area of silver halide grains contained in the emulsion layer has an aspect ratio of 3 or more. More preferably, it is occupied by particles of It is most preferable that the entire projected area is occupied by a flat plate having an aspect ratio of 3 or more in terms of exhibiting excellent sensitivity and granularity. The aspect ratio is preferably 3 or more in terms of exhibiting high sensitivity, and is preferably 20 or less in that no deterioration in pressure characteristics is observed. Here, the aspect ratio is a value obtained by dividing a diameter (hereinafter, referred to as a particle diameter) when a projected image of a particle is converted into a circular image having the same area by the thickness of the particle. The coefficient of variation of the particle size of the tabular emulsion is not more than 20%,
Below 5% is preferred from the viewpoint of further improving the graininess of the image. If it is less than 5%, the fluctuation during storage with time will be rather large, which is not preferable. Here, the variation coefficient of the particle diameter is defined as the following equation when the average particle diameter and the standard deviation of the particle diameter are obtained for 1000 or more particles in the emulsion.

Coefficient of variation of grain size = (standard size of grain size / average grain size) × 100 In the silver halide emulsion used in the light-sensitive material of the present invention, the grain size of the silver halide grains is 0.05 to 30.
Microns, preferably 0.1 to 10 microns.

In the process of forming and / or growing the silver halide grains, cadmium salts, zinc salts,
Adding a metal ion using at least one selected from a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt), and These metal elements can be contained on the particle surface. In addition, by placing in an appropriate reducing atmosphere, a reduction sensitizing nucleus can be imparted to the inside and / or the surface of the grain.

The silver halide emulsion used in the light-sensitive material of the present invention may be one from which unnecessary soluble salts have been removed after the growth and completion of silver halide grains, or may be one in which the soluble salts are still contained. When removing the salts, use Research Disclosure (Research Disc).
Closure (hereinafter abbreviated as RD)) No. 17643 No. II. More specifically, in order to remove the soluble salts from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method performed by gelatinizing gelatin may be used, and inorganic salts, anionic surfactants, A sedimentation method (flocculation) using an anionic polymer (for example, polystyrene sulphonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additive used in such a process is RD176
43, 18716 and 308119.

The following shows the places to be described.

[0048]

[Table 1]

Known photographic additives which can be used in the present invention are also described in the above RD. The relevant sections are described below.

[0050]

[Table 2]

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention.

Examples of the yellow coupler include, for example, US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. JP-B-58-10739, British Patent Nos. 1,425,020 and 4,314,023
No. 4,511,649, European Patent 249,473
Those described in No. A or the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 3,061,432, 3,725,067, 4,310,619, and 4,351. , 897, EP 73,636, Research Disclosure (hereinafter referred to as RD) 24220, 24230 (June 1984), JP-A-55-118034, and JP-A-60-335.
No. 52, No. 60-35730, No. 60-43659
No. 60-185951, No. 61-72238,
U.S. Pat. Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication WO88 / 04
No. 795.

In the present invention, a magenta coupler represented by the following formula [M] is particularly preferably used.

[0055]

Embedded image

(Wherein R ¹¹ is a hydrogen atom or an aromatic 1
Represents a group capable of leaving by reaction with an oxidized form of a secondary amine color developing agent. R ¹² represents an aryl group. R ¹³ represents a substituent, and n ₁ represents an integer of ₁ to 5. When n ₁ is 2 or more, R
¹³ may be the same or different. In the general formula [M], R ¹¹ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹¹ is preferably a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoint of saving silver and improving resistance to harmful gases.

R ¹² represents an aryl group, for example, phenyl, pentachlorophenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-
Dichlorophenyl group, 2,6-dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4-dichloro-6-methoxyphenyl group, 2,
4-dichloro-6-methylphenyl group and the like.

R ¹³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy groups, 2,6
-Dichlorobenzoylamino group, benzoylamino group such as 2,6-dimethoxybenzoylamino group, alkylsulfonyl group such as hexadecylsulfonyl, acylamino group such as acetylamino group, cyano group, nitro group, carboxyl group, amino group, Examples thereof include an alkoxycarbonyl group such as an ethoxycarbonyl group, and an alkyl group such as a methyl group, an ethyl group, and an isopropyl group. Of course, other monovalent substituents may be used.

It is preferable that at least one atom or group of R ¹³ is a halogen atom or an alkoxy group in terms of color development and spectral absorption wavelength.

Examples of the cyan coupler include known phenol couplers and naphthol couplers. For example, US Pat. Nos. 4,228,233, 4,296,200, 2,369,929 and 2,810, Nos. 171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173 No. 3,329,729, European Patent 121,36.
Nos. 5A and 249,453A; U.S. Pat.
No. 622, No. 4,333,999, No. 4,775,6
No. 16, 4,451, 559, 4,427,76
No. 7, 4,690,889, 4,254,212
No. 4,296,199, JP-A-61-42658.
No. 1 are preferred.

For the purpose of correcting unnecessary absorption of a coloring dye, a coupler described in US Pat. No. 4,744,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and US Pat. , No. 120, it is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (Published) 3,234. No. 533 is preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820, 4,080,
No. 211, No. 4,367,282, No. 4,409,3
20 and 4,576,910, British Patent 2,10
2,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent 2,097,1 discloses a coupler.
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye which becomes bicolor after release, RD11449, JP-A-24241, JP-A-61-61
Bleaching accelerator releasing couplers described in
Examples thereof include a ligand releasing coupler described in U.S. Pat. No. 4,553,477 and a leuco dye releasing coupler described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 described above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081
19, XIV, etc. can be added.

As the support in the color photographic material, any one can be used. In the case of a transparent support, a dye may be contained in the support for the purpose of preventing the light piping phenomenon (edge fog) that occurs when light enters the transparent support provided with the photographic emulsion layer from the edge. preferable. The dye to be compounded for such purpose is not particularly limited, but a dye excellent in heat resistance is preferable in the film forming process, and examples thereof include an anthraquinone dye. The color tone of the transparent support is preferably gray dyeing as seen in a general photosensitive material, and one or more dyes can be used in combination. SUMIPL manufactured by Sumitomo Chemical Co., Ltd.
AST, Diaresin, Bayer manufactured by Mitsubishi Kasei
Dyes such as MACROLEX manufactured by the company can be used alone or in an appropriate mixture.

The transparent support used in the present invention may be, for example, a copolymer polyester, or an antioxidant optionally blended with the copolymer polyester, or a group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxyammonium. After thoroughly drying the copolymerized polyester composition containing at least one selected, an extruder controlled to a temperature range of 260 to 320 ° C.,
The sheet is melted and extruded through a filter and a base, and the molten polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. Thereafter, the unstretched film can be manufactured by biaxially stretching the film in the machine direction and the transverse direction, and heat-setting.

The stretching conditions of the film vary depending on the copolymer composition of the copolymerized polyester and cannot be uniformly defined. However, in the longitudinal direction, the stretching ratio is set within the glass transition temperature (Tg) to Tg + 100 ° C. of the copolymerized polyester. 2.5 to 6.0 times, Tg + 5 ° C to Tg + 50 ° C in the horizontal direction
In the temperature range of 2.5 to 4.0 times.

The biaxially stretched film obtained as described above is usually heat-set at 150 to 240 ° C. and cooled. In this case, it may be relaxed in the vertical and / or horizontal direction if necessary.

The transparent support may be a single-layer film or sheet formed by the method described above.
Further, it may have a multilayer structure in which a film or sheet of another material and a film or sheet formed by the above method are laminated by a coextrusion method or a laminating method.

The thickness of the transparent support thus obtained is not particularly limited, but is usually 120 μm or less, preferably 40 to 120 μm, more preferably 50 to 120 μm.
110 μm. The local variation in the thickness of the transparent support is preferably within 5 μm, more preferably within 4 μm, and particularly preferably within 3 μm.

When the thickness of the transparent support is within the above range, no problem is caused in the strength and curl characteristics of the film after the photographic constituent layer is applied, and the thickness is within the range of the desired total film thickness. Can be. Further, when the thickness of the transparent support has a local variation of 5 μm or less, it is possible to prevent the occurrence of coating unevenness and drying unevenness when the photographic constituent layer is applied.

If necessary, a surface activation treatment such as corona discharge and / or an undercoat layer is applied to the surface of the transparent support on the side on which the photographic constituent layer is to be formed, prior to the formation of the photographic constituent layer. be able to.

The undercoat layer is described in, for example,
19941, 59-77439, 59-224
No. 841 and Japanese Patent Publication No. 58-53029, etc., can be mentioned as suitable examples. The undercoat layer provided on the surface of the transparent support opposite to the photographic component layer is also called a back layer.

When the color light-sensitive material of the present invention is used in the form of a roll, it is preferable that the color light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, cartridges proposed in the following patents can be used.

Japanese Utility Model Application Laid-Open No. 58-67329 and 58-19
No. 5236, JP-A-58-181035, 58-1
No. 82634, U.S. Pat. No. 4,221,479, JP-A Nos. 1-231045, 2-170156 and 2-1.
No. 99451, No. 2-124564, No. 2-2014
No. 41, No. 2-205584, No. 2-210346
Nos. 2-211443, 2-214853, 2-264248, 3-37645, and 3-37
No. 646, U.S. Pat.
Nos. 8,693 and 4,832,275.

Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" of JP-A-5-210201.

To obtain a dye image using the color light-sensitive material of the present invention, a generally known color developing process is performed after exposure. That is, the aforementioned RD17643, pages 28 to 29, R
D18716, 647 and RD308119, 101
It can be developed by the usual method described on page 0, section XIX.

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably provided on the side opposite to the photographic component layer with respect to the support, and the undercoat layer, the antistatic layer (conductive layer), It is preferable that a magnetic recording layer and a slip layer are formed.

As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small in consideration of the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The amount of magnetization of the magnetic recording layer per 1 m ² of the photosensitive material is preferably 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation once with oe is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic photosensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
m is preferred, more preferably 0.05 to 15 μm, and still more preferably 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
-93641, 2-181749, 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

In the present invention, the supports preferably used are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer or the undercoat layer, the same binder as that for the magnetic recording layer can be used.

It is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax or the like as a sliding layer on the magnetic recording layer.

When the light-sensitive material of the present invention is a roll-shaped color light-sensitive material for photographing, not only can a camera and a patrone be miniaturized, but also resources can be saved, and a storage space for a developed negative film can be saved. , The film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² , preferably 400 to 600 mm ² , it is possible to make a small format without deteriorating the image quality of the final photographic print, and a smaller patrone and a smaller camera than before can be achieved. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

[0097]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Emulsion >> Preparation of Emulsion Em-1 According to the method of preparing Emulsion-1 described in Example 1 of JP-B-3-18695, the diameter of the projected area was 1.
0 μm, having an average silver iodide content of 10 m comprising a core having a silver iodide content of 20 mol% and a shell having a mol content of 0 mol%.
ol% of emulsion Em-1 was prepared.

Preparation of Emulsion Em-2 According to the preparation method of Em-1, the core / shell volume ratio was set to 1: 4, whereby the grain size was 1.0 μm and the average silver iodide content was 4 mol%. Emulsion Em-2 was prepared.

Preparation of Emulsion Em-3 According to the preparation method of Emulsion A described in Example 1 of JP-B-5-60574, the diameter of the projected area converted to a circle was 1.0.
An emulsion Em-3 consisting of tabular silver halide grains having a micron size and a silver iodide content of 4 mol% was prepared. Em
In No.-3, 50% or more of the projected area of all the grains was occupied by grains having an aspect ratio of 5.0 or more, and the variation coefficient of the grain size was 30%.

Preparation of Emulsion Em-4 A projection area equivalent circle diameter was 1.0 μm and a silver iodide content was 10 mol% according to the preparation method of Em-3.
Emulsion Em-4 comprising tabular silver halide grains was prepared. In Em-4, 50% or more of the projected area of all the grains was occupied by grains having an aspect ratio of 5.0 or more, and the variation coefficient of the grain size was 35%.

Preparation of Emulsion Em-5 According to the preparation method of Emulsion B described in Example 1 of JP-B-5-60574, the diameter of the projected area converted to a circle was 1.0.
An emulsion Em-5 comprising tabular silver halide grains having a micron size and a silver iodide content of 4 mol% was prepared. Em
In the case of -5, 50% or more of the projected area of all the grains was occupied by grains having an aspect ratio of 5.0 or more, and the variation coefficient of the grain size was 18%.

<< Preparation of Multilayer Color Photographic Material >> On a triacetyl cellulose film support provided with an undercoat layer, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic material sample 101. Produced.

However, each silver halide emulsion is spectrally sensitized by the sensitizing dyes described below, and is also optimally chemically sensitized by using sodium thiosulfate, chloroauric acid and the like. .

The amounts added are in grams per m ² unless otherwise specified. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.12 Gelatin A 1.53 Second layer: Middle layer Color stain inhibitor (SC-1) 0.06 High boiling organic solvent (Oil-2) 0.08 Gelatin A 0.80 Third layer: Low sensitivity red-sensitive layer Silver iodobromide emulsion a 0.43 Iodobromide Silver emulsion b 0.15 sensitizing dye (SD-1) 2.8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^{− 4} Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 High boiling solvent (Oil-1) 0.49 Gelatin A 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion c 0 .89 silver iodobromide emulsion a 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1 0.6 × 10 ^-4 cyan coupler (C-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 high boiling point solvent (Oil-1) 0.39 gelatin A 1.01 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion EM-1 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitizing dye (SD-3) 1.6 x 10 ^-4 cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High Boiling point solvent (Oil-1) 0.57 Gelatin A 1.10 6th layer: Intermediate layer Color stain inhibitor (SC-1) 0.075 Boiling point organic solvent (Oil-2) 0.095 Gelatin A 1.00 7th layer: Intermediate layer Gelatin A 0.45 8th layer: Low sensitivity green-sensitive layer Silver iodobromide emulsion a 0.64 Silver iodobromide emulsion b 0.21 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.48 Colored magenta coupler (CM- 1) 0.12 High boiling point solvent (Oil-2) 0.81 Gelatin A 1.89 Ninth layer: Medium-sensitive green-sensitive layer Silver iodobromide emulsion c 0.76 Sensitizing dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0.102 Colored magenta coupler (CM- 2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling solvent (Oil-2) 0.37 Gelatin A 0.76 10th layer: Highly sensitive green-sensitive layer Silver iodobromide emulsion EM-1 1.46 Sensitizing dye (SD-6) 0.93 × 10 ^{− 4} Sensitizing dye (SD-7) 0.97 × 10 ^-4 Sensitizing dye (SD-8) 0.93 × 10 ^-4 Magenta coupler (M-1) 0.150 Colored magenta coupler (CM-2) 0 .014 High boiling solvent (Oil-1) 0.15 High boiling solvent (Oil-2) 0.42 Gelatin A 1.08 11th layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling point solvent (Oil-2) 0.21 Gelatin A 0.73 12th layer: Intermediate layer Formalin scavenger (HS-1) 0.18 Gelatin A 60 Layer 13: Low feeling Blue-Sensitive Layer Silver iodobromide emulsion c 0.073 Silver iodobromide emulsion a 0.16 Silver iodobromide emulsion b 0.20 Sensitizing dye (SD-9) 2.1 × 10 -4 Sensitizing dye (SD -10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling solvent (Oil-2) 0.37 Gelatin A 1.51 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion EM-1 0.95 Sensitizing dye (SD-9) 7.3 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y -1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin A 0.80 Fifteenth layer: First protective layer Silver iodobromide emulsion (average grain size 0.05 μm, silver iodide content 3. 0 mol%) 0.30 UV absorber (UV-1) 0.094 UV absorber (UV-2) 0.10 Formalin scaven (HS-1) 0.38 High boiling point solvent (Oil-1) 0.10 Gelatin A 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent PM-1 (average particle size 2 μm) 0.15 poly Methyl methacrylate (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin A 0.55 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizer ST-1, dyes AI-1, AI-2, antifoggant AF-1, two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, Membrane agents H-1, H-2 and preservative DI
-1 was added. The amount of DI-1 added was 9.4 mg / m ^2.
Met.

The structure of the compound used in the above sample is shown below.

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

The third layer, the fourth layer, the fifth layer
Samples 102 to 112 were prepared in the same manner as in Sample 101 except that the emulsions of the layers, the eighth layer, the ninth layer, the tenth layer, the thirteenth layer, the fourteenth layer, and the gelatin of all layers were changed as shown in Table 3. Was prepared.

However, the characteristics of each emulsion and each gelatin are as described in Tables 4 and 5.

Table 3 also shows the average silver iodide content of each emulsion layer and the average value obtained by dividing the total by the number of emulsion layers.

[0120]

[Table 3]

[0121]

[Table 4]

[0122]

[Table 5]

The samples 101 to 11 prepared as described above
2 was exposed according to the performance evaluation shown below, and the color development processing (1) and / or (2) shown below was performed to evaluate the performance.

A) Photosensitivity A sample is subjected to gradation exposure with white light, and subjected to the following color development processes (1) and (2) to give a density of minimum density +0.3 from the characteristic curve of each magenta image. The logarithmic value of the reciprocal of the exposure amount was determined, and the value of the color development processing (1) of the sample 101 was set to 100, and the relative sensitivity S was calculated based on this value. Here, the higher the value of the relative sensitivity S, the higher the sensitivity.

Further, the sensitivity difference ΔS between the samples of the color development processes (1) and (2), that is, ΔS = S ₍₂₎ -S ₍₁₎ was calculated. The closer the ΔS value is to 0, the better the rapid processing suitability is.

B) Graininess (RMS value) A part giving a green density of 0.3 + the minimum density of the sample whose photographic sensitivity was previously determined by the color development processing (2) was used as a ratten filter W-99 manufactured by Eastman Kodak Company. Through
Scan with a microdensitometer having an opening area of 1800 μm ² (slit width 10 μm, slit length 180 μm),
1000 times the standard deviation of the fluctuation of the density value for the density measurement sampling number of 1000 or more was calculated, and the value of the sample 101 was changed to 10 times.
The relative values were set to 0.

C) Raw preservability After the sample was conditioned for 6 hours at a temperature of 23 ° C. and a relative humidity of 65%, it was sealed in a sealable bag and stored at a temperature of 55 ° C. for one week. The raw preservation (substitute evaluation) sample thus obtained was exposed and processed in the same manner as in the determination of the photographic sensitivity of the color development process (2) in a), and a characteristic curve of a magenta color image was obtained. The difference (Δfog) between the minimum density value of the characteristic curve and the minimum density value obtained when the photographic sensitivity was obtained in a) was evaluated as the fog increase width during raw storage. The smaller the change, the better the raw preservability.

<< Color development processing (1) >> (Processing step) Process Processing time Processing temperature Supply amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Preparation of Color Developing Solution) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g 2.0 l, potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

(Formulation of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

(Bleach solution formulation) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, the pH is adjusted to 4.4 using glacial acetic acid.

(Preparation of bleach replenisher) Water 700 ml 1,3-diaminopropanetetraacetate ammonium iron (III) 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 with water or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid.

(Formulation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

<< Color Development Processing (2) >> (Processing Step) Process Processing Time Processing Temperature Replenishment Rate (ml / m ² ) Color Development (1 tank) 1 minute 30 seconds 40 ° C. 500 Bleaching (1 tank) 15 seconds 38 ° C 100 Settling (1 tank) 45 seconds 38 ° C 600 Stabilization (3 tanks cascade) 30 seconds 38 ° C 700 Drying 1 minute 0 seconds 40-80 ° C <Preparation of processing agent> (Formulation of color developing solution) Potassium carbonate 30 g sodium hydrogen carbonate 2.5 g potassium sulfite 3.0 g sodium bromide 1.3 g potassium iodide 0.6 mg hydroxylamine sulfate 2.5 g sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N- (Β-hydroxyethyl) aniline sulfate 9.0 g diethylenetriaminepentaacetic acid 3.0 g polyvinylpyrrolidone 0.10 g potassium hydroxide 1.2 g Adjust to 1 l and adjust to pH 10.00 with potassium hydroxide or 20% sulfuric acid.

(Formulation of color developing replenisher) 35 g of potassium carbonate 3 g of sodium hydrogen carbonate 5 g of potassium sulfite 0.1 g of sodium bromide 3.5 g of hydroxylamine sulfate 3.5 g of 4-amino-3-methyl-N-ethyl-N- (β- (Hydroxyethyl) aniline sulfate 11.0 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g polyvinylpyrrolidone 0.15 g Add water to make 1 liter, and add potassium hydroxide or 20%
Adjust to pH 10.20 with sulfuric acid.

(Bleach composition) 1,3-propanediaminetetraacetic acid ferric ammonium monohydrate 0.35 mol ethylenediaminetetraacetic acid 10 g potassium bromide 60 g imidazole 10 g succinic acid 0.35 mol maleic acid 0.1 mol carbonic acid The pH is adjusted to 3.0 with potassium and nitric acid, and water is added to make up to 1 liter.

(Preparation of Bleach Replenisher) The concentration of each additive in the above-mentioned bleach was 1.2 times and the pH was 2.5.

(Formulation of Fixing Solution and Replenisher) Potassium thiosulfate (70% solution) 300 ml Sodium thiocyanate 20 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g 3-mercapto-1,2,4-triazole 1.5 g 0.5 g of disodium ethylenediaminetetraacetate 0.5 g of water was added to make 1 liter, and the pH was adjusted with acetic acid and aqueous ammonia.
Adjust to 6.0.

(Preparation of Stabilizing Solution and Replenishing Solution) m-hydroxybenzaldehyde 1.5 g sodium lauryl sulfate 0.2 g disodium ethylenediaminetetraacetate 0.6 g lithium hydroxide monohydrate 0.7 g Water is added to make up to 1 liter.

Table 6 shows the evaluation results obtained as described above.

[0143]

[Table 6]

As is evident from Table 6, the light-sensitive material of the present invention maintains high sensitivity even in rapid processing, and is excellent in granularity and raw storage stability. In the present invention, the effect of using a tabular emulsion in which an emulsion layer having a silver iodide content of 7 mol% or less occupies 50% or more of the total projected area by grains having an aspect ratio of 3 or more is effective. Large, and the coefficient of variation of the grain size of the emulsion is 2
It can be seen that the effect is greater when using one having 0% or less.

Further, with respect to the yellow image and the cyan image, a) photographic sensitivity, b) graininess (RMS value),
c) When the raw storability was evaluated, the same effect as that of the magenta color image was obtained.

[0146]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in storage stability over time and granularity while having appropriate processing speed.

Claims (3)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The gelatin used in the light-sensitive material is a gelatin containing 5 ppm or less of iron ions and 40% by weight or more of an α component having a molecular weight of about 100,000, and all halogens contained in the light-sensitive material are used. When the average silver iodide content of silver halide grains contained in each emulsion layer of the silver halide emulsion layer was determined, the average value of the average silver iodide content of each layer was 7 mol% or less. A silver halide photographic light-sensitive material. 2. A silver halide emulsion layer having an average silver iodide content of at most 7 mol% in at least one layer contained in the silver halide photographic material according to claim 1. 2. The silver halide photographic material according to claim 1, wherein 50% or more of the total projected area of the silver halide grains is occupied by grains having an aspect ratio of 3 or more. 3. The silver halide photographic material according to claim 2, wherein the coefficient of variation of the particle size of the silver halide grains contained in the emulsion layer is 20% or less.