JPH05176522A - Silver halide color photography sensitive material - Google Patents

Abstract

PURPOSE:To provide high sensitivity of a silver halide color photography sensitive material excellent in desilvering efficiency and maintaining efficiency and having improved color balance variation in the case of taking a picture under a fluorescent light. CONSTITUTION:At least one layer of silver halide emulsion layers of blue, green and red sensitivities and at least one layer of non-sensitive auxiliary layers are provided on a bearing body. At least 50% of the whole projection area of silver halide particles in at least one layer of sensitive silver halide emulsion layers have two or more average aspect ratio and are occupied with flat silver halide particles provided with dislocation. At least one layer of the sensitive silver halide emulsion layers contains a trimethylane-cyanine coloring matter or a monomethythane-cyanine coloring matter. An oxidizing body of aromatic first class amine system color development main chemicals acts on at least one layer of hydrophile-colloid layers to contain a compound releasing a bleaching accelerator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has high sensitivity, excellent desilvering property and storability, and has improved color balance change when photographed under a fluorescent lamp. And a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, silver halide light-sensitive materials have been highly sensitized and have a small format, and photographic light-sensitive materials having high sensitivity and excellent image quality have been strongly desired.

For this reason, the demand for silver halide emulsions for photography is becoming more and more severe, and higher level requirements are being made for photographic performance such as high sensitivity, high contrast, excellent graininess and sharpness.

Although various efforts have been made to increase the sensitivity of emulsions to meet such demands, the spectral sensitization technique is used for producing a light-sensitive material having high sensitivity and excellent color reproduction. Is an extremely important and essential technology. The spectral sensitizer has a function of absorbing light in a long wavelength region, which is essentially not absorbed by the silver halide photographic emulsion, and transmitting the light absorption energy to the silver halide. Therefore, an increase in the amount of light captured by the spectral sensitizer is advantageous for increasing photographic sensitivity.

Regarding the improvement of the spectral sensitization technique, for example, as a silver halide emulsion having enhanced spectral sensitivity in the green wavelength region, for example, a conventional oxacarbocyanine dye and an imidacarbocyanine dye are used in combination (for example, JP-A-59). -1166
No. 46, No. 59-116647, No. 59-14044.
3 and 59-149346) or a combination of an oxacarbocyanine dye and an oxathiacarbocyanine dye (for example, JP-B-46-11627, JP-A-60-42750).
No.) and a combination of two or more oxacarbocyanine dyes (for example, JP-A No. 52-23931) are known.

However, the color photographic light-sensitive materials using these photographic emulsions have low spectral sensitivity in the green short wavelength region,
Even if the color reproducibility is improved due to the interlayer suppression effect and the like, it cannot be said that the color reproducibility is sufficient, and there has been a serious drawback and dissatisfaction that the image becomes green especially when photographing under a fluorescent lamp.

Therefore, a technique for increasing the spectral sensitivity in the green short wavelength region is required, and a benzimidazolooxazolocarbocyanine dye conventionally known as a sensitizing dye having a maximum value of the spectral sensitivity in this wavelength region. (For example, Japanese Patent Publication 4
4-14030) and dimethine merocyanine dyes (for example, US Pat. No. 2,493,
No. 748, No. 2,519,001, No. 3,48
Compounds described in No. 0,439) are not suitable for combined use, because the emulsions to which these are added show increased fog or decreased sensitivity at high temperature or high temperature and high humidity after emulsion coating. Conceivable.

Regarding the method of using a combination of a monomethinecyanine dye and a trimethinecyanine dye, for example, Japanese Patent Publication Nos. 56-38936 and 54-345.
35, JP-A-63-298240, JP-A 2-24
644, JP-A-58-153926, 62-16.
No. 0450, these sensitizing dyes had the drawback of being easily desorbed at high humidity.

Furthermore, when the spectral sensitivity centroid of the green-sensitive silver halide emulsion layer is set relatively to the short-wave side by the technique of increasing the spectral sensitivity in the green short wavelength region, the absorption wavelength region of the yellow filter layer overlaps. Becomes large, which causes a problem that the sensitivity of the green sensitive layer is lowered.

On the other hand, generally, a silver halide color photographic light-sensitive material is basically processed by a color development step and a desilvering step. In the color developing step, the exposed silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. The silver formed here is oxidized by a bleaching agent in the subsequent desilvering step, further converted into a soluble silver complex by the action of a fixing agent, and dissolved and removed.

In recent years, in the industry, speeding up of processing,
That is, there is a strong demand for shortening the processing time, and in particular, shortening the desilvering process, which occupies nearly half of the processing time, is a major issue.

Conventionally, as means for accelerating the desilvering process,
Aminopolycarboxylic acid ferric iron complex salt and thiosulfate described in German Patent No. 866,605 are used.
A bleach-fixing solution contained in a solution is known. However, in this case, since the ferric aminopolycarboxylic acid complex salt, which originally has a weak oxidizing power (bleaching power), is allowed to coexist with the thiosulfate having a reducing power, the bleaching power is significantly weakened, and particularly high sensitivity, It was extremely difficult to sufficiently desilver a high-silver color photographic material for photography, and there was a drawback that it could not be put to practical use.

On the other hand, as a method of increasing the bleaching power, there has been proposed a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath or a prebath thereof. Such bleaching accelerators are described in, for example, US Pat. No. 3,893,858,
British Patent No. 1138842, JP-A-53-14
1623, various mercapto compounds, compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-
A thiazolidine derivative as described in JP 9854, an isothiourea derivative as described in JP-A-53-94927, JP-B-45-8506,
Thiourea derivatives as described in JP-B-49-26586, thioamide compounds as described in JP-A-49-42349, JP-A-55-2650.
6 are dithiocarbamates, and arylenediamine compounds are described in US Pat. No. 4,552,834.

Although some of these bleaching accelerators certainly show a bleaching promoting effect, they are expensive and have insufficient stability in a bath having a bleaching ability, and further bleaching The accelerating effect itself is still inadequate, and it is not yet satisfactory in terms of practicality.

Further, the above-mentioned various bleaching accelerators are contained in a bleaching bath, a bleach-fixing bath or a pre-bath thereof for processing, and when the bleaching accelerator is a compound having a mercapto group, these are added. The mercapto compound forms a poorly soluble silver salt with undeveloped silver halide or silver halide produced by the bleaching reaction in the emulsion layer of the light-sensitive material,
It may not be solubilized by the fixing agent, resulting in poor fixing.

Further, using a processing bath having a bleach-fixing ability,
In a method in which processing is continuously performed while replenishing, silver ions are accumulated in the bleach-fixing bath. This silver ion forms a sparingly soluble silver salt with the mercapto compound,
This reaction is likely to occur especially when iodide ions are present in the bleach-fix solution to be processed.

As described above, there are many restrictions on the use of the bleaching accelerator in the bleaching bath, the bleach-fixing bath or the pre-baths thereof.

Further, a method is known in which the mercapto compound or the precursor thereof by the bleaching accelerator is present in the light-sensitive material for processing. However, when the mercapto compound is contained in the light-sensitive material, the influence on the photographic properties is large and the reason why the undeveloped silver halide and the mercapto compound in the light-sensitive material form a sparingly soluble salt. So, this method has many problems.

On the other hand, Research Disclosure Item Nos. 24241 and 11449 and Japanese Patent Application Laid-Open No. 61-201247 describe bleach accelerating compound releasing couplers.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which has high sensitivity and has an improved color balance change when photographed under a fluorescent lamp.

Another object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and excellent desilvering property and storability.

[0022]

The above-mentioned objects of the present invention can be achieved by the following means.

(1) A silver halide color photographic light-sensitive material having at least one of each of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and at least one non-photosensitive auxiliary layer on a support. At least 50% of the total projected area of silver halide grains in at least one of the functional silver halide emulsion layers contains tabular silver halide grains having an average aspect ratio of 2 or more and containing dislocations, and At least one of the photosensitive silver halide emulsion layers contains a trimethine cyanine dye and a monomethine cyanine dye, and at least one hydrophilic colloid layer is reacted with an oxidant of an aromatic primary amine type color developing agent. A silver halide color photographic light-sensitive material comprising a compound that releases a bleaching accelerator.

(2) The trimethine cyanine dye and the monomethine cyanine dye are represented by the general formula (A) shown in the following chemical formula 3 and the general formula (B) shown in the following chemical formula 4, respectively. ) The silver halide color photographic light-sensitive material as described in 1).

[0025]

[Chemical 3] In the general formula (A), A ₁ , A ₂ , A ₃ and A ₄ are each a hydrogen atom, lower alkyl group, alkoxy group, halogen atom, hydroxyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, tri group. It represents a fluoromethyl group, an amino group, an acylamide group, an acyl group, an acyloxyl group, an alkoxycarbonylamino group, and a carboalkoxy group. A ₁ and A ₂ , and A ₃ and A ₄ may be linked to each other to form a naphthoxazole nucleus.

R ₀ represents a hydrogen atom, a lower alkyl group or an aryl group.

R ₁ and R ₂ each represent an alkyl group. However, at least one of R ₁ and R ₂ is an alkyl group having a sulfo radical. X ₁ ^- represents an anion. n represents 1 or 2, and 1 is when the dye forms an intramolecular salt.

[0028]

[Chemical 4] In the general formula (B), Z ₁ and Z ₂ are each a nonmetal atom necessary for completing a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, and a pyridine nucleus. Represents a group.

R ₃ and R ₄ each represent an alkyl group. X ₂ ⁻ represents an anion. m represents 1 or 2, 1 being when the dye forms an intramolecular salt.

(3) In the above (1) or (2), the silver halide grains occupying 80% or more of the total projected area of the silver halide grains have an average aspect ratio of 3 or more and less than 8. The described silver halide color photographic light-sensitive material.

(4) Silver halide grains occupying 80% or more of the total projected area of the silver halide grains are tabular grains having dislocations with an average silver iodide content of 5 mol% or more and 15 mol% or less. The silver halide color photographic light-sensitive material as described in (1) or (2) above, which is characterized in that

(5) The silver halide grains occupying 80% or more of the total projected area of the silver halide grains have an average aspect ratio of 3 to less than 8 and an average silver iodide content of 5 mol% to 1
The silver halide color photographic light-sensitive material as described in (1) or (2) above, which is a tabular grain having dislocations at 5 mol% or less.

The present invention will be described in detail below.

The emulsion of the present invention contains one or more tabular silver halide grains having an aspect ratio of 2 or more. Here, tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship. This tabular grain has a triangular shape when the grain is viewed from above,
Hexagons or these have rounded circular shapes, triangular ones have triangular outer surfaces, hexagonal ones have hexagonal shapes, and circular ones have circular outer surfaces that are parallel to each other. ing.

In the present invention, the average aspect ratio of tabular grains is a value obtained by dividing the grain diameter of each tabular grain having a grain thickness of less than 0.5 μm and a grain diameter of 0.3 μm or more (aspect ratio). Ratio), the projected areas of particles with a large aspect ratio are sequentially added, and when a certain ratio (for example, 50%) of the total projected area is reached, the average value of the aspect ratio of each particle up to that point is calculated. can get. The particle thickness can be easily measured by evaporating the metal from the diagonal direction of the particle together with the reference latex, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is 0.3 to 5.0.
It is preferably μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm.

The proportion of the tabular grains of the present invention in the emulsion is preferably 50%, particularly preferably 80% or more of the projected area of all silver halide grains in the emulsion. Furthermore, the average aspect ratio of tabular grains occupying these constant areas is preferably 3 or more and less than 8. Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are
For example, according to the description of JP-A No. 63-151618, the shape thereof is briefly described. 70% or more of the total projected area of silver halide grains has a maximum length with respect to a side length having a minimum length. The hexagonal tabular silver halide grains are hexagonal in which the ratio of the sides having a height is 2 or less, and are occupied by tabular silver halide having two parallel parallel surfaces as outer surfaces. The coefficient of variation of the grain size distribution [the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area by the average grain size] has a monodispersity of 20% or less.

Further, the tabular grains of the present invention have dislocations.

It is well known that a dislocation is a displacement (shift) of a series of atomic arrangements in a crystal lattice, and its general definition is, for example, by Shuji Suzuki, An Introduction to Dislocation Theory, Agne Publishing Co., 1968, P24. ~ 31.

Regarding the fact that dislocations (lines) existing in the crystal can be observed by an electron microscope and the change in contrast due to sample inclination, etc., see Hirsch et al.
electron Microscopy of Thin
Crystals, P169-188. Butter
Worths, London, 1965).

Examples of observation of dislocation lines in silver halide grains include, for example, Hamilton (Photgr. Sc).
i. Eng. , 11 , 57 (1967)), Shiozawa (Nikkan, 34 , 16 (1971), 35 , 213 (197).
There is 2)).

The preparation and observation of a sample for observing silver halide grains by an electron microscope are described in Shiozawa's literature (Nissha, 34 , 16 (19
71)).

When the silver halide grains are observed with an electron microscope, in addition to dislocation lines, equi-tilt interference fringes, stacking faults, printout silver and moire images produced by electron beam irradiation during observation with an electron microscope are observed. All of these images are generally known.

The cause of the contrast generation of these images and the identification method are generally described by Hirsch et al. (Supra), and Hami is described for silver halide grains.
It is reported by Lton (supra) and can be distinguished from the dislocation image.

The dislocation of tabular grains is described in detail in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by the direct method described in (1972) using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample is placed to prevent damage (printout etc.) due to electron beam. Observation is performed by a transmission method in a cooled state. In this case, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μ). .. From the photograph of the grains obtained by such a method, it is possible to determine the position of dislocation for each grain when viewed from the direction perpendicular to the main plane.

The positions of dislocations in the tabular grains of the present invention occur in the major axis direction of the tabular grains from the distance x% of the length from the center to the side to the side, and the value of x is preferably. 10 ≦ x <100, more preferably 30 ≦
X <98, and more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but may not be a perfect similar shape and may be distorted. The direction of the dislocation line is approximately from the center to the side, but it often meanders.

The number of dislocations in the tabular grains of the present invention is 1
It is preferable that 50% (number) or more of grains containing 0 or more dislocations are present. 80% (number) or more of grains containing 10 or more dislocations are particularly preferable, and 20 are particularly preferable.
It is preferable that 80% (number) or more of grains containing at least one dislocation are present.

The method for producing the tabular grains of the present invention will be described.

The tabular grains of the present invention are described in, for example, "Theory and Practice of Photography" by Cleeve (Cleve, Photograph.
y Theory and Practice (193
0)), 131; Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and E
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1
It can be prepared by modifying the method described in No. 57.

Any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used in the tabular silver halide emulsion used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

The silver halide emulsion of the present invention may have a structure with respect to the halogen composition in the grains.

Dislocations of the tabular grains of the present invention are introduced by providing a high iodine phase inside the grains.

The high iodine phase is a silver halide solid solution containing iodine. In this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable, but silver iodide or It is preferably silver iodobromide, and particularly preferably silver iodide.

The amount of silver halide forming the high iodine phase is, in terms of silver amount, 30 mol% or less of the total silver amount of the grains,
More preferably, it is 10 mol% or less.

The phase to be grown outside the high iodine phase must be lower than the iodine content of the high iodine phase, and the preferable iodine content is 0 to 12 mol%, more preferably 0.
˜6%, most preferably 0 to 3 mol%.

The preferred trimethine cyanine dye used in the present invention is represented by the general formula (1) shown below.

[0059]

[Chemical 5] In the formula (1), Z ¹¹ and Z ¹² are benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, or naphthoselenazole. Represents the atomic group necessary to form a nucleus. The above-mentioned naphthoxazole nucleus, naphthothiazole nucleus and naphthoselenazole nucleus are naphtho [1,2-
d] oxazole nucleus, naphtho [2,1-d] oxazole nucleus, naphtho [1,2-d] thiazole nucleus, naphtho [2,1-d] thiazole nucleus, naphtho [2,3-d] thiazole nucleus, naphtho It includes a [1,2-d] selenazole nucleus and a naphtho [2,1-d] selenazole nucleus.

The aromatic ring contained in these nuclei may have various substituents. For example, halogen atom (eg chlorine atom, bromine atom, fluorine atom), carbon number 6
Up to alkyl groups (eg methyl, ethyl, isopropyl, 3-propyl, butyl, t-amyl), cyano groups,
Carboxy group, alkoxycarbonyl group having up to 4 carbon atoms (eg ethoxycarbonyl), alkylcarbonyl group having up to 4 carbon atoms (eg acetyl), alkylsulfonyl group having 4 or less carbon atoms (eg methylsulfonyl), aromatic hydrocarbon group ( For example, phenyl, p-tolyl), halogen-substituted alkyl group (eg, trifluoromethyl), hydroxy group, alkoxy group having up to 4 carbon atoms (eg, methoxy, ethoxy), or alkylcarbonylamino group having up to 4 carbon atoms (eg, acetylamino). ) Can be included. On the 1-position nitrogen atom of the benzimidazole nucleus, for example, an alkyl group having up to 4 carbon atoms (for example, methyl,
It may have ethyl, propyl), alkenyl groups having up to 4 carbon atoms (eg allyl), or aromatic hydrocarbon groups (eg phenyl).

R ¹¹ and R ¹² represent an aliphatic hydrocarbon group having up to 8 carbon atoms which may be substituted and whose carbon chain may be interrupted by an oxygen atom, a sulfur atom or the like.

R ¹⁰ is a hydrogen atom, an alkyl group having up to 3 carbon atoms (eg methyl, ethyl, propyl) or 8 carbon atoms.
Up to and including aralkyl groups such as phenethyl. X
₍₁₎ ^- represents an acid anion, s is 1 or 2.
However, s is 1 when the dye forms an inner salt.

A preferred monomethinecyanine dye used in the present invention is represented by the general formula (2) shown below.

[0064]

[Chemical 6] In the formula, Z ¹³ and Z ¹⁴ are pyrroline nucleus, pyridine nucleus, thiazoline nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, indolenine nucleus, benzimidazole nucleus, benzoxazole nucleus, benzthiazole nucleus, benzselenazole nucleus, naphthoxazole, respectively. Represents a group of atoms necessary to complete a nucleus, a naphthothiazole nucleus, or a naphthoselenazole nucleus. The naphthoxoxazole nucleus includes a naphtho [1,2-d] oxazole nucleus and a naphtho [2,1]
-D] oxazole nucleus, naphtho [1,2-d] thiazole nucleus, naphtho [2,1-d] for naphthothiazole nucleus
A thiazole nucleus and a naphtho [2,3-d] thiazole nucleus are included, and a naphthoselenazole nucleus includes a naphtho [1,2-d] selenazole nucleus and a naphtho [2,1-d] selenazole nucleus. Various substituents may be present on the aromatic hydrocarbon ring of these nuclei, and those substituents are the same as the substituents on the aromatic hydrogen ring in the case of Z ¹¹ and Z ^12. Can be used. A lower alkyl group having up to 3 carbon atoms (eg methyl) on the 3-position carbon atom of the indolenine nucleus
Can be useful as a substituent.

At least one of R ¹³ and R ¹⁴ represents an aliphatic group having up to 8 carbon atoms, which is substituted with a hydroxy group, a carbonyl group, or a sulfo group, and the rest is a fatty acid group having up to 8 carbon atoms. Indicates a group. These aliphatic groups may further have another substituent (for example, hydroxy),
It may also be an aliphatic group whose carbon chain is interrupted by an oxygen atom or a sulfur atom.

[0066] X ₍₂₎ ^- represents an acid anion, t represents 1 or 2. When the dye forms an inner salt, t is 1.

Specific examples of the heterocyclic nuclei completed by Z ¹¹ or Z ¹² in the sensitizing dyes having the general formulas (1) and (2) used in the present invention are as follows. That is, 1-methyl-5-chlorobenzimidazole, 1-
Methyl-5-fluorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-methyl-
5,6-Difluorobenzimidazole, 1-ethyl-
5-chlorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-propyl-5-chlorobenzimidazole, 1-propyl-5-fluorobenzimidazole, 1-propyl-5,6-dichlorobenzimidazole, 1-propyl-5,6-difluorobenzimidazole, 1-allyl (a1lyl) -5-chlorobenzimidazole, 1-allyl -5,6-Dichlorobenzimidazole, 1-allyl-5,6-difluorobenzimidazole, 1-ethyl-5-methoxycarbonylbenzimidazole, 1-ethyl-5-methylsulfonylbenzimidazole, 1-phenyl-5-chloro Benzimidazole 1-phenyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-phenyl-5,6-difluorobenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole: oxazole, 4- Methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, 4-p-tolyloxazole, benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole , 5-
Methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6-di-
Methoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole: naphtho [1,2-d] oxazole: thiazole,
4-methylthiazole, 4-phenylthiazole, 4,
5-dimethylthiazole, 4-methyl-5-phenylthiazole, benzthiazole, 5-chlorobenzthiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-ethoxybenzothiazole, 6-methoxy Benzthiazole, 6-chlorobenzothiazole, 5-carboxybenzothiazole, 5-acetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5, 6-dimethylbenzothiazole, 5-acetylaminobenzothiazole, 6-methoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole, naphtho [1,2 d] thiazole, selenazole,
4-methylselenazole, 4-phenylselenazole,
4,5-dimethylselenazole, benzoselenazole,
With the core of 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, naphtho [1,2-d] selenazole, etc. is there.

Specific examples of the heterocyclic ring nucleus completed by Z ¹³ or Z ¹⁴ include, in addition to the above, pyrroline, thiazoline, pyridine, 3,3-dimethylindolenine, 3,
3,6-Trimethylindolenin, 6-chloro-3,3
Examples include nuclei such as dimethylindolenine and 3,3,5,6-tetramethylindolenine.

In the above general formulas (1) and (2), R
Specific examples of the substituents represented by ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as follows. That is, methyl, ethyl, propyl, butyl, 2-methoxyethyl, 2-ethylthioethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,
3-carboxybutyl, 2 (2-carboxyethoxy)
Ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-
Sulfobutyl, 4-sulfobutyl, 2 (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, vinylmethyl.

[0070] X ₍₁₎ ^- and X ₍₂₎ ^- is an acid anion represented by, for example, iodide ion, bromide ion, chloride ion, p- toluenesulfonate ion, naphthalene disulfonic acid ion, benzenesulfonate ion, sulfate It is an acid anion such as an ion, a perchlorate ion, and a rhodanate ion, which are used for ordinary cyanine dye salts.

Specific examples of the sensitizing dyes used in the present invention are shown in the following chemical formulas 7 to 24, but the present invention is not limited to these.

[0072]

[Chemical 7]

[0073]

[Chemical 8]

[0074]

[Chemical 9]

[0075]

[Chemical 10]

[0076]

[Chemical 11]

[0077]

[Chemical 12]

[0078]

[Chemical 13]

[0079]

[Chemical 14]

[0080]

[Chemical 15]

[0081]

[Chemical 16]

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

[0088]

[Chemical formula 23]

[0089]

[Chemical formula 24] Among the trimethine cyanine dyes that can be used in the present invention, a particularly preferable one is the general formula (A) shown in the following chemical formula 25.
And a particularly preferred monomethinecyanine dye that can be used in the present invention is represented by the general formula (B) shown in the chemical formula 26 below, and it is further preferable to use both of them together. preferable.

[0090]

[Chemical 25] In the general formula (A), A ₁ , A ₂ , A ₃ and A ₄ are each a hydrogen atom, lower alkyl group, alkoxy group, halogen atom, hydroxyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, tri group. It represents a fluoromethyl group, an amino group, an acylamide group, an acyl group, an acyloxyl group, an alkoxycarbonylamino group, and a carboalkoxy group. A ₁ and A ₂ , and A ₃ and A ₄ may be linked to each other to form a naphthoxazole nucleus.

R ₀ represents a hydrogen atom, a lower alkyl group or an aryl group.

R ₁ and R ₂ each represent an alkyl group. However, at least one of R ₁ and R ₂ is an alkyl group having a sulfo radical. X ₁ ^- represents an anion. n represents 1 or 2, and 1 is when the dye forms an intramolecular salt.

[0093]

[Chemical formula 26] In the general formula (B), Z ₁ and Z ₂ are each a nonmetal atom necessary for completing a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, and a pyridine nucleus. Represents a group.

R ₃ and R ₄ each represent an alkyl group. X ₂ ⁻ represents an anion. m represents 1 or 2, 1 being when the dye forms an intramolecular salt.

General formulas (1) and (2) used in the present invention
The compound represented by is a known compound and can be easily synthesized by the methods described in the following documents and the like.

For example, FM Harmer (FM).
Hamer) "Heterocyclic Compounds-
Cyanine Soybean and Relative Compounds- (Heterocyclic Compound
-Cyanine yes and related c
omounds-) ", John Willie &
John Wiley & Sons, New York, London, (1964). , DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry- (He
terocyclic Compounds-Spec
ial tops in heterocycle
c chemistry-) ”, Chapter 18, Section 14,
Pp. 482-515, John Wiley & Sons, New York, London, (1977). , Day J
D.J.Fry, "Rods Chemistry of Carbon Compounds (Rodd's Ch
emissary of Carbon Compound
ds) ", (2nd. Ed. vol. IV, part B,
(1977), Chapter 15, 369-422; (2
nd. Ed. vol. IV, part B, 1985), Chapter 15, pages 267-296, Elsvier Science Publishing Company, Inc.
ng Company Inc. ) Publications such as company publications and New York.

It is well known that addition of a certain cyanine dye is extremely effective as a means for increasing the photosensitivity of a silver halide photographic emulsion. In this case, the cyanine dye added to the silver halide emulsion is adsorbed on the silver halide grains in the emulsion, and a longer wavelength absorption band is added to the absorption band specific to silver halide. This is "spectral sensitization"
It is called. On the other hand, in addition to this dye, the presence of a second specific dye or other organic substance significantly increases the efficiency of color sensitization. It is known to give additive high sensitivity, and this effect is called "supersensitization". Generally, even if two or more kinds of dyes are used in combination, the sensitivity does not increase or the sensitivity decreases in many cases, so supersensitization is a very unique phenomenon.

For such supersensitization, it is also known that a combination of two or more kinds of dyes, for example, a mixture of a monomethine dye and a trimethine dye is used (for example, Japanese Patent Publication Nos. 48-1762 and 54-62). -34535, 56-3
8936, JP-A-50-28826, 51-14.
No. 313, No. 58-153926, No. 62-1604.
50).

In the present invention, the higher the sensitivity of the photographic light-sensitive material, the higher the effect. In other words, when shooting a subject under multiple light sources, there are many dark places, and when using a low-sensitivity photographic light-sensitive material, the flash will shine when shooting with a camera equipped with an automatic strobe. Since there is a high possibility that it is very difficult to see except the part where the flash light reaches. For this reason, it is not necessary to be aware that different types of light sources are being irradiated. However, when using a high-sensitivity photographic light-sensitive material, it is highly possible that the flash will not shine when shooting with a camera equipped with an automatic strobe when it has a certain level of brightness, and it is not suitable for different light sources. Illumination is a particular problem. Even if the flash shines, the one with high sensitivity has a higher background depiction power, so the color balance difference between the part of the main subject illuminated by the flash and the part of the background illuminated by a different light source tends to be a problem. ..

Further, one of the effects of the present invention is that the color reproducibility is improved without causing a decrease in sensitivity. However, when the color reproducibility is improved by using the conventional technique, the sensitivity is deteriorated. This is unavoidable, and in order to compensate for this decrease in sensitivity, the size of silver halide grains is often increased to deal with it, but at this time, graininess deteriorates. Here, due to the inefficiency of the property that silver halide grains have, "the larger the grain size, the lower the sensitivity / volume ratio", so the sensitivity is increased by increasing the grain size in the large grain, that is, the high-sensitivity region. The deterioration of the graininess when exposed is larger than in the low sensitivity region. Therefore, the photographic light-sensitive material of the present invention, which can improve color reproducibility without lowering the sensitivity, is more useful as a photographic light-sensitive material having higher sensitivity.

The light-sensitive material of the present invention shows an improving effect in all photographic sensitivities, but it is more preferable that the photographic sensitivity determined by the above method is 320 or more. If the sensitivity is less than 320, in addition to the above reason, the probability of failure such as out-of-focus during normal shooting and underexposure increases.

The "compound which reacts with the oxidant of the aromatic primary amine color developing agent to release the bleaching accelerator" in the present invention is hereinafter referred to as a bleaching accelerator releasing compound. The bleach accelerator releasing compound is included in at least one hydrophilic colloid layer. Here, the hydrophilic colloid layer is a layer having a hydrophilic colloid represented by gelatin as a binder, and in the present invention, it means either a photosensitive silver halide emulsion layer or a non-photosensitive auxiliary layer.

The bleaching accelerator releasing compound used in the present invention is preferably represented by the following general formula (C). Formula (C) A- in (L _{1) p} -Z formula, A is by reaction with the developing agent oxidation product (L _{1) p} -Z
A group capable of cleaving a bond with and L ₁ , a group capable of cleaving a bond with Z after cleavage with a bond with A, p represents an integer of 0 or 1, and Z represents a bleaching accelerator.

The compound represented by formula (C) is described in detail below.

In the general formula (C), A is (L ₁ ) due to the coupling reaction with the oxidized aromatic primary amine developing agent.
_{It represents a} coupler residue capable of leaving _p- Z or a reducing agent residue capable of leaving (L ₁ ) _p- Z after redox reaction with an oxidized product of a developing agent.

When A represents a coupler residue, a yellow coupler residue (for example, an open chain ketomethylene type), a magenta coupler residue (for example, 5-pyrazolone type, a pyrazoloimidazole type, a pyrazolotriazole type), a cyan coupler residue ( Examples thereof include phenol type, naphthol type), and non-color-forming coupler residues (eg, indanone type, acetophenone type). Also, US Pat. No. 4,315,
070, 4,183,752, 3,961,9
It may be a heterocyclic coupler residue described in No. 59 or No. 4,171,223.

Preferred examples of A are represented by the general formulas (Cp-1), (Cp-2), (Cp-3), and
(Cp-4), (Cp-5), (Cp-6), (Cp-
7), (Cp-8), (Cp-9) or (Cp-1
0) when it is a coupler residue. These couplers are preferred because of their high coupling speed.

[0108]

[Chemical 27]

[0109]

[Chemical 28] The free bond derived from the coupling position in the above formula represents the bonding position with (L ₁ ) _p -Z.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ and R
_{When 55} , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a diffusion resistant group, it has a total number of carbon atoms of 8 to 40, preferably 10 to 30. Otherwise, the total number of carbon atoms is preferably 15 or less. In the case of a bis type, telomer type or polymer type coupler, one of the above substituents represents a divalent group,
Connect repeating units. In this case, the range of carbon number may be out of regulation.

R _{51 to} R ₆₃ , a and b will be described in detail below.

R ₅₁ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. R ₅₂ and R ₅₃ each represent an alkyl group, an aryl group or a heterocyclic group. R ₅₄ is an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamido group, a sulfonamide group, an acyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxy group, an aryloxy group, an alkylthio group. Represents an arylthio group or a cyano group.

R ₅₅ represents an alkyl group, an aryl group or a heterocyclic group. R ₅₆ and R ₅₇ each represent a group having the same meaning as R ₅₄ , a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group or an alkoxycarbonyl group. R ₅₈ has the same meaning as R ₅₁ . R ₅₉ represents a group having the same meaning as R ₅₄ or a halogen atom. a represents an integer of 0 to 3. When a is plural, plural R ₅₉ may be the same or different. Also, two adjacent R ₅₉ may be bonded to each other to form a ring structure. R ₆₀ represents an aryl group, preferably a phenyl group having an electron-withdrawing group such as Cl and CN at the m- and / or p-positions. R ₆₁ represents a group having the same meaning as R ₅₁ .
R ₆₂ represents a group having the same meaning as R ₅₉ except for a hydrogen atom. R
₆₃ represents a group having the same meaning as R ₅₉ except a hydrogen atom, a nitro group, a carboxyl group or a sulfo group. b represents an integer of 0 to 4. When b is plural, plural R ₆₃ may be the same or different.

When A represents a coupler residue, A is preferably a magenta coupler residue or a cyan coupler residue, particularly preferably a cyan coupler residue [more preferably a coupler residue represented by the general formula (Cp-8)]. Group]
Is. Furthermore, among the cyan coupler residues represented by the general formula (Cp-8), the general formula (Cp-
The cyan coupler residue represented by 11) is most preferable.

[0115]

[Chemical 29] In the general formula (Cp-11), R ₆₄ has 8 to 3 carbon atoms.
Represents an alkyl group having 6 (preferably 10 to 30), an aryl group having 6 to 36 (preferably 10 to 30) carbon atoms or a heterocyclic group having 6 to 36 (preferably 10 to 30) carbon atoms, and R ₆₅ is a hydrogen atom, a carbonamido group having 1 to 36 (preferably 2 to 18) carbon atoms, and 1 carbon atom
It represents a sulfonamide group having from 36 (preferably 1 to 18) or an alkoxycarbonylamino group having from 2 to 36 (preferably 2 to 18) carbon atoms. General formula (Cp-1
As R ₆₄ in 1), an alkyl group or an aryl group is preferable, and an alkyl group is particularly preferable. Similarly, R ₆₅ is preferably a hydrogen atom or an alkoxycarbonylamino group, and particularly preferably an alkoxycarbonylamino group.

When A in the general formula (C) represents a reducing agent residue, examples thereof include hydroquinones, naphthohydroquinones, catechols, pyrogallols, aminophenols, o- and p-sulfonamidophenols or hydrazines. Is mentioned. Preferred examples of A are the general formulas (R-1), (R-2) and (R-
3), (R-4), (R-5) or (R-6).

[0117]

[Chemical 30] The free bond in the above formula represents the bond position with (L ₁ ) _p -Z.

In the above formula, R ₇₁ , R ₇₂ , R ₇₃ or R ₇₄
If contains a non-diffusible group, it has a total of 8 carbon atoms.
-50, preferably 10-40,
In other cases, the total number of carbon atoms is preferably 12 or less. In the case of a bis-to-tetrakis-type, telomer-type, oligomer-type or polymer-type coupler, they are bonded to each other by any of the above substituents. In this case, the number of carbon atoms may be out of the regulation.

Below, R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ and c,
d and e will be described in detail.

R ₇₁ and R ₇₂ are each a hydrogen atom or a group (for example, acetyl or trifluoro) in which the bond with O is cleaved by the action of a component in the developing solution (eg, hydroxide ion, hydroxylamine, sulfite ion, developer). Acetyl, chloroacetyl, methylsulfonyl, 2-cyanoethyl). R ₇₃ is an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, a carbonamido group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, carbamoyl group,
It represents a sulfamoyl group, a sulfonyloxy group, an acyloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl group, an imide group, a nitro group, a halogen atom, a carboxyl group or a sulfo group. R ₇₄ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group. c is 1
Represents an integer of 3. d represents an integer of 1 to 5. e is 1
Represents an integer of ~ 5. Here, when c, d, or e are plural, plural R ₇₃ may be the same or different. Further, adjacent R _73's may be bonded to each other to form a cyclic structure.

When A represents a reducing agent residue, A is preferably a group represented by formula (R-1) or (R-2).

In the description of the general formulas (Cp-1) to (Cp-10) and (R-1) to (R-6), the alkyl group is a saturated group having 1 to 50 carbon atoms, preferably 1 to 36 carbon atoms. Or, it is an unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group. Representative examples are methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl, (t) -amyl, hexyl, cyclohexyl, 2-ethylhexyl,
Examples include octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aryl group represents a substituted or unsubstituted phenyl group which may be condensed. Typical examples are phenyl, 1-naphthyl, 4-biphenylyl, 4
-T-octylphenyl, 3-tetradecylphenyl,
There are 4-dodecyloxyphenyl, 2-chlorophenyl and pentafluorophenyl.

The heterocyclic group is a 3- to 8-membered (preferably 1 to 36-membered, preferably 1- to 18-membered, heterocyclic group having at least one hetero atom selected from N, S or O in the ring). (5 to 7 members) represents a heterocyclic group which may be condensed or substituted. 2-pyridyl as a typical example,
There are 4-pyridyl, 4-pyrimidyl, 4-quinolyl, 2-thienyl, 2-furyl, 1-pyrazolyl, 1-imidazolyl, 1,3,4-thiadiazol-2-yl.

In the general formula (C), L ₁ preferably includes the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
249148 and 60-249149. (2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction.

Examples include timing groups described in US Pat. No. 4,248,292. (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, US Pat. No. 4,409,323,
U.S. Pat. No. 4,421,845, JP-A-57-188035.
No. 58-98728, 58-209736,
Groups described in Nos. 58-209737 and 58-209738. (4) A group that utilizes a cleavage reaction due to hydrolysis of an ester.

For example, West German Published Patent No. 2,626,315
Linking group described in No. (5) A group that utilizes a cleavage reaction of imino ketal.

A linking group described in, for example, US Pat. No. 4,546,073.

L ₁ is preferably a group represented by (2) or (3).

P represents an integer of 0 or 1, but p = 0
That is, a compound in which A and Z are directly bonded is preferable.

The following chemical formula 31 shows a specific example of L ₁ . However, * indicates a bonding position with A, and ** indicates a bonding position with Z, respectively.

[0133]

[Chemical 31] The group represented by Z in the general formula (C) is a bleaching accelerator which accelerates bleaching or bleach-fixing of developed silver after the bond with (L ₁ ) _p or A is cleaved, and consequently promotes desilvering. It is a residue, and specifically, a known bleaching accelerator residue can be mentioned.
For example, U.S. Pat. No. 3,893,858, British Patent No. 1138842, JP-A-53-14162.
No. 3, various mercapto compounds, compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-98.
A thiazolidine derivative as described in Japanese Patent No. 54,
Isothiourea derivatives as described in JP-A-53-94927, thiourea derivatives as described in JP-B-45-8506 and JP-B-49-26586, JP-A-49-42349. Thioamide compounds as described in JP-A-55-26506, dithiocarbamate salts as described in JP-A-55-26506, and arylenediamine compounds as described in US Pat. No. 45-52834. These compounds have a substitutable heteroatom contained in the molecule,
It is a preferred example to bond with A- (L ₁ ) _p- in the general formula (C).

The group represented by Z is preferably the following:
In the general formula (BA-1), (BA-2) or (BA
-3) is a group.

[0135]

[Chemical 32] In the formula, * indicates the position at which A- (L ₁ ) _p − is bonded,
R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5, R ₃₂ represents a group having the same meaning as R ₃₁ , a divalent aromatic group having 6 to 10 carbon atoms, or 3 to 8 members. Membered ring, preferably 5
A 6-membered or 6-membered divalent heterocyclic group, X ₁ is-
O -, - S -, - COO -, - SO 2 -, - N (R 33)
_{-, - N (R 33)} -CO -, - N (R 33) -SO 2 -,
-S-CO -, - CO - , - N (R 33) -COO -, -
N = C (R ₃₃ )-, -N (R ₃₃ ) -CO- (NR ₃₄ )-
Or _{-N (R 33) -SO 2 -N} (R 34) - represents,
X ₂ represents an aromatic group having 6 to 10 carbon atoms, and X ₃ is a 3-membered to 8-membered ring, preferably a 5-membered or 6-membered ring having at least one carbon atom bonded to S in the ring. Represents a heterocyclic group, Y ₁ is a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (may be substituted with an aliphatic group having 1 to 4 carbon atoms) , -NHSO ₂ -R ₃₅ or -S
O ₂ NH—R ₃₅ group (here, salt means, for example, sodium salt, potassium salt or ammonium salt), Y ₂ represents a group or hydrogen atom having the same meaning as described for Y ₁ , and r Represents 0 or 1, i represents an integer of 0 to 4, j represents an integer of 1 to 4, and k represents an integer of 0 to 4. However, j Y ₁ is R
_{31 - {(X 1) r} -R 32} i and _{X 2 - {(X 1)} r
-R ₃₂ } is bonded to the substitutable position of _i , and k Y
₁ is bonded at a substitutable position of X ₃ -{(X ₁ ) _r —R ₃₂ } _i , and when k and j are plural, k and j are respectively.
Y _1's represent the same or different, and when i is plural, i (X ₁ ) _r —R _32's represent the same or different. Here, R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R ₃₁ to R ₃₅ represent an aliphatic group, they may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. It is preferably unsubstituted, but examples of the substituent include a halogen atom,
Examples thereof include an alkoxy group (eg methoxy, ethoxy) and an alkylthio group (eg methylthio, ethylthio).

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. For example, those enumerated as the aliphatic group substituents may be mentioned.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₃₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. For example, pyridine ring, imidazole ring, piperidine ring, oxirane ring, sulfolane ring, imidazolidine ring, thiazepine ring, pyrazole ring, triazole ring, thiadiazole ring, oxadiazole ring, thiazole ring, oxazole ring, isoxazole ring, isothiazole ring , A pyrimidine ring, and a pyridazine ring. Examples of the substituent include those enumerated as the aliphatic group substituents.

Specific examples of the group represented by formula (BA-1) include those represented by the following chemical formula 33.

[0139]

[Chemical 33] Specific examples of the group represented by formula (BA-2) include those represented by the following chemical formula 34.

[0140]

[Chemical 34] Specific examples of the group represented by the general formula (BA-3) include those shown in the following chemical formulas 35 to 36.

[0141]

[Chemical 35]

[0142]

[Chemical 36] Specific examples of the compound that releases the bleaching accelerator, which are preferably used in the present invention, are shown in Chemical Formulas 37 to 44 below, but the present invention is not limited thereto.

[0143]

[Chemical 37]

[0144]

[Chemical 38]

[0145]

[Chemical Formula 39]

[0146]

[Chemical 40]

[0147]

[Chemical 41]

[0148]

[Chemical 42]

[0149]

[Chemical 43]

[0150]

[Chemical 44] Others, Research Disclosure Item No.2
No. 4241, No. 11449 and JP-A No. 61-20124.
No. 7, No. 63-106749, No. 63-121843
The compounds described in No. 63-121844 are also used in the same manner.

Further, the bleaching accelerator releasing compound used in the present invention can be easily synthesized based on the description in the above patent specification.

[0152] Formula addition amount structures by different but preferably 1 mol per mol of silver 1 × 10 ^-5 existing in the same layer or an adjacent layer of a compound a compound of component (C), particularly preferably 1 × 10 ^{- 4} to 0.5 mol.

The light-sensitive material of the present invention is blue-sensitive on a support,
It suffices that at least one of each of the green-sensitive and red-sensitive silver halide emulsion layers is provided, and the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited.
As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material,
Generally, the unit photosensitive layers are arranged in order from the support side, that is, a red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

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

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
For example, JP-A-57-112751, JP-A-62-2003.
No. 50, No. 62-206541, No. 62-20654
As described in No. 3, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, 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) / Low-sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH.

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

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

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

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436, and JP-A-62-160448.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

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

The silver halide grains other than the tabular grains of the present invention will be described below.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, those having regular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ", and No. 187 of the same.
16 (November 1979), p.648, ibid. No. 3071.
05 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L. Monetl, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
The monodisperse emulsion described in No. 748 is also preferable.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, No. 18716 and No. 18716.
No. 307105, the relevant parts are summarized in the table below.

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

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

The silver halide forming the inner core of a fogged core / shell type silver halide grain may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but is 0.01 to 0.75 as an average grain size.
μm, and particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

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

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

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

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

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

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

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, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant page 24 to 25, page 649, right column, page 868 to 870, stabilizer 6. 6. Light absorber, pages 25-26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent, page 25, right column, page 650, left column to page 872, right column 8. Dye image stabilizer, page 25, page 650, left column, page 872 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

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

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

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

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

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

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, No. 3,725,067, Research Disclosure No. 24220 (6 June 1984).
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4 , 296,200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,433,99.
9, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
Those described in JP-A No. 6,199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,
The imidazole couplers described in No. 672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282 and 4,409. No. 320, No. 4,576,910,
British Patent No. 2,102,137, European Patent 341,
188A.

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

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, No. 307105, VII-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

For example, R. D. No. 11449, 242
No. 41, JP-A-61-201247, the bleaching accelerator releasing coupler is effective in shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when it is added to.

A coupler capable of releasing a nucleating agent or a development accelerator imagewise during development is described in British Patent No. 2,092.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds which release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. 308A, a coupler that releases a dye that recolors after release, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a coupler that releases a leuco dye described in JP-A-63-75747. Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 1
Specific examples of the high boiling point organic solvent having a temperature of 75 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (for example, triphenyl phosphate, tricresyl phosphate) , 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, di-2-ethylhexylphenylphosphonate , Benzoic acid esters (e.g., 2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate),
Amides (eg, N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (paraffin, dodecyl) Benzene, diisopropyl naphthalene).
As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

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

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, same No. 18
No. 716, right column, page 647 to left column, page 648.
307105, page 879.

The film swelling speed T _1/2 of the light-sensitive material of the present invention is 3
It is preferably 0 seconds or less, and more preferably 20 seconds or less. The film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. in a color developing solution, 1/3
90% of the maximum swollen film thickness reached after 5 seconds of treatment is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

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

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

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, same No. 18
716, page 651, left column to right column, and No. 30710.
No. 5, 880-881 can be used for development processing.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Mention may be made of N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution includes, for example, pH buffers such as carbonates, borates or phosphates of alkali metals, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifoggant such as
If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developing solution contains known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. The classes can be used alone or in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, the contact area with air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation.

The contact area between the photographic processing liquid and air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-60
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set within a range of 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, organic complex salt of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A No. 50-140129;
JP-B-45-8506, JP-A-52-20832,
53-32735, U.S. Pat. No. 3,706,561.
Derivatives described in Japanese Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,43.
Polyoxyethylene compounds described in No. 0; JP-B-45
Polyamine compounds described in JP-A-8836;
9-40,943, 49-59,644, 53
-94,927, 54-35,727, 55-
26,506 and 58-163,940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect, and in particular, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable.
These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain, in addition to the above compounds. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferable.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2 for adjusting the pH. It is preferable to add 0.1 to 10 mol / l of imidazoles such as methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used, such as a coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, etc. It can be set in a wide range depending on the conditions. Of these, the relationship between the number of washing tanks and the water amount in the multi-stage countercurrent system is described in the Journal of the Soc.
yety of Motion Picture an
d Television Engineers No. 6
Volume 4, P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, a solution to such a problem is disclosed in JP-A-62-288,8.
The method of reducing calcium ion and magnesium ion described in No. 38 can be used very effectively.
Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described in Hiroshi Horiguchi, "Fungicide and Antifungal Agent". Chemistry "(1986
Year) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) It is also possible to use the bactericide of.

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

In addition, there is a case where the washing treatment is further followed by a stabilizing treatment. As an example thereof, a stabilizing agent containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure
No. 14,850 and No. 15,159 Schiff base type compounds, No. 13,924 aldol compounds, U.S. Pat. No. 3,719,492 metal salt complexes, JP-A-53- The urethane type compound described in No. 135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A Nos. 56-64339 and 57-57.
-144547 and 58-115438.

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

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

Preferred embodiments will be described below.

1) 80% of the total projected area of silver halide grains
It is preferable that the silver halide grains occupying% or more have an average aspect ratio of 3 or more and less than 8.

2) 80% of the total projected area of silver halide grains
It is preferable that the silver halide grains accounting for at least 5% are tabular grains having an average silver iodide content of 5 mol% or more and 15 mol% or less and containing dislocations.

3) 80% of the total projected area of silver halide grains
It is preferable that the silver halide grains occupying at least 5% are tabular grains having an average aspect ratio of 3 or more and less than 8 and an average silver iodide content of 5 mol% or more and 15 mol% or less and containing dislocations.

[0232]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of emulsion D-1 (grains containing dislocation lines)) (i) Aqueous solution 1 containing 12 g of gelatin and 3.2 g of KBr.
000 ml was kept at 60 ° C. and stirred. (Ii) Silver nitrate aqueous solution (AgNO ₃ 8.2 g) and halide aqueous solution (K
Br 5.7 g and KI 0.35 g were included) was added by a double jet over 1 minute. (Iii) After adding 21.5 g of gelatin, the temperature was raised to 75 ° C. (Iv)
Thereafter, an aqueous silver nitrate solution (136.3 g of AgNO ₃ ) and an aqueous halide solution (containing 3.1 mol% of KI with respect to KBr) were accelerated by a double jet and added over 51 minutes. At this time, the silver potential was kept at −60 mV against the saturated calomel electrode for the first 46 minutes, and then +90 mV.
Changed the silver potential. (V) The temperature was lowered to 40 ° C., and an aqueous silver nitrate solution (containing 3.2 g of AgNO ₃ ) and an aqueous KI solution (containing _2.3 g of KI) were added over 5 minutes. Then, (vi) an aqueous silver nitrate solution (containing 25.4 g of AgNO ₃ ) and an aqueous KBr solution were added by a double jet over 5.35 minutes. At this time, the silver potential was kept at -50 mV against the saturated calomel electrode. (Vii) The produced emulsion was desalted by the flocculation method, gelatin was added, and the pH was adjusted to 5.5 and pAg 8.8. Emulsion D-1 was a tabular grain having 80% of the total projected area occupied by tabular grains, an average equivalent circle diameter of 1.5 μm, an average thickness of 0.19 μm, an average aspect ratio of 7.9, and an average silver iodide content of 4 mol%. It was a particle. (Preparation of emulsion D-2 (grains containing dislocation lines)) Emulsion D-1
Emulsion D-2 was prepared in the same manner as in Emulsion D-1, except that the silver potential was kept at 0 mV with respect to the saturated calomel electrode for the first 46 minutes in the preparation procedure (iv) of 1.
Emulsion D-2 had an average equivalent circular diameter of 1.35 μm and an average thickness of 0.
It was a tabular grain having a particle size of 23 μm, an average aspect ratio of 5.9, and an average silver iodide content of 4 mol%. (Preparation of emulsion D-3 (grains containing dislocation lines)) Emulsion D-1
In the preparation procedure (iv) of
Emulsion D-3 was prepared in the same manner as Emulsion D-1, except that I was changed to 10.0 mol% with respect to KBr.
Emulsion D-3 had an average equivalent circle diameter of 1.43 μm and an average thickness of 0.
The tabular grains had a thickness of 20 μm, an average aspect ratio of 7.2, and an average silver iodide content of 9.4 mol%. (Preparation of emulsion D-4 (grains containing dislocation lines)) Emulsion D-1
In the preparative procedure (iv) of (1), the silver potential was grown at 0 mV against a saturated calomel electrode for the first 46 minutes,
And the KI of the aqueous halide solution is 10.
Emulsion D-4 was prepared in the same manner as Emulsion D-1, except that the content was changed to 0 mol%. Emulsion D-4 was a tabular grain having an average equivalent circle diameter of 1.3 µm, an average thickness of 0.25 µm, an average aspect ratio of 5.2, and an average silver iodide content of 9.4 mol%. (Preparation of emulsion D-5 (grains containing no dislocation lines)) Emulsion D
-1 in preparation procedure (iv), the silver potential was adjusted to the first 46
For 1 minute, the growth was performed while maintaining 0 mV against the saturated calomel electrode, and the KI of the aqueous halide solution was set to 1 against KBr.
0.0 mol%, and in the preparation procedure (v), the KI aqueous solution (KI 2.3 g) was added to the KBr aqueous solution (K
Prepared in the same way except replacing with Br 8.8 g). Emulsion D-5 was a tabular grain having an average equivalent circle diameter of 1.4 μm, an average thickness of 0.23 μm, an average aspect ratio of 6.0, and an average silver iodide content of 9.4 mol%. (Observation of Dislocation Lines of Grains) Dislocation lines were directly observed for each of the emulsions D-4 and D-5 using a transmission electron microscope. The electron microscope is JEM-2000F manufactured by JEOL Ltd.
Observation was performed using XII at an acceleration voltage of 200 kV and a temperature of -120 ° C. FIG. 1 is an observation photograph of Emulsion D-4, and FIG. 2 is Emulsion D-.
5 shows the observation result. In Emulsion D-4, dislocation lines are observed around the grains, but in Emulsion D-5, no dislocation lines are observed.
In both FIGS. 1 and 2, the enlargement ratio is 45,000 times. (Preparation of Coating Sample and Evaluation thereof) Onto an undercoated cellulose triacetate film support, each layer having the composition shown below was multilayer coated to prepare Sample 101 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 B-5 0.07 Second layer (intermediate) Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1. 8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0. 070 HBS-1 0.060 gelatin 0.87 4th layer (Second Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.20 ExC-2 0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 Fifth layer ( Third red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.097 ExC -2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) Cpd-1 0.040 HBS-10 .020 Gelatin 0.80 Seventh layer (first green-sensitive emulsion layer) Emulsion C Silver 0.30 ^{xS-4 2.6 × 10 -5 ExS} -5 1.8 × 10 -4 ExS-6 6.9 × 10 -4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY- 1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green emulsion layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS-5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^{− 3} Gelatin 0.50 9th layer (3rd green emulsion layer) Emulsion D-5 Silver 1.55 Sensitizing dye ExC-1 0.015 ExM-1 0.013 ExM-4 0.065 ExM- 5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 1st Layer (yellow filter layer) Yellow colloidal silver Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95 Eleventh layer (first blue sensitive emulsion layer) Emulsion C Silver 0.18 ExS-78 6 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1.10 12th layer (second blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7. 4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.15 HBS-1 0.050 Gelatin 0.78 13th layer (third blue sensitive emulsion layer) Emulsion F Silver 0.70 ExS− 7 2.8 × 10 ⁻⁴ ExY-2 0.20 HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0. 17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 15th layer The second protective layer) H-1 0.40 B-1 ( diameter ^{1.7μm) 5.0 × 10 -2 B-} 2 ( diameter 1.7μm) 0.10 B-3 0.10 S -1 0. 20 Gelatin 1.20 Furthermore, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property in all layers, W-1,
W-2, W-3, B-4, F-1, F-2, F-3, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-12, F-13, F-14, F-
15, F-16, F-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. The emulsions used in the preparation of Sample 101 are shown in Table 1 below.

[0233]

[Table 1] In Table 1, (1) Emulsions A to G were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to G are described in JP-A-2-34090.
According to the examples of No. 1, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dyes described in each photosensitive layer and sodium thiocyanate.

(3) Preparation of tabular grains is described in JP-A-1-1.
Low molecular weight gelatin is used according to the example of 58426.

[0236]

[Chemical 45]

[0237]

[Chemical 46]

[0238]

[Chemical 47]

[0239]

[Chemical 48]

[0240]

[Chemical 49]

[0241]

[Chemical 50]

[0242]

[Chemical 51]

[0243]

[Chemical 52]

[0244]

[Chemical 53]

[0245]

[Chemical 54]

[0246]

[Chemical 55]

[0247]

[Chemical 56]

[0248]

[Chemical 57] (Sample 102 to Sample 112) Fifth Layer Coupler ExC-
Samples 102 to 112 were prepared in exactly the same manner as Sample 101, except that the emulsion D-5 and the sensitizing dye in the third and ninth layers were changed as shown in Table 2 below.

[0249]

[Table 2] The samples 101 to 112 were exposed to white with a light source having a color temperature of 4800 ° K to perform sensitometry, and the color development processing described below was performed to measure the magenta image density and evaluate the photographic performance.

Treatment method Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C. 33 ml 20 liters Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 liters Water wash 2 minutes 10 seconds 24 ° C. 1200 ml 20 liters Fixed 4 Minutes 20 seconds 38 ℃ 25ml 30 liters Washed with water (1) 1 minute 05 seconds 24 ℃ 10 liters from (2) to (1) Countercurrent piping system. Washing with water (2) 1 minute 00 seconds 24 ° C 1200 ml 10 liters Stability 1 minute 05 seconds 38 ° C 25ml 10 liters Dry 4 minutes 20 seconds 55 ° C Replenishment amount per 35 mm width 1 m length Next, describe the composition of the treatment liquid. .. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-3.0 3.2 Diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxy 4.5 5.5 Ethylamino] -2-methylaniline Sulfate Water was added 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching solution) Mother liquor (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ferric nato 100 .0 120.0 Lithium trihydrate Disodium salt of ethylenediaminetetraacetic acid 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35. Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7 (fixer) mother liquor (g) replenisher (g) ethylenediaminetetraacetic acid sodium salt 0 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Water was added to 1.0 liter 1.0 liter pH 6. 7 6.6 (Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononyl 0.3 0.45 Phenyl ether (average degree of polymerization 10) Ethylenediamine Tetraacetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0 Samples 101-112 were processed for camera photography. After that, the color chart manufactured by Macbeth Co., Ltd. was photographed by irradiating it separately with sunlight (color temperature was 5850 ° K) and with a fluorescent lamp having a relative spectral distribution of F10 three-wavelength region emission type defined in JIS Z8719. Then, the color development processing described above was performed. Further, the processed negative film was stretched on a color photographic paper (stretching ratio 6.7 times), and the change in tint was evaluated using this photograph. The evaluation was performed by visually observing the tint of a gray plate having an optical density of 0.7 taken under a fluorescent lamp.

Further, the above-mentioned treatment was applied to the sample uniformly exposed with an exposure amount giving a magenta density higher than the fog density by 2.0, and the amount of residual silver was measured. A fluorescent X-ray method was used to measure the amount of silver.

The pressure resistance test was conducted as follows. After being placed in an atmosphere having a relative humidity of 55% for 3 hours or more, a load of 4 g was applied with a needle having a thickness of 0.1 mmφ in the same atmosphere, and the emulsion surface was scratched at a speed of 1 cm / sec. After developing this sample, the density was measured with an aperture of 25 μmφ.

The above results are shown in Table 3 below.

[0254]

[Table 3] As is clear from the results shown in Table 3, the sample of the present invention can improve color reproduction (especially when photographing under a fluorescent lamp) without lowering the sensitivity, and also increases the sensitivity. Regardless, the change in fog density due to bending is small,
Further, it exhibits excellent desilvering performance, and it is understood that the effect of the present invention is remarkable.

[Brief description of drawings]

FIG. 1 is an electron micrograph showing the grain structure of silver halide grains of emulsion D-4 of Example 1.

2 is an electron micrograph showing the grain structure of silver halide grains of Emulsion D-5 of Example 1. FIG.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has high sensitivity, excellent desilvering property and pressure property , and has improved color balance change when photographed under a fluorescent lamp. And a silver halide color photographic light-sensitive material.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Another object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and excellent in desilvering property and pressure property .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

Embedded image General formula (1) In the formula (1), Z ¹¹ and Z ¹² are a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus,
Represents an atomic group necessary for forming a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, or a naphthoselenazole nucleus. The above naphthoxazole nucleus, naphthothiazole nucleus and naphthoselenazole nucleus are naphtho [1,2
-D] oxazole nucleus, naphtho [2,1-d] oxazole nucleus, naphtho [2,3-d] oxazole nucleus, naphtho [1,2-d] thiazole nucleus, naphtho [2,1-d] thiazole nucleus, Naphtho [2,3-d] thiazole nucleus, naphtho [1,2-d] selenazole nucleus, and naphtho [2,1]
-D] includes a selenazole nucleus.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

[0064]

Embedded image General formula (2) In the formula, Z ¹³ and Z ¹⁴ are a pyrroline nucleus, a pyridine nucleus, a thiazoline nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an indolenine nucleus, a benzimidazole nucleus, a benzoxazole nucleus, a benzthiazole nucleus, a benzselenazole nucleus, and a naphthoxazole, respectively. Represents a group of atoms required to complete a nucleus, naphthothiazole nucleus, or naphthoselenazole nucleus. The naphtho [1,2-d] oxazole nucleus and the naphtho [2,1-
d] oxazole nucleus and naphtho [2,3-d] oxa
The azole nucleus has naphtho [1,2-
d] thiazole nucleus, naphtho [2,1-d] thiazole nucleus and naphtho [2,3-d] thiazole nucleus, the naphthoxazole benzoselenazole nucleus naphtho [1,2-d] selenazole and naphtho [2,1 -D] selenazole nucleus and the like are included. The aromatic hydrocarbon ring of these nuclei may have various substituents, and those substituents are the same as the substituents on the aromatic hydrogen ring in the case of Z ¹¹ and Z ^12. Can be used. On the 3-position carbon atom of the indolenine nucleus, lower alkyl groups having up to 3 carbon atoms (eg methyl) can be useful as substituents.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0249

[Correction method] Change

[Correction content]

[0249]

[Table 2] The samples 101 to 112 were exposed to white with a light source having a color temperature of 4800 ° K to perform sensitometry, and the color development processing described below was performed to measure the magenta image density and evaluate the photographic performance.

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and at least one non-photosensitive auxiliary layer on a support, said photosensitive material being used. At least 50% of the total projected area of the silver halide grains in at least one of the silver halide emulsion layers is occupied by tabular silver halide grains having an average aspect ratio of 2 or more and having dislocations, and At least one of the photosensitive silver halide emulsion layers contains a trimethine cyanine dye and a monomethine cyanine dye, and at least one hydrophilic colloid layer contains an oxidized product of an aromatic primary amine-based color developing agent. A silver halide color photographic light-sensitive material containing a compound which reacts with a compound to release a bleaching accelerator. 2. The trimethine cyanine dye and the monomethine cyanine dye each have the general formula (A) shown in the following chemical formula 1.
And a silver halide color photographic light-sensitive material according to claim 1, which is represented by the general formula (B) shown below. [Chemical 1] In the general formula (A), A ₁ , A ₂ , A ₃ and A ₄ are each a hydrogen atom, lower alkyl group, alkoxy group, halogen atom, hydroxyl group, aryl group, carboxyl group, alkoxycarbonyl group, cyano group, tri group. It represents a fluoromethyl group, an amino group, an acylamide group, an acyl group, an acyloxyl group, an alkoxycarbonylamino group, and a carboalkoxy group. A ₁ and A ₂ , and A ₃ and A ₄ may be linked to each other to form a naphthoxazole nucleus. R ₀ represents a hydrogen atom, a lower alkyl group or an aryl group. R ₁ and R ₂ each represent an alkyl group. However, R ₁ and R
_At least one of ₂ is an alkyl group having a sulfo radical. X ₁ ^- represents an anion. n
Represents 1 or 2 and 1 is when the dye forms an intramolecular salt. [Chemical 2] In the general formula (B), Z ₁ and Z ₂ are each a nonmetal atom necessary for completing a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, and a pyridine nucleus. Represents a group. R ₃ and R ₄ each represent an alkyl group. X ₂ ^-
Represents an anion. m represents 1 or 2, 1 being when the dye forms an intramolecular salt. 3. The total projected area of the silver halide grains is 80.
The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the silver halide grains accounting for at least 3% have an average aspect ratio of 3 or more and less than 8. 4. The total projected area of the silver halide grains is 80
%. The silver halide color according to claim 1 or 2, wherein the silver halide grains accounting for at least 5% are tabular grains having an average silver iodide content of 5 mol% or more and 15 mol% or less and having dislocations. Photographic material. 5. The total projected area of the silver halide grains is 80.
% Or more of the silver halide grains are tabular grains having an average aspect ratio of 3 or more and less than 8 and an average silver iodide content of 5 mol% or more and 15 mol% or less and having dislocations. 2. A silver halide color photographic light-sensitive material as described in 2.