JP2001290234A - Photosensitive silver halide photographic emulsion and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive silver halide photographic emulsion excellent in color reproduction in photographing under a fluorescent lamp as a light source, having high sensitivity and less liable to fog in long-term storage. SOLUTION: The photosensitive silver halide photographic emulsion contains at least one compound of formula (1) and at least one compound of formula (2). In the formulae, R1, R2, R5 and R6 are each sulfoalkyl, at least one of R1 and R2 is sulfoethyl; R3 and R4 are each alkyl, alkoxy, aryl or Cl; and M1 and M2 are each a counter ion equilibrated with an electric charge.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion containing a sensitizing dye and a silver halide photographic light-sensitive material containing the emulsion. In addition, the present invention
The present invention relates to the use of a sensitizing dye in a blue-sensitive silver halide photographic emulsion.

[0002]

2. Description of the Related Art As a method of using a sensitizing dye in a blue-sensitive photographic emulsion, it is useful to have a dye absorption around 435 nm, which is the emission line wavelength of a fluorescent lamp, for color reproduction in photographing under a fluorescent lamp light source. Are known. International Congress on
Imaging Science (1998) .Volume1, P.219.440
It is known to use two dyes, dye 1 of oxathiocyanine shown below having an absorption maximum at nm and dye 2 of thiacyanine shown below having an absorption maximum at 470 nm. An oxathiocyanine dye having an absorption maximum at 440 nm is required as a sensitivity corresponding to the emission line wavelength of a fluorescent lamp. Dye 1

[0003]

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Dye 2

[0005]

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Dye 1 and Dye 2 as blue-sensitive photographic emulsions
The combination is useful for color reproduction in photographing under a fluorescent lamp light source, but has a problem in fog during long-term storage of the photographic material, and it has been desired to have high sensitivity and small fog during long-term storage.

[0007]

The present invention particularly relates to a silver halide photographic light-sensitive material for photography which is excellent in color reproduction in photography under a fluorescent light source, has high sensitivity, and has little fog during long-term storage. An object of the present invention is to provide a photosensitive silver halide photographic emulsion which can be used in a photosensitive material.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have been able to achieve the above object by combining a dye having a specific structure having an absorption maximum near 440 nm and 470 nm.

That is, the object of the present invention can be achieved by the following photosensitive silver halide photographic emulsion and silver halide photographic material.

(I) A photosensitive composition comprising at least one compound represented by the following general formula (1) and at least one compound represented by the following general formula (2): Silver halide photographic emulsion. General formula (1)

[0011]

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General formula (2)

[0013]

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In the formula, R1, R2, R5 and R6 independently represent a sulfoalkyl group, but one of R1 and R2 is a sulfoethyl group. R3 and R4 are, independently of each other,
Represents an alkyl group, an alkoxy group, an aryl group, or a chlorine atom. M1 and M2 each represent a charge balancing counter ion.

(II) The emulsion has a silver iodide content of 1 in the emulsion.
The photosensitive silver halide photographic emulsion according to (I), which is a silver iodobromide or silver chloroiodobromide emulsion of 0 mol% or less.

(III) The main plane parallel to which at least 50% of the total projected area of all silver halide grains in the emulsion is (111)
Silver iodobromide or silver chloroiodobromide tabular silver halide grains having an aspect ratio of 2 or more and containing 10 or more dislocation lines per grain. The photosensitive silver halide photographic emulsion described in (1).

(IV) The photosensitive silver halide photographic emulsion according to any one of (I) to (III), wherein the emulsion has been subjected to reduction sensitization. (V) The silver halide grains in the emulsion have a surface silver iodide content of 5 mol% or less (I) to (I).
V) The photosensitive silver halide photographic emulsion according to any one of the above items.

(VI) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide photographic emulsion layer is preferably composed of (I) to (V).
A silver halide photographic material comprising the photosensitive silver halide photographic emulsion described in any one of the above. (VII) The silver halide photographic material as described in (VI), wherein the silver halide photographic material is a color photographic material for photography.

Hereinafter, the present invention will be described in detail.

The general formulas (1) and (2) will be described in detail. Wherein R 1, R 2, R 5 and R 6 are independently of each other a sulfoalkyl group (eg, 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl), and one of R1 and R2 is a 2-sulfoethyl group. R3 and R4 each independently represent an alkyl group (eg, methyl, ethyl, propyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), an aryl group (eg, phenyl, p-tolyl, etc.), or a chlorine atom Represents

M1 and M2 each represent a charge balancing counter ion.
Typical ions include inorganic ions such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, ammonium ion). Ion, triethylammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion)
And other organic ions.

Preferred examples of the general formula (1) include the following compounds. 2-sulfoethyl as R1, 3-sulfopropyl as R2, phenyl as R3,
Compound of chlorine atom as R4. R1 is 3-sulfopropyl, R2 is 2-sulfoethyl, R3 is phenyl, R4
As a chlorine atom compound. 2-sulfoethyl as R1,
A compound of 3-sulfopropyl as R2, a chlorine atom as R3, and phenyl as R4. 3-sulfopropyl as R1,
Compounds of 2-sulfoethyl as R2, a chlorine atom as R3, and phenyl as R4.

The representative compounds of the general formula (1) useful in the present invention are shown below, but the present invention is not limited thereto.

[0024]

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[0025]

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Preferred examples of the general formula (2) include the following compounds. Compounds of 3-sulfopropyl as R5 and R6. Compounds of 3-sulfobutyl as R5 and R6. Compounds of 4-sulfobutyl as R5 and R6.

The representative compounds of the general formula (2) useful in the present invention are shown below, but the present invention is not limited thereto.

[0028]

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[0029]

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The total amount of the sensitizing dyes of formulas (1) and (2) of the present invention added to the tabular grain emulsion is from 1 × 10 ^-4 mol to 1 × 10 ⁴ mol per mol of silver halide. It is preferable to use it at ^-2 mol or less.

The sensitizing dye represented by the general formula (1) and the sensitizing dye represented by the general formula (2)
The mixing ratio of the sensitizing dyes is arbitrary, preferably 1: 9.
From 9: 1.

The sensitizing dye of the general formula (1) and the sensitizing dye of the general formula (2) can be added at any time during the emulsion preparation step from the grain formation step to coating. For example, it may be added before the completion of silver halide grain precipitation to start spectral sensitization, added at the time after the completion of chemical sensitization and before coating, and further disclosed in U.S. Pat.
It is also possible to add the sensitizing dye separately as taught in U.S. Pat. No. 25,666, that is, to add part of the sensitizing dye prior to chemical sensitization and add the remainder after chemical sensitization. It can be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756. Preferably, it is added after completion of grain formation and before completion of chemical sensitization. For example,
Performing prior to chemical sensitization as described in JP-A-58-113928, and U.S. Pat.
As described in US Pat. Nos. 8,969 and 4,225,666, spectral sensitization can be performed simultaneously with chemical sensitization by adding the compound at the same time as the chemical sensitizer.

The method of adding the sensitizing dye of the general formula (1) and the sensitizing dye of the general formula (2) may be mixing addition or separation addition, but is preferably separation addition. In the case of the separate addition, the order of addition may be either the sensitizing dye of the general formula (1) or the sensitizing dye of the general formula (2) first, and the addition interval is preferably 3 minutes or more.

The photosensitive silver halide emulsion of the present invention is preferably a silver iodobromide or silver chloroiodobromide emulsion having a silver iodide content of 10 mol% or less in the emulsion. Further, as the present invention, a silver iodobromide or silver chloroiodobromide tabular grain emulsion is preferable.

The tabular grains in the tabular grain emulsion preferably used in the present invention have a parallel main surface (111), a main surface having a main surface opposing the (111) main surface, and side surfaces connecting the main surfaces. The tabular grain emulsion preferably comprises silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. Regarding the silver iodide content, since the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 25% or less, the silver iodide content is preferably 20% by mol or less, more preferably 10% by mol or less (preferably , 0.5 mol% or more, more preferably 1.0 mol%
Is more preferable. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less.

Regardless of the silver iodide content, the variation coefficient of the distribution of the silver iodide content between grains is preferably 20% or less, particularly preferably 1% or less.
0% or less is preferable.

The tabular grain emulsion preferably used in the present invention preferably has a structure within the grains with respect to silver iodide distribution. In this case, the structure of the silver iodide distribution is a double structure,
There can be a double structure, a quadruple structure, or even more structures.

The tabular grain emulsion preferably used in the present invention accounts for at least 50% of the total projected area of all silver halide grains.
It is occupied by particles having an aspect ratio of 2 or more. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. Tabular grains are generally hexagonal when viewed from a direction perpendicular to the main surface,
Although it has a triangular or circular shape, the value obtained by dividing the diameter of a circle having an area equal to the projected area by the thickness is the aspect ratio. The shape of the tabular grains is preferably as high as the ratio of hexagons, and the ratio of the lengths of adjacent sides of the hexagons is 1: 2.
The following is preferred.

Since the effect of the present invention is more remarkable as the aspect ratio is higher, the tabular grain emulsion accounts for 50% or more of the total projected area by grains having an aspect ratio of 5 or more. More preferably, the aspect ratio is 8 or more, and particularly preferably, the aspect ratio is 10 or more. If the aspect ratio is too large, the variation coefficient of the particle size distribution described above tends to increase, so that the aspect ratio is usually preferably 50 or less.

In the present invention, the tabular grains in the preferred tabular grain emulsion have opposing (111) main surfaces and side surfaces connecting the main surfaces. At least one twin plane exists between the main surfaces. In the tabular grain emulsion of the present invention, usually 2
Two twin planes are observed. The interval between these twin planes is U
It can be less than 0.012μ as described in US Pat. No. 5,219,720. Furthermore, as described in JP-A-5-249585, the value obtained by dividing the distance between the (111) main surfaces by the twin plane spacing can be 15 or more.

It is extremely preferable that 75% or less of all side surfaces connecting the opposing (111) main surfaces of the tabular grain emulsion are composed of (111) surfaces. Here, that 75% or less of all the side surfaces are composed of the (111) plane means that a crystallographic plane other than the (111) plane exists at a ratio higher than 25% of the entire side surface. Usually the aspect is (1
Although it can be understood as the (00) plane, it may include other planes, that is, the (110) plane and a plane having a higher index.

The tabular grains in the present invention preferably have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F.
Hamilton, Photo. Sci. Eng. , 1
1, 57, (1967); Shiozawa, J .;
Soc. Photo. Sci. Japan, 35, 21
3, (1972), can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main surface can be obtained.

The number of dislocation lines is preferably 10 or more per grain on average. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

The dislocation lines can be introduced, for example, near the outer periphery of the tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main surfaces of the tabular grains. When dislocation lines are formed over the entire main surface, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main surface. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main surface, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to the outer periphery, the main surface, or a local position, or may be formed by combining these.
That is, they may be present simultaneously on the outer periphery and on the main surface.

In the present invention, dislocation lines are most preferably formed by adding a sparingly soluble silver halide emulsion to the above silver bromide, silver chlorobromide, silver chloroiodobromide or silver iodobromide tabular grain emulsion. Introduce. Here, the sparingly soluble silver halide emulsion means that it is more sparingly soluble than a tabular grain emulsion in a halogen composition, and is preferably a silver iodide fine grain emulsion.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the above-mentioned tabular grain emulsion. This step is essentially composed of two steps: a step of rapidly adding a silver iodide fine grain emulsion to a tabular grain emulsion, and a step of growing silver bromide or silver iodobromide to introduce dislocation lines. is there. These two steps may be performed completely separately, or each may be performed at the same time with repetition. It is preferably performed separately. The step of rapidly adding a silver iodide fine grain emulsion to the first tabular grain emulsion will be described.

When the silver iodide fine grain emulsion is rapidly added,
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred. There is no particular limitation on pBr when the silver iodide fine grain emulsion is added.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
And α-isomer or α-isomer-like structure as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before addition as described in US Pat. No. 5,400,479, or may be any of those which have been subjected to a usual washing step. In the present invention, those which have been subjected to the ordinary washing step are preferably used. Used. The silver iodide fine grain emulsion can be easily formed by the method described in the aforementioned US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the grains are formed while the pI value during grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. There are no particular restrictions on the temperature, pI, pH, type and concentration of protective colloid such as gelatin, the presence / absence, type and concentration of a silver halide solvent, but the size of the grains is 0.1 μm or less, more preferably 0.1 μm or less. 08 μm
The following are convenient for the present invention. Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size. Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.07 μm or less and 0.02 μm or less.
As described above, the variation coefficient of the particle size distribution is 18% or less.

After the above-described grain formation, the silver iodide fine grain emulsion is preferably subjected to ordinary washing described in US Pat. No. 2,614,929 or the like, and adjustment of the concentration of protective colloid agents such as pH, pI, and gelatin, and adjustment of the concentration of contained silver iodide. Will be pH 5
It is preferably at least 7 and at most 7. The pI value is preferably set to a pI value at which the solubility of silver iodide is at a minimum or a pI value higher than that value. As the protective colloid, ordinary gelatin having an average molecular weight of about 100,000 is preferably used.
Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver content in terms of silver atoms per kg of the emulsion is preferably 10 g or more and 100 g or more.
g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The addition amount of the silver iodide fine grain emulsion is preferably 1 mol% or more and 10 mol% or less in terms of silver amount based on the tabular grain emulsion. Most preferably, it is 2 mol% or more and 7 mol% or less. By selecting this addition amount, dislocation lines are preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved and added beforehand, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, an antifoaming agent described in Examples of US Pat. No. 5,275,929 is used.

After the silver iodide fine grain emulsion is rapidly added to the tabular grain emulsion, dislocation lines are introduced by growing silver bromide or silver iodobromide. The growth of silver bromide or silver iodobromide may be started before or simultaneously with the addition of the silver iodide fine grain emulsion, but preferably after the addition of the silver iodide fine grain emulsion, the growth of silver bromide or silver iodobromide is started. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is 3 seconds or more within 5 minutes. More preferably, it is within one minute. This time interval is preferably as short as possible, but preferably before the start of silver bromide or silver iodobromide growth.

The growth after the addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 3 mol% with respect to the layer. The amount of silver in the layer grown after the addition of the silver iodide fine grain emulsion is preferably 5 to 100 when the total silver content of the finished tabular grain emulsion is 100.
Not less than 50. Most preferably, it is 10 or more and 30 or less. Temperature, pH and pBr for forming this layer
Is not particularly limited, but the temperature is 40 ° C to 90 ° C, pH is
Is usually 2 or more and 9 or less. More preferably 50
The temperature ranges from 3 ° C to 80 ° C, and the pH ranges from 3 to 7.
Regarding pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer. Preferably, pBr at the beginning of the formation of the layer is 2.9 or less, and pBr at the end of the formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of the formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less. The dislocation lines in the present invention are preferably introduced by the above method.

The emulsion used in the present invention is preferably subjected to reduction sensitization. Reduction sensitization is a method in which a reduction sensitizer is added to silver halide, a pA called silver ripening.
a method of growing or ripening silver halide grains in a low pAg atmosphere of g1 to 7, pH 8 called high pH ripening
Either of the methods of growing or ripening under a high pH atmosphere of ~ 11 can be selected. In addition, two or more of these methods can be used in combination.

In particular, the method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amines and polyamines, hydrazine and its derivatives, paraphenylenediamine and its derivatives Derivatives, formamidinesulfinic acid (thiourea dioxide), silane compounds and borane compounds can be mentioned. These reduction sensitizers can be selected for use in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat.
Nos. 518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867. The method of use is described in JP-B-57-33572 and JP-B-58.
-1410 and the method disclosed in JP-A-57-179835 can be used. Stannous chloride, thiourea dioxide, dimethylamine borane (borane-
Dimethylamine complex), 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 an appropriate range is 10 ^-7 to 10 ^-2 mol 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.

When a reduction sensitizer is added, it is preferably carried out in the presence of a 3,5-disulfocatechol disodium salt compound.

Examples of the silver halide solvent usable in the present invention include US Pat. Nos. 3,271,157, 3,531,289 and 3,574,628, and JP-A-54-1019. (A) Organic thioethers described in JP-A-53-824 and JP-A-54-158917.
(B) thiourea derivatives described in JP-A Nos. 08-55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-4319, (d) imidazoles described in JP-A-54-100717, e) ammonia, (f) thiocyanate and the like.

Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferred amount is
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

As a method for changing the plane index of the side surface of the tabular grain emulsion, EP515894A1 or the like can be referred to. Also, polyalkylene oxide compounds described in US Pat. No. 5,252,453 can be used. US4680254, US4680255,
Surface index modifiers described in US Pat. No. 4,680,256 and US Pat. No. 4,684,607 can be used. Ordinary photographic spectral sensitizing dyes can also be used as modifiers having the same plane index as described above.

In the present invention, silver iodobromide or silver chloroiodobromide tabular grain emulsions can be prepared by various methods as long as the above requirements are satisfied. The preparation of a tabular grain emulsion usually comprises basically three steps of nucleation, ripening and growth. US47 in the nucleation process
Use of gelatin having low methionine content described in US Pat. No. 13320 and US Pat.
The nucleation at a high pBr described in No. 4014 and the nucleation in a short time described in JP-A-2-222940 are extremely effective in the nucleation step of the tabular grain emulsion of the present invention. US Pat. No. 5,254,453 in the aging step
In the presence of low-concentration bases as described in US
Performing at a high pH described in JP 5013641 may be effective in the ripening step of the tabular grain emulsion of the present invention. In the growth step, the growth is performed at a low temperature described in US Pat. No. 5,248,587, US Pat.
The use of silver iodide fine grains described in US Pat. No. 4,693,964 and US Pat. No. 4,693,964 is particularly effective in the step of growing a tabular grain emulsion of the present invention. Further, it is also preferable to use a silver bromide, silver iodobromide, silver chloroiodobromide fine grain emulsion to be added and ripened for growth. The fine grain emulsion can be supplied by using a stirring device described in JP-A-10-43570.

The silver iodide content on the grain surface of the emulsion (especially tabular grain emulsion) of the present invention is preferably 10 mol% or less (preferably 0.5 mol% or more, more preferably
1.0 mol% or more), and particularly preferably 5 mol% or less. The silver iodide content of the grain surface of the present invention is XPS (X
-Ray Photoelectron Spectr
oscopy). Regarding the principle of the XPS method used for analyzing the silver iodide content near the surface of silver halide grains, refer to Aihara et al., “Electron Spectroscopy” (Kyoritsu Library-16, published by Kyoritsu Shuppan, 1978). can do. The standard measurement method of XPS uses Mg-Kα as an excited X-ray, and photoelectrons (usually I-3d5) of iodine (I) and silver (Ag) emitted from silver halide in an appropriate sample form. / 2, Ag-3d5 / 2). To determine the iodine content, a calibration curve of the intensity ratio of photoelectrons of iodine (I) and silver (Ag) (intensity (I) / intensity (Ag)) using several kinds of standard samples whose iodine content is known. Can be determined from this calibration curve. In a silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like. A tabular grain emulsion having a silver iodide content of 10 mol% or less on the grain surface is defined as an emulsion grain contained in one emulsion.
A substance having a silver iodide content of 10 mol% or less when analyzed by PS. In this case, when two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as a centrifugal separation method or a filtration method and then analyze the same type of emulsion.

The tabular grain emulsion has a grain surface of 10 mol%
The effect of the present invention is remarkable to contain the following silver iodide, and it is more preferable that the surface contains 5 mol% or less and 1 mol% or more of silver iodide. The structure of the tabular grain emulsion is preferably a triple structure grain composed of, for example, silver bromide / silver iodobromide / silver bromide or a higher order structure.
Even though the boundary of silver iodide content between structures is clear,
Even if it changes continuously and gently, any may be sufficient. Normally, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the skirt is shifted toward the high silver iodide content. Such an X-ray diffraction profile is shown.

In the present invention, the silver iodide content of the layer inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the layer inside the surface is preferably 5%. Mol% or more, more preferably 7 mol% or more. The silver iodide content on the surface is preferably at most 5 mol%.

In the emulsion of the present invention, examples of the sensitizing dye which can be used in combination with the sensitizing dyes represented by formulas (1) and (2) of the present invention include, for example, JP-A-2-68539 No. 4 4th line from the lower right column of the page to the lower right column of the 8th page.
No. 58041, page 12, lower left column, line 8 to lower right column, line 19, and in addition, German Patent No. 929,080.
No. 2,493,748 and US Pat. No. 2,502.
No. 3,776, No. 2,519,001, No. 2,9
No. 12,329, No. 3,656,959, No. 3,
Nos. 672,897 and 4,025,349, British Patent No. 1,242,588, and JP-B-44-14030.

When the sensitizing dyes of the formulas (1) and (2) of the present invention are used in combination with other sensitizing dyes, the sensitizing dyes of the formulas (1) and (2) of the present invention are used in combination. 50% used
The above is preferred.

These sensitizing dyes may be used alone or in combination of two or more. The combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862 and 4,026,707, British Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
2-110618, 52-109,925, 5
No. 2-110618.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization in any step of the production process of a silver halide emulsion. Can be. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose, but the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization, alone or in combination, and is described by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 1977
Year, (THJames, The Theory of the Photographic Proc
ess, 4th ed, Macmillan, 1977), using active gelatin, as described on pages 67-76, and also in Research Disclosure, Volume 120, 1
April 974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_Two PdCl_Four , (NH_Four)_Two 
PdCl₆ , Na_Two PdCl_Four , (NH_Four)_Two PdCl
_Four , Li_Two PdCl_Four , Na_Two PdCl₆ Or K_Two P
dBr _Four Is preferred. Gold and palladium compounds
Is used in combination with thiocyanate or selenocyanate
Is preferred.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-4 mol, and more preferably 5 × 10 ^-7 to 1 × 10 ^-5 mol, per mol of silver halide. The preferred range of the palladium compound is from 5 × 10 ^-7 to 1 × 10 ^-3 . The preferred range of the thiocyan compound or selenocyan compound is from 1 × 10 ⁻⁶ to 5 × 10 ⁻² .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
10 ^-7 to 1 × 10 ^-4 mol, more preferably 5
X 10 ^-7 to 1 X 10 ^-5 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

In the present invention, the thiocyanate is preferably added before the addition of the above-mentioned spectral sensitizing dye and chemical sensitizer. Preferably, it is added after particle formation, more preferably after the end of the desalting step. Preferably, the thiocyanate is added even during chemical sensitization, so that the thiocyanate is added twice or more. As the thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and the like are used.

The thiocyanate is usually added after being dissolved in an aqueous solution or a water-soluble solvent. The addition amount is from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol per mol of silver halide,
More preferably, it is from 5 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
No. 16, P30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. As a water washing method, a noodle water washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, or an ion exchange method can be used. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core part, only the shell part, only the epitaxial part, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. For example, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ ,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH
₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ R
hCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent.
In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr) or alkali halides (eg KCl,
NaCl, KBr, NaBr) can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or a water-soluble alkali halide (eg, NaCl, KBr, KI) and added continuously during silver halide grain formation. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The emulsion of the present invention has a silver content during the manufacturing process.
It is preferable to use an oxidizing agent. However, the particle surface
Hole trapping silver nuclei must remain to some extent. Against silver
Oxidizers act on silver metal to convert it into silver ions.
Refers to a compound that has the action of Especially for silver halide grains
Extremely by-produced during formation and chemical sensitization
Compounds that convert small silver particles into silver ions are effective
It is. The silver ions generated here are silver halide,
Silver salts that are hardly soluble in water such as silver
Alternatively, a silver salt easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be inorganic or organic.
You may. Ozone and hydrogen peroxide as inorganic oxidants
And its adducts (eg, NaBO_Two ・ H_Two O_Two ・ 3
H_Two O, 2NaCO_Three ・ 3H_Two O_Two , Na_Four P_Two O₇ ・
2H_Two O_Two , 2Na_Two SO_Four ・ H_TwoO_Two ・ 2H_Two O),
Peroxy acid salt (for example, K_Two S_Two O₈ , K_Two C_Two O₆ ,
K_TwoP_Two O₈), Peroxy complex compounds (eg, K_Two 
[Ti (O_Two) C_Two O_Four ] 3H _Two O, 4K_Two SO_Four ・ T
i (O_Two) OH ・ SO_Four ・ 2H_Two O, Na_Three [VO (O_Two)
(C_Two H_Four)_Two ・ 6H_Two O], permanganate (for example,
KMnO_Four), Chromates (eg, K_Two Cr_Two O₇)Such
Oxyacid salts, halogen elements such as iodine and bromine,
Salts of high valent metals (e.g. potassium periodate)
(Eg potassium hexacyanoferrate) and thio
And sulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).

In the present invention, preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as tetraazaindenes and pentaazaindenes;
Many compounds can be added. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-212.
No. 932. Antifoggants and stabilizers are used at various times before, during and 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 according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

Techniques such as layer arrangement and the like which can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (published October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, Intermediate layer: page 61, 36-40
Row, 3. 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34; 7. Emulsion manufacturing method: page 62, lines 35 to 40; 8. Silver halide grain size distribution: page 62, lines 41 to 42, Tabular grains: page 62, 43
~ 46 lines, 10. Particle internal structure: page 62, line 47 to 53
Row, 11. 11. Emulsion latent image formation type: page 62, line 54 to page 63, line 5, Physical ripening and chemical ripening of emulsion: page 63, 6-9
Row, 13. 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: page 63, lines 14 to 31, 15. Non-light-sensitive emulsion:
Page 63, lines 32-43; Silver coated amount: 49 to 50 on page 63
Row, 17. Photographic additives: Research Disclosure (RD) Item 17643 (December 1978), Item
18716 (November 1979) and Item 30710
5 (November 1989). The following shows each item and its related description.

Types of Additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 866 2 Sensitivity enhancer page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column 866-868 Color sensitizer ~ page 649 right column 4 Brightener 4 page 647 page right column 868 page 5 Antifoggant, 24-25 page 649 right column 868-870 page stabilizer 6 light absorber, 25-26 649 Page right column 873 page Filter dye, ~ 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left column to right column 872 8 Dye image stabilizer 25 page 650 left column 872 9 Hardener 26 Page 651 Left column 874-875 10 Binder Page 26 651 Left column 873-874 11 Plasticizer, lubricant 27 Page 650 Right column 876 Page 12 Coating aid, 26-27 Page 650 Right column 875- Page 876 Surfactant 13 Static page 27 Page 650 right column 876-877 Inhibitor 14 Matting agent 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 24. Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70 pages 34-38, 48. Use for film with lens: page 70, lines 39-41.

A bleaching solution containing a 2-pyridinecarboxylic acid or a 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate described in EP-A-602600 is also available. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain the compound in a range of 2 mol / liter (hereinafter, liter is also referred to as “L”).

The silver halide color photographic light-sensitive material preferably used in the present invention is usually provided in the order of red-sensitive layer, green-sensitive layer and blue-sensitive layer from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,470 or GB 923,045
It is preferred that the two layers of the high-sensitivity emulsion layer and the low-sensitivity emulsion layer are arranged so that the sensitivity gradually decreases toward the support. Also, Japanese Patent Application Laid-Open Nos.
As described in 200350, 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near 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 (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH.

As described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL. Also, JP-A-56
As described in -25738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
Donor layer (CL) with a multilayer effect that has a different spectral sensitivity distribution from the main photosensitive layers such as BL, GL, and RL described in JP-A-63-89850.
Is preferably disposed adjacent to or close to the main photosensitive layer.

The light-sensitive material used in the present invention preferably uses non-light-sensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%,
If necessary, it may contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm.
02-0.2 μm is more preferred.

The fine silver halide grains can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The amount of silver applied to the light-sensitive material used in the present invention
Is 10.0 g / m^TwoThe following is preferred, 6.0 g / m ^TwoThe following are the most preferred
New

Various dye-forming couplers can be used in the light-sensitive material used in the present invention, and the following couplers are particularly preferable.

Yellow coupler: Formula (I) of EP 502,424A
, (II); EP 513,496A of formula (1)
, (2) (especially Y-28 on page 18); EP 5
A coupler of the formula (I) in claim 1 of Claim 68,037A; U
S Couplers represented by general formula (I) in column 1, lines 45 to 55 of 5,066,576; general formula in paragraph 0008 of JP-A-4-274425
Couplers represented by (I); couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); EP 447,96
Coupler represented by formula (Y) on page 4 of 9A1 (especially Y-1 (17
), Y-54 (p. 41)); columns 7, 36-58 of US 4,476,219.
Couplers represented by formulas (II) to (IV) in the row (especially II-17,
19 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 45
6,257 (A-4) -63 (p.134), (A-4) -73, -75 (139
Pp. 486,965, M-4, -6 (page 26), M-7 (page 27); EP 57
M-45 of 1,959A (page 19); (M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631.

Cyan coupler: CX-1 described in JP-A-4-204843,
3, 4, 5, 11, 12, 14, 15 (pages 14 to 16);
5 C-7, 10 (page 35), 34, 35 (page 37), (I-1), (I-1
7) (pages 42 to 43); JP-A-6-67385, the general formula (Ia) of claim 1
Or a coupler represented by (Ib).

Polymer coupler: P-1 described in JP-A-2-44345
, P-5 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred.

Couplers for correcting unnecessary absorption of a coloring dye are represented by the formulas (CI), (CII) and (C) described on page 5 of EP 456,257A1.
(CIII), yellow colored cyan couplers represented by (CIV) (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249) described in the EP,
EX-7 (page 251), Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US 4,833,069, US
4,837,136 (2) (column 8), a colorless masking coupler of the formula (A) in claim 1 of WO 92/11575 (especially 36
-Exemplified compounds on page 45).

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Formulas (I), (II), (III) and (I) described on page 11 of EP 378,236A1.
V) (especially T-101 (page 30), T-104 (31
), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-
158 (page 58)), the compound represented by the formula (I) described on page 7 of EP 436,938A2 (particularly D-49 (page 51)) and the compound of the formula of EP 568,037A.
Compounds represented by (1) (especially (23) (p. 11)), EP440,195
Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of A2 (especially I- (1) on page 29); Bleaching accelerator releasing compounds: EP 310,125 on page 5 of A2 Compounds represented by formulas (I) and (I ') (especially (60) and (61) on page 61) and compounds represented by formula (I) in claim 1 of JP-A-6-59411 (especially (7) (Page 7); Ligand releasing compound: LIG- described in claim 1 of US Pat. No. 4,555,478.
A compound represented by X (especially, a compound in rows 21 to 41 of column 12); a leuco dye releasing compound: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; a fluorescent dye releasing compound: US 4,774,1
Compound represented by COUP-DYE of Claim 1 of 81 (especially compounds 1 to 11 of columns 7 to 10); Development accelerator or fogging agent releasing compound: Formulas (1) and (2) of column 3 of US 4,656,123
, (3) (especially (I-22) of column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2; a compound which releases a group which becomes a dye only after leaving: US 4,857,447, the compound of formula (I) of claim 1 (especially column 25-
36 Y-1 to Y-19).

As the additives other than the coupler, the following are preferable.

Dispersion medium for oil-soluble organic compound: JP-A-62-215
272 P-3s, 5, 16, 19, 25, 30, 42, 49, 54, 55, 6
6, 81, 85, 86, 93 (pages 140 to 144); latex for impregnation of oil-soluble organic compound: latex as described in US 4,199,363;
Oxidized developing agent scavenger: a compound of the formula (I) in column 2, lines 54 to 62 of US 4,978,606 (especially I-,
(1), (2), (6), (12) (columns 4 to 5), US Pat. No. 4,923,787, column 2, lines 5 to 10 (especially compound 1 (column 3);
Anti-stain agent: Formula (I) on page 30 to 33 of page 4 of EP 298321A
(III), especially I-47, 72, III-1, 27 (pages 24 to 48); anti-fading agent: A-6, 7, 20, 21, 23, 24, 25, 2 of EP 298321A
6, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (69-118
P.), U.S. 5,122,444, columns 25-38, II-1 to III-23,
In particular, III-10, I-1 to III-4 on pages 8 to 12 of EP471347A,
In particular, II-2, A-1 to 48 of columns 32 to 40 of US 5,139,931, especially A-39, 42; a material for reducing the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, page 5 to 24 I -1 to II-15,
In particular I-46; Formalin Scavenger: EP 477932A 24
SCV-1 to 28 on page 29, especially SCV-8; hardener: JP-A 1-2148
Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1, 4, 6, 8, 14, U.S. Pat.
4) a compound (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, especially H-14, a compound described in claim 1 of US 3,325,287; a development inhibitor precursor: JP 62
-168139, P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US 5,019,492, especially columns 28 and 29; preservatives and fungicides: columns 3 to 15 of US 4,923,790 I-1 to III-4
3, especially II-1, 9, 10, 18, III-25; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially
I-1, 60, (2), (13), compounds 1-65, especially 36, in columns 25-32 of US 4,952,483: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; Dyes: JP-A-3-156450 a-1 to b-20 on pages 15 to 18, especially a-1, 12,
18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1
Pp. 33-55 of EP 445627A, FI-1 to F-II-43, especially FI
-11, F-II-8, III-1 to 36 on pages 17 to 28 of EP 457153A,
In particular, III-1 and III, 8-88 Dye-1 to 124 of WO 88/04794
Compounds 1-2 on page 6-11 of EP 319999A
2, especially compound 1, compounds D-1 to 87 represented by formulas (1) to (3) of EP 519306A (pages 3 to 28), formula of US 4,268,622
Compounds 1 to 22 represented by (I) (columns 3 to 10), US
Compounds (1) to (31) represented by the formula (I) of 4,923,788 (columns 2 to 9); UV absorbers: compounds (18b) to (18r) represented by the formula (1) of JP-A-46-3335 , 101-427 (pages 6-9),
Compounds (3) to (66) (10) represented by the formula (I) in EP 520938A
To page 44) and the compound HBT-1 to 10 (14
Page), compounds of formula (1) of EP 521823A
(31) (columns 2-9).

The silver halide photographic light-sensitive material of the present invention is preferably a color light-sensitive material for photographing (a color negative film for general use or a movie, a color reversal film for slides or a television, etc.). Further, the present invention can be applied to various color photosensitive materials such as color paper, color positive film and color reversal paper.
It is also suitable for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784.

Suitable supports which can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. No. 307105, page 879. It is described in.

The photosensitive material preferably used in the present invention includes:
The total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is
It is preferably 28 μm or less, more preferably 23 μm or less.
More preferably, it is 18 μm or less, more preferably 16 μm or less.
preferable. The film swelling speed T _1/2 Is preferably 30 seconds or less
And 20 seconds or less are more preferable. T_1/2 Is a color developer
Maximum swelling film thickness of 90 reached at 30 ° C for 3 minutes 15 seconds
% As the saturated film thickness, until the film thickness reaches half
Is defined as the time in The film thickness is controlled at 25 ° C and relative humidity 55%.
The film thickness measured under (2 days) means T_1/2 Is A
Photographic Saie from A. Green
And Engineering (Photogr. Sci. En
g.), serometer of the type described in Vol. 19, pages 2, 124-129.
-(Swelling meter). T_1/2 
Add hardener to gelatin as binder
Or by changing the aging conditions after application.
Can be adjusted. The swelling ratio is preferably 150-400%.
Good. The swelling ratio is the maximum swelling under the conditions described above.
From the film thickness, measured by the formula: (maximum swollen film thickness-film thickness) / film thickness
Can be calculated.

The photosensitive material preferably used in the present invention includes:
On the side opposite to the side with the emulsion layer, the total dry film thickness is 2 μm
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) of about 20 μm. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The photosensitive material preferably used in the present invention includes:
No. 17643, pages 28 to 29; No. 18716, page 651 left to right columns; and No. 307105, pages 880 to 881.

Next, a processing solution for a color negative film will be described. The color developing solution includes ninth of JP-A-4-121739.
The compounds described in page 1, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, 2-methyl-4- [N-ethyl-N-
(2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (4-hydroxy Butyl) amino] aniline is preferred.

These color developing agents are preferably used in the range of 0.01 to 0.08 mol per liter of the color developing solution.
In particular, it is preferably used in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher of the color developing solution preferably contains a color developing agent having a concentration of 1.1 to 3 times, more preferably 1.3 to 2.5 times the concentration.

As a preservative of the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in an amount of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, and particularly preferably in the range of 0.02 to 0.04 mol. The replenisher is preferably used at a concentration 1.1 to 3 times the above.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a higher value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishment amount of the color developing solution is preferably from 80 to 1300 ml per m ² of the photographic material (hereinafter also referred to as “mL”), but from the viewpoint of reducing the environmental pollution load.
A smaller amount is preferable, and specifically 80 to 600 mL, and more preferably 80 to 400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: Bromide ion concentration in the color developing replenisher (mol / L) A: Target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when the bromide ion concentration is set to a high value, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

The processing solution having bleaching ability is described in JP-A-4-1255.
58, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied. The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include those described in JP-A-5-72694 and JP-A-5-73312, and in particular, 1,3-diaminopropanetetraacetic acid, and Ferric complex salts of the compounds of Example 1 on page 7 of US Pat.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability.
It is preferred to design with a mole to 0.15 mole. When the bleaching solution is a bleaching solution, 0.2 mol / L
Preferably, it contains 1 mol of bromide, especially 0.3 mol.
It is preferred to contain up to 0.8 mole.

The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.

CR = CT × (V1 + V2) / V1 + CP CR: Concentration of the component in the replenishing solution CT: Concentration of the component in the mother liquor (processing tank liquid) CP: Concentration of the component consumed during the processing V1: 1m amount of replenisher having bleaching ability for ² of the photosensitive material (mL) V2: amount carried from previous bath by the photographic material of 1 m ² (m
L).

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish the bleaching replenisher of mL, especially 80 to
It is preferable to replenish 500 mL, more preferably 100-300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied.

Particularly, in order to improve the fixing speed and the preservability, a processing solution having a fixing ability by using the compounds represented by the general formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but it is more preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .

In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309590.

The replenishing amount of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 mL, preferably from 150 to 700 mL, particularly preferably from 200 to 600 mL, per m ² of the light-sensitive material.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement in preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, see JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, page 16.
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizing solution described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
m is preferably from ² per 80~1000mL, in particular 100 ~500mL,
Further, 150 to 300 mL is a preferable range from the viewpoints of both securing the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a replenishing amount, thiabendazole,
1,2-benzisothiazoline-3-one, 5-chloro-
It is preferable to use water that has been deionized with a known fungicide such as 2-methylisothiazolin-3-one, an antibiotic such as gentamicin, or an ion exchange resin. It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, JP-A-3-53246, JP-A-355542, JP-A-3-12144
8, it is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment according to 3-126030, the reverse osmosis membrane in this case,
Preferably, it is a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing solution disclosed in the Japan Institute of Invention and Innovation Technical Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

[0151] In the container for storing these treating agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm and are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, a processing solution for a color reversal film, which is preferable as the light-sensitive material of the present invention, will be described.

Regarding the processing for the color reversal film,
Aztec Co., Ltd. No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to line 24
It is described in detail in line 2 of the page, and any of the contents can be preferably applied. In processing color reversal films, the image stabilizer is contained in a conditioning or final bath. Such image stabilizers include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

A preferred color reversal film treating agent containing the above contents is Eastman Kodak E-6.
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

The color photographic light-sensitive material used in the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXI manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film).
Films processed into the AP system format such as AA, NEXIA F, and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned.
These AP system cartridge films are used by being mounted on a camera for an AP system such as an Epion series (Epion 300Z or the like) manufactured by Fuji Film. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

The film photographed by the above is printed through the following steps in the minilab system.

(1) Acceptance (exposed cartridge film received from customer) (2) Detach step (transfer film from cartridge to intermediate cartridge for development step) (3) Film development (4) Retouch step (development (Return the used negative film to the original cartridge.) (5) Printing (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipping (collating cartridges and index prints with ID numbers and shipping with prints).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B /
FP362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP
1258AR / PP1258A / PP728AR / PP728A; recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII
It is. For Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer
LP-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, you can load the developed AP system cartridge film directly into the Aladdin 1000, or transfer image information of negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also transfer digital information directly to a floppy disk, Zip disk, or via a CD writer.
You can also output to CD-R.

On the other hand, at home, the developed AP system cartridge film is transferred to a photo player AP manufactured by FUJIFILM.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0162]

Examples of the present invention will be described below. However, it is not limited to this embodiment.

(Example 1) Gelatin-1 to gelatin-4 used as a dispersion medium in the following emulsion preparation are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein gelatin using bovine bone as a raw material. -NH ₂ in the gelatin
No chemical modification of the group.

Gelatin-2: In an aqueous solution of gelatin-1,
A gelatin obtained by adding phthalic anhydride at 50 ° C. and a pH of 9.0 to cause a chemical reaction, removing residual phthalic acid, and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-3: In an aqueous solution of gelatin-1,
Gelatin obtained by adding succinic anhydride under conditions of 50 ° C. and pH 9.0 to cause a chemical reaction, removing remaining succinic acid, and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-4: Gelatin obtained by reducing the molecular weight of gelatin-1 by the action of an enzyme to make the average molecular weight 15,000, inactivating the enzyme, and drying. No chemical modification of -NH ₂ groups in the gelatin.

After the above gelatin-1 to gelatin-4 were all deionized, the pH of a 5% aqueous solution at 35 ° C. was 6.
Adjustment was made so as to be zero.

(Preparation of Emulsion A-1) KBr was added at 1.0
g, aqueous solution 1300 containing 1.1 g of the above gelatin-4
The mL was kept at 35 ° C. and stirred. (Preparation of 1st liquid) Ag
-1 (containing 4.9g of AgNO ₃ in 100mL) solution and 38 mL, (containing 5.2g of KBr in 100mL) X-1 aqueous solution 29 mL, and G-1 aqueous solution (10
(0 mL contains 8.0 g of the above gelatin-4)
5 mL was added by a triple jet method at a constant flow rate over 30 seconds (addition 1). Thereafter, 6.5 g of KBr was added, and the temperature was raised to 75 ° C. After an aging step for 12 minutes after the temperature was raised, 300 mL of an aqueous G-2 solution (containing 12.7 g of the above gelatin-1 in 100 mL) was added. Further, 2.1 g of disodium 4,5-dihydroxy-1,3-disulfonate monohydrate and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute to effect reduction sensitization.

Next, an aqueous solution of Ag-2 (Ag in 100 mL)
157 mL of NO ₃ (containing 22.1 g) and an aqueous solution of X-2 (containing 15.5 g of KBr in 100 mL) were added by the double jet method over 39.2 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be 4 times, and the aqueous solution of X-2 was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 6.80 (addition 2). Next, an aqueous solution of Ag-3 (containing 32.0 g of AgNO ₃ in 100 mL) 32
9 mL and an X-3 aqueous solution (21.5 mL of KBr in 100 mL).
g, KI 1.8 g) by the double jet method.
4. Added over 2 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 6.80. This was done to keep (addition 3). Further, an Ag-4 aqueous solution (100 mL of AgN
O ₃ and containing 32.0 g) and 156 mL, and the X-4 solution (containing 22.4g of KBr in 100mL) was added over 17 minutes at the double jet method. At this time, Ag
The aqueous solution of X-4 was added at a constant flow rate, and the aqueous solution of X-4 was added at a pAg of 7.52 for the bulk emulsion solution in the reaction vessel.
(Addition 4).

Thereafter, 0.0025 g of sodium benzenethiosulfonate and 125 mL of an aqueous G-3 solution (containing 12.0 g of the above gelatin-1 in 100 mL) were added to 1
It was added sequentially at intervals of minutes. Then KBr4
3.7 g of pAg of the bulk emulsion solution in the reaction vessel
Was adjusted to 9.00, and then an AgI fine particle emulsion (13.0 g of AgI fine particles having an average particle size of 0.047 μm in 100 g) was used.
110.9 g), and 2 minutes later, A
249 mL of g-4 aqueous solution and X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added to the first 3.3.
The pAg of the bulk emulsion solution in the reaction
The addition was carried out so as to maintain the pAg of the bulk emulsion solution in the reaction vessel to be finally 8.4 (addition 5). Thereafter, desalting is carried out by a usual flocculation method, and then water, NaOH and the above-mentioned gelatin-1 are added while stirring, and
It adjusted so that it might become pH6.4 and pAg8.6 at 6 degreeC.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The grain volume weighted average of the aspect ratio is 1.5, silver halide grains having an aspect ratio of less than 2 account for 50% or more of the total projected area, the average AgI content is 3.94 mol%, and the The main surface was composed of tabular silver halide grains having a (111) plane, and the AgI content of the silver halide grains was 2.5 mol%.

Subsequently, the following operations were performed for the addition of the sensitizing dye and the chemical sensitization step. The first sensitizing dye was added, and after 5 minutes, the second sensitizing dye was added (the first and second sensitizing dyes and the time intervals between additions are shown in the table of Examples). continue,
After potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea are sequentially added and optimally sensitized, 1- (3-carboxyphenyl)
Chemical sensitization was terminated by adding -5-mercaptotetrazole and 4- (3-carboxyphenyl) -3-mercapto-1,2,4-triazole. In the emulsion A-1, the chemical sensitization was optimally performed when the addition amount of each of the first and second sensitizing dyes was 1.6 × 10 ⁻⁴ mol per mol of silver halide.

(Preparation of Emulsion B-1) Emulsion A-1
Emulsion B-1 was prepared under the following modification with respect to the preparation condition of

(1) The addition time of the aqueous solution of Ag-2 of (addition 2) was 33.3 with the addition amount kept at 157 mL.
Change the addition flow rate to 6 minutes. The flow rate acceleration is such that the final flow rate is 3.4 times the initial flow rate. Also, X-
2 The addition of the aqueous solution depends on the pA of the bulk emulsion solution in the reaction vessel.
Perform so that g maintains 7.20.

(2) Addition of the aqueous solution of Ag-3 of (addition 3) was carried out for 63.times.
Change the addition flow rate to 6 minutes. The flow rate acceleration is such that the final flow rate is 1.6 times the initial flow rate. Also, X-
(3) The addition of the aqueous solution depends on the pA of the bulk emulsion solution in the reaction vessel.
Perform so that g maintains 7.20. The resulting emulsion had a sphere equivalent diameter of 0.99 μm, an aspect ratio of 2.1 in grain volume weighted average, and silver halide grains having an aspect ratio of 2.1 or more accounted for 50% or more of the total projected area, The average value of the AgI content is 3.94 mol%, and the parallel main surface is (111).
The silver halide grains were composed of tabular silver halide grains, and the AgI content of the silver halide grains was 2.5 mol%. In addition,
In the emulsion B-1, the chemical sensitization was optimally performed when the amounts of the first and second sensitizing dyes were 1.7 × 10 ⁻⁴ mol per mol of silver halide.

(Preparation of Emulsion C-1) Emulsion A-1
Emulsion C-1 was prepared under the following conditions, with the following changes.

(1) The gelatin in the aqueous solution G-2 added after a ripening step of 12 minutes after the temperature was raised to 75 ° C. was changed from the above-mentioned gelatin-1 to gelatin-3.

(2) In the addition of the Ag-2 aqueous solution in (Addition 2), the addition flow rate was changed so that the addition time was 14 minutes with the addition amount kept at 157 mL. The flow rate acceleration is such that the final flow rate is 3.4 times the initial flow rate. The addition of the X-2 aqueous solution is performed so that the pAg of the bulk emulsion solution in the reaction vessel is maintained at 8.30.

(3) The addition flow rate of the aqueous solution Ag-3 of (addition 3) was changed so that the addition time was 27 minutes while the addition amount was 329 mL. The flow rate acceleration is such that the final flow rate is 1.6 times the initial flow rate. The addition of the X-3 aqueous solution is performed so that the pAg of the bulk emulsion solution in the reaction vessel is maintained at 8.30. The resulting emulsion had a sphere equivalent diameter of 0.99 μm and an aspect ratio of 1
2.5, the silver halide grains having an aspect ratio of 12.5 or more account for 50% or more of the total projected area, the average value of the AgI content is 3.94 mol%, and the parallel main surface is (111).
The silver halide grains were composed of tabular silver halide grains, and the AgI content of the silver halide grains was 2.9 mol%. In addition,
In the emulsion C-1, the chemical sensitization was optimally performed when the addition amount of the first and second sensitizing dyes was 3.3 × 10 ⁻⁴ mol per mol of silver halide.

(Preparation of Emulsion C-2) Emulsion C-1
Emulsion C-2 was prepared under the following conditions, except that the emulsion C-2 was prepared as follows.

(1) AgI added two minutes before (addition 5)
The added amount of the fine grain emulsion is 133.0 g.

(2) The addition time of the Ag-4 aqueous solution of (Addition 5) was reduced to 8.37 minutes without changing the flow rate.
The addition time of the X-4 aqueous solution is reduced to 2.67 minutes. The resulting emulsion had a sphere equivalent diameter of 0.99 μm, an average particle volume weighted average of aspect ratio of 12.5, and an aspect ratio of 1
Tabular silver halide grains in which 2.5 or more silver halide grains are 50% or more of the total projected area, the average value of the AgI content is 5.94 mol%, and the parallel main surface is the (111) plane. And the AgI content of the silver halide grains was 9.5.
Mole%. The emulsion C-2 was optimally chemically sensitized when the amounts of the first and second sensitizing dyes were 3.3 × 10 ⁻⁴ mol per mol of silver halide.

(Preparation of Emulsion C-3) Emulsion C-1
Emulsion C-3 was prepared under the following modification with respect to the preparation conditions of

(1) AgI added 2 minutes before (addition 5)
The added amount of the fine grain emulsion is 167.0 g.

(2) The addition time of the Ag-4 aqueous solution of (Addition 5) was reduced to 8.03 minutes without changing the flow rate,
The addition time of the X-4 aqueous solution is reduced to 2.32 minutes. The resulting emulsion had a sphere equivalent diameter of 0.99 μm, an average particle volume weighted average of aspect ratio of 12.5, and an aspect ratio of 1
Tabular silver halide grains in which 2.5 or more silver halide grains account for 50% or more of the total projected area, an average AgI content of 7.01 mol%, and a parallel main surface of a (111) plane. And the AgI content on the surface of the silver halide grains measured by XPS was 10.9 mol%. The emulsion C-3 was optimally chemically sensitized when the amounts of the first and second sensitizing dyes were 3.3 × 10 ⁻⁴ mol per mol of silver halide.

Emulsions A-1, B-1, C-1 to C-
Observation of No. 3 at a liquid nitrogen temperature using a transmission electron microscope of 400 kV revealed that all the grains had 10 or more dislocation lines in the fringe portion of the tabular grains.

Each emulsion was dissolved in a cellulose triacetate film support provided with an undercoat layer at 40 ° C. for 30 minutes with lapse of time, and the above emulsion A was coated under the coating conditions shown in Table 1 below.
-1, B-1 to B-3 and C-1 to C-3 were applied.

[0189]

[Table 1]

Samples were prepared by changing the emulsion to be coated as shown in the following table.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was carried out for 1/100 second through a continuous wedge, and the density of the developed sample was measured with a green filter to determine the photographic sensitivity and the fog density before long-term storage. The sensitivity was represented by a relative value of the reciprocal of the exposure necessary to reach the density of fog density plus 0.2. To evaluate the storage fog of the photosensitive material, the sample was stored for 14 days at 40 ° C. and a relative humidity of 60%, exposed for 1/100 second, and the density of the developed sample was measured using a green filter. The fog density after storage was determined, and the difference in fog density before and after storage was determined.

The development was performed by an automatic processor F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-362B.

The processing steps and the composition of the processing solution are shown below.

(Processing Step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C. 15 mL 10.3 L Bleaching 50 seconds 38 ° C. 5 mL 3.6 L Fixing (1) 50 seconds 38 ° C.-3 6.6L fixing (2) 50 seconds 38 ° C 7.5mL 3.6L stable (1) 30 seconds 38 ° C-1.9L stable (2) 20 seconds 38 ° C-1.9L stable (3) 20 seconds 38 ° C 30mL 1 0.9 L drying 1 minute 30 seconds 60 ° C

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 mL of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. Further, the color developing solution is replenished by dividing the replenishing solution of the color developing solution (A) and the replenishing solution of the color developing solution (B) of the following formula into 12 mL and 3 mL, respectively, corresponding to the replenishing amount, to a total of 15 mL. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 mL per 1.1 m of 35 mm width photosensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process.

The composition of the processing liquid is shown below.

(Color developing solution (A)) [Tank solution] [Replenisher] Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Disodium -N, N-bis (sulfonatoethyl) hydroxylamine 10.0 g 15.0 g sodium sulfite 4.0 g 9.0 g hydroxylamine sulfate 2.0 g-potassium bromide 1.4 g-diethylene glycol 10.0 g 17.0 g ethylene Urea 3.0 g 5.5 g 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 g 11.4 g Potassium carbonate 39 g 59 g Add water 1.0 L 1. 0L pH (prepared with sulfuric acid and KOH) 10.05 10.50 The above tank solution is as follows (color developing solution B)) showing the composition after mixing.

(Color developing solution (B)) [Tank solution] [Replenisher] Hydroxylamine sulfate 2.0 g 4.0 g Water was added to 1.0 L 1.0 L pH (prepared with sulfuric acid and KOH) 10.05 4.0 The above tank liquid shows the composition after the mixing of the (color developing solution (A)).

(Bleach solution) [Tank solution] [Replenisher] 1,3-diaminopropanetetraacetic acid ferric ammonium salt-hydrate 120 g 180 g ammonium bromide 50 g 70 g succinic acid 30 g 50 g maleic acid 40 g 60 g imidazole 20 g 30 g water 1.0 L 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 4.6 4.0.

(Fixing solution) Tank solution Replenisher Ammonium thiosulfate (750 g / L) 280 mL 1000 mL Ammonium bisulfite aqueous solution (72%) 20 g 80 g Imidazole 5 g 45 g 1-Mercapto-2- (N, N-dimethylaminoethyl) -tetrazole 1 g 3 g Ethylenediaminetetraacetic acid 8 g 12 g Water was added to add 1 L 1 L pH (adjusted with aqueous ammonia and nitric acid) 7.0 7.0.

(Stabilizing solution) [Common to tank solution and replenisher] Sodium p-toluenesulfinate 0.03 g p-nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 0.4 g Disodium ethylenediaminetetraacetate 0.05 g 1 1,2,4-Triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2-benzoisothiazolin-3-one 0.10 g 0 L pH 8.5.

The results of evaluation by the above method are shown in the following table. The sensitivity was represented by a relative value of the reciprocal of the exposure necessary to reach the density of fog density plus 0.2.

[0203]

[Table 2]

Comparative compound 1

[0205]

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Comparative compound 2

[0207]

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From the results in Table 2, the following matters are clear. It can be seen that when both the first sensitizing dye and the second sensitizing dye use the compound of the present invention, the photographic sensitivity is good, and the fog density increase during long-term storage is small and good. Furthermore,
Aspect ratio = 12.5 AgI content in emulsion was 2.
As is clear from the results of the emulsions of 9 mol%, 9.5 mol%, and 10.9 mol%, the AgI content was 2.9 mol%, 9.9 mol%, and 9.9 mol%.
It can be seen that, when the compound of the present invention is used for both the first sensitizing dye and the second sensitizing dye at 5 mol%, the increase in fog density during long-term storage is even smaller and good. As is apparent from the results of the 1.5 emulsion, 2.1 emulsion, and 12.5 emulsion, the first sensitizing dye and the second sensitizing dye in the 2.1 emulsion and the 12.5 emulsion. Both show that the use of the compound of the present invention further improves the fog density during long-term storage and is favorable.

As the first sensitizing dye, compounds 1-2 and 1-
3, 1-4, 1-5, 1-6, 1-7, 1-8
Compounds 2-2, 2-3, 2-4, 2-
In the case of using No. 5, good results were obtained similarly to the results of the present invention shown in Table 2.

Example 2 Silver halide emulsions D to R were prepared by the following production method.

(Production Method of Emulsion D) Phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000.
7g and 42.2L of an aqueous solution containing 31.7g of KBr were added to 35
The mixture was kept at 0 ° C and stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ , 221.5 g of KBr, 1583 mL of an aqueous solution containing 52.7 g of gelatin-4 of Example 1
Was added by the double jet method over 1 minute. Immediately after the completion of the addition, 52.8 g of KBr was added, and ₃ g of AgNO ₃ was added.
2485 mL of an aqueous solution containing 98.2 g and 291 of KBr.
2581 mL of an aqueous solution containing 1 g was added over 2 minutes by the double jet method. Immediately after completion of the addition, KBr, 44.
8 g were added. Thereafter, the temperature was raised to 40 ° C. and the product was aged.
After ripening, 923 g of gelatin-2 of Example 1 and KB
Then, 79.2 g of r was added, and 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 10 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.90. After washing with water, gelatin-1 of Example 1 was added, and the pH was adjusted to 5.7 and pA
g, 8.8, mass in terms of silver per kg of emulsion 131.
The seed emulsion was adjusted to 8 g and the gelatin weight to 64.1 g. 46 g of gelatin-2 of Example 1 and 1.7 g of KBr
Was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the above seed emulsion, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. 5.5 pH by the addition of H ₂ SO ₄
And then adjusted to an aqueous solution 6 containing 7.0 g of AgNO _3.
7.6 mL and the KBr aqueous solution were added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 105.6 g of AgNO ₃ , 328 mL
And KBr aqueous solution were added by a double jet method over a period of 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI having a particle size of 0.037μ was used.
The fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.60. 4 AgNO ₃
121.3 mL of an aqueous solution containing 5.6 g and an aqueous KBr solution were added by a double jet method over 22 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. The temperature was raised to 82 ° C., and KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.80. Then, 6.33 g of the above-described AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition was completed, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the initial 5 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80 with an aqueous KBr solution. After washing with water, Example 1
Gelatin-1 at 40 ° C., pH 5.8, pA
g, adjusted to 8.7, 2,4-bis (hydroxyamino) -6-diethylamino-1,3,5-triazine was added, and the temperature was raised to 60 ° C. Adding a first sensitizing dye,
After 5 minutes, the second sensitizing dye was added (the first and second sensitizing dyes were added in equimolar amounts). Subsequently, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N
-Dimethylselenourea was added for optimal chemical sensitization.
At the end of chemical sensitization, compound 2 and compound 3 were added.
The amount of each of the first and second sensitizing dyes was 2.2 × 10
^-4 mol. Here, optimal chemical sensitization means that each compound is selected from the range of 10 ^-1 to 10 ^-8 mol per mol of silver halide. Emulsion D had an aspect ratio grain volume weighted average of 11.5, and silver halide grains having an aspect ratio of 11.5 or more accounted for 50% or more of the total projected area. Comparative compound 1

[0212]

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Comparative compound 2

[0214]

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[0215]

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[0216]

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(Preparation of Emulsion E) Gelatin of Example 1
4 containing 0.96 g of KBr and 0.9 g of KBr
2 mL was kept at 40 ° C. and stirred vigorously. AgNO ₃ ,
37.5 mL of an aqueous solution containing 1.49 g and 1.05 KBr
37.5 mL of an aqueous solution containing g was added over 30 seconds by the double jet method. After addition of 1.2 g of KBr, 75 ° C
And aged. After ripening, the gelatin of Example 1
3g was added and the pH was adjusted to 7. 6 mg of thiourea dioxide were added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added by double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate.
At this time, the pAg of the bulk emulsion solution in the reaction vessel was increased to 8.1.
It was kept at 5. Aqueous solution 4 containing 110.2 g of AgNO ₃
40.6 mL and KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 5.1 times the initial flow rate, and 30
Added over minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was adjusted to have a silver iodide content of 15.8 mol%.
And the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. Ag
96.5 mL of an aqueous solution containing 24.1 g of NO ₃ and an aqueous KBr solution were added by a double jet method over 3 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., an aqueous KBr solution was added, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.80. The above AgI fine grain emulsion was converted to a KI mass of 8.5.
g was added. Immediately after the addition was completed, 228 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 5 minutes. At this time,
It was adjusted with an aqueous KBr solution so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.75. Emulsion D
Washed with water in almost the same manner as described above and chemically sensitized. The amount of each of the first and second sensitizing dyes is 3.5 × 10 ^-4 mol. Emulsion E had an aspect ratio of 1 grain volume weighted average.
The ratio was 3.6, and silver halide grains having an aspect ratio of 13.6 or more accounted for 50% or more of the total projected area.

(Preparation of Emulsion F) Gelatin of Example 1
2 containing 1.02 g of KBr and 0.9 g of KBr
The mL was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.
42 mL of an aqueous solution containing 47 g and 42 mL of an aqueous solution containing 3.16 g of KBr were added by a double jet method over 9 seconds. After adding 2.6 g of KBr, the temperature was raised to 63 ° C. to ripen. After ripening, gelatin-3 of Example 1 was added.
2 g and 18.5 g of NaCl were added. pH 7.2
After adjusting to, dimethylamine borane, 8 mg, was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and KBr
The final flow rate of the aqueous solution is double jet method and the final flow rate is 3.
It was added so as to be 8 times. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.65. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over a period of 24 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was added.
Was kept at 8.50. After 10.7 mL of a 1N aqueous solution of potassium thiocyanate was added, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.05. KB
r aqueous solution to add pA of the bulk emulsion solution in the reaction vessel.
g was adjusted to 9.25. 6.4 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition was completed, 404 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 45 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.65. The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized. The amount of each of the first and second sensitizing dyes was 4.7 ×
10 ^-4 mol. Emulsion F described above had a particle volume weighted average of 13.5 in aspect ratio and an aspect ratio of 13.3.
Five or more silver halide grains accounted for 50% or more of the total projected area.

(Preparation of Emulsion G) In the preparation of Emulsion F, the amount of AgNO ₃ added during nucleation was changed to 2.3 times. Then, 404 mL of an aqueous solution containing 57 g of the final AgNO ₃
Was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 6.85 with an aqueous KBr solution. Other than that, it was prepared almost in the same manner as Emulsion F.
The amount of each of the first and second sensitizing dyes was 6.2 × 10
^-4 mol. In the above emulsion G, the grain volume weighted average value of the aspect ratio was 11.2, and silver halide grains having an aspect ratio of 11.2 or more accounted for 50% or more of the entire projected area.

(Production Method of Emulsion H) Emulsion C-1 of Example 1
Before the chemical sensitization, the compound of the present invention (the presence or absence of addition is shown in the table of Examples) is added as necessary, and a sensitizing dye added at the beginning of the chemical sensitization Ex
The combination was changed to a combination of S-4, ExS-5 and ExS-6. Other than that, it was prepared almost in the same manner as Emulsion C-3. The amount of each sensitizing dye used was 5.50 × 10 ⁻⁴ mol of ExS-4 and 1 mol of ExS− per mol of silver halide.
5 was 1.30 × 10 ^-4 mol, ExS-6 was 4.65 × 1
0 ^-5 mol.

[0221]

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(Preparation of Emulsion I) Gelatin of Example 1
4 containing 0.75 g of KBr and 0.9 g of KBr
0 mL was kept at 39 ° C., the pH was adjusted to 1.8, and the mixture was stirred vigorously. An aqueous solution containing 1.85 g of AgNO ₃ and 1.5 m
An aqueous KBr solution containing ol% KI was added over 16 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After aging,
20 g of gelatin-2 of Example 1 was added. pH 5.
After adjusting to 9, KBr, 2.9 g was added. AgN
288 mL of an aqueous solution containing 27.4 g of O ₃ and an aqueous KBr solution were added over 53 minutes by a double jet method. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%,
The pAg of the bulk emulsion solution in the reaction vessel was kept at 9.40. After adding 2.5 g of KBr, AgNO ₃ ,
An aqueous solution containing 87.7 g and an aqueous KBr solution were added by a double jet method over 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the above Ag
The I fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.50. AgNO
₃ , 132 mL of an aqueous solution containing 41.8 g and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.15. pH 7.
Adjusted to 3 and added 1 mg of thiourea dioxide. KB
After adjusting the pAg of the bulk emulsion solution in the reaction vessel to 9.50 by adding r.g.
5.73 g in terms of mass was added. Immediately after the addition,
609 mL of an aqueous solution containing 66.4 g of gNO ₃ was added over 10 minutes. During the initial 6 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50 with an aqueous KBr solution. After washing with water, gelatin-1 of Example 1 was added and added.
PH was adjusted to 6.5, pAg, and 8.2 at ℃. It was chemically sensitized in the same manner as in Emulsion H. The amount of the sensitizing dye used was 1.08 × 10 ⁻³ for ExS-4 per mol of silver halide.
Mol, ExS-5 is 2.56 × 10 ^-4 mol, ExS-6
Is 9.16 × 10 ^-5 mol.

(Preparation of Emulsion J) Gelatin of Example 1
4 in 0.70 g, KBr, 0.9 g, KI, 0.175
g, modified silicone oil 0.2 used in the preparation of Emulsion D
g of an aqueous solution containing 33 g at 33 ° C.
8 and stirred vigorously. An aqueous solution containing 1.8 g of AgNO ₃ and an aqueous KBr solution containing 3.2 mol% of KI were added over 9 seconds by a double jet method. At this time, K
The excess concentration of Br was kept constant. The temperature was raised to 62 ° C. and ripened. After ripening, 27.8 g of gelatin-3 of Example 1 was used.
Was added. After adjusting the pH to 6.3, KBr, 2.9
g was added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, the aqueous solution of gelatin-4, the aqueous solution of AgNO _{3, and the} aqueous solution of KI of Example 1 were used in JP
The AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing immediately before addition in another chamber having a magnetic coupling induction type stirrer described in No. 3570 so that the silver iodide content becomes 4.1 mol%. And the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.15. After adding 2.6 g of KBr, 8 g of AgNO ₃ was added.
An aqueous solution containing 7.7 g and an aqueous KBr solution were added over 49 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing immediately before the addition was accelerated simultaneously so that the silver iodide content became 7.9 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was 9.30. Kept. After adding 1 mg of thiourea dioxide, AgNO
₃ , 132 mL of an aqueous solution containing 41.8 g and a KBr aqueous solution were added over 20 minutes by a double jet method. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 7.90. After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.70.
5.73 g of the AgI fine grain emulsion used in the preparation of Emulsion D was added in terms of KI mass. Immediately after the addition is completed, AgNO
₃ 321 mL of an aqueous solution containing 66.4 g was added over 4 minutes. During the first two minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.70 with an aqueous KBr solution. Emulsion H
Washed with water in almost the same manner as described above and chemically sensitized. The amount of the sensitizing dye used was 1.25 × 10 ^-3 mol for ExS- ^{4 and} 2.85 × 10 ^{-4 for} ExS-5 per mol of silver halide.
Mol, ExS-6 is 3.29 × 10 ^-5 mol.

(Preparation of Emulsion K) Gelatin of Example 1
1 in 17.8 g, KBr, 6.2 g, KI, 0.46 g
The aqueous solution containing was kept at 45 ° C. and stirred vigorously. AgNO
_Three , Containing an aqueous solution containing 11.85 g and 3.8 g of KBr
The aqueous solution was added by the double jet method over 45 seconds.
After the temperature was raised to 63 ° C, 24.1 g of gelatin-1 of Example 1 was used.
Added and aged. After aging, AgNO_Three 133.
Aqueous solution containing 4 g and KBr aqueous solution by double jet method
20 minutes so that the final flow rate is 2.6 times the initial flow rate
Added over. At this time, the bulk emulsion solution in the reaction vessel
Was maintained at 7.60. 10 minutes after the start of addition
K_Two IrCl₆ Was added. 7 g of NaCl
After the addition, AgNO_ThreeSolution containing 45.6 g of KB and KB
Add the aqueous solution by the double jet method over 12 minutes
Was. At this time, the pAg of the bulk emulsion solution in the reaction vessel was
It was kept at 6.90. Also, yellow for 6 minutes from the start of addition
100 mL of an aqueous solution containing 29 mg of blood salt was added. KBr
Was added and Ag used in the preparation of Emulsion D was added.
6.3 g of I fine grain emulsion was added in terms of KI mass. Addition
AgNO immediately after finishing_Three With an aqueous solution containing 42.7 g of
Add KBr aqueous solution over 11 minutes by double jet method
did. At this time, the pAg of the bulk emulsion solution in the reaction vessel was
It was kept at 6.90. Rinse almost the same as Emulsion H,
I felt it. The amount of the sensitizing dye used was 1 silver halide
ExS-4 is 5.79 × 10 ^-FourMol, ExS
−5 is 1.32 × 10^-FourMol, ExS-6 1.52 ×
10^-FiveIs a mole.

(Preparation of Emulsion L) Emulsion K was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C. The amount of the sensitizing dye used was 9.66 × 10 ⁻⁴ mol of ExS-4 per mol of silver halide, and
xS-5 is 2.20 × 10 ^-4 mol, ExS-6 is 2.5
4 × 10 ^-5 mol.

(Preparation of Emulsion M) Gelatin of Example 1
Aqueous solution 120 containing 0.75 g of KBr, 0.9 g of KBr
0 mL was kept at 39 ° C., the pH was adjusted to 1.8, and the mixture was stirred vigorously. Aqueous solution containing 0.34 g of AgNO ₃ and 1.5 m
An aqueous KBr solution containing ol% KI was added over 16 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After aging,
20 g of the gelatin-2 of Example 1 was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. After adding 3 mg of thiourea dioxide, AgNO ₃ , 2
288 mL of an aqueous solution containing 8.8 g and an aqueous KBr solution were added by a double jet method over 58 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.40. K
After adding 2.5 g of Br, 87.7 g of AgNO ₃
And KBr aqueous solution are accelerated by double jet method so that the final flow rate is 1.2 times the initial flow rate.
Added over 9 minutes. At this time, the above AgI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.50. AgNO ₃ , 41.
132 mL of an aqueous solution containing 8 g and an aqueous KBr solution were added over 27 minutes by the double jet method. The addition of the KBr aqueous solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 8.15. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50, and then the above AgI fine grain emulsion was converted to 5.7 in terms of KI mass.
3 g were added. Immediately after the addition, AgNO ₃ , 66.
609 mL of an aqueous solution containing 4 g was added over 11 minutes.
During the initial 6 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50 with an aqueous KBr solution. After washing with water, gelatin was added, the pH was adjusted to 6.5, pAg and 8.2 at 40 ° C, and the temperature was raised to 56 ° C. The sensitizing dyes ExS-4 and ExS-7 are added, followed by potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added and ripened for optimal chemical sensitization. At the end of the chemical sensitization, compound 3 and compound 4 were added. The amount of the sensitizing dye used was ExS per mole of silver halide.
-4 is 3.69 × 10 ^-4 mol, ExS-7 is 8.19 ×
10 ^-4 mol.

[0227]

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(Preparation of Emulsion N) Gelatin of Example 1
2, an aqueous solution 1200 containing 0.38 g of KBr and 0.9 g of KBr
The mL was kept at 60 ° C., the pH was adjusted to 2 and stirred vigorously.
An aqueous solution containing 1.03 g of AgNO ₃ and 0.8% of KBr
An aqueous solution containing 8 g and 0.09 g of KI was added by a double jet method over 30 seconds. After completion of the ripening, 12.8 g of gelatin-3 of Example 1 was added. After adjusting the pH to 5.9, KBr, 2.99 g, NaCl, 6.2 g
Was added. An aqueous solution containing 27.3 g of AgNO ₃ 60.
7 mL and an aqueous KBr solution were added by the double jet method over 39 minutes. At this time, p of the bulk emulsion solution in the reaction vessel
Ag was kept at 9.05. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over a period of 46 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, A used in the preparation of Emulsion D
The gI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 6.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.05. After adding 1.5 mg of thiourea dioxide, AgNO ₃ , 41.
132 mL of an aqueous solution containing 8 g and an aqueous KBr solution were added over 16 minutes by a double jet method. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 7.70. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.80. 6.2 g of the above AgI fine grain emulsion in terms of KI mass
Was added. Immediately after the addition, AgNO ₃ , 88.5 g
Was added over 10 minutes. The pAg of the bulk emulsion solution in the reaction vessel at the end of the addition is 7.4.
It was adjusted to 0 by adding an aqueous KBr solution. After washing with water, gelatin-1 of Example 1 was added and pH was adjusted at 40 ° C.
It adjusted to 6.5, pAg, 8.2, and heated up to 58 degreeC.
After addition of the sensitizing dyes ExS-8, ExS-9 and ExS-10, K ₂ IrCl ₆ , potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, compound 3 and compound 4 were added.

[0229]

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(Preparation of Emulsion O) In the preparation of Emulsion N, the amount of AgNO ₃ added at the time of nucleation was 1.96 g.
, The amount of KBr to 1.67 g, and the amount of KI to 0.172 g.
g, and the temperature at the time of chemical sensitization is 58 ° C.
Was changed to 61 ° C. Other than that, it was prepared in substantially the same manner as in emulsion N.

(Preparation of Emulsion P) Gelatin of Example 1
4, an aqueous solution 1200 containing 4.9 g of KBr and 5.3 g of KBr
The mL was kept at 40 ° C. and stirred vigorously. AgNO ₃ , 8.7
27 mL of an aqueous solution containing 5 g and 36 mL of an aqueous solution containing 6.45 g of KBr were added over 1 minute by the double jet method. After the temperature was raised to 75 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2 minutes. NH ₄ NO ₃ ,
After sequentially adding 26 g, 1 N, NaOH and 56 mL,
Matured. After aging, the pH was adjusted to 4.8. AgN
438 mL of an aqueous solution containing 141 g of O ₃ and 10 mL of KBr.
458 mL of an aqueous solution containing 2.6 g was added by a double jet method so that the final flow rate was four times the initial flow rate. After cooling to 55 ° C., an aqueous solution 240 containing 7.1 g of AgNO ₃
An aqueous solution containing 6.46 g of mL and KI was added over 5 minutes by the double jet method. After adding 7.1 g of KBr,
Sodium benzenethiosulfonate, 4mg and K ₂ Ir
0.05 mg of Cl ₆ was added. AgNO ₃ , 57.2
g of an aqueous solution containing 177 mL of KBr and 223 mL of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. The emulsion was washed with water in almost the same manner as in Emulsion N and chemically sensitized.

(Preparation of Emulsions Q and R) Emulsions K and L were prepared almost in the same manner. However, the chemical sensitization was carried out in substantially the same manner as for emulsion O.

Table 3 summarizes the characteristic values of the silver halide emulsion. The surface iodine content can be determined by XPS as follows. The sample was cooled to −115 ° C. in a vacuum of 6.7 × 10 ⁻⁴ Pa or less, and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA, and Ag3d5 / 2, Br3d, I3d5 / Two electrons were measured, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content on the surface was determined from the intensity ratio. In the silver halide grains of the emulsions D to R, dislocation lines as described in JP-A-3-237450 were observed using a high-pressure electron microscope. Emulsions S and T are non-photosensitive silver iodobromide emulsions.

[0234]

[Table 3]

[0235]

[Table 4]

1) Support The support used in this example was:
Created by the following method.

100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 326 (manufactured by Ciba-Geigy) and 2 parts by weight, and then melted at 300 ° C.
It was extruded from the die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to form a 90 μm-thick PEN (polyethylene). A naphthalate) film was obtained. Note that this P
The EN film has a blue dye, a magenta dye and a yellow dye (disclosed in Japanese Patent Publication No. 94-6023).
-1, I-4, I-6, I-24, I-26, I-2
7, II-5) was added in an appropriate amount. Furthermore, diameter 20cm
And a heat history of 110 ° C. for 48 hours was given to obtain a support that is less likely to have a curl.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment and a glow discharge treatment on both surfaces, and then gelatin was applied to each surface at 0.1 g / m 2.
² , sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ^2
2 , p-chlorophenol 0.2 g / m ² , (CH ₂ =
CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012
g / m ² , and an undercoat solution of polyamide-epichlorohydrin polycondensate of 0.02 g / m ² was applied (10 cc / m 2
² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer
Specific resistance of 005 μm tin oxide-antimony oxide composite
Is a dispersion of fine particle powder of 5Ω · cm (secondary aggregated particle diameter
0.08 μm) to 0.2 g / m^Two , Gelatin 0.05g
/ M^Two , (CH_Two = CHSO _Two CH_Two CH_Two NHCO)
_Two CH_Two 0.02 g / m^Two , Poly (degree of polymerization 10) oxy
Ethylene-p-nonylphenol 0.005 g / m^Two Passing
And resorcinol.

3-2) Coating of Magnetic Recording Layer Cobalt-γ coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass)
Iron oxide (specific surface area 43 m ² / g, major axis 0.14 μm,
Uniaxial 0.03 μm, saturation magnetization 89 emu / g, Fe ^{+ 2} /
Fe ⁺³ = 6/94, the surface of which is treated with aluminum oxide silicon oxide at 2% by mass of iron oxide) 0.06 g / m ² to diacetyl cellulose 1.2 g / m ² (iron oxide dispersion is an open kneader and it was carried out in a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) as a curing agent N
0.3 g / m ² of CO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a 1.2 μm-thick magnetic recording layer. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as matting agents (10 mg each) / M ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). X-
The light (blue filter) increases the DB color density of the magnetic recording layer by about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3 × 10 ⁴ A /.
m and the squareness ratio were 65%.

3-3) Adjustment of Sliding Layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H
₂₀ COOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H
₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ²
) The mixture was applied. This mixture was mixed with xylene / propylene monomethyl ether (1/1) in 105
Propylene monomethyl ether (1 ° C)
(0-fold volume), and then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as an abrasive are each 15 mg / m 2. ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer is
Dynamic friction coefficient 0.06 (5mmφ stainless steel hard ball, load 100g, speed 6cm / min), static friction coefficient 0.07
(Clip method), and the coefficient of kinetic friction between the emulsion surface and the sliding layer described later was excellent at 0.12.

4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers.
A sample as a color negative photosensitive material was prepared.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (Specific compounds are numbered after symbols in the following description. These chemical formulas are shown below.)

The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion T Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-20 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.011 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.014 solid disperse dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion S silver 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion R silver 0.065 silver iodobromide emulsion Q silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-40 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver iodobromide emulsion P silver 0.21 silver iodobromide emulsion O silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion N silver 1.47 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY- 5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84.

Eighth Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Silver iodobromide emulsion M 0.560 Cpd-3 0.020 Cpd-4 0.030 ExM-2 0.096 ExM-30 028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.39 silver iodobromide emulsion K silver 0.28 silver iodobromide emulsion J silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 Cpd-3 0.010 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver iodobromide emulsion I Silver 0.45 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM- 4 0.028 ExG-1 0.005 Cpd-3 0.006 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion H 0.99 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM- 5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1. 11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.010 Cpd-1 0.16 Oil-soluble Dye ExF-5 0.010 Solid Dispersion Dye ExF-6 0.020 HBS-1 0.082 Gelatin 1 .057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.18 silver iodobromide emulsion E silver 0.20 silver iodobromide emulsion F silver 0.07 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-10 .24 gelatin 1.41.

Fourteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd- 2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91.

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion S Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-5, B-4 to B -6, F
-1 to F-18, and iron salts, lead salts, gold salts, platinum salts,
It contains palladium, iridium, ruthenium and rhodium salts. Further, 8.5 × 10 ^-3 g per mol of silver halide to the coating solution of the eighth layer, a 7.9 × 10 ^-3 grams of calcium in the 11th layer was added with an aqueous solution of calcium nitrate to form Sample .

Preparation of Dispersion of Organic Solid Disperse Dye
ExF-3 was dispersed by the following method. That is, 21.7 mL of water
3 mL of p-octylphenoxyethoxyethoxyethoxyethanesulfonate in 5% aqueous solution and p in 5% aqueous solution
-0.5 g of octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed in a 700 mL pot mill,
5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (1 mm in diameter) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles is 0.
It was 44 μm.

Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.52 μm. E
xF-2 is disclosed in European Patent Application Publication (EP) 549,489.
Microprecipitation described in Example 1 of the specification of A (Microp
(recipitation) dispersion method.
The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method. ExF-6 wet cake 2 containing 18% water
In 800 g, 4.0 kg of water and a 3% solution of W-2 were added to 37 g.
6 g was added and stirred to obtain a slurry having a concentration of ExF-6 of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was charged into Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m through the slurry.
/ Sec at a discharge rate of 0.5 L / min for 8 hours.

The compounds used for forming each of the above layers are as shown below.

[0267]

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[0268]

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[0269]

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[0270]

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[0271]

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[0272]

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[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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[0278]

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[0279]

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(Preparation of Samples) The sensitizing dyes used in Emulsion D, Emulsion E, Emulsion F and Emulsion G are shown in the tables in the Examples.

Emulsions D, E, F and G were emulsions having 10 or more dislocation lines per grain.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was carried out for 1/100 second through a continuous wedge. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992. Photographic sensitivity and fog density before long-term storage were determined by measuring the density of the developed sample with a blue filter. The sensitivity was represented by a relative value of the reciprocal of the exposure necessary to reach the density of fog density plus 0.2. To evaluate the storage fog of the photographic material, the sample was stored for 14 days under conditions of 40 ° C. and 60% relative humidity, exposed for 1/100 second, and the sample subjected to the same development treatment was measured for density using a blue filter. The fog density after storage was determined, and the difference in fog density before and after storage was determined.

The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5 L Rinsing 30 seconds 38.0 ℃ 17 mL 3 L stable (1) 20 seconds 38.0 ℃-3 L stable (2) 20 seconds 38.0 ℃ 15 mL 3 L drying 1 minute 30 seconds 60.0 ℃ Is per 35 m of photosensitive material and 1.1 m in width (equivalent to 24 Ex. 1 line)

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processor was 10
0 cm ^2, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing solution is shown below.

(Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0.

(Fixing (1) Tank Liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH:
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR manufactured by Rohm and Haas Co.)
-120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L.
L was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

[0294]

[Table 5]

As is clear from Table 4, long-term storage by using both the first sensitizing dye and the second sensitizing dye of Emulsion D, Emulsion F, Emulsion G with the compound of the present invention was carried out. It can be seen that the increase in fog density is small and good.

As a method of using a sensitizing dye in a blue-sensitive photographic emulsion, it is known that absorption of the dye at around 435 nm, which is the emission line wavelength of a fluorescent lamp, is useful for color reproduction in photographing under a fluorescent lamp light source. However, by combining the sensitizing dye of the present invention, it was possible to obtain a blue-sensitive emulsion having small storage fog.

Example 3 Except that the emulsions of the blue-sensitive emulsion layers of the fourteenth, fifteenth and sixteenth layers were changed in the preparation method of sample 201 of Example 2 described in JP-A-9-5912. Produced full-layer silver halide color reversal photographic light-sensitive materials 1601 to 1608 in the same manner. 14th layer, 15th layer
In the chemical sensitization step of the emulsion preparation for the layer and the sixteenth layer, samples were prepared by changing the sensitizing dye of each emulsion to the sensitizing dye of the present invention, and photographic performance was evaluated.

[0298]

As is apparent from the above Examples and the like, the photosensitive silver halide photographic emulsion of the present invention, in particular, a silver halide photographic material containing the photographic emulsion (preferably a silver halide photographic material for photography) In the case of (2), an effect was obtained in which color reproducibility was excellent particularly when photographing under a fluorescent light source, high sensitivity, and small fog during long-term storage.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/29 G03C 1/29 7/00 510 7/00 510 (72) Inventor Naoki Hanaki Minamiashigara, Kanagawa 210 Nakanuma Fuji Photo Film Co., Ltd. F-term (reference) 2H016 BA00 BB02 BB04 BD02 BM05 2H023 BA02 BA04 CA03 CA07 CA10

Claims (6)

[Claims] 1. A photosensitive halogen comprising at least one compound represented by the following general formula (1) and at least one compound represented by the following general formula (2): Silver halide photographic emulsion. General formula (1) General formula (2) In the formula, R1, R2, R5 and R6 independently represent a sulfoalkyl group, but one of R1 and R2 is a sulfoethyl group. R3 and R4 independently of one another, an alkyl group,
Represents an alkoxy group, an aryl group, or a chlorine atom. M
1 and M2 each represent a charge balancing counter ion. 2. The emulsion according to claim 1, wherein the silver iodide content in the emulsion is 10 mol.
2. The light-sensitive silver halide photographic emulsion according to claim 1, wherein the emulsion is a silver iodobromide or silver chloroiodobromide emulsion having a concentration of not more than 10%. 3. A dislocation of not less than 10% per grain, wherein at least 50% of the total projected area of all silver halide grains in the emulsion is a (111) plane having a parallel principal plane and an aspect ratio of 2 or more. 3. The photosensitive silver halide photographic emulsion according to claim 1, wherein the emulsion is a tabular silver halide grain containing silver iodobromide or silver chloroiodobromide. 4. A light-sensitive silver halide photographic emulsion according to claim 1, wherein said emulsion has been subjected to reduction sensitization. 5. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide photographic emulsion layer is a light-sensitive material according to any one of claims 1 to 4. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion. 6. The silver halide photographic light-sensitive material according to claim 5, wherein said silver halide photographic light-sensitive material is a color photographic light-sensitive material for photography.