JPH07159913A - Silver halide photographic emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve photographic characteristics in high sensitivity exposure by incorporating silver halide grains having a specified aspect ratio and a specified average silver chloride content occupying >=50% of the projection areas of the total silver halide grains, and iron ions. CONSTITUTION:This photosensitive maternal contains the flat silver halide grains having parallel principal crystal faces of (100) and an aspect ratio of >=2 and an average silver chloride content of >=60mol% in an amount of >=50% of the projection areas of the total silver halide grains, and containing the iron ions, and they are controlled during grain formation by adding an iridium compound, and it is preferred that a sensitivity at 1/10000sec to that at 1/100sec ratio is>=80%. The iron ions providing compound are iron salts or complex salts soluble in water in the concentration range to be used and embodied by ferrous arsenide, bromide, carbonate, chloride, and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent suitability for rapid processing.
The present invention relates to a silver halide color photographic light-sensitive material which has high sensitivity and exhibits excellent photographic characteristics even when exposed to high illuminance such as stroboscopic light.

[0002]

2. Description of the Related Art There are a wide variety of commercially available silver halide color photographic light-sensitive materials and image forming methods using them, and they are used in all fields. The halogen composition of silver halide emulsions used in many of these light-sensitive materials is mainly silver bromide, silver iodobromide, silver chloroiodobromide, or chloroodor for the purpose of achieving high sensitivity. Often silver halide. On the other hand, the demand for rapid processing of color photographic light-sensitive materials has become stronger and stronger in recent years, but for that purpose we provide silver halide color photographic light-sensitive materials using silver halide emulsions mainly containing silver chloride. There is a need to. However, a silver halide emulsion mainly composed of silver chloride has a large decrease in sensitivity when exposed at high illuminance and cannot be used particularly for a photographic light-sensitive material for stroboscopic photography. Under such circumstances, a method of preparing a silver halide emulsion in the presence of an iridium compound as disclosed in JP-A-1-105940, or JP-A-1-183647.
As disclosed in No. 1, a method of incorporating iron ions into silver halide grains has been attempted to improve the reciprocity law of high illuminance of silver chloride emulsion, but it is still used as a photographic light-sensitive material. I wasn't at the level I could.

On the other hand, a tabular silver halide emulsion is mainly used as a silver halide emulsion mainly containing silver bromide because of its superiority in light scattering property and spectral sensitization property. Regarding tabular grains mainly containing silver chloride, US Pat.
399, 215, 4,400, 463, etc. (11
1) A method for preparing tabular grains of silver chloride having a plane as a main plane is disclosed. However, the silver chloride tabular grains mainly composed of the (111) plane are unstable and have a serious drawback that they cannot be chemically sensitized satisfactorily. This drawback is (1
It was expected that this could be solved by preparing tabular silver chloride grains mainly composed of (00) plane. U.S. Pat. No. 4,063,95
No. 1, No. 5,264,337 and the like disclose a method for preparing a silver chloride tabular emulsion having a (100) plane as a main plane. However, these silver chloride tabular emulsions also have a serious drawback that the high illuminance reciprocity law characteristics are poor as described above.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion and a silver halide which are excellent in rapid processing suitability, have high sensitivity, and exhibit excellent photographic characteristics even in exposure to high illumination such as strobe exposure. It is to provide a color photographic light-sensitive material.

[0005]

The above object of the present invention can be achieved by the following method. (1) The two parallel main planes are (100) planes, the aspect ratio is 2 or more, and the average silver chloride content of the grains is 6
A silver halide photographic emulsion characterized in that tabular silver halide grains of 0 mol% or more occupy 50% or more of the total projected area of silver halide grains and contain iron ions. (2) The silver halide photographic emulsion according to (1), which is prepared by adding an iridium compound during grain formation. (3) The silver halide photographic emulsion according to (1) or (2), which is chemically sensitized with a selenium sensitizer and a gold sensitizer. (4) A silver halide color photographic light-sensitive material containing at least one photosensitive emulsion layer containing silver halide grains on a support, wherein the photosensitive emulsion layer has two parallel main planes (100) planes. A tabular silver halide grain having an aspect ratio of 2 or more and an average silver chloride content of the grain of 60 mol% or more occupies 50% or more of the total projected area of the silver halide grain. A silver halide color photographic light-sensitive material containing a silver emulsion and having a sensitivity of 1 / 10,000 second exposure to 1/100 second exposure of 80% or more. (5) The silver halide color photographic light-sensitive material as described in (4), wherein the silver halide emulsion contains iron ions. (6) The silver halide color photographic light-sensitive material according to (6), wherein the silver halide emulsion is prepared by adding an iridium compound during grain formation. (7) The silver halide color photograph described in any one of (4) to (6), wherein the silver halide emulsion is chemically sensitized with a selenium sensitizer and a gold sensitizer. Photosensitive material.

The present invention will be described in detail below.

The color photographic light-sensitive material of the present invention is 1/100
The sensitivity of 1/10000 second exposure to second exposure is preferably 80% or more. This is because when evaluated by the method described below, the exposure amount at a certain density when exposed for 1/10000 seconds in all color-sensitive layers and all density regions of the color photographic light-sensitive material was 1 / 100 seconds means that the exposure amount is 1.25 times or less (100/80) that gives the same density when the exposure is performed.

(Exposure) Sensitometer M from EG & G
1/100 sec and 1/1000 with ARKVII
Exposure is performed for 0 seconds. However, both of the exposures are performed by inserting a correction filter having a color temperature of 4800 ° K and an ND filter having the same exposure amount. (Development) A development process is carried out 1 hour after the exposure.
The development processing is carried out by the rapid processing for silver chloride emulsion described in Example 1.

The high silver chloride emulsion is characterized by being excellent in suitability for rapid processing. However, as described above, it is not only a drawback that the reciprocity law failure of high illuminance is large, but also in a cubic emulsion which is generally used. It had a decisive defect that the sensitivity was remarkably low even in the exposure for a normal exposure time (about 1/100 second), as compared with the silver bromide emulsion. In order to solve this drawback, it has been attempted to prepare a tabular emulsion of high silver chloride for the purpose of increasing the color sensitization efficiency as has been attempted with silver iodobromide. It has become possible to prepare not only the tabular emulsions having the above formula, but also the high silver chloride tabular emulsions whose principal plane is the (100) plane. In the present invention, in order to provide a silver halide color photographic light-sensitive material having rapid processing suitability and high sensitivity, two parallel main planes are (100) planes, and an aspect ratio is 2 or more,
The tabular silver halide grains having an average silver chloride content of 60 mol% or more are 5% of the total projected area of the silver halide grains.
A silver halide emulsion occupying 0% or more is used. High silver chloride tabular silver halide emulsions whose main plane is the (100) plane are disclosed in U.S. Pat. Nos. 4,063,951 and 4,386,1.
56, No. 5,264,337, Japanese Patent Application No. 5-2640
It can be prepared by the method disclosed in No. 59. It can also be prepared by the method described below,
In the present invention, this method is the most preferable method for preparing a high silver chloride tabular silver halide emulsion. The tabular grain emulsion having a high silver chloride content of the present invention can be produced as follows.

1) Nucleation Process The tabular nuclei, which serve as nuclei for tabular grains, have a high production ratio under the condition that the introduction of lattice defects easily occurs. As a method for obtaining plate nuclei with high reproducibility and a high production ratio, a method utilizing halogen conversion of product nuclei is effective. In this method, first, silver halide nucleation is carried out, and subsequently, halogen ions for forming a more sparingly soluble silver halide are introduced to carry out halogen conversion. More specifically, the halogen composition structure of the nuclei formed during nucleation is, for example, (AgX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₂ ).
gX ₁ | AgX ₄ | AgX ₃ ). The structure is obtained, for example, by simultaneously mixing and adding a silver salt aqueous solution (hereinafter referred to as “Ag ⁺ liquid”) and a halide salt aqueous solution (hereinafter referred to as “X ⁻ liquid”), and adding X ⁻ liquid at the gap surface. Can be formed by discontinuously changing the halogen composition of. Or a dispersion medium solution X ^- solution was added, followed by the addition of Ag ⁺ solution to form AgX _1, then another X ^- adding liquid, followed by addition of Ag ⁺ solution, (AgX ₁ The | AgX ₂ ) structure can be prepared, or a combination thereof can be prepared.

AgX ₁ and AgX ₂ and AgX ₁ and Ag
X ₄ , AgX ₄ and AgX ₃ are Cl ⁻ content or Br ⁻
The contents differ by 25 to 100 mol%, preferably 50 to 100 mol%, more preferably 75 to 100 mol%.
Further / or the I ^- contents differ by 5-100 mol%, preferably 10-100 mol%, more preferably 30-100 mol%. In addition, an embodiment in which the difference in Cl ⁻ content or the difference in Br ⁻ content is in accordance with the above definition and the difference in I ⁻ content is 0 to 5 mol% can be mentioned. The size of the nucleus is 0.15
It is preferably not more than μm, more preferably 0.01 to 0.1 μm. AgX ₁ : Ag in the case of (AgX ₁ | AgX ₂ ).
X ₂ molar ratio, and (AgX ₁ | AgX ₄ | Ag
The molar ratio of AgX ₁ : AgX ₂ : AgX ₃ in X ₃ ) can be variously changed, and the molar ratio that provides the most preferable embodiment of the present invention can be selected and used.

The atmosphere of the dispersion medium solution at the time of nucleation is {10
It is necessary to create a 0} plane forming atmosphere. In the case of nucleation performed under Cl ^- excess concentration, most of the usual conditions (pCl
0.8-3.0, pH 2-9) is a {100} plane forming atmosphere. The defect formation frequency is pH 1 to 7
Becomes higher and the pCl value becomes higher, the frequency of defect formation becomes higher. Here, pCl = −log [mol of Cl ⁻ / liter].

The dispersion medium concentration of the dispersion medium solution at the time of nucleation is 0.
1 to 10% by weight is preferable, and 0.3 to 5% by weight is more preferable. 1-10 are preferable and, as for pH, 2-8 are more preferable. The temperature is preferably 10 to 80 ° C, more preferably 30 to 60 ° C. The excess Br ⁻ concentration is preferably 10 ⁻² mol / liter or less, more preferably 10 ^−2.5 mol / liter or less. The excess Cl ⁻ concentration is preferably pCl = 0.8 to 3.0, more preferably 1.2 to 2.8.

It can be included salt solution in the dispersion medium ^- [0014] silver salt solution and / or X during nucleation is added to allow for uniform nucleation. Dispersion medium concentration is 0.1% by weight
The above is preferable, 0.1 to 2% by weight is more preferable,
0.2 to 1% by weight is more preferable. Molecular weight 3000-6
10,000, preferably 8,000 to 40,000 low molecular weight gelatin is more preferable. Furthermore Ag ⁺ solution and X ^- liquid addition porosities 3
10 ^15, preferably through 30 to 10 ¹⁵ porous addition system, it is more preferably added directly to the liquid. The details are described in JP-A-3-21339 and 4-193336.
The description in Japanese Patent Application No. 4-240283 can be referred to. Gelatin having a lower methionine content has a higher frequency of defect formation. Methionine content is 1 to
From 60 μmol / g of gelatin, the most preferable gelatin can be selected and used according to each case.

Excess X ^- salt concentration during nucleation, or excess A
By lowering the g ⁺ salt concentration, the mixing ratio of twin grains can be reduced.

An aqueous silver salt solution and a halide salt (hereinafter, referred to as "dispersion medium solution containing at least a dispersion medium and water" with stirring).
X ^- salt) solution is added by a double-mix method to form nuclei. The Cl ⁻ concentration in the dispersion medium solution during nucleation is preferably 10 ^−1.5 mol / liter or less, and the Ag ⁺ concentration is preferably 10 ⁻² mol / liter or less. The pH is preferably 2 or more,
5-10 are more preferable. The gelatin concentration is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight.

The temperature during nucleation is not limited, but usually 1
0 degreeC or more is preferable and 20-70 degreeC is preferable. After the nucleation, physical ripening is performed to eliminate non-tabular grains and grow the tabular grains. The addition rate of the aqueous silver salt solution is 1 for container solution.
0.5-20 g / min is preferable per liter, 1-1
5 g / min is more preferred. The pH of the container solution is not particularly limited, but is usually pH 1 to 11, preferably pH 3 to 10.
Is used. The most preferable pH value can be selected and used according to the combination of excess silver salt concentration, temperature, and the like.

2) Aging Process It is not possible to separately prepare tabular grain nuclei during nucleation. Therefore, in the next ripening process, Ostwald ripening causes the tabular grains to grow and the other grains to disappear. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C.

Aging is preferably performed in a {100} plane forming atmosphere. Aging conditions are preferably selected from the nucleation condition range. The ripening rate generally becomes faster in the region of pH 1 to 6 as the pH becomes higher, and in the region of pCl1 to 3 as the Cl ^- concentration increases.

In the present invention, it is preferable that a silver halide solvent is not substantially allowed to coexist during ripening. Here, substantially means that the silver halide solvent concentration d ₀ is preferably d ₀ ≦ 0.5 mol / liter, more preferably d _0.
<0.1 mol / liter, more preferably d ₀ <0.0
Refers to 2 mol / liter.

The pH during aging is 1 to 12, preferably 2 to
8, more preferably 2-6.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for silver halide emulsions can be used, but the methionine content is particularly preferably 0-5.
0 μmol / g, more preferably 0 to 30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. Also, Japanese Examined Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, 29 volumes (1), 17, 22 (1966), 30 volumes (1),
10, 19 (1967), 30 volumes (2), 17 (1)
967), 33 (3), 24 (1967). Further, the crystal habit controlling agent described in European Patent 0534395A1 can be used in combination. The dispersion medium concentration is 0.1 to
10 wt% is preferable, and the control agent is preferably 10 ^-1 to
10 ⁻⁶ mol / liter, more preferably 10 ⁻² to 10 ⁻⁵
It can be used in mol / liter. These can be added at any time from before nucleation to the end of growth. It can be added in the form of additional addition to the existing dispersion medium, or can be added after removing the existing dispersion medium by centrifugation or the like. 3) Growth process After increasing the tabular grain ratio by aging, a solute is added next to further grow the tabular grains. As a solute addition method, 1) a solution addition method (a method of adding a silver salt aqueous solution and a halide salt aqueous solution), 2) a method of previously forming fine silver halide grains and adding the fine grains, 3) a combination of both A method can be mentioned. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. The method 2) is more preferable because it enables this.

In the method of adding fine grain emulsion, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
A silver halide fine grain emulsion having a grain size of 06 μm or less is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying an aqueous solution of silver salt and an aqueous solution of halide salt in a mixer provided in the vicinity of the reaction vessel, and can be continuously added to the reaction vessel immediately or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner. It is preferable that the fine particles are substantially free of twin grains. The term “substantially free” means that the twin crystal grain number ratio is 5% or less, preferably 1% or less, and more preferably 0.1% or less.

The halogen composition of the fine grains may be silver chloride, silver bromide, silver iodide, or a mixed crystal of two or more kinds thereof.

The solution conditions during grain growth are the same as the above-mentioned aging conditions. This is because both are steps in which tabular grains are grown by Ostwald ripening and other fine particles are eliminated, and they are mechanically the same. For details of the method for adding a fine grain emulsion, see Japanese Patent Application No. 2-142635,
The description in JP-A-4-77261 and JP-A-1-183417 can be referred to. In order to form fine particles having substantially no twin planes, the excess halogen ion concentration or the excess silver ion concentration is preferably 10 ^-2 mol / liter or less, and the silver salt aqueous solution and the halide salt aqueous solution are simultaneously mixed and added. It may be added by a method.

The fine particle formation temperature is preferably 50 ° C. or lower,
5-40 degreeC is more preferable, and 10-30 degreeC is still more preferable. The dispersion medium preferably has a molecular weight of 2000 to 6 × 10.
⁴ , more preferably 5000-4 × 10 ⁴ low molecular weight gelatin, preferably 30% by weight or more, more preferably 6
Gelatin occupying 0% by weight or more, and more preferably 80% by weight or more is preferable. The dispersion medium concentration is preferably 0.2% by weight or more, more preferably 0.5 to 5% by weight.

NH during the nucleation process is substantially₃Coexist with
Preferably not. Here, “substantially” means according to the above rules.
U NH during growth₃It is preferred not to coexist.
Here, “substantially” means NH₃Concentration Z₁Is Z₁≤ 0.5 mol
/ Liter, more preferably Z ₁<0.1 mol / lit
And more preferably Z₁<0.02 mol / liter
Means that. NH for nucleation and growth process₃Other than
It is preferable that substantially no AgX solvent is also allowed to coexist.
Here, “substantially” means Z₁It is the same as the concentration regulation. N
H₃Other than AgX solvent, thioethers, thio
Urea, thiocyanate, organic amine compounds, tetra
Antifoggants such as Zaindene compounds
Thioethers, thioureas, thiosines
Anionate.

Dislocation lines can be introduced into the grains during the grain formation by the halogen composition gap method, the halogen conversion method, the epitaxial growth method and the combination thereof. The pressure fog characteristics and reciprocity law characteristics and the color sensitization characteristics are further improved, which is preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, ibid 3-189642, ibid 3-175440, ibid 2
-123346, European Patent 0460656A1 Journal
of Imaging Science, 32 volumes, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines inside may be formed using the particles as a core.
In addition, using the grains as a substrate, a silver halide layer having a halogen composition different from that of the substrate is laminated,
It is also possible to make particles of various known particle structures. Regarding these, it is possible to refer to the description of the literature described later.

Further, a shallow inner latent emulsion may be formed by using the tabular grains as a core. It is also possible to form core / shell type particles. Regarding this, JP-A-59-
133542, 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, 3,367,778. Can be referred to.

As described above, the most important parameter for finally obtaining a silver halide grain having a high aspect ratio is pAg during ripening / growth, and the aspect ratio of the tabular grain in the present invention is 2 or more. It is 15 or less. The aspect ratio is preferably 3 or more and 13 or less, and more preferably 4 or more and 10 or less. The aspect ratio is preferably in the above range mainly due to the balance between sensitivity and pressure.

As used herein, "aspect ratio" refers to the ratio of the thickness between major planes to the average edge length that forms the major plane of the grain, and "major plane" substantially forms the cuboid emulsion grains. Of the crystal surfaces, the area is defined as a set of parallel planes having the largest area, and the fact that the main plane is the {100} plane can be examined by an electron beam diffraction method or an X-ray diffraction method. A substantially rectangular parallelepiped emulsion grain has a main plane of {10
Although it is formed from the 0} plane, it means that it may have 1 to 8 {111} crystal planes. That is, 1 to 8 out of the eight corners of the rectangular parallelepiped may have a cornered shape. The "average edge length" is defined as the length of one side of a square having an area equal to the projected area of each grain seen in the micrograph of the emulsion grain sample.

By forming a salt, which is less soluble than silver chloride, on the surface of tabular grains of high silver chloride having the {100} plane as the principal plane without unevenness between grains, a sensitizing dye can be obtained without unevenness between grains. Adsorption is the preferred method. Examples of silver salts that are less soluble than silver chloride include silver bromide, silver iodide, silver iodobromide, silver thiocyanate, silver selenocyanate, and mixed crystals thereof. It is preferably silver halide. The amount of the silver salt, which is less soluble than silver chloride, is 20 mol% or less, preferably 10 mol%, based on the whole grains.
It is at most mol%, more preferably at most 5 mol%, even more preferably at most 3 mol% and at least 0.001 mol%.

As a method of allowing a silver salt, which is less soluble than silver chloride, to be present on the surface of the tabular grains, a method of adding a water-soluble halide salt and a water-soluble silver salt having a corresponding composition by a double jet, and fine particles are used. Method of adding and bromide ion,
A method using a sustained release agent of iodine ions can be mentioned. In the method in which the water-soluble halide salt and the water-soluble silver salt are added by a double jet, the halogen ions are added in a free state even if the halide salt aqueous solution is diluted and added. There are limits to trying to reduce locality. On the other hand, the method of adding in the form of fine particles or the method of using a sustained-release agent is a preferable method for forming a salt, which is less soluble than silver chloride, on the surface of the particles without unevenness among the particles.

When added in the form of fine particles, the average spherical phase equivalent diameter of the fine particles is preferably 0.1 μm or less, and preferably 0.06 μm.
The following are more preferable. Further, the fine particles are continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a salt capable of forming a silver salt having a solubility lower than that of silver chloride in a mixer provided in the vicinity of the reaction vessel, and immediately added to the reaction vessel. You can also
It is also possible to add it after preparing it in a batch manner beforehand in another container. The method using a sustained-release agent is described in JP-B 1-285.
942, Japanese Patent Application No. 5-58039.

The tabular grains in the present invention occupy 50% or more, preferably 60% or more, and more preferably 70% or more of the total projected area of silver halide grains. In both cases, the upper limit is 100%.

The high silver chloride tabular silver halide emulsion described above has a drawback that it has a large reciprocity law failure under high illuminance. As a means for solving this, the inventors have found that the inclusion of iron ions in silver halide grains is very effective.

The iron ion-providing compound used in the present invention is a divalent or trivalent iron ion-containing compound, preferably an iron salt or an iron complex salt which is water-soluble in the concentration range used in the present invention. Specifically, ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, Ferrous hydroxide, ferrous iodide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate, ferrous succinate, ferrous sulfate, thiocyanate Iron, ferrous nitrate, ferrous ammonium nitrate, basic ferric acetate, ferric albuminate, ferric ammonium acetate, ferric bromide, ferric chloride, ferric chlorate, citric acid Ferric acid, ferric fluoride, ferric formate, glycero-ferric phosphate, ferric hydroxide, ferric acid phosphate, ferric nitrate, ferric phosphate, pyrroline Ferric acid, sodium ferric pyrophosphate, ferric thiocyanate, ferric sulfate, ferric ammonium sulfate, ferric guanidine sulfate, ferric ammonium citrate, Potassium Sanshiano iron (II) acid, ferrous potassium preventor cyano ammine, ethylene dinitrilo tetraacetic acid ferric sodium, potassium hexacyanoferrate (III), tris chloride (dipyridyl) ferric,
Ferric bentacyanonitrosylferric acid, ferric hexarea chloride, especially hexacyanoferrate (II), hexacyanoferrate (III), ferric thiocyanate and ferric thiocyanate show remarkable effects. .

The above iron compound is preferably added during the formation of silver halide grains. As the addition position, even if it is evenly distributed in the particles, the initial, middle stage of particle formation,
Although it may be localized in the latter stage, it is preferably added in the latter stage of grain formation, that is, after 50%, more preferably 80% of the final grain size is formed.

The amount of iron ions providing compound added is, 5 × 10 ^{over 9} to 1 × 1 per mole of silver halide used
^0-3 mole and preferably 1 × 10 ^over 8 to 1 × 10 ^-4. If the amount is too small, the effect will not be obtained, and if it is too large, desensitization or fog will occur. In the present invention, iron ions are preferably doped in the silver halide grains.

In the present invention, another metal contained in Group VIII, that is, cobalt, nickel, iridium, palladium, platinum or the like may be used in combination. In the present invention, it is very effective to contain iron ions and to add an iridium compound during grain formation in order to improve the high illuminance reciprocity law failure. It is known that the addition of an iridium compound during grain formation remarkably improves the reciprocity law characteristics of a silver halide emulsion, and is an essential technique for silver iodobromide emulsions that are usually used in color photographic light-sensitive materials. ing. However, in the cubic emulsion generally used in high silver chloride emulsions, although the high illuminance reciprocity rule is improved by the doping of the iridium compound, its effect is smaller than that of the silver iodobromide emulsion and still remains. , High illumination reciprocity law failure was left. However, even in high silver chloride emulsions, the effect of the iridium compound is unexpectedly large in the tabular silver halide emulsion having the (100) plane in the principal plane of the present invention, and when it is applied to an emulsion containing iron ions, the It has been found that the high intensity reciprocity law is improved to a level close to that of silver bromide emulsion.

As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, an iridium halide (trivalent) compound, an iridium halide (tetravalent) compound, or an iridium complex salt having halogens, amines, oxalate, etc. as a ligand, for example, hexachloroiridium (trivalent) or (4 Valent) complex salt, hexaammineiridium (trivalent) or (tetravalent) complex salt, trioxalatoiridium (trivalent)
Alternatively, (tetravalent) complex salt and the like can be mentioned. In the present invention, among these compounds, trivalent and tetravalent compounds can be used in any combination. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the iridium compound, for example, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, fluoric acid, etc.). ), Or an alkali halide (eg KCl, NaCl, KBr, NaB
In addition to using a water-soluble iridium compound for which the method of adding r etc.), another silver halide grain which has been previously doped with iridium at the time of preparing the silver halide grain according to the present invention is added and dissolved. It is also possible. The total addition amount of the iridium compound added at the time of preparing the silver halide grains according to the present invention is 5 × 10 ⁻⁹ to 1 × 1 per 1 mol of finally formed silver halide.
^0-3 mol are suitable, preferably 1 × 10 ^over 8 to 1 × 1
It is ^0-4 mol, most preferably 1 × 10 ^-7 to 1 × 10 ^-4 mol.

The silver halide emulsion of the present invention is preferably subjected to gold sensitization and selenium sensitization.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. Speaking to a person skilled in the art as an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447, No. 33320069, No. 3408196, No. 34.
No. 08197, No. 3442653, No. 34206
70, 3591385, French Patent 269.
No. 3038, No. 2093209, Japanese Patent Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-192241 and 6
0-150046, 60-151637, 61
-246738, JP-A-3-42221, Japanese Patent Application No. 1-
287380, 1-250950, 1-254
441, 2-34090 and 2-110558.
No. 2-130976, No. 2-139183, No. 2-229300, and British Patent No. 255546,
No. 861984 and HE Spencer et al., Journal
of Photographic Science, Volume 31, 158-16
It is disclosed on page 9 (1983).

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or they are disclosed in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 4
It is 5 ° C or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example pH
The effect of the present invention can be obtained in a wide range from 4 to 9.
Selenium sensitization is more effective when performed in the presence of a silver halide solvent.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Particularly, in the silver halide emulsion of the present invention, it is the most preferred embodiment to carry out gold sensitization and sulfur sensitization together with selenium sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. The gold sensitization is usually carried out at a high temperature, preferably 40, by adding a gold sensitizer.
It is carried out by stirring the emulsion at a temperature of not lower than 0 ° C. for a certain time.
For sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. Other U.S. Pat. Nos. 1,574,944 and 2,410,68
No. 9, No. 2,278, 947, No. 2,728, 6
No. 68, No. 3,501,313, No. 3,656.
955 specifications, German Patent 1,422,869,
The sulfur sensitizers described in JP-B-56-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, size of silver halide grains, etc., but is 1 per mole of silver halide.
It is preferably from 10 ^-7 mol to 5 10 ^-4 mol.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to particularly limit the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. Alternatively, for example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer have a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

In the photographic light-sensitive material of the present invention, at least one silver halide emulsion layer provided on the support has a silver halide emulsion of the present invention of 30% or more, preferably 50% or more, more preferably. It is a silver halide photographic light-sensitive material containing 70% or more. Most preferably, all the light-sensitive silver halide emulsions are composed of the silver halide emulsion of the present invention. The silver halide emulsion of the present invention can be used in combination with a conventional silver iodobromide emulsion. For example, a method in which a silver iodobromide emulsion is used in a layer farther from the support and a silver halide emulsion of the present invention is used in a side closer to the support can be used.

About 3 silver halides other than the silver halide of the present invention contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less of silver iodide is preferable. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. However, it is preferable that the content of silver bromide contained in the entire light-sensitive material is low, and the content of silver iodide is also low.

The silver halide grains other than the silver halide of the present invention in the photographic emulsion include those having regular crystals such as cubes, octahedra and tetradecahedrons, and irregular grains such as spheres and plates. Those having different crystal forms, those having crystal defects such as twin planes, or a composite form thereof may be used.

The grain size of the silver halide other than the silver halide of the present invention may be fine grains of about 0.2 micron or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a single grain. It may be a dispersion emulsion.

The silver halide emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or other noble metal sensitization and reduction sensitization, and a process for producing a silver halide emulsion. Can be applied in any step.
As described above, it is most preferable to use a combination of gold, sulfur and selenium sensitization. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

During the manufacturing process of the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are silver halide, silver sulfide, and selenium.
It may form a sparingly soluble silver salt such as silver halide, or silver nitrate.
A silver salt which is easily soluble in water may be formed. Oxidation for silver
The agent may be an inorganic substance or an organic substance. inorganic
Oxidizing agents include ozone, hydrogen peroxide and its addition
Thing (eg NaBO₂・ H₂O₂・ 3H₂O, 2NaC
O₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2N
a₂SO_Four・ H₂O₂・ 2H₂O), peroxy acid salt
(Eg K₂S₂O₈, K₂C₂O₆, K₂P
₂O₈), A peroxy complex compound (for example, K₂[Ti
(O₂) C₂O _Four] ・ 3H₂O, 4K₂SO_Four・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na₃[VO
(O₂) (C₂H_Four)₂] ・ 6H₂O), permanganate
Salt (eg KMnO_Four), Chromates (eg, K₂
Cr₂O₇) Such as oxygenates, halogens such as iodine and bromine
Element, perhalogenate (eg potassium periodate),
High valent metal salts (eg, hexacyanoferric acid
Lithium) and thiosulfonate.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B) as examples. Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and Japanese Patent Publication No. 52-28660 can be used. One of the preferred compounds is JP-A-6
There are compounds described in 3-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifogging and stabilizing effects, in addition to controlling the crystal habit of grains, reducing the grain size, reducing the solubility of grains, controlling chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12,375, and JP-A-52. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-8-969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

The silver halide emulsion of the present invention is preferably spectrally sensitized with a cyanine dye, and the sensitizing dye is preferably added to the emulsion at the same time as the chemical sensitizer. More preferably, it is done in advance.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The above-mentioned various additives are used in the emulsion according to the present invention, but various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (December 1978) and Item 18716 (December 1979).
Mon) and Item 308119 (December 1989)
Month), and the relevant parts are summarized in Table A below. Table A Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer 23 pages 648 right column 866 2 Sensitivity enhancer page 648 right column 3 Spectral Sensitizer, pages 23 to 24, page 648, right column to 866 to 868, supersensitizer, page 649, right column 4, whitening agent, page 24, page 647, right column, page 868, 5 antifoggant, pages 24 to 25, page 649, right Column 868 to 870 Stabilizer 6 Light absorber, Page 25 to 26 Page 649 Right column to Page 873 Filter dye, Page 650 Left column UV absorber 7 Anti-stain agent Page 25 Right column Page 650 Left column to Right column Page 872 8 Dye image stabilizer Page 25 Page 650 Left column 872 Page 9 Hardener 26 Page 651 Left column 874-875 Page 10 Binder 26 Page 651 Left column 873-874 Page 11 Plasticizer, Lubricant 27 Page 650 Right Column 876 Page 12 Coating aid, Pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 13 Static page 27 Page 650 Right column 876 to 877 Anticorrosion agent 14 Matting agent 876 to 879 pages

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain diameter (average value of the equivalent circle diameters of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in Table 1 below.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with the formaldehyde described in No. 7 and No. 4,435,503.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,433,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. In addition, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD.
17643, Item VII-F and No. 307105, V
Patents described in the section II-F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator in an image form at the time of development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. R.K. D. N
o. 11449, 24241, JP-A-61-2012
47, etc., bleaching accelerator releasing couplers, US Pat. No. 4,555,477, etc., ligand releasing couplers, JP-A-63-75747, leuco dye releasing couplers, US Pat. , 774,181, and the like, which release a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2)
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (e.g. 2-ethylhexylbenzoate), dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-te).
rt-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene)
And so on. The auxiliary solvent has a boiling point of about 3
An organic solvent having a temperature of 0 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. To be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The photographic light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-2.
No. 72248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various photographic light-sensitive materials. Typical examples are color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

The light-sensitive material of the present invention comprises the emulsion layer-containing side.
The total thickness of all hydrophilic colloid layers is 28 μm or less
Preferably, it is preferably 23 μm or less, more preferably 18 μm.
m or less is more preferable, and 16 μm or less is particularly preferable.
Also, the film swelling speed T_1/2Is preferably 30 seconds or less, 20 seconds
The following is more preferable. The film thickness is adjusted to 25 ° C and 55% relative humidity
Means the film thickness measured under humidity (2 days), and the film swelling rate T
_1/2Measured according to methods known in the art
can do. For example, A Green (A. Gr
een) et al. Photographic Science
And Engineering (Photogr. Sci. E
ng. ), Vol. 19, No. 2, pages 124-129
By using the swellometer of
Can be set, T _1/2Is a color developer at 30 ° C for 3 minutes 15 seconds
90% of the maximum swollen film thickness reached when
Is defined as the time required to reach 1/2 of the saturated film thickness.
It

The film swelling speed T _1/2 can be adjusted by giving a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The light-sensitive material according to the present invention has the RD.
No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
β-methoxyethylaniline, 4-amino-3-methyl-N-
Methyl-N- (3-hydroxypropyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N -Ethyl-N
-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline,
4-Amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-methyl-N-
Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3
-Methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2
-Methylpropyl) aniline, 4-amino-3-methyl-N, N
-Bis (4-hydroxybutyl) aniline, 4-amino-3-
Methyl-N, N-bis (5-hydroxypentyl) aniline,
4-Amino-3-methyl-N- (5-hydroxypentyl) -N- (4-
Hydroxybutyl) aniline, 4-amino-3-methoxy-N
-Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-
3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl)
Examples thereof include aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol per liter of the color developing solution.
It is 0.1 mol.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate 5-sulfosalicylate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzoic acid salt. It generally contains a development inhibitor such as a thiazole or a mercapto compound or an antifoggant. In addition, hydroxylamine, diethylhydroxylamine, etc. may be used, if necessary.
Hydroxylamines represented by the general formula (I) of No. 144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers and competitive couplers. , Various chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Representative examples thereof include nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. . Of the above,
As the preservative, substituted hydroxylamine is most preferable, and among them, those having an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group as a substituent are preferable. The most preferable example is N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salt. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is JP-A-6
3-146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751.
JP-A-2-229146 and JP-A-3-18684.
No. 1, German Patent 3739610, European Patent 468325
Examples thereof include chelating agents described in No. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developer in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 3 for the light-sensitive material for photography.
It is 0 seconds to 3 minutes and 20 seconds. It is more preferably 40 seconds to 2 minutes and 30 seconds, and for printing materials, 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 40 seconds.

When the reversal process is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4
No. 121739, a bleaching agent including a 1,3-propylenediaminetetraacetic acid iron complex salt in the lower right column of the fourth page to the upper left column of the fourth page, and a carbamoyl-based bleaching agent described in JP-A-4-73647. Bleaching agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts. Japanese Patent Application No. 3-252775 including ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric acetic acid
Bleaching agent, bleaching agent described in EP-A-501479, bleaching agent described in JP-A-4-127145,
The ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of JP-A-3-144446 are preferably used. The organic aminocarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

These bleaching processes are preferably carried out immediately after color development, but in the case of reversal processes, they are generally carried out via a preparation bath (which may be a bleaching promoting bath). These preparation baths may contain an image stabilizer described later. In the present invention, in the desilvering bath, in addition to the bleaching agent, the above-mentioned JP-A-3-144446 (12)
Rehalogenating agents, pH buffers and known additives described on the page, aminopolycarboxylic acids, organic phosphonic acids and the like can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath.
For such a bleaching accelerator, for example, U.S. Pat. No. 3,893,858, German Patent No. 1,29.
No. 0,821, British Patent No. 1,138,842, Japanese Patent Laid-Open No. 53-95630, Research Disclosure No. 17129 (July 1978).
A compound having a mercapto group or a disulfide group described in JP-A-50-140129, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in US Pat. No. 3,706,561, and JP-A-58-16235. Iodide described in Japanese Patent Publication No. 2,748,430, and polyethylene oxides described in German Patent No. 2,748,430.
The polyamine compounds described in JP-A-8836 can be used. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. Particularly preferred are mercapto compounds as described in British Patent 1,138,842 and JP-A-2-190856.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is 2 to 5.5, and dibasic acid is particularly preferable. The organic acid is specifically acetic acid as a monobasic acid,
Propionic acid, hydroxyacetic acid and the like are preferable, and more preferable dibasic acids include succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, adipic acid and the like. Most preferred are succinic acid, glutaric acid and maleic acid.

The total desilvering time is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41 3rd edition (1982), Eastman Kodak Company, BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice is disclosed in JP-A-3-3384.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent Publication No. 7 can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The processing solution having the bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for preparing the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having a bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
e Society of MotionPicture and Tele-vision Engine
ers, 64, pp. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition, JP-A-57
-8,542 isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, sterilization and antifungal technology of microorganisms" edited by the Society for Hygiene Technology (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1986)
It is also possible to use the bactericide described in.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

Various surfactants can be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645 and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By treating the color negative film and the color paper with the same treatment liquid, the cost of the treatment machine can be reduced and the treatment can be simplified.

[0135]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of emulsion 1-A (silver iodobromide tabular emulsion)> Silver bromide tabular grains having a thickness of 0.1 μm and a circle-equivalent diameter of 0.7 μm were prepared as seed crystals. Seed crystals containing 6 g of Ag 1.0
Dissolve in liters of distilled water, pAg 8.2, pH 5
The temperature was controlled to 75 ° C., the temperature was kept at 75 ° C., and the mixture was vigorously stirred. continue,
Particle formation was performed by the following procedure.

(I) AgNO ₃ (141 g) aqueous solution and K
The Br aqueous solution was added while keeping the pAg at 8.4.

(Ii) The temperature was lowered to 55 ° C., and KI (4 g) aqueous solution was added at a constant flow rate.

(Iii) AgNO ₃ (63 g) aqueous solution and KB
The aqueous r solution was added while keeping the pAg at 8.9.

The mixture was cooled to 35 ° C., washed with water by a conventional flocculation method, added with 50 g of gelatin, pH 6.0, p.
Prepared to Ag 8.2. A tabular grain having an average sphere-equivalent diameter of 1.1 μm and an aspect ratio of 3.0 or more was used as a total projected area of 70
% Contained.

Gold-sulfur-selenium sensitization was performed as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
After adding xS-6, 9, and 10 in the amounts and ratios to obtain the desired spectral sensitivity, sodium thiosulfate 7.4 was added.
× 10 ^-6 mol / mol Ag, chloroauric acid 1.9 × 10 ^-6 mol / mol Ag, potassium thiocyanate 1.9 × 10 ^-3 mol / mol Ag, N, N-dimethylselenourea 1.5 × 1
Optimum chemical sensitization was carried out by adding 0 ^-6 mol / mol Ag.

<Emulsion 1-B (Preparation of silver chloride cubic emulsion)
> 32 g of lime-processed gelatin was added to 1000 ml of distilled water, dissolved at 40 ° C., and 3.3 g of sodium chloride was added to raise the temperature to 52 ° C. N, N'- in this solution
3.2 ml of dimethylimidazoline-2-thione (1% aqueous solution) was added. Subsequently, 32.0 g of silver nitrate was added to distilled water 2
A solution prepared by dissolving 11.0 g of sodium chloride in 200 ml of distilled water and a solution prepared by dissolving it in 00 ml was kept at 52 ° C. for 24 hours.
The above solution was added and mixed over a period of time (nucleation). Further, a solution prepared by dissolving 128 g of silver nitrate in 560 ml of distilled water and a solution prepared by dissolving 44 g of sodium chloride in 560 ml of distilled water were added and mixed for 20 minutes while maintaining 52 ° C. One minute after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, 2- [5-phenyl-2- {2- [5-phenyl-
3- (2-sulfonatoethyl) benzoxazoline-2
-Ylidenemethyl] -1-butenyl} -3-benzoxazolio] ethanesulfonic acid pyridinium salt 286.7
mg was added. After maintaining at 52 ° C. for 15 minutes, the temperature was lowered to 40 ° C., desalting and water washing were performed. Furthermore, after adding 90 g of lime-processed gelatin and adjusting the pAg to 7.2 using sodium chloride, the sensitizing dyes ExS-4, 5 and 6 described below were added in amounts and ratios so as to obtain the desired spectral sensitivity. After that, 2 mg of triethylthiourea was added for optimum chemical sensitization. A silver chloride cubic emulsion having an average equivalent spherical diameter of 1 μm was obtained.

<Emulsion 1-C (Preparation of silver chloride cubic emulsion {iridium-doped})> In the method of preparing emulsion 1-B,
After the nucleation, 2 × 10 with respect to the number of moles of silver in the entire grain
Emulsion 1-C was prepared in the same manner except that ^-6 mol of potassium hexachloroiridium (trivalent) was added.

<Emulsion 1-D (Preparation of silver chloride cubic emulsion {iron ion dope})> In the method for preparing emulsion 1-B, 2
Emulsion 1-C was prepared by the same method except that 5 mg of potassium hexacyanoferrate (divalent) trihydrate was added to the aqueous sodium chloride solution to be added for the second time.

[0146] <Emulsion 1-E (Preparation of cubic silver chloride emulsion {iridium and iron-doped})> in preparation of Emulsion 1-B, 2 × 10 number of moles of the whole particles after completion of nucleation of silver ^- Emulsion 1 was prepared by the same method except that ⁶ mol of potassium hexachloroiridium (trivalent) acid was added, and then 5 mg of potassium hexacyanoferrate (divalent) trihydrate was added to the aqueous sodium chloride solution which was added for the second time. -D was prepared.

<Preparation of Emulsion 1-F (silver chloride (100) tabular emulsion)> A reaction vessel containing 1200 ml of an aqueous gelatin solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3). ) And set the temperature to 4
While maintaining at 3 ° C, Ag-1 solution (100 mL of AgNO ₃
14 g, 0.8 g of the gelatin, 0.2 ml of HNO ₃ 1N solution
And X-1 solution (6.9 g of NaCl in 100 ml,
(Contains 0.8 g of the gelatin and 0.3 ml of 1N NaOH solution)
Was simultaneously mixed and added at a rate of 12 ml at 24 ml / min. After stirring for 2 minutes, Ag-2 solution (2 mL of AgNO ₃ in 100 ml) was added.
g, 0.8 g of the gelatin, and 0.2 ml of HNO ₃ 1N solution) and X-2 solution (1.4 g of KBr in 100 ml, 0.8 g of the gelatin and 0.2 mL of 1N NaOH solution).
Simultaneous addition of only 19 ml at ml / min. After stirring for 2 minutes, the Ag-1 solution and the X-1 solution were simultaneously mixed and added at 36 ml at 48 ml / min. NaCl-liquid (NaCl in 100 ml)
20 ml (including 10 g) was added to adjust the pH to 4.8 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature is 60 ℃
To pH 5.0 and then Ag at 130 mV silver potential
-3 liquid (containing 10 g of AgNO _{3 in} 100 ml) and X-
CD 3 liquid (containing 3.6 g of NaCl in 100 ml)
J. (controlled double jet) was added. The flow rate at the start of addition was 7 ml / min, and the flow rate was accelerated at 0.1 ml / min per minute, and 400 ml of Ag-3 solution was added.

Next, Ag having an average spherical phase equal diameter of 0.03 μm
The Br fine particles were added in an amount of 0.2 mol% per mol of silver halide and ripened for about 5 minutes to complete the halogen conversion.

Then, a precipitating agent was added, the temperature was lowered to 30 ° C., the mixture was washed with settling water, and an aqueous gelatin solution was added.
It was adjusted to H6.2 and pCl3.0. The silver halide emulsion thus prepared had an average equivalent spherical diameter of 1.2 μm, an average silver chloride content of 95.6 mol%, and contained 80% of the total projected area of tabular grains having an aspect ratio of 2.0 or more. It was This emulsion was gold-sulfur-selenium sensitized as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
xS-4, 5 and 6 are the amounts and amounts to obtain the desired spectral sensitivity.
Sodium thiosulfate 9.4 ×
10 ^-6Mol / mol Ag, chloroauric acid 3.3 × 10^-6Mol /
Molar Ag, potassium thiocyanate 2.9 × 10^-3Mol /
Molar Ag, N, N-dimethylselenourea 2.5 × 10
^-6Mol / mol Ag is added for optimum chemical sensitization.
It was

<Preparation of Emulsion 1-G (silver chloride (100) tabular emulsion {iron ion doped})> In the preparation method of Emulsion 1-F, after addition of Ag-1 to the number of moles of silver in the entire grain, Emulsion 1 was prepared in the same manner except that 2 × 10 ^-6 mol of potassium hexachloroiridium (trivalent) was added.
-G was prepared.

<Preparation of Emulsion 1-H (silver chloride (100) tabular emulsion {iron ion doped})> In the preparation method of Emulsion 1-F, potassium hexacyanoferrate (divalent) trihydrate was added to Solution X-3. Emulsion 1-H was prepared in the same manner except that 3 mg was added.
Was prepared.

<Preparation of Emulsion 1-I (Silver chloride (100) tabular emulsion {iridium and iron doped})> In the preparation method of Emulsion 1-F, after the addition of Ag-1 was completed, the number of moles of silver in the whole grain was determined. Emulsion 1 was prepared in the same manner except that 2 × 10 ^-6 mol of potassium hexachloroiridium (trivalent) acid was added, and further, 3 mg of potassium hexacyanoferrate (divalent) acid trihydrate was added to solution X-3. -I was prepared.

The following compounds were added to Emulsions 1-A to I prepared as described above, and a triacetyl cellulose film support having an undercoat layer was used together with a protective layer so that the amount of silver was 0.
The coating was carried out by the simultaneous extrusion method so as to obtain 5 g / m ² . (1) Emulsion layer-Emulsion ... Emulsion-Compound shown in Chemical formula 1 below

[0155]

[Chemical 1]

Tricresyl phosphate-stabilizer 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ・ Coating aid sodium dodecylbenzene sulfonate (2) Protective layer ・ Polymethylmethacrylate fine particles ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin Made sensitometer MARK
Using VII, a correction filter that makes the color temperature 4800 ° K, an ND filter that makes the exposure amount equal, and 1/100 second and 1/10000 through a yellow filter to block light of 500 nm or less.
Second sensitometric exposure was applied and the following color development processing was performed.

<Normal Processing for Silver Iodobromide> Sample 1-1 was subjected to the development processing shown below. The developing process used here was carried out at 38 ° C. under the following conditions.

1. Color development: 2 minutes 45 seconds 2. Bleach ... 6 minutes 30 seconds 3. Wash with water ... 3 minutes 15 seconds 4. Fixed arrival ... 6 minutes 30 seconds 5. Rinse with water 3 minutes 15 seconds 6. Stability: 3 minutes and 15 seconds The treatment composition used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β hydroxyethylamino) -2- Methyl-aniline sulfate 4.5 g Water was added to 1 liter Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Water was added 1 liter Fixation Liquid Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water added 1 liter Stabilized liquid Formalin 8.0 ml Water added 1 liter <for silver chloride Rapid Processing> For Samples 1-2 to 7 below It was developed by treatment to rapid type. (Processing step) Processing time Processing temperature Color development 45 seconds 38 ° C Bleach 30 seconds 38 ° C Fixing 45 seconds 38 ° C Stable (1) 20 seconds 38 ° C Stable (2) 20 seconds 38 ° C Stable (3) 20 seconds 38 ° C Dry 30 seconds 60 ° C. * Stability was a countercurrent system from (3) to (1).

The composition of the processing liquid is shown below. (Color developer) Ethylene dian tetraacetic acid 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid 2-sodium salt 0.3 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Disodium-N, N-bis (sulfonate ethyl) ) Hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added to 1.0 liter pH (with potassium hydroxide and sulfuric acid. Preparation) 10.00

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 liter pH (prepared with ammonia water and acetic acid) 7.4

(Stabilizing Solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 g Ethylenediamon tetraacetic acid disodium salt 0.05 g 1,2, 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added to 1.0 liter pH (prepared with ammonia water and acetic acid) 8.5

The rapid processing described above was performed on Sample 1-1, but Samples 1-2 to 7 containing the high silver chloride emulsion were used.
It was also confirmed that only a color density of 1/10 or less was obtained, and there was no suitability for rapid processing.

The density of the sample developed as described above was measured with a green filter.

The sensitivity is defined as the reciprocal of the exposure amount that gives a density of fog + 0.2, and the value of 1/100 second exposure of sample 1 is 1
It was expressed as a relative value of 00. In addition, the gradation of all samples is 2
It is within ± 0.2, and it is possible to compare the sensitivity as it is. Table 1 shows the sensitivity values of 1/100 second exposure and 1/10000 second exposure thus obtained.

[0166]

[Table 1]

According to Table 1, the silver chloride cube is suitable for rapid processing as compared with the tabular emulsion of silver iodobromide, although it is 1/10.
Both the 0-second sensitivity and the 1 / 10000-second sensitivity are significantly low, and it can be seen that the improvement of the sensitivity of the high-illuminance exposure is not so large even when the iridium compound or the iron ion is doped. On the other hand, by using a silver chloride (100) plate, 1/10
The 0 second sensitivity is improved, but the high illumination failure is still large. Therefore, when the iron ion doping or iridium and iron ion doping of the present invention is performed, surprisingly, the high illuminance sensitivity is greatly restored, and the sensitivity of 1/10000 second exposure is 1/100.
The sensitivity was 80% or more of the second sensitivity. The silver chloride tabular emulsion of the present invention is slightly inferior to the silver iodobromide emulsion in sensitivity and high-illuminance reciprocity law characteristics, but is at a sufficiently practicable level, and provides a light-sensitive material having an unobtainable characteristic of rapid processing suitability. be able to.

Example 2 <Preparation of Sample 2-1 (Comparative Example)> On the undercoated cellulose triacetate film support, each layer having the composition shown below was multilayer-coated to obtain high silver chloride (100). Sample 2-1 which is a multilayer color light-sensitive material composed of a tabular emulsion was prepared. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 2-1) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver chlorobromide emulsion A Silver 0.25 Silver chlorobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver chlorobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver chlorobromide emulsion E Silver 0.15 Silver chlorobromide emulsion F Silver 0.10 Silver chlorobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion J Silver 0.09 Silver chlorobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.2

14th layer (second protective layer) Silver chloride emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S- 1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0184]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) The tabular grains were prepared by the emulsion 1 of Example 1 of the present invention.
-4 is prepared.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) (0.5 g) were put in a 700 ml pot mill, and the dye was added. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0188]

[Chemical 2]

[0189]

[Chemical 3]

[0190]

[Chemical 4]

[0191]

[Chemical 5]

[0192]

[Chemical 6]

[0193]

[Chemical 7]

[0194]

[Chemical 8]

[0195]

[Chemical 9]

[0196]

[Chemical 10]

[0197]

[Chemical 11]

[0198]

[Chemical 12]

[0199]

[Chemical 13]

[0200]

[Chemical 14]

[0201]

[Chemical 15]

[0202]

[Chemical 16]

[0203]

[Chemical 17]

[0204]

[Chemical 18]

<Preparation of Sample 2-2 (Invention)> Sample 2-
In Preparation Method 1, all tabular grains were prepared by the method according to the preparation method of Emulsion 1-G of Example 1 and constituted by the high silver chloride tabular emulsion containing iridium and iron ion of the present invention. Sample 2-2 of the multi-layer color photographic light-sensitive material was prepared.

<Preparation of Sample 2-3 (Comparative Example)> Sample 2-
Sample No. 2-3 of the multilayer color photographic light-sensitive material constituted by the conventional silver iodobromide emulsion was prepared by changing the layer constitution and the silver halide emulsion as described in 1 above.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-8 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-8 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-8 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-9 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-9 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

[0221]

[Table 3]

In Table 3, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

The samples 2-1 to 3 prepared as described above were exposed and developed according to the method of Example 1 and the sensitivity was measured. However, Samples 2-1 and 2 are the rapid processing for silver chloride emulsion, Sample 2-3 is the normal processing for silver iodobromide,
Development was carried out at a developing time of 3'15 ". Samples 2-1 to 3-3 thus developed all had almost the same gradation in each color-sensitive layer and were evaluated only by the sensitivity. It was confirmed that the sample 2-3 was subjected to rapid processing, but only the color density of ⅕ or less of the samples 2-1 and 2-2 was obtained, and the conventional iodine smell was obtained. It was confirmed that the light-sensitive material composed of silver halide emulsion was not suitable for rapid processing, and the results are shown in Table 4.

[0224]

[Table 4]

Sample 2-2 of the present invention has a low sensitivity to a light-sensitive material using a conventional silver iodobromide tabular emulsion,
It is a light-sensitive material that has excellent suitability for rapid processing and has little deterioration in sensitivity even when exposed to high illuminance. Further, it can be seen that the high-illuminance reciprocity law can be significantly improved while maintaining the rapid processing suitability as compared with Sample 2-1 using the silver chloride tabular emulsion. Further, the sample 2-2 of the present invention has a 1/1 ratio to 1/100 second exposure in all density regions of all color-sensitive layers.
It was confirmed that the sensitivity of exposure for 0000 seconds was 80% or more, and good photographic properties were exhibited even when stroboscopic photography was performed.

Claims (7)

[Claims] 1. A tabular silver halide grain having two parallel major planes (100) planes, an aspect ratio of 2 or more, and an average silver chloride content of the grain of 60 mol% or more is halogenated. A silver halide photographic emulsion characterized by occupying 50% or more of the total projected area of silver grains and containing iron ions. 2. A silver halide photographic emulsion according to claim 1, which is prepared by adding an iridium compound during grain formation. 3. The silver halide photographic emulsion according to claim 1, which is chemically sensitized with a selenium sensitizer and a gold sensitizer. 4. A silver halide color photographic light-sensitive material comprising at least one photosensitive emulsion layer containing silver halide grains on a support, said photosensitive emulsion layer comprising two parallel main planes (100 ) Surface and has an aspect ratio of 2
The tabular silver halide grains having an average silver chloride content of 60 mol% or more contain a silver halide emulsion occupying 50% or more of the total projected area of the silver halide grains, and , 1/100 for 1/100 second exposure
A silver halide color photographic light-sensitive material having a sensitivity of 80% or more for 00 second exposure. 5. The silver halide color photographic light-sensitive material according to claim 4, wherein the silver halide emulsion contains iron ions. 6. The silver halide color photographic light-sensitive material according to claim 5, wherein the silver halide emulsion is prepared by adding an iridium compound during grain formation. 7. The silver halide color photograph according to claim 4, wherein the silver halide emulsion has been chemically sensitized with a selenium sensitizer and a gold sensitizer. Photosensitive material.