JPH01185631A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness, desilvering performance and further sensitivity by using a specific bleaching accelerator and specific sensitizing dye together with an emulsion having 5-8 aspect ratio. CONSTITUTION:The light scattering by the emulsion layers of a color photographic sensitive material having at least one silver halide emulsion layers on a base is extremely decreased and the sharpness is improved if at least 50% of the total projection area of the emulsion particles in said material are the planar silver halide particles having 5-8 aspect ratio and at least one kind of the compds. which releases the bleaching accelerator by reacting with the oxidant of an arom. primary amine color developing agent is incorporated into at least one layer. Further, the excellent desilvering performance and sharpness are satisfied and the sensitivity is improved by incorporating the sensitizing dye expressed by formula therein. In formula, Z1: an oxygen atom, etc., Z2: thiazole, etc.; R3: a hydroxyl group, etc., R1, R2: a lower alkyl, etc., R4: a hydrogen atom, etc., V is a hydrogen atom forms a condensed benzene ring by bonding to the same.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a silver halide color photographic material.

(Prior art) Generally, silver halide color photographic materials are basically processed through a color development process and a desilvering process, but in recent years, the industry has been trying to speed up the process, that is, shorten the processing time. Strong demand (in particular, shortening the desilvering process, which accounts for nearly half of the processing time, is a major issue.

Conventionally, as a method of increasing the bleaching strength to speed up the desilvering process, methods have been proposed in which various bleach accelerators are added to bleach baths, bleach-fixing baths, or their pre-baths. Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893.8.
58 specification, British Patent No. 1138842, and JP-A-53-141623, various mercapto compounds having a disulfide bond as described in JP-A-53-95630. Compounds, thiazolidine derivatives as described in Japanese Patent Publication No. 53-9854, isothiourea derivatives as described in Japanese Patent Publication No. 53-94927, Japanese Patent Publication No. 45-8
Thiourea derivatives such as those described in Japanese Patent Publication No. 506, Japanese Patent Publication No. 49-26586, Japanese Patent Publication No. 49-42349
These include thioamide compounds as described in JP-A No. 55-26506, dithiocarbamates as described in JP-A-55-26506, and arylene diamine compounds as described in US Pat. No. 4,552,834.

Some of these bleaching agents do indeed show a bleaching accelerating effect, but they are expensive, have insufficient stability in bleaching baths, and furthermore, the bleaching accelerating effect itself is insufficient. However, it has not yet reached the point where we can be satisfied in terms of practicality.

Also known is a method of processing a photosensitive material in which a mercapto compound or a precursor thereof is present in the photosensitive material using the bleach accelerator. However, when a nuclear mercapto compound is contained in a light-sensitive material, it has a large effect on photographic properties, and the mercapto compound forms a sparingly soluble salt with silver halide in the undeveloped area of the light-sensitive material. However, this method also has many problems.

In contrast, research disclosure
m No. 24241, No. 11449 and JP-A-61
No. 201247 describes bleach-accelerating compound-releasing couplers.

On the other hand, in recent years, silver halide photosensitive materials, especially photographic photosensitive materials, have been developed using ultra-high-sensitivity photosensitive materials such as 15O1600 film, 110, and large magnification materials suitable for small-format cameras such as disks. There is a growing demand for photosensitive materials that have high image quality and high sharpness that can be used in printing.

As a main technique to meet these demands, it is known to use tabular silver halide grains with a diameter-to-thickness ratio (aspect ratio) of 8:1 or more (for example, in Japanese Patent Application Laid-Open No. (Sho 58-113934).

Japanese Unexamined Patent Application Publication No. 1983-1987 concerning the bleach-accelerating compound-releasing coupler mentioned above.
1-2012-47 also describes that tabular silver halide grains are preferably used.

(Problems to be Solved by the Invention) However, although the sharpness is improved when such tabular grains are used, the specific surface area of the grains increases, so desilvering properties are extremely deteriorated, and bleach-accelerating compound-releasing couplers It was found that even if the method was used, it was still insufficient for practical use. In particular, it has been found that this deterioration in desilvering performance is even more remarkable when a J-band forming type sensitizing dye, which is effective for improving the sensitivity of tabular emulsions, is used.

Therefore, an object of the present invention is to provide a silver halide color photographic material that can simultaneously satisfy excellent desilvering performance and excellent sharpness.

Furthermore, the object of claim (2) is to provide a silver halide color that can simultaneously satisfy excellent desilvering performance and excellent sharpness even when using a J-band forming type sensitizing dye that is effective for improving sensitivity. Our objective is to provide photographic materials.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the total projected area of the silver halide emulsion grains is At least 50% are tabular silver halide grains with an average aspect ratio of 5:1 or more and less than 8:1, and at least 1
A silver halide color photographic light-sensitive material characterized in that the layer contains at least one compound that releases a bleaching accelerator by reacting with an oxidized product of an aromatic primary amine color developing agent. It was found that this could be achieved.

As mentioned above, bleach accelerator-releasing compounds are known (JP-A-61-201247, etc.).

However, it has been found that by specifying the average aspect ratio of the silver halide grains used as in the present invention, remarkable effects in both sharpness and desilvering properties can be exhibited.

Next, the tabular silver halide emulsion used in the present invention will be explained in detail.

In the tabular silver halide emulsion used in the present invention, the average aspect ratio means the average value of the ratio of the diameter to the thickness of the halide root grains.

That is, it is the average value obtained by subtracting the diameter of each silver halide grain by its thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the grains when the silver halide emulsion is observed using a microscope or an electron microscope. Therefore, an average aspect ratio of 5:1 or more means that the diameter of this circle is 5 times or more the thickness of the particle, and an average aspect ratio of less than 8:1 means that the diameter of this circle is 5 times or more the thickness of the particle. It means that the diameter of the circle is less than 8 times the thickness of the particle. Further, the proportion of the tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more.

By using such an emulsion, a silver halide photographic material with excellent sharpness can be obtained. The reason for the excellent sharpness is that light scattering by an emulsion layer using such an emulsion is extremely small compared to a conventional emulsion layer.

This can be easily confirmed by experimental methods routinely used by those skilled in the art. The reason why the light scattering of the emulsion layer using the tabular silver halide emulsion is small is not clear, but it is thought to be because the main plane of the tabular silver halide emulsion is oriented parallel to the support surface.

In addition, the diameter of the tabular silver halide grains is 0°2 to 2
The thickness of the 0 particles is 0 μ, preferably 0.3 to 10.0 μ, particularly preferably 0.4 to 3.0 μ.
Preferably it is 0.5μ or less. Here, the tabular silver halide grain diameter refers to the diameter of a circle having an area equal to the projected area of the grain. Further, the grain thickness is expressed as the distance between two parallel grains constituting a tabular silver halide grain.

In the present invention, more preferred tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or less, a grain thickness of 0.3 μm or less, and an average (diameter/thickness) of 5 or more and 10 μm or less. It is as follows.

If the particle diameter exceeds this, it is undesirable because the photosensitive material may be bent, tightly rolled up, or when it comes into contact with a sharp object, abnormalities may occur in photographic performance. , average (diameter/
This is the case of a silver halide photographic emulsion in which grains having a thickness of 5 or more and less than 8 account for 85% or more of the total projected area of all silver halide grains.

The tabular silver halide grains used in the present invention include silver chloride,
Any of silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide may be used, but silver bromide, silver iodobromide containing less than 30 mol% of silver iodide, or less than 50 mol% of silver chloride Silver chloroiodobromide and silver chlorobromide containing 2 mol % or less of silver iodide are more preferred, and the composition distribution in the mixed silver halide may be uniform or localized.

Further, the particle size distribution may be narrow or wide.

The tabular silver halide grain agent used in the present invention is Cu
Reports from gnac+ Chateau and Duffin
Author: Photographic Emulsion
Chemistry” (FocalPress
(Pub., New York, 1966), pp. 66-72, and A, P, H, Trivelli, W, F.
, Sm1thi"Photo, Journal" 8
0 (1940), p. 285, but can be easily prepared by referring to the methods described in JP-A-58-113927, JP-A-58-113928, and JP-A-5B-127921. .

For example, form a seed crystal in which tabular grains exist in an amount of 40% or more by weight in an atmosphere with a relatively high pBr of 1.3 or less. It can be obtained by growing seed crystals while adding During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of parent crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and quality of the solvent, the silver salt used during grain growth, the addition rate of the halide, etc.

When producing the tabular silver halide grains of the present invention, by using a halogenated m solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of the solvent used is preferably in the range of 10-t to 1.0% by weight of the reaction solution, particularly preferably in the range of to-'' to 10-1% by weight.A0 In the present invention, increasing the amount of the solvent used with G
While it is possible to make the particle size distribution monodisperse and increase the growth rate, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

In the present invention, known λ silver halide solvents can be used. Examples of frequently used halogenated carriers include ammonia, thioethers, thioureas, thiocyanate salts, thiazolinthiones, and the like. Regarding thioethers, U.S. Pat. 271. No. 157, No. 3,574,62
No. 8, No. 3,790.387, etc. may be referred to. Regarding thioureas, JP-A-53-824
No. 08, US Pat. No. 55-77737, and U.S. Pat. No. 2.222.264, US Pat.
No. 8.534, No. 3.320,069, and Jikai No. vA53-144319 can be referred to with respect to thiazolinthiones.

In the process of forming or physically ripening silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may coexist. .

When producing the tabular silver halide grains used in the present invention, a silver salt solution (for example, A
gN0. A method of increasing the addition rate, amount, and concentration of the aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used.

These methods are described, for example, in U.S. Pat.
．． No. 925, U.S. Patent No. 3. 650. No. 757, No. 3.672.900, No. 4,242.445,
Reference may be made to the descriptions in JP-A-55-142329, JP-A-55-158124, and the like.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. For chemical exacerbation, for example, H
0Friese? vA Die Grundlag
Ender Photography
Prozesse m1tSilberha'l
“Ogeniden” (Akademische V
erlagsgesellschaft, 1968), pages 675 to 735, can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); Reductive amputation method using noble metal compounds (e.g., gold complex salts, PtS I
A noble metal aggravation method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
, No. 574,944, No. 2. 278゜947, same No. 2.410,689, same No. 2゜728.668,
No. 3,656,955, etc., and U.S. Patent No. 2. 419. No. 974, No. 2,983.
No. 609, US Pat. No. 4,054.458, etc., and US Pat. No. 2,399.083, US Pat. No. 2.
448° OSO and British Patent No. 618,061.

Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.

In the present invention, it is particularly effective to use a sensitizing dye represented by the following general formula (A).

General formula (A) (wherein, Zl represents an oxygen atom, a sulfur atom, a selenium atom, or '>NR).

Z2 is thiazole, benzothiazole, naphtho(1,2
-d) thiazole, naphtho(2,3-d)thiazole,
selenazole, benzoselenazole, naphtho(1,2-
d) selenazole, naphtho[23-d]selenazole,
Benzimidazole, naphtho(1,2-d) imidazole, natuto[2゜3-d]imidazole, benzoxazole, naphtho(1,2-d)oxazole, natuto[
2゜3-d] In addition to representing the oxazole nucleation atomic group,
When m represents 0, the 2-quinoline nucleating atom group is also included; when m represents 1 and Zl represents]N-R3, thiazoline, selenazoline, oxazole or 3.3
- Represents a dialkylindolenine nucleating atom group. These heterocyclic nuclei may be substituted.

R3 is a hydroxyl group, a phenyl group, an alkoxy group,
Represents an alkyl group or alkenyl group having 6 or less carbon atoms which may be substituted with a halogen atom or an alkoxycarbonyl group [for example, a methyl group, an ethyl group, a propyl group, a methoxyethyl group, an ethoxycarbonylmethyl group,
2-fluoroethyl group, phenethyl group, etc.].

R1 and R2 represent an optionally substituted lower alkyl group or alkenyl group. More preferably 8 carbon atoms, which may have a substituent such as a lower alkoxy group, a halogen atom, a carbamoyl group, a carboxy group, an alkoxycarbonyl group, a sulfo group, an acylamino group, an optionally substituted phenyl group, or a hydroxy group. Represents the following lower alkyl group or lower alkenyl group [e.g., methyl group, ethyl group, propyl group, pentyl group, methoxymethyl group, ethoxyethyl group, 2,2.2-trifluoroethyl group, 2,2,3 .3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, carboxymethyl group, carboxyethyl group, 2-sulfoethyl group,
3-sulfoethyl group, 3-sulfobutyl group, 4-sulfobutyl group, phenethyl group, p-sulfophenethyl group, ethoxycarbonylethyl group, 2-hydroxy-3-sulfopropyl! , 2-(2-hydroxyethoxy)ethyl group, 2-acetylaminoethyl group, 2-methylsulfonylaminoethyl group, allyl group, etc.].

R1 represents that it can be linked with a hydrogen atom or R to form a 5- or 6-membered ring.

R4 represents a hydrogen atom when at least Zl represents; , Zl is]N
Z2 does not represent Rs and is also benzimidazole, naphtho (1
, 2-d) imidazole or naphtho(2,3-d) imidazole When the nucleating atomic group is not represented, an ethyl group, propyl group, butyl group, benzyl group, phenethyl group or an optionally substituted phenyl group is used. [Preferable substituents for the phenyl group include a chlorine atom, an alkyl group having 4 or less carbon atoms, and an alkoxy group having 4 or less carbon atoms].

(2) 1 represents a hydrogen atom or a condensed benzene ring formed by linking with V2.

(2) In the case where Zl represents; Preferred examples include an alkylsulfonyl group having 4 or less carbon atoms or a perfluoroalkyl group having 4 or less carbon atoms. When Zl represents an oxygen atom, a sulfur atom, or a selenium atom, 2 is an optionally branched lower alkyl group having 7 or less carbon atoms, a lower alkoxy group having 6 or less carbon atoms, a hydroxy group, or a hydroxy group having 4 or less carbon atoms. represents an acylamino group, a halogen atom, an alkoxycarbonyl group having up to 5 carbon atoms, a carboxy group, an optionally substituted phenyl group having up to 8 carbon atoms, or a hydrogen atom.

■, is V! In addition to expressing the same meaning as , it also indicates that a condensed benzene ring can be formed by connecting with
When R3 is represented, it also represents a hydrogen atom.

The condensed benzene ring represented by the connection of vl and V2 or (2) and (2) may have a substituent, and preferred substituents include an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms. group, a hydroxy group, a halogen atom, a 7syl amino group having 4 or less carbon atoms, or an alkoxycarbonyl group having 5 or less carbon atoms.

m represents 0 or 1. Xo is the acid anion residue u (for example, C1e, Bre, Ie.

, @ e e e CIl SOz , CzHsO3Ox ,
P Fb.

θ BF4), and n represents 0 or 1.

Preferred examples of the heterocycle represented by Zl or Zz include thiazoline, 4-methylthiazoline, selenazoline, thiazole, 4-methylthiazole, 5-methylthiazole, 4-ethylthiazole, 4-phenylthiazole, 4.5-dimethyl. Thiazole, 4.5-diphenylthiazole, 4-methylselenazole, 4-methyloxazole, 4,5-dimethyloxazole, 4-
Phenyloxazole, 5-methyl-4-phenyloxazole, benzothiazole, 5-methylbenzothiazole, 5-ethylbenzothiazole 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-chlorobenzothiazole, 5-chloro-6- Methylbenzothiazole, 5゜6-dimethylbenzothiazole, 5-phenylbenzothiazole, 5-acetylaminobenzothiazole, 6-propionylaminobenzothiazole,
5.6-Simethoxybenzothiazole, benzoxazole, 5-methylbenzoxazole, 5-inpropylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 5-chloro-6-methyl Benzoxazole, 5-phenylbenzoxazole, 5-p-)
Lylbenzoxazole, benzoselenazole, 5-methylbenzoselenazole 1.5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 6-methylbenzoselenazole 1.5-ethylbenzoselenazole 1.5-phenylbenzo selenazole, 5-chlorobenzoselenazole, 5-chloropenzimitasole, 5,
6-cyanobenzimidazole, 5-cyanobenzimidazole, 6-chloro-5-cyanobenzimidazole, 6-chloro-5-trifluthiobenzimidazole,
5-Butoxycarbonylbenzimidazole, 5-ethoxycarbonylbenzimidazole, 5-methylsulfonylbenzimidazole, 6-chloro-5-ethoxycarbonylbenzimidazole, naphtho(1,2-d)thiazole, naphtho[2°3-d] Thiazole, naphtho (
1,2-d) selenazole, naphtho(2,3-d) selenazole, naphtho(1,2-d)oxazole, naphtho[2°3-d]oxazole, 8-methylnaphtho[1°2-d]oxazole, naphtho(2,3-d)imidazole, naphtho(1,2-d)imidazole, 2-quinoline, 6-methyl-2-quinoline, 6-hydroxy-2-
Quinoline, 6-medoxy 2-quinoline, 3,3-dimethylindolenine, 3゜3-diallylindolenine, 3
-Ethyl-3-phenethylindolenine and many others.

In the general formula (A), more preferable compounds are those represented by the following general formula (B) or (C).

General formula (B) In the formula, 22+ represents the same meaning as Zl. Z! ! represents a sulfur atom, a selenium atom,;NR, , -CH=CI(-, and R23 has the same meaning as R3.

RZ+ and R1 have the same meaning as R1 or R2.

More preferably, total carbon atoms may be substituted with a hydroxy group, a fluorine atom, a chlorine atom, a carboxy group, an alkoxycarbonyl group, or a sulfo group, and the carbon atoms in the chain may be substituted with an oxygen atom or a sulfur atom. It represents an alkyl group or alkenyl group having 6 or less carbon atoms, or a phenylalkyl group having 7 or less carbon atoms in total which may have the above-mentioned substituents.

V21 and VZa represent the same meaning as V. ■2□ and Z when Z2 represents;N-R;
VZS when representing R, , has the same meaning as (2) when Z represents ]N-R3. Also, 2g+)N-
■t□ and Zo when expressing something other than R3; N-R,
, when vz% represents something other than , has the same meaning as ①8 when 2° represents something other than]N-R1. Particularly preferable examples of ■2□ when Z21 represents an oxygen atom include:
Even if substituted with a chlorine atom, an alkyl group having 6 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, an alkyl group having 4 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, a chlorine atom, a hydroxy group, etc. When Z21 represents a sulfur atom or a selenium atom, particularly preferred v2□ and Z2□ represent a sulfur atom,
Alternatively, particularly preferred VtS when representing a selenium atom include the substituent shown as an example of particularly preferred (3) when Zzl above represents an oxygen atom, an acylamino group having 2 or less carbon atoms, or an alkylcarbonyl having 5 or less carbon atoms. This is a case where Z22 represents a group, a carboxy group, or a hydrogen atom.
Particularly preferred VZ when represents -CH=CH-5
S represents an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, or a chlorine atom.

vii when L+ represents N−R, Zl2 is;N
-Vt & and Zll when representing -RZ3)N-R3
Vt3.222 when expressing something other than] N-R.

When vzh represents something other than Zl, respectively]N-R3
■3 and Zl when representing]N-R.

It has the same meaning as ``■'' when representing something other than, and in the latter case, a particularly preferable example is a hydrogen atom, a carbon number of 4
This refers to the following alkyl groups, alkoxy groups having 4 or less carbon atoms, hydroxy groups, alkylcarbonylamino groups having 3 or less carbon atoms, or chlorine atoms.

VZI represents that a fused benzene ring can also be formed by connecting with ■ or Vt3, and VtS means that when Z2□ represents a sulfur atom, a selenium atom, or N-R2, This means that it can also be formed. These condensed benzene rings may be further substituted with an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, a chlorine atom, or the like.

xP represents an acid anion residue, and nz+ represents 0 or 1.

General formula (C) In the formula, Zl1 and Z32 have the same meaning as Zl.

R31 and R3□ have the same meaning as R21 or R2□, and R21 or R2□ is more preferable.
It has the same meaning as the more preferable one.

R33 is a hydrogen atom or connected to R31 to form 50 or 6
Indicates that a member ring can be formed.

R34 is at least one of Zl1 or Z3□)NR
When s represents a hydrogen atom, Zl1 and Z
When both 32 represent something other than; N-R, an ethyl group,
It represents a propyl group, a butyl group, a phenyl group, or a phenethyl group, and among the latter, an ethyl group and a propyl group are particularly preferred.

V3. and 'lh4 represent the same meaning as VZI or Vt4.

vo and V33, when Z1+ represents]N-R, and when C represents]N-R, ■2 and ■ko,
When 231 represents an oxygen atom, selenium atom or sulfur atom, it has the same meaning as (2) and (3) when Zl represents something other than:NR.

v3s and Vj& are respectively ■ and ■ when Zl represents]N-R1 when Zzz crab l:NRs, and when 23K represents an oxygen atom, selenium atom or sulfur atom, ■□ and ■, respectively, when Z represents something other than]N to R3.

and V33 when Z and 1 represent)N-R1 and V)6 when Lx represents)N-RS, respectively.
More preferable examples include a hydrogen atom, a chlorine atom, and a trifluoromethyl group, and V when Zl1 represents something other than]N-R. and V when 21m) represents something other than m-RS. is more preferable.

Examples include a hydrogen atom, an alkyl group having 6 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, and an alkylcarbonylamino group having 4 or less carbon atoms in total. Also, ■3□ and Z32 when Zl1 represents N-R6
More preferable examples of V3S when represents UN-R6 include a chlorine atom, a fluorine atom, an alkylcarbonyl group having a total of 5 or less carbon atoms, an alkylsulfonyl group having 3 or less carbon atoms, and a perfluorocarbon group having 4 or less carbon atoms. Particularly preferable examples of an alkyl group or a cyano group include a chlorine atom, a trifluoromethyl group, and a cyano group. More preferred examples of V'Jt when 231 represents an oxygen atom and V3S when Z3□ represents an oxygen atom include a chlorine atom, a phenyl group (substituted with a methyl group, an ethyl group, a methoxy group, a chlorine atom, etc.). Zl
■3□ when 1 represents a sulfur atom or selenium atom and V3 when Z3□ represents a sulfur atom or selenium atom
More preferable examples of S include a chlorine atom, a phenyl group (
methyl group, ethyl group, methoxy group, chlorine atom, etc.), alkyl group having 6 or less carbon atoms, alkoxy group having 4 or less carbon atoms, hydroxy group, alkylcarbonylamino group having 4 or less carbon atoms in total , an alkoxycarbonyl group having a total carbon number of 5 or less, a carboxy group, or a hydrogen atom.

Furthermore, v, 2 is connected with ■, 1 or ■33, and VS
S represents that it can also be linked to V34 or V3b to form a condensed benzene ring, respectively. These condensed benzene rings may further have a substituent. Preferred substituents include, for example, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, a chlorine atom, or an alkoxycarbonyl group having 3 or less carbon atoms in total.

X? 1 represents an acid anion residue, and n31 represents 0 or 1.

Next, specific examples of compounds used in the present invention are listed,
The present invention is not limited to these.

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In order to incorporate the sensitizing dyes used in the present invention into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or they may be dispersed in water, acetone, methanol, ethanol, propatool,
It may be added to the emulsion after being dissolved in a solvent such as methyl cellosolve, 2,2,3,3-tetrafluoropropatol, N,N-dimethylformamide or a mixture thereof. Ultrasonic waves can also be used for dissolution. Also,
As a method for adding this sensitizing dye, US Pat. No. 3,469,
987, a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 4
6-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion;
No. 89, Special Publication No. 44-27,555, Special Publication No. 57-2
A method of dissolving in an acid and adding the solution to an emulsion as described in No. 2,091, etc., or a method of making an aqueous solution in the presence of an acid or a base and adding it to an emulsion; US Pat. No. 3,822.135; A method in which an aqueous solution or colloidal dispersion in which a surfactant is present is added to an emulsion as described in U.S. Pat. No. 4,006,025, etc.;
No. 3, a method of directly dispersing in a hydrophilic colloid and adding the dispersion to an emulsion as described in JP-A-58-105,141; as described in JP-A-51-74,624;
It is also possible to use a method in which a red-shifting compound is used to dissolve the compound and the solution is added to the emulsion.

The sensitizing dye represented by formula (A) may be added to the emulsion at any stage of emulsion preparation known to be useful. For example, US Patent 2,7
No. 35,766, U.S. Pat. No. 3,628,960, U.S. Pat. 183. No. 756, U.S. Pat. No. 4,225.
No. 666, JP-A-58-184,142, JP-A-60
- a period prior to the silver halide grain formation step or/and desalting as disclosed in No. 196°749;
As disclosed in JP-A No. 58-113,920, etc., the period immediately before or during chemical ripening; the period after chemical ripening and before coating; any period or process before the emulsion is coated; It may be added in. Furthermore, as disclosed in the specifications of U.S. Pat. Compounds and compounds to be added separately, such as during the formation process and during the chemical ripening process or after the completion of chemical ripening, or before or during the chemical ripening process and after the completion of chemical ripening. may be added in different combinations.

The amount of the sensitizing dye represented by the general formula (A) of the present invention is 4 x 10-'8 x 10 per mole of silver halide.
-" mole, but for the more preferred silver halide grain size of 0.2 to 1.2 .mu.m, about 5.times.10.sup.-" to 2.times.1O-3 mol is more preferred.

The tabular silver halide grains of the present invention can be spectrally sensitized with methine dyes other than those mentioned above, if necessary. In addition to the above-mentioned improvement in sharpness, the tabular silver halogenide grains of the present invention also have a high spectral velocity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Useful sensitizing dyes include, for example, German Patent No. 929.
No. 080, U.S. Patent No. 2,493,148, U.S. Patent No. 2,
No. 503,776, No. 2,519.001, No. 2
．． No. 912,329, No. 3,656,959, No. 3,672,897, No. 4,025,349, British Patent No. 1゜242.588, Japanese Patent Publication No. 1973-1403
Examples include those described in No. 0.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of superchromic enhancement.

Representative examples are U.S. Patent No. 2.688.545 and U.S. Pat.
, 911,229, 3.391.060, 3,522,052, 3,527.641, 3,617.293, 3,628,964 ,
Same 3rd. 666, 480, same No. 3,672,89
No. 8, No. 3,679.428, No. 3.814,6
No. 09, No. 4.026,707, British Patent No. 1.
344゜281, Special Publication No. 43-4936, 53-
No. 12375, JP-A-52-109925, JP-A No. 52-
No. 110618.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptothiazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes,
For example, triazaindenes; tetraazaindenes (
antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as can be added.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The bleach accelerator-releasing compound used in the present invention will be described in detail below.

The compound that releases the bleach accelerator in the present invention includes:
Preferably, compounds represented by the following general formula (I) can be mentioned.

General formula CI) A-(L), -Z (wherein, A reacts with the oxidized developing agent to form (L), -Z)
represents a group whose bond with Z is cleaved, and represents a group whose bond with Z is cleaved upon reaction with a timing group or an oxidized developing agent, p represents an integer from 0 to 3, and when p is a plurality of p Each symbol represents the same or different, and Z represents a group that exhibits a bleaching accelerating effect when the bond with A-(L) is cleaved. ) Furthermore, compounds represented by the following general formula (II) are preferred.

General formula (I') A-(L, ), -(L, iZ (wherein, A is (L, ),
-(Lz)b represents a group whose bond with -z is cleaved,
L represents a timing group or a group whose bond with (L, ), -Z is cleaved upon reaction with an oxidized developing agent;
2 represents a timing group or a group whose bond with Z is cleaved by reaction with the developed crude drug oxidized product, and Z represents A (L+
)-(Lz) represents a group that exhibits a bleaching promoting effect when the bond with b is cleaved, and a and b each represent 0 or 1.

)-i In formulas (1) and (vi), A specifically represents a coupler residue or a redox group.

As the coupler residue represented by A, known ones can be used. For example, yellow coupler residues (e.g., open chain ketomethylene type coupler residues), magenta coupler residues (e.g., 5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc. coupler residues), cyan coupler residues (e.g., phenol type coupler residues), , naphthol-type coupler residues), and colorless coupler residues (for example, indanone-type, acetonephenone-type coupler residues). Also, U.S. Patent No. 4,315,070;
．． 183. 752, 3.96L 959 or 4,171,223.

-i Preferred examples when A represents a coupler residue in formula (I') are the following general formulas (Cp-1), (Cp-2
), (Cp-3), (Cp-4), (Cp-5), (C
p-6), (Cp-7), (Cp-8), (Cp-9)
Or, when it is a coupler residue represented by (Cp-10).

These couplers are preferred because of their high coupling speed.

General formula (Cp-1) Rs , CCHCN HRs t General formula (Cp-2) R5ZNHCCHCNHR53 General formula (Cp-3) General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) General formula (C
p-8) (Rbz)e General formula (Cp-9) General formula (Cp-10) In the above formula, the free bond derived from the camping position represents the bonding position of the coupling end and leaving group.

In the above formula, R5l+ R52+ R51+ R54+
R5S+Ra6. Rsy, Rs, Rs
l, Rh. + R61+ Rb2 or Rb3
If it contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is from 8 to 40, preferably from 10 to 30, otherwise the total number of carbon atoms is preferably 15 or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above-mentioned substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range.

R5I to R63, d and e will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group, or a heterocyclic group, R4□ represents an aromatic group or a heterocyclic group, and R431R44 and R4S represent a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group.

R5I represents the same meaning as R41. Rsi and R5
3 each represents the same meaning as R4□. R54 is R41R
,,5OZN- group, R,, S- group, R43〇-group 2■ Rss represents a group having the same meaning as R41. R5 & and Rst each have the same meaning as the R43 group, R,, S- group,
R = 30- group, R,, C0N- group, or R,, SO
, represents an N- group. R58 represents a group having the same meaning as R41. R59 is a group having the same meaning as R41, R,, C0N-
group, R410CON- group, R43R4ff R4,5O2N- group, R4x N CON- group, R4:
l R44Ra5 R4, 〇- group, Ra + S- group, halogen atom, or when d is plural, plural R39s represent the same substituent or different substituents. Moreover, each R59 may become a divalent group and connect to form a cyclic structure.

As an example of a divalent group for forming a cyclic structure, 43
43 is a typical example. Here f is 0 to 4
and g is an integer from 0 to 2, respectively. R4° represents a group having the same meaning as R41. R6 is a group with the same meaning as R41, R6□ is a group with the same meaning as Ra +, Ra
, CON H- group. R6□ represents the same group as R41, R,,0CONH- group, R,,5O2NH- group, R,,NC0N- group, R44R4゜halogen atom or R4,N- group, R63 is R
a a R45 R43NGO- group, R,, SO□N- group, R44Ra
a R,3NSO□- group, R,, SO,- group, Ra 30
Represents a CO- group, R, 3O-3o□- group, halogen atom, nitro group, cyano group, or R,, CO-, W. e
represents an integer from 0 to 4. Multiple R6□ or R
63 each represents the same or different thing.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Typical examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, (1)-butyl group, (
i)-butyl group, D)-amino group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, 1,
Examples thereof include a 1°3.3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

The aromatic group is preferably a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

Typical examples of heterocyclic groups include 2-pyridyl group, 2-thienyl group, 2-furyl group, 1-imidazolyl group, 1-indolyl group, phthalimido group, and 1゜3.4-thiadiazol-2-yl group. , 2-quinolyl group, 2,4-dioxo-1,3-imidazolidin-5-yl group, 2,4-dioxo-1,3-imidazolidin-3-yl group, succinimide group, 1.2.4 -triazol-2-yl group or 1-pyrazolyl group.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R470- group, R,, S- group, R4? C-group, Raq
OCO- group, R43CCO- group, R46R,,R,.

group, R,, O3O□- group, cyano group or nitro group. Here, R46 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R4? , R4B and R49 each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

Next, preferred ranges of RS l to R61, d and e will be explained.

RSt is preferably an aliphatic group or an aromatic group.

RSZ+ R53 and R5S are preferably aromatic groups.

RS4 is preferably an R4,C0NH- group or an R4,-N- group. R16 and R57 are aliphatic groups, R4, O-
or R4,S- group is preferred. Rss is preferably an aliphatic group or an aromatic group. In general formula (Cp-6), R59 is a chloro atom, an aliphatic group, or R4, C0N
The H- group is preferred. d is preferably 1 or 2. Rbo
is preferably an aromatic group. In general formula (Cp-7), R
59 is preferably an R,,C0NH- group. General formula (Cp-
In 7), d is preferably 1. R61 is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), e is preferably O or 1. R6□ is R,,0C
ONH- group, Ra ICON H- group or R,, SO
, NH- groups are preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In general formula (Cp-9), Rb3
As R4,C0NH- group, R4,5O2NH- group,
A nitro group or a cyano group are preferred.

In general formula (Cp-10), R63 is R,,NC0-
group, R43CCO- group or R,3CO- group is preferred.

Next, typical examples of R5I to Rh30 will be explained.

RSt includes (1)-butyl group, 4-methoxyphenyl group, phenyl group, '3-(2(2,4-di-t-
Examples include amylphenoxy)butanamido)phenyl group and methyl group. 2 for RSt and R53
-chloro-5-dodecyloxycarbonylphenyl group,
2-chloro-5-hexadecylsulfonamidophenyl group, 2-chloro-5-tetradecanamidophenyl group,
2-chloro-5-+4- (2,4-di-amylphenoxy)butanamido) phenyl group, 2-chloro-5
-(2-(2,4-di-t-amylphenoxy)butanamide) phenyl group, 2-methoxyphenyl group, 2-methoxy-5-tetradecyloxycarbonylphenyl group, 2-chloro-5-(1-ethoxyphenyl group) carbonylethoxycarbonyl) phenyl group, 2-pyridyl group, 2-chloro-
5-octyloxycarbonylphenyl group, 2.4-dichlorophenyl group, 2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenyl group, 2-
Examples include chlorophenyl group or 2-ethoxyphenyl group.

R54 is a 3-(2-(2,4-di-monoamylphenoxy)butanamido)benzamide group, 3-
[4-(2,4-di-t-amylphenoxy)butanamide)benzamide group, 2-chloro-5-tetradecanamideaniline group, 5-(2,4-di-t-amylphenoxyacetamide)benzamide group, 2- Chloro-5
-dodecenylsuccinimideanilino group, 2-chloro-
5-(2-(3-t-butyl-4-hydroxyphenoxy)tetradecanamide)anilino group, 2.2-dimethylpropanamide group, 2-(3-pentadecylphenoxy)butanamide group, pyrrolidino group or N, N -dibutylamino group.

As R5, 2,4.6-) dichlorophenyl group,
2-chlorophenyl group, 2.5-dichlorophenyl group,
2,3-dichlorophenyl group, 2,6-dichloro-4-
methoxyphenyl group, 4-(2-(2,4-di-monoamylphenoxy)butanamido)phenyl group or 2.
A preferred example is 6-dichloro-4-methanesulfonylphenyl group. R5& is a methyl group, an ethyl group,
Isopropyl group, methoxy group, ethoxy group, methylthio group, ethylthio group, 3-phenylureido group, or 3
-(2,4-di-t-amylphenoxy)propyl group. Rst is 3-(2゜4-di-monoamylphenoxy)propyl group, 3-(4-(2-(
4-(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamido)phenyl]propyl group, methoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2-(2-octyloxy-5-[2-octyloxy) -5-(1,1,3,3-tetramethylbutyl)
phenylsulfonamide] phenylsulfonamide] ethyl L 3-(4-(4-dodecyloxyphenylsulfonamido) phenyl) propyl group, L 1-dimethyl-2-(2-octyloxy-5-(1,1,3 ,3
-tetramethylbutyl) phenylsulfonamide] ethyl group, or dodecylthio group. Rss includes 2-chlorophenyl group, pentafluorophenyl group, heptafluoropropyl group, 1-(2,4-di-t-
amylphenoxy)propyl group, 3-(2,4-di-1
-amylphenoxy)propyl group, 2,4-di-t-amylmethyl group, or furyl group. R59 is a chlorine atom, a methyl group, an ethyl group, a propyl group,
Butyl group, isopropyl group, 2-(2,4-di-t-amylphenoxy)butanamide group, 2-(2,4-di-
t-amylphenoxy)hexanamide group, 2-(2,
4-di-t-octylphenoxy)octanamide group,
2-(2-chlorophenoxy)tetradecanamide group,
2- (4-(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamide group, or 2- (2-
A (2,4-di-t-amylphenoxyacetamido)phenoxy)butanamide group is mentioned. R1,. Examples include 4-cyanophenyl group, 2-cyanophenyl group, 4
-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-chloro-3-cyanophenyl group, 4
-Ethoxycarbonylphenyl group or 3,4-dichlorophenyl group. R61 is a dodecyl group, hexadecyl group, cyclohexyl group, 3-(2,4
-di-t-amylphenoxy)propyl group, 4-(2,
4-di-t-amylphenoxy)butyl group, 3-dodecyloxypropyl group, t-butyl group, 2-methoxy-5
-dodecyloxycarbonylphenyl group or 1-naphthyl group. R6□ is an isobutyloxycarbonylamino group, an ethoxycarbonylamino group,
Phenylsulfonylamino group, methanesulfonamide group, benzamide group, trifluoroacetamide group, 3-
Examples include phenylureido group, butoxycarbonylamino group, or acetamido group. R43 is a 2,4-di-t-amylphenoxyacetamide group,
2-(2,4-di-L-amylphenoxy)butanamide group, hexadecylsulfonamide group, N-methyl-N
-octadecylsulfamoyl group, N,N-dioctylsulfamoyl group, 4-t-octylbenzoyl group, dodecyloxycarbonyl group, chlorine atom, nitro group,
Cyano group, N-(4-(2,4-di-t-amylphenoxy)butyl)carbamoyl group, N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl group,
Examples include methanesulfonyl group and hexadecylsulfonyl group.

When A represents a redox group in general formula (1), it is specifically represented by the following general formula (n).

General formula (n) A, -P-(X=Y), 1-Q-At In the formula, P and Q each independently represent an oxygen atom or a monosubstituted or unsubstituted imino group, and n X and Y
At least one of represents a methine group having -(Ll), -(L2)b-Z as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is 1 to n XXn representing an integer of 3
(Y represent the same or different things), A,
and A2 each represent a hydrogen atom or a group that can be removed by an alkali. Here, the case where any two substituents of P, X, Y, Q, A1 and A2 become divalent groups and connect to form a cyclic structure is also included. For example (X=
Y) forms a benzene ring, a pyridine ring, etc.

When P and Q represent a substituted or unsubstituted imino group, preferably an imino group substituted with a sulfonyl group or an acyl group, P and Q are represented as shown below.

General formula (N-1) General formula (N-2) *-N-**
* -N -**SO□-G
Co-G Here, the * mark represents the bonding position with A1 or A2,
The mark ** represents the position where -(X = Y-)- is bonded to one of the free bonds.

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (e.g. methyl group, ethyl group). benzyl group, phenoxybutyl group, isopropyl group, etc.), substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms (e.g. phenyl group, 4-methylphenyl group, 1-naphthyl group, 4-dodecyloxyphenyl group) ), or a 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom, or an oxygen atom as a hetero atom (e.g., 2-pyridyl, 1-phenyl-4-imidazolyl, 2-furyl, benzothienyl group, etc.) are preferred examples.

In general formula (It), P and Q are preferably each independently an oxygen atom or a group represented by general formula (N-1).

When A and Az represent a group that can be removed by an alkali (hereinafter referred to as a precursor group), preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, A type of precursor group using the reverse Michael reaction described in Patent No. 4,009,029, and an anion generated after the ring cleavage reaction described in U.S. Patent No. 4,310,612 are used as an intramolecular nucleophilic group. Precursor group of the type, U.S. Pat. No. 3,674,478, No. 3,
No. 932,480 or US Pat. No. 3,993.661, the anion transfers electrons through a conjugated system, thereby causing a cleavage reaction, as a precursor group, U.S. Pat. No. 4,3
35,200, or a precursor group that causes a cleavage reaction by electron transfer of the reacted anion after ring cleavage, or U.S. Pat. Nos. 4,363,865 and 4,410,6.
Examples include a precursor group using an imidomethyl group described in No. 18.

In general formula (II), preferably P represents an oxygen atom and A2 represents a hydrogen atom.

More preferably in general formula (II), X and Y
is a methine group having -(L,), -(L,), or -Z as a substituent, except when X and Y are substituted or unsubstituted methine groups.

Among the groups represented by the general formula (n), particularly preferred groups are represented by the following general formula (I [I) or (IV).

General formula CI[) -At General formula (IV) * In the formula, the * mark represents the bonding position of -(L,), -(LZ)b -Z, and P, Q, A, and A2 are the general formula (n
), Rba represents a substituent, and q represents an integer from 0.1 to 3. q
When is 2 or more, two or more Rha may be the same or different, and when two Rba are substituents on adjacent carbons, it also includes the case where they are connected as divalent groups to represent a cyclic structure. do. At that time, a benzene condensed ring is formed, such as naphthalenes, penzonorhornenes, chromans, indoles, benzothiophenes, quinolines, benzofurans, 2,3-dihydrobenzofurans, indanes, or indenes. It becomes a ring structure,
These may further have one or more substituents. Examples of preferred substituents when these fused rings have substituents, and Rba when R84 does not form a fused ring
Preferred examples are listed below. That is, R
4,5, halogen atom, R430- group, R43S, group,
R,, Nso;- group, R43CON- group, R44R43 R,, SO□N- group, R, 3C0- group, R4, Coo-
group, R43NCON- group, R,, R,S.

Here, R41%, R43, R44 and R4% have the same meanings as previously explained. The following are typical examples of Rba. That is, methyl group, ethyl group, t-butyl group, methoxy group, methylthio group, dodecylthio group, 3-(2,4-di-L-amylphenoxy)
Propylthio group, N-3-(2,4-di-monoamylphenoxy)propylcarbamoyl group, N-methyl-N-
Examples include octadecyloxycarbamoyl group, methoxycarbonyl group, dodecyloxycarbonyl group, propylcarbamoyl group, hydroxyl group, or N,N-dioctylcarbamoyl group. An example of two R64s forming a ring structure is H.

In general formulas (III) and (IV), P and Q
preferably represents an oxygen atom.

-C in formulas (III) and (IV) A1 and A
2 preferably represents a hydrogen atom.

The group represented by L2 in general formula (I') may or may not be used in the present invention. Although it is preferable not to use it, it is selected as appropriate depending on the purpose. When L and L2 represent a timing group, the following known linking groups may be mentioned.

(1) A group that utilizes the cleavage reaction of hemiacetal, for example, U.S. Pat. No. 4,146.396, JP-A-60-2491
This group is described in No. 48 and No. 60-249149 and is represented by the following general formula. Here, the * mark is the general formula (n
) represents the bonding position on the left side, and ** represents the bonding position on the right side in general formula (n).

In the formula, W represents an oxygen atom, a sulfur atom or a -N-Rh'r group, Rh and R1 represent a hydrogen atom or a substituent, RAT represents a substituent, and t represents 1 or 2. When t is 2, there are two... was. When R6S and Rbb represent a substituent, representative examples of R67 are R69 group, Rh-Co- group,
R,, SO, - group, R,, NGO- group are groups having the same meaning as R11 explained in Mataha, and R7° is a group having the same meaning as R43. R65% Each of Rbb and R67 represents a divalent group, and the case where they are linked to form a cyclic structure is also included. Specific examples of the group represented by general formula (T-1) include the following groups.

噸H2CH3 (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction Examples include timing groups described in US Pat. No. 4,248,962. It can be expressed by the following general formula.

General formula (T-2) *-Nu-Li nk-E-** In the formula, the * mark represents the bonding position on the left side in general formula (II), and the ** mark represents the bonding position on the right side in general formula (n). Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E represents an electrophilic group, which undergoes nucleophilic attack from Nu and forms a bond with **. is a group that can cleave, and Link represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by general formula (T-2) are as follows.

NO□ *-0(CH,), NC-** CH(CI-13)2 (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, U.S. Pat. No. 4,409,323 or U.S. Pat.
It is a group described in No. 21,845 and represented by the following general formula.

General formula (T-3) In the formula, *, **, W, R, , Rb2 and t are (
It has the same meaning as explained for T-1). Specifically, the following groups may be mentioned.

(4) A group that utilizes a cleavage reaction due to ester hydrolysis.

For example, the linking groups described in West German Published Patent Application No. 2.626.315 include the following groups.

In the formula, * and ** have the same meaning as explained for general formula (T-1).

General formula (T-4) General formula (T-5) (5) A group that utilizes the cleavage reaction of iminoketal, for example, a linking group described in U.S. Patent No. 4,546.073, and is represented by the following general formula. It is a group that can be used.

General formula (T-6) In the formula, * marks, ** marks and W have the same meanings as explained in general formula (T-1), and R6[1 represents the same meaning as R67. Specific examples of the group represented by general formula (T-6) include the following groups.

In general formula (1'), when the group represented by is a group that reacts with the oxidized developing agent after being cleaved from A to cleave (L,)b-Z, specifically, after cleavage from A, A group that becomes a coupler or a group that becomes a redox group. Similarly, when the group represented by L2 represents a group that cleaves Z by reacting with the oxidized developing agent after being cleaved from A-(L,)b, more specifically, after being cleaved from A(L+)b, the group cleaves Z. A group that becomes a redox group or a group that becomes a redox group.

For example, in the case of a phenol type coupler, the group serving as a coupler is a group that is bonded to A- or A (L+)b- at an oxygen atom other than a hydrogen atom of a hydroxyl group. In the case of 5-pyrazolone type couplers, 8- or A
-(L,), -. In these examples, a phenol type coupler or a 5-pyrazolone type coupler is formed only after separation from 8- or A (L+)b-, respectively. Their coupling positions are (1,,
) It has b-2 or Z.

When Ll and L2 represent a group serving as a coupler, preferably the following general formula (V), (Vl), (■) or (■
). In the formulas below, the symbol * is the general formula (I
) represents the bonding position on the left side, and the ** mark represents the bonding position on the right side.

General formula (V) General formula (■) t General formula (■) General formula (■) In the formula, ■1 and ■2 represent substituents, ■1, ■4,
■, and ■ represent a nitrogen atom or a substituted or unsubstituted methine group, ■ represents a substituent, X represents an integer from 0 to 4, and when X is plural, ■, are the same or different. and two (1) may be connected to form a cyclic structure. ■8 is -CO- group, SOz-
group, an oxygen atom or a substituted imino group, (1)9 represents a group of nonmetallic atoms for constituting a membered ring, and Vlo represents a hydrogen atom or a substituent. However ■.

and ■2 each represent a divalent group and are connected to ＼ * You may.

■1 preferably represents an Rt+ group, and ■2 represents R? Z group,
RtzCO- group, RlxNCO- group, R? 4 R7zSOtl! s, R,, S- group, RtzO- group,
or Rq3SOzN- group is a preferred example. ■.

Examples of when 1, 4 and 7 are linked to form a ring include indenes, indoles, pyrazoles, and benzothiophenes.

When (1), (4), (3), and (3) represent a substituted methine group, the preferred substituent is R? 1 group, R, 30- group,
Examples include an R,, S- group, or an R,, CONH- group.

(2) Preferred examples of halogen atom, Rt+ group, R
,, C0NH- group, R,, SO, LNH- group, R1, 〇- group, R,, S- group, Rt3Nco- group, R? 4 R? The 300C- group is a preferred example. ■Multiple ■.

Examples of when these are linked to form a cyclic structure are naphthalenes, quinolines, oxindoles, benzodiazepine-2,4-diones, benzimidazole-2-
ions or benzothiophenes.

When ① represents a substituted imino group, preferably R'r x
It is based on N.

The ring structures are indoles, imidazolinones, ■.

2.5-Thiadiazoline-1,1-dioxides, 3-
Pyrazolin-5-ones, 3-isooxazoline-5-
Examples include on-class and 蒐类.

Vl. A preferred example of R? 3 groups, R130-groups, and groups.

In the above, R? + and R7□ represent an aliphatic group, an aromatic group, or a heterocyclic group, and R? 1, R74 and R7
S represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Here, the aliphatic group, aromatic group and heterocyclic group have the same meanings as previously explained for R41. However, the total number of carbon atoms contained in these groups is preferably 10 or less.

Representative examples of the group represented by general formula (V) include the following groups.

Representative examples of the group represented by the -ta formula (Vl) include the following groups.

CH3 Representative examples of the group represented by the general formula (■) include the following groups.

* * * * * * * * * * * * Representative examples of the group represented by the general formula (■) include the following groups.

* * In the -S formula (II), when the group represented by L2 represents a group that becomes a redox group, it is preferably a group represented by the following general formula (IX).

General formula ([X) *-P'-(X' = Y') -Q'-A'
2n' In the formula, the * mark represents the bonding position to the left side in general formula (1), and A', P', Q' and n' are in the general formula (1).
A, , P, Q and n each have the same meaning as explained in n), and n' pieces of X' and n' pieces of Y'
At least one of represents a methine group having +L--Z or Z as a substituent, and the other X' and Y' represent a substituted or unsubstituted methine group or a nitrogen atom.

Here, the case where any two substituents of A'2, P', Q', X' and Y' become divalent groups to form a cyclic structure is also included. Such ring structures are, for example, benzene rings or pyridine rings.

In formula (IX), P' preferably represents an oxygen atom, and Q' preferably represents an oxygen atom or one represented below. Here, the * mark represents a bond that is bonded to (X'=Y')n', and the ** mark represents a bond that is bonded to A'z.

In the formula, Q' has the same meaning as G explained in general formulas (N-1) and (N-2).

Q' is particularly preferably an oxygen atom or *-N-**SO
It is a group represented by □G'.

Among the groups represented by the general formula (IX), particularly preferred groups are those represented by the following general formula (X) or (XI).

General formula (X) ■ General formula (XI) H In the formula, the mark * represents the position where Ll or li is bonded to the left side in general formula (1), and the mark ** represents the position where it is bonded to the right side. RT& has the same meaning as R 64 explained in general formula (I) or (IV). y represents 0 to 3, and when y is plural, R76 represents the same or different. It also includes a case where two R1s are linked to form a cyclic structure.

R? Particularly preferred examples of 6 include the following groups. That is, alkoxy groups (e.g. methoxy groups, ethoxy groups, etc.), acylamino groups (e.g. acetamido groups,
benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, etc.)
, alkylthio group (e.g. methylthio group, ethylthio group, etc.), carbamoyl group (e.g. N-propylcarbamoyl M, N-t-butylcarbamoyl group, N-1-propylcarbamoyl group, etc.), alkoxycar, carbonyl group (e.g. methoxycarbonyl group) group, propoxycarbonyl group, etc.), aliphatic group (e.g., methyl group, t-butyl group, etc.), halogen atom (e.g., fluoro group, chloro group, etc.), sulfamoyl group (e.g., N-propylsulfamoyl group, sulfamoyl group, etc.) ), an acyl group (eg, acetyl group, benzoyl group, etc.), a hydroxyl group, or a carboxyl group. R again? A typical example of a case where two & is connected to form a cyclic structure is H (which has the same meaning as explained in general formula (XI)).

Specifically, the group represented by Z in general formula (II) includes a known bleach accelerator residue. For example, U.S. Patent No. 3.
Various mercapto compounds as described in JP 893.858, British Patent No. 1138842, JP 53-141623, JP 53-956
Compounds having a disulfide bond as described in Japanese Patent Publication No. 30, thiazolidine derivatives as described in Japanese Patent Publication No. 53-9854, Japanese Patent Publication No. 53-94927
isothiourea derivatives as described in Japanese Patent Publication No. 45-8506, thiourea derivatives as described in Japanese Patent Publication No. 49-26586, Japanese Patent Publication No. 49-26586;
Thioamide compounds as described in Japanese Patent Application No. 42349, dithiocarbamates as described in JP-A-55-26506, US Pat. No. 45-5283
These include arylene diamine compounds such as those described in Specification No. 4. Preferred examples of these compounds include A-(Ll) and -(Lx)b- in the general formula (I') at the substitutable heteroatom contained in the molecule.

The group represented by Z is more preferably represented by the following general formula (XI
It is a group represented by [), (XI[) or (χV).

General formula (x■) General formula (XI[l) General formula (XIV) In the formula, * represents the bonding position with A-(L, ), -(LX)b-, and R31 has 1 to 8 carbon atoms. Preferably, it represents a divalent aliphatic group having 1 to 5 carbon atoms, and R3□ is a group having the same meaning as R31, a divalent aromatic group having 6 to 10 carbon atoms, or a 3- to 8-membered divalent aliphatic group.
Represents a divalent heterocyclic group with a membered ring, preferably a 5- or 6-membered ring, X is -0-2-S-1-COO-1-SO, -1,
Xt represents an aromatic group having 6 to 10 carbon atoms; Represents a cyclic group, from Y+4 a ruboxyl group or a salt thereof,
Represents a sulfo group or a salt thereof, a hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (which may be substituted with an aliphatic group having 1 to 4 carbon atoms), -NH3O□-R3S or -3O□NHR3S group. Here, salt means sodium salt, potassium salt, ammonium salt, etc.), Y2 represents the same group or hydrogen atom as explained for Yl, r represents 0 or 1, and 2 represents 0 to 4. m represents an integer from 0 to 4, and U represents an integer from 0 to 4. However, the m Yl's are bonded at possible positions, and when m is a plurality of m, the m Yl's represent the same or different things, and l represents the same or different things. Here, R33, R34 and R3% each represent a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R31 to R3S represent an aliphatic group, it may be chain or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Although unsubstituted is preferred, examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy group, ethoxy group), an alkylthio group (eg, methylthio group, ethylthio group), and the like.

The aromatic group represented by X2 and the aromatic group when R12 represents an aromatic group may have a substituent. for example,
The aliphatic group substituents include those listed above.

When the heterocyclic group represented by be. Examples include a pyridine ring, an imidazole ring, a piperidine ring, an oxirane ring, a sulborane ring, an imidazolidine ring, a thiazepine ring, and a pyrazole ring. Examples of the substituent include those listed above as the aliphatic group substituent.

Specific examples of the group represented by the general formula (Xll) include the following.

SCH! CHt COt H, S CH! COz
H.

-3(CHI), C0fH, -3CHCO,H.

CH.

13CH, C0NHCHICO, H.

S　CHz　CHt　OCHt　CO! H.

-3CH2COOCH,CH,OH.

-3CHzCHzOCHzCHzOCH, CHzOH.

-3CH, CHI5CHICo□H.

-3CH, CH, CH, CO□H.

Specific examples of the group represented by the formula -a (XI[[) include the following.

/ Co! H Specific examples of the group represented by the general formula (XIV) include the following.

CH.

The compound represented by the general formula (■') of the present invention includes cases where it is a bis-form, a telomer, or a polymer. For example, in the case of a polymer, a polymer derived from a monomer represented by the following general formula (XV) and having a repeating unit represented by the general formula (XVI), or an oxidized product of an aromatic primary amine developing agent and a cup It is a copolymer with one or more non-chromic monomers containing at least one ethylene group that does not have ringing ability. Here, the general formula (XV
) may be polymerized in two or more types at the same time.

General formula (XV) CH2=C+AI! h-+AI3+T-(-AII)T
QQ general formula (XVI) -(-CH, -C→ (AIT-+Al3-)-7-+A1.←rIn the QQ formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom , All is -CON)(-1-NH
CONH-1-NHCOO-1-COO-25Ot-1
-CO-1-NHCO-1-3O, NH-5-NH5O
□-1-OCO-1-OCONH-1-N) I- or -
0-, A and 8 represent -CONH- or -COO-, A12 represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group, or an unsubstituted or substituted arylene group; may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene,
trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and arylene groups such as phenylene and naphthylene).

QQ represents a compound residue represented by the -i formula (1'), and may be bonded at any position of the substituent described above except for the group represented by Z.

i, j, and k represent 0 or 1, but 1%J,
and k are never 0 at the same time.

Here, substituents for the alkylene group, aralkylene group, or arylene group represented by A13 include an aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group ( (e.g., phenoxy group), acyloxy group (e.g., acetoxy group), acylamino group (e.g., acetylamino group), sulfonamide group (e.g., methanesulfonamide group), sulfamoyl group (e.g., methylsulfamoyl group), halogen atom (e.g., fluorine, chlorine, bromine, etc.), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), and a sulfonyl group (eg, methylsulfonyl group). When there are two or more of these substituents, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and their acrylic acids. Examples include derived esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylpyridines, and the like. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used at the same time.

The present invention also includes a case where any two of the groups represented by A, L, , L, and Z in general formula (■') have a bond in addition to the bond represented by general formula (bi). The effects of the present invention can be obtained even if this second bond is not broken during development. Examples of such bonds are as follows.

A L+ (Lz)b Z \, -ノ/ Among the above, a particularly preferable example is the following general formula (X■
).

General formula (X■) (Lz)b Z In the formula, Lx, b, Z, Rs++ and R5
9 represents the same meaning as described above, h and V each represent O or 1, and represent a divalent organic residue forming a 5- to 8-membered ring as in Product A.

-S　-CHX　group etc. are mentioned.

Next, specific examples of compounds that release bleaching accelerators used in the present invention will be given, but the present invention is not limited thereto.

C1 N () z CH, CO□H 101111 1-layer IJFCH3 The compound represented by the general formula (I') of the present invention includes cases where it is a bis form, a telomer, or a polymer. For example, in the case of a polymer, a polymer derived from a monomer represented by the following general formula (XV) and having a repeating unit represented by the general formula (XVI), or an oxidized product of an aromatic primary amine developing agent and a cup It is a copolymer with one or more non-chromogenic monomers containing at least one ethylene group without ringing ability. Here, the general formula (XV
) may be polymerized in two or more types at the same time.

General formula (XV) "CHz = C+A + zto"kiA Hato r→A +
+←rQ Q general formula (XVI) -(-CH, -C→ (A lz 'FT-fArz-HA++ ← "In the QQ formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom , A1. is -CONH-1-NH
CONH-1-NHCOO-1-COO-1-SO,-
1-CO-1-N) (CO-1-3O, NH-1-NH
3O, -1-OCO-1-OCONH-1-NH- or -O-, A1□ is -CONH- or -COO-
and Al1 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 1 to 10 carbon atoms, and the alkylene group may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene,
trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and arylene groups such as phenylene and naphthylene).

QQ represents a compound residue represented by the general formula (■'), and may be bonded at any position of the substituent described above except for the group represented by Z.

1% js and k represent 0 or 1, but iS
j and k are never 0 at the same time.

Here, as a substituent for the alkylene group, aralkylene group, or arylene group represented by A13, the aryl group (
For example, phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenoxy group), acyloxy group (e.g. acetoxy group), acylamino group (e.g. acetylamino group), Sulfonamide group (e.g. methanesulfonamide group), sulfamoyl group (e.g. methylsulfamoyl group), halogen atom (e.g. fluorine, chlorine, bromine, etc.), carboxy group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbonyl group ( Examples include methoxycarbonyl group) and sulfonyl groups (eg methylsulfonyl group). When there are two or more of these substituents, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and their acrylic acids. Examples include derived esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylpyridines, and the like. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used at the same time.

The present invention also includes a case where any two of the groups represented by A, L, , L, and Z in general formula (■') have a bond in addition to the bond represented by general formula (bi). The effects of the present invention can be obtained even if this second bond is not broken during development. Examples of such bonds are as follows.

A-L, -(Lz)b-Z \, -2/ Among the above, particularly preferred examples include the following general formula (X■
).

General formula (X■) (Lri b-Z In the formula, L2, b, Z, Rss and R5
9 represents the same meaning as described above, h and V each represent 0 or 1, and A (4 represents a divalent organic residue forming a 5- to 8-membered ring).

Examples include -3-CH, and groups.

Next, specific examples of compounds that release bleaching accelerators used in the present invention will be given, but the present invention is not limited thereto.

l ■ CH, CHCO□H N.H.

O2 CHtCO□II 1Nsu2 11U, l; CO□IICH,C
HCH,OH CI+.

I CH, CHCO□HC O NH2 all+7(t) Cz Hs t SCH, CH2C00H CsH+7(mu) C11° leak! M□ CHz CHz CHz COz H (t)C3fiz C1l□CO211 SCH2CHCod( H2 Call+t(t) cheer] (i) CnllqOCON+l SC+LfuONH(
C1lz)i0c+zllzs[1iCHCHtOH CONII (C1lt)a○C1zllzs, C1
1□011 H5CI1. COO1l (7I) Other, Research, Disclosure I ten Kan2
No. 4241, No. 11449, JP-A-61-20124
Publication No. 7, Japanese Patent Application No. 61-252847, No. 61-26
Compounds described in No. 8870 and No. 61-268871 can also be used in the same manner.

Further, the bleach accelerator-releasing compound used in the present invention can be easily synthesized based on the description in the above-mentioned patent specifications.

The amount of the bleach accelerator-releasing compound according to the present invention added to the light-sensitive material ranges from 1X10-' mol to 1 mol per 1 d of the light-sensitive material.
Preference is given to X 10-' mol, particularly from IX 10-'' mol to 5 X 10-'' mol. The bleach accelerator-releasing compound according to the present invention can be added to all layers of a light-sensitive material, but it is preferable to add it to a light-sensitive emulsion layer, and furthermore, when it is added to more light-sensitive emulsion layers, the effect becomes more effective. becomes significant.

Next, the silver halide color photographic window optical material used in the present invention will be explained.

In the emulsion layer of the light-sensitive material, silver halide emulsions other than the silver halide emulsion of the present invention include silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, and chloroiodide. Although any silver halide of silver may be used, silver iodobromide is particularly preferred.

The above-mentioned silver halide grains may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape, or may have a twin crystal shape. It may be one with crystal defects such as planes or a composite form thereof.

Also, mixtures of particles of various crystal forms may be used.

The silver halide mentioned above may be a monodisperse emulsion with a narrow distribution or a polydisperse with a wide distribution.

The crystal structure of the emulsion grains mentioned above may be uniform, or the inside and outside may have different halogen compositions (or may have a layered structure). , 027,146, U.S. Patent No. 3,505,0
No. 68, No. 4,444゜877 and Patent Application No. 1983-2
No. 48469 and the like. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The emulsion of the present invention may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grains, or a type in which latent images are formed both on the surface and inside the grains. Furthermore, particles whose interiors have been chemically aggravated may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced using any known method, for example, Research Disclosure, Vol. 176, No. 17643 (December 1978), pp. 22-23, "■.

Emulsion Preparation
and Types), Vol. 187, Magnetics 18716 (November 1979), p. 648.

In the preparation of the photographic emulsion of the present invention, various silver halide solvents (for example, ammonia, Rodankali, U.S. Pat.
No. 0, JP-A-53-82408, JP-A-53-144
It is also possible to use thioethers and 1,000-ion compounds described in No. 319, JP-A No. 54-100717, or JP-A-54-155828.

Furthermore, as a monodisperse emulsion, silver halide grains having an average grain diameter of more than about 0.1 micron, at least 9
Emulsions in which the fivefold diameter is within ±40% of the average grain diameter are typical. The average grain diameter is between 0.25 and 2 microns, and at least 95% by weight of the silver halide grains have an average grain diameter of 0.25 to 2 microns.
Emulsions such as those within the range of 0% can be used in the present invention.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure Kan 17643 (December 1978
18716 (November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD 17643 RD 187
161 Chemical aggravating agents Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 - Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column and stabilizer 6 Light absorber, film Page 25-26 Page 649 Right column - Ilter dye Page 650 Left side Ultraviolet absorber 7 Anti-stin agent Page 25, right column, page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 1O binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right page 12 Coating aid, table
Pages 26-27 Same as Top Surface Active Agent 13 Static Prevention Page 27 Same as Top Stop 1 In addition to the above-mentioned spectral aggravating agents, various known ones can be used in combination with the color photographic window optical material of the present invention.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned Research Disclosure (R)
D) It is described in the patent described in No. 17643, ■-〇-G. As dye-forming couplers, couplers that provide the three subtractive primary colors (i.e., yellow, magenta, and cyan) through color development are important;
Specific RD1764 equivalent or 2-equivalent couplers
3. In addition to the couplers described in the patents described in Sections C and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group.

As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. In addition, couplers that can form cyan dyes that are stable against humidity and temperature are
Typical examples of preferred examples include phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus, 2,5-diacylamino-substituted as described in U.S. Pat. No. 3,772.002. These include phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and a diacylamino group at the 5-position, and the 5-amidonaphthol cyan coupler described in European Patent No. 161.626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Examples of magenta couplers are described in US Pat. No. 4,366,237, and examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
It is written in No. 0, etc.

Specific examples of polymerized magenta couplers are described in U.S. Pat.
．． 367.282, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers described in Section -F are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2. 097゜140, same No. 2,131
, No. 188. Others, JP-A-60-1
DIR redox compound-releasing couplers such as those described in European Patent No. 85950, couplers that release dyes that recover color after separation as described in European Patent No. 173.302A, and the like can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-ice dispersion method is U.S. Patent No. 2,322,027.
It is written in the number etc.

Further, the process of latex dispersion method, effects, and specific examples of latex for impregnation are disclosed in U.S. Pat. It is written in the number etc.

The photosensitive material used in the present invention contains hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, etc. as color antifogging agents or color mixing inhibitors. May contain.

Known anti-fading agents can be used in the photosensitive material used in the present invention. Known anti-fading agents include hydroquinones, milow hydroxychromans, 5-hydroxyclamanes, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, Representative examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film commonly used in photographic materials.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, a dip coating method, a roller coating method, a curtain coating method,
Various known coating methods such as extrusion coating can be used.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

The color developing solution used in the processing of the light-sensitive material of the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N-diethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-)lienesulfonic acid salts, tetraphenylborate, p-(t-octyl)benzenesulfonate, and the like. These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used.

Examples of aminophenol derivatives include 0-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
(1966) (L, F, A.

Mason, “Photographic Proc.
essing Chemistry''.

Focal Press), pages 226-229, US Pat. No. 2,193,015, US Pat. If necessary, two or more color developing agents may be used in combination.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. preservatives such as hydroxylamine, triethanolamine, the compounds described in West German Patent No. M1 (OLS) No. 2622950, sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, class ammonium salts, amici,
Development accelerators such as thiocyanate, 3,6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride;
Auxiliary developers such as 1-phenyl-3-pyrazolidone; tackifying agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the compounds described in JP-A-58-195845, l-hydroxy Ethylidene-1,1'-diphosphonic acid, organic phosphonic acid described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylenediamine-N-, N, N', N'-tetramethylene phosphonic acid A chelating agent such as an aminophosphonic acid such as an acid or a phosphonocarboxylic acid described in Research Disclosure 18170 (May 1979) can be contained.

The color developing agent is approximately 0.0.
A concentration of 1 g to about 30 g, more preferably color developer 1
Use at a concentration of about 1 g to about 15 g per 2 ml. Further, the pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 9 to 13.

In the present invention, the silver halide color photographic material is imagewise exposed, then subjected to color development treatment as described above, and then treated with a processing solution having bleaching ability.

Here, the processing solution having bleaching ability refers to a processing solution that oxidizes the metallic silver produced by the development reaction and the colloidal silver contained in the photosensitive material. It refers to a processing solution that has the ability to convert into salt, such as a bleach solution, a bleach-fix solution, and the like. In the present invention, it is preferable to immediately process with a processing solution having bleach-fixing ability after the color development process.

Bleaching agents used in the treatment solution having bleaching ability of the present invention include ferric complex salts such as ferricyanide complex salts and ferric citrate complex salts, peroxides such as persulfates and hydrogen peroxide,
Among them, ferric aminopolycarboxylic acid complex salts are preferred, which are complexes of ferric ions and aminopolycarboxylic acids or salts thereof.

Representative examples of these aminopolycarboxylic acids and their salts include: ■ Diethylenetriaminepentaacetic acid ■ Diethylenetriaminepentaacetic acid pentasodium salt ■ Ethylenediamine-N-(β-oxyethyl)-N
, N', N'-triacetic acid■ Ethylenediamine-N-(β-oxyethyl)-N
, N', N'-Triacetic acid trisodium salt■ Ethylenediamine-N-(β-oxyethyl)-N
, N',N'-triammonium salt of triacetate■ 1,2-diaminopropanetetraacetic acid■ 19.2
-Diaminopropanetetraacetic acid disodium salt ■ Nitrilotriacetic acid ■ Nitrilotriacetic acid sodium salt [Phase] Cyclohexanediaminetetraacetic acid ■ Cyclohexanediaminetetraacetic acid disodium salt ON -Methyl-iminodiacetic acid 0 Iminodiacetic acid ■ Dihydroxyethylglycine ■ Ethyl ether diamine tetraacetic acid [Phase] Glycol ether diamine tetraacetic acid 0 Ethylene diamine tetrapropionic acid [Phase] 1,3 diamine propane tetra acetic acid 0 Ethylene diamine tetra acetic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds.

Among these compounds, ■, ■, ■, ■, 0, ■, 0
, [phase] and [phase] are particularly preferred.

Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts, or may be used in the form of ferric salts, such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution using ferric sulfate, ferric ammonium sulfate, ferric phosphate, etc., and aminopolycarboxylic acid. When used in the form of complex salts,
One type of complex salt may be used, or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. Also,
In either case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

In addition, the above [phase] is removed (aminopolycarboxylic acid Fe (■
) at least one complex salt and ethylenediaminetetraacetic acid Fe
(ml) may be used in combination with a complex salt.

Further, the treatment liquid having bleaching ability and containing the above-mentioned ferric complex salt may contain complex salts of metal ions such as cobalt, nickel, and copper other than iron ions.

The amount of bleaching agent per 1β of the processing liquid having bleaching ability of the present invention is 0.1 mol to 1 mol, preferably 0.2 mol to 0.
．． It is 5 moles. The pH of the bleaching solution is 4.0 to 8.0.
It is preferable that it is, and it is especially preferable that it is 5.0-7.5.

In addition to bleaching agents and the above-mentioned compounds, the treatment bath having bleaching ability constituting the present invention may contain bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride. can include rehalogenating agents such as. In addition, the pH buffering capacity of nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid. Additives commonly known for use in bleach-fixing solutions can be added, such as one or more inorganic acids, organic acids, and salts thereof having the following.

In the present invention, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, ammonium thiocyanate, and potassium thiocyanate are added to the fixing bath following the bleaching bath or the processing bath having bleach-fixing ability. thiocyanate,
Known compounds such as thiourea and thioether can be included as fixing agents. The amount of these fixing agents added is preferably 3 mol or less, particularly preferably 2 mol or less, per 11 processing liquids having fixing ability or bleach-fixing ability.

The processing solution having bleach-fixing ability of the present invention includes so-called sulfite ion-releasing compounds, such as sulfites and bisulfites such as sodium sulfite and ammonium sulfite, or aldehyde and bisulfite adducts such as carbonyl bisulfide. can be contained.

Furthermore, aminopolycarboxylic acid salts as shown in A-1 to A-24, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,3 diaminopropanetetrakismethylenephosphonic acid, nitrilo-N, N, N -trimethylenephosphonic acid, 1-hydroxyethylidene-1,
Organic phosphonic acid compounds such as 1'-diphosphonic acid can be included.

In the present invention, the treatment solution having bleaching ability may contain at least one bleach accelerator selected from compounds having a mercapto group or disulfide bond, isothiourea derivatives, and thiazolidine derivatives. . The amount of these compounds per 11 having bleach-fixing ability is preferably from 1 x 10-S to I x 10-
'molar, particularly preferably lXl0-' to 5X
10-" moles.

In the present invention, the bleach accelerator contained in the treatment having bleaching ability is a compound having a mercapto group or a disulfide bond selected from thiazolidine derivatives, thiourea derivatives and isothio derivatives,
Any material may be used as long as it has a bleaching accelerating effect. Preferably, compounds and specific examples of general formulas (a) to (g) described on pages 63 to 77 of Japanese Patent Application No. 61-313598 can be mentioned.

When adding these compounds to a treatment solution, it is common to dissolve them in water, alkaline organic acid organic solvents, etc. beforehand, but add them immediately as a powder to a treatment bath with bleaching ability. However, it has no effect on its bleaching promotion effect.

Furthermore, in the present invention, the bleaching accelerator can also be incorporated into the light-sensitive material. In this case, the bleaching accelerator is used in any of the blue, green, and red emulsion layers, the top layer, the middle layer,
It can be contained in a gelatin layer such as the bottom layer.

The processing bath having bleach-fixing ability of the present invention may be a process consisting of one tank, but it may be a process consisting of two or more tanks, and the replenisher may be supplied in a multi-stage countercurrent system in the acid tank group. , and the replenisher may be supplied to one bath of the tank group by alternately circulating the process liquid in the tank group to provide a generally -like process liquid.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (J
our own of the 5ociety of
Motion Picture and Te1evis
ion Engineers) Volume 64, P, 248-
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A-57-8542, and other benzotriazoles, "Chemistry of Disinfectant and Antifungal Agents" by Hiroshi Horiguchi, It is also possible to use the disinfectants described in the sanitary technology complete volume "Microbial sterilization, sterilization, and anti-mold technology" and "Encyclopedia of anti-bacterial and anti-mold agents" edited by the Japanese Society of Antibacterial and Antifungal.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
No. 4, No. 59-184343, No. 60-220345,
No. 60-238832, No. 60-239784, 60-
No. 239749, No. 61-4054, No. 61-11874
All known methods described in No. 9 etc. can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazoline-
Stabilizing baths containing 3-one, bismuth compounds, ammonium compounds, etc. are preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 30 g of inert gelatin, 6 g of potassium bromide, 12 g of distilled water
Stir the aqueous solution in which is dissolved at 75°C, and add 35 cc of an aqueous solution in which 5.0 g of silver nitrate is dissolved, 3.2 g of potassium bromide, and 098 g of potassium iodide in an aqueous solution 3.
After adding 5 cc each at a flow rate of 70 cc for 30 seconds, the PAg was increased to 10 and ripened for 30 minutes to prepare a seed emulsion.

Next, a predetermined amount of the aqueous solution 11 in which 145 g of silver nitrate was dissolved and an equimolar amount of the aqueous solution of a mixture of potassium bromide and potassium iodide were added at a predetermined temperature, at a predetermined ]'Ag, and at an addition rate close to the exfoliation growth rate. A flat core emulsion was prepared. Subsequently, equimolar amounts of the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion were added at a rate close to the critical growth rate to coat the core. Core/shell type silver iodobromide tabular emulsions A to D were prepared.

Aspect ratio control was obtained by selecting pAg during core and shell preparation. The results are shown in Table 1-1.

Table 1-1 1) For 1,000 emulsion grains, measure the aspect ratio of each individual grain, select grains that account for 50% of the total projected area from grains with larger aspect ratios, and Average value.

2) Similarly to 1), the average value of the aspect ratio of particles corresponding to 85% of the total projected area.

Next, on the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in a multilayer manner to prepare a multilayer color brightening material 101.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rrr of silver for silver halide and colloidal particles, and the amount expressed in g/rrf for couplers, additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer.

1st layer (halation prevention N) Black colloid 0.2
Gelatin ・・・・・・ 1.3E
xM-8-0,06 UV-1...0. l UV-2...0.2 Solv-1-0,01 Solv-2-0,01 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ)...・・・ 0.10
Gelatin ・・・・・・ 1. 5
UV-1... 0.06 UV-2... 0.03 ExC-2... 0.02 ExF-1... 0.004 Solv- 1-0,1 Solv-2 = 0.09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 2 mol%, internal cylinder Agl type, equivalent sphere diameter 0.3μ, equivalent sphere diameter Coefficient of variation 29%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5) Coating amount: 0.4 gelatin
・・・・・・ 0.6P-1・・・・・・
・ 3.0XIO-'P-2... 3.0XI
O-'ExC-3-0,06 ExC-4...0.06 ExC-7-0,04 ExC-2...0.03 Solv-1=0. 03 So 1v-3-0,012 4th layer (second red emulsion layer) Silver iodobromide emulsion (Ag1 5 mol%, internal high Agl type,
Equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4) Coated silver amount ・・・・・・ 0.7 Gelatin ・・・・・・ 0 .5P
-1... 2X10-' P-2... 2 X 10-'ExC-3...
...... 0.24 ExC-4... 0.24 Snake xC-7... 0.04 ExC-2-=・0. 04 Solv-1-0, 15 Solv-3-...0. 02 5th layer (3rd red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 1. 0 gelatin
・・・・・・ 1.0P-1...
... 2X10-' P-2... 2 .01 Solv-2-" 0.05 6th layer (middle layer) Gelatin 1.0C
pd-1...0.03 Solv-1--0,05 7th layer (first green emulsion N) Silver iodobromide emulsion (AgI 2 mol%, internal high Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coating size: 0. 30ExS-
4-5X10-' ExS-6= 0.3X10-' ExS-5-... 2xlO-' Gelatin 1.0E
xM-9-0,2 ExY-14...0.03 ExM-8...0.03 Solv-1-=0. 5 8th layer (second green emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high Agl type, equivalent sphere diameter 0.6μ, coefficient of variation of equivalent sphere diameter 38%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 4) Coating i 11 ・・・・・・ 0.4 gelatin
・・・・・・ 0.5ExS-4・・
... 5 X 10-'ExS-5-... 2X1
0-'ExS-6...0.3X10-'ExM9
・・・・・・ 0.25EχM −
8...0.03 Snake xM-10-0,015 ExY-14-0,01 Solv-1-...-= 0. 2 9th layer (third green emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 80%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 1.2) Coated silver amount...0.85 Gelatin...1.0E
xS-7= 3.5X10-' ExS-8... 1.4X10-'ExM-1
1...0.01 ExM-12...0.03 ExM-13...0.20 ExM-8...0.02 ExY-15= 0. 02 Solv-1...0. 20 Solv-2...0.05 10th layer (yellow filter layer) Gelatin...1.2 Yellow colloidal silver...0.08C
pd-2...0.1 Solv-1...=0.3 11th layer (first blue emulsion N) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type, sphere (Equivalent diameter: 0.5μ, coefficient of variation of sphere equivalent diameter: 15%, octahedral particles) Coated silver amount: 0.4 Gelatin: 1.0E
xS-9...2X10-'ExY-16...
...0.9 ExY-14...0.07 Solv-1-...0. 2 12th layer (second blue emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high Agl type,
Equivalent sphere diameter 1.3 μ, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Coating amount: 0. 5 gelatin
・・・・・・ 0.6ExS-9・・
... lXl0-'ExY-16...0
．． 25 Solv-1=0. 07 13th layer (first protective layer) Gelatin ・・・・・・ 0. 8
uv-1/old... 0. l UV-2/Old... 0. 2 So 1v-1-0,Ol 5olv-2-0,01 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ) ...... 0. 5 Gelatin 0.45 Polymethyl methacrylate particles (1.5μ in diameter) Old... 0. 2H-1
...... 0.4 cpa-3・old... 0. 5 cpd-4/old... 0.5 In addition to the above components, a surfactant was added as a coating aid to each layer. Sample 10 was prepared as above.
It was set to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

ExC-2: 0H ExY-14: CH, C) 13 ExY-15: ■ H3 ExC-5: ■ C(CI(3)3 ExC-6: H U to tlz1.;1lzsLIIz-L;0URExC
-7: υ H2 ExM-9: ExM-12: ExM-13: (t) SI'I.

Cpd-1: H H cpci-2: 0 -I ExS-4: ExS-5: C2H
.

硼ExS-6: ExS-7: ExS-8: ExS-9: H-1; CH,: CH-SO□-CL C0NHCf1zC
I□= CIl −So□−GHz C0N)I
CHIpd-3 CH.

l pa-4 Preparation of samples 102 to 125 From sample 101, the emulsion and coupler of the fifth layer and the third to
Sample 101 was prepared in the same manner as sample 101 except that the sensitizing dyes in the five layers were changed as shown in Table (2) (equimolar exchange).

After cutting the obtained samples 101 to 125 to a width of 35 m/m, a standard subject was photographed, and the following processing steps (1) to (
II), a 500 m running test was conducted for each. After the running was completed, Samples 101 to 125 were exposed to light at 20 CMS with the tip of the tip, and the following development process was performed. Further, in order to evaluate the sharpness, the film was exposed to light through an MTF measurement chart and developed. The sample for MTF measurement was processed through Fuji Film CN-16 treatment to remove the influence of residual silver.
It was measured and evaluated using a microdensitometer.

The amount of residual silver in the developed sample was analyzed using fluorescent X-rays, and the results are shown in Table 3. Remain! It can be said that the amount of Ii is within a practically acceptable range if it is within 30 mg/ryf.

Treatment Step (, 1) (Temperature: 38°C) In the above treatment steps, water washing (1) and (2) were performed using a countercurrent water washing method to (2) and (3). Next, the composition of each treatment liquid will be described.

<Color developer> Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.11-Hydroxyaminethene-1,1-diphosphonic acid 2. Q 2.2 Sodium sulfite 4.0 4.9 Potassium carbonate
30.0 42.0 Potassium Bromide 1
．． 6- Potassium iodide 2.0 mg -Hydroxyamine 2.4 3.64-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 5.0 7.3 Add water 12 11 pH 10 ,0010,0
5 Bleaching solution> Common to mother liquor and replenisher ethylenediaminetetraacetic acid ferric ammonium salt 120.0g ethylenediaminetetraacetic acid disodium salt 10.0g ammonium nitrate 10.0g ammonium bromide 100.0g bleaching accelerator
I
1.01 <Bleach-fix solution> Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240mj! Add ammonia water p) 17.3,
Add water and add water. g/I
Water with a water quality of 1.2 mg/f and 1.2 mg/f of magnesium was used.

Stabilizing liquid> Mother liquor (g) Replenishing solution (g) Formalin (37% w/v) 2.0 ml 3.0 ml polyoxyethylene-p-monononyl 0.3 0.45 Phenyl ether (average degree of polymerization 10) 5 -Chloro0-2-methyl-4-inthiazolin-3-one 0.03 0.045 Add water 11 11 Treatment step (■) (
Temperature: 38°C) *Color developing solution per 35m/m width and 1m length> Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.21-Hydroxyethyrythene-1,1-diphosphone Acid 2.0 2.4 Sodium sulfite 2.0 4.8 Potassium carbonate 4x
35.0 45.0 Potassium bromide
1.6 - Potassium iodide 2.0 mg
-Hydroxylamine 2.0 3.6
4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 5.0 7.5 Add water and bleach to 12 12 pH (using potassium hydroxide 10.20 10.35) Fixer> Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium salt 40 45 Diethylenetriaminepentaacetic acid ferric ammonium salt 40 45 Ethylenediaminetetraacetic acid di-sodium salt 10 10 Sodium sulfite 15 2゜Ammonium thiosulfate aqueous solution ( 70% w/v) 240 270 Bleach accelerator 0.1 0.15 Aqueous ammonia (2
6%) 14mf 12mj! add water
If 1fpH6,76,5 Washing water> The following three types were used.

(1) Tap water Calcium 26 mg/f Magnesium 9 mg / IPH 7,2 (2) Ion exchange treated water The above tap water was treated using Mitsubishi Kasei Corporation's bullet-loaded acidic cation exchange resin (Na type), and the water quality was as follows. And so.

Calcium 1. 1 mg/l Magnesium 0.5 mg/l pH 6,6 (3) Tap water added with chelating agent 500 mg/f of ethylenediaminetetraacetic acid di-sodium salt was added to the tap water.

pH6,7 The experiment was carried out using the steps and treatment liquid as described above.

As is clear from Table I, when an emulsion with an average aspect ratio of 5 or more is used, the MTF is significantly improved (up by 20% or more), but the desilvering property is greatly deteriorated. However, when used in combination with the bleach accelerator-releasing coupler of the present invention, this can be improved, but when the aspect ratio is 8 or more, it does not penetrate into a practically sufficient root area, and it can be seen that there is a wide difference in desilvering performance.

Therefore, it has been found that only by using an emulsion having an aspect ratio of 5 to 8 and the bleaching accelerator of the present invention can an improvement in MTF and a practically sufficient desilvering performance be ensured.

It can be seen that when a sensitizing dye according to a preferred embodiment of the present invention is used, the above-mentioned difference becomes remarkable and the sensitivity also increases.

(Effect of the invention) By using the light-sensitive material of the present invention, it is possible to obtain excellent sharpness and desilvering properties. Name: Silver halide color photographic light-sensitive material 3. Relationship to famous case to be amended: Patent applicant name (520) Fuji Photo Film Co., Ltd. 4. Agent address: 13th Kasumiga I!, Chiyoda-ku, Tokyo, 100 Japan. No. 2-5 Kasumigaseki Building 29th Floor Kasumi Ga Illll Pill Delivery Office Box 11 No. 49 @ Eikou Patent Office (1) Amend the !iLi machine in the "Scope of Claims" section of the Memorandum as shown in the attached sheet.

(2) The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) "Nuclear" on page 6, line 16 of the specification is amended to "the".

2) “Excluded” in lines 2 to 5 of page 10 of the same book is “excluded”
and correct it.

3) On page 10, line 7 of the same book, ``f arutowa'' is amended to ``f arutowa''.

A) "Parallel space" on page 11, line 12 of the same book is corrected to "between parallel surfaces."

5) "Abnormal" on page 11, line 20 of the same book is corrected to "more than".

6) On page 13, line 9 of the same book, ``Oyatana'' is amended to ``new''.

7) General formula (A) on page 17 of Dobara, " V, R, J and correct it.

8) “Potassium bromide and 3.21” on page 198, line 2 of the same book
14 is corrected as “potassium bromide!1.2.9 J.

9) In the same book, page 198, line 9, ``sekai'' is corrected to ``criticality''.

10) In the same book, page 262, line 6, "root zone" is corrected to "area."

Claims (1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least 50 of the total projected area of the silver halide emulsion grains
% is tabular silver halide grains with an average aspect ratio of 5:1 or more and less than 8:1, and at least one layer reacts with an oxidized product of an aromatic primary amine color developing agent to release a bleaching accelerator. 1. A silver halide color photographic material containing at least one compound.

(2) The silver halide color photographic material according to claim (1), which contains an aggravating dye represented by the following general formula (A).

One-ship formula (A) (wherein, Zl represents an oxygen atom, a sulfur atom, a selenium atom, or ':; N-Rs.

Z2 is thiazole, benzothiazole, naphtho(1,2
-d) thiazole, naphtho(2,3-d)thiazole,
selenazole, benzoselenazole, naphtho(1,2-
d) selenazole, naphtho[2°3-d]selenazole, benzimidazole, naphtho(1,2-d)imidazole, naphtho[2°3-d]imidazole, benzoxazole, naphtho(1,2-d)oxazole, In addition to representing the naphtho[2゜3-d]oxazole nucleating atomic group, when m represents O, it also represents the 2-quinoline nucleating atomic group; when m represents 1 and Zl represents N-Rs, include thiazoline, selenazoline, oxazole or 3
．． It also represents a 3-dialkylindolenine nucleating atom group, where R3 is an alkyl group or alkenyl having 6 or less carbon atoms, which may be substituted with a hydroxyl group, phenyl group, alkoxy group, halogen atom or alkoxycarbonyl group. represents a group.

R1 and R2 represent an optionally substituted lower alkyl group or alkenyl group.

R3 represents a hydrogen atom or can be linked to R3 to form a 5- or 6-membered ring.

R1 represents at least Z; N-R, or a hydrogen atom when Z2 represents benzimidazole, naphtho(1,2-d]imidazole or naphtho(2,3-d)imidazole nucleating atomic group; represents, Z, is; N-R
, Z2 also represents benzimidazole, naphtho (1,
2-d] ethyl group when it does not represent imidazole or naphtho(2,3-d)imidazole nucleating atomic group,
Represents a propyl group, a butyl group, a benzyl group, a phenethyl group, or an optionally substituted phenyl group.

(2) represents that it is linked with a hydrogen atom or (2) to form a condensed benzene ring.

■□ is 2. When represents CN-Rs, it represents an electron-withdrawing group. 2. When represents an oxygen atom, a sulfur atom, or a selenium atom, v2 is an optionally branched lower alkyl group having up to 7 carbon atoms, a lower alkoxy group having up to 6 carbon atoms, a hydroxy group, or an acylamino group having up to 4 carbon atoms. group, halogen atom, alkoxycarbonyl group having 5 or less carbon atoms,
Represents a carboxyl group, an optionally substituted phenyl group having 8 or less carbon atoms, or a hydrogen atom.

■, In addition to representing the same meaning as ■2, it also represents that it can be connected with ■2 to form a condensed benzene ring, and Zt is: l:
When N-R5 is represented, it also represents a hydrogen atom.

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least 50 of the total projected area of the silver halide emulsion grains
% is tabular silver halide grains with an average aspect ratio of 5:1 or more and less than 8:1, and at least one layer reacts with an oxidized product of an aromatic primary amine color developing agent to release a bleaching accelerator. 1. A silver halide color photographic material containing at least one compound. (2) The silver halide color photographic light-sensitive material according to claim (1), which contains a sensitizing dye represented by the following general formula (A). General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_1 represents an oxygen atom, a sulfur atom, a selenium atom, or ■N-R_5. Z_2 represents thiazole, benzothiazole, naphtho[1,
2-d]thiazole, naphtho[2,3-d]thiazole, selenazole, benzoselenazole, naphtho[1,2
-d] selenazole, naphtho[2,3-d] selenazole, benzimidazole, naphtho[1,2-d]imidazole, naphtho[2,3-d]imidazole, benzoxazole, naphtho[1,2-d]oxazole , in addition to representing the naphtho[2,3-d]oxazole nucleating atomic group, when m represents 0, it also represents the 2-quinoline nucleating atomic group, m represents 1, and Z_1 represents ■N-R_5. In some cases, it also represents thiazoline, selenazoline, oxazole or 3,3-dialkylindolenine nucleating atoms. Here, R_5 represents a hydroxyl group, a phenyl group, an alkoxy group, an alkyl group or an alkenyl group having 6 or less carbon atoms, which may be substituted with a halogen atom or an alkoxycarbonyl group. R_1 and R_2 represent an optionally substituted lower alkyl group or alkenyl group. R_3 represents a hydrogen atom or can be linked to R_1 to form a 5- or 6-membered ring. R_4 is at least Z_1 represents ■N-R_5,
When Z_2 represents a benzimidazole, naphtho[1,2-d]imidazole or naphtho[2,3-d]imidazole nucleation atomic group, it represents a hydrogen atom, and Z_1
does not represent ■NR_5 and Z_2 also represents benzimidazole, naphtho[1,2-d]imidazole or naphtho[2
, 3-d] When the imidazole nucleus-forming atomic group is not represented, it represents an ethyl group, a propyl group, a butyl group, a benzyl group, a phenethyl group, or an optionally substituted phenyl group. V_1 represents a hydrogen atom or connects with V_2 to form a condensed benzene ring. When Z_1 represents ■NR_5, V_2 represents an electron-withdrawing group. When Z_1 represents an oxygen atom, a sulfur atom, or a selenium atom, V_2 represents an optionally branched lower alkyl group having 7 or less carbon atoms, a lower alkoxy group having 6 or less carbon atoms, a hydroxy group, or a hydroxy group having 4 or less carbon atoms. Acylamino group, halogen atom, alkoxycarbonyl group having 5 or less carbon atoms, carboxy group, optionally substituted carbon number 8
Represents the following phenyl group or hydrogen atom. V_3 has the same meaning as V_2, and also represents that it can be linked with V_2 to form a condensed benzene ring, and Z_1
When represents ■NR_5, it also represents a hydrogen atom. m represents 0 or 1. X^■ represents an acid anion residue, and n_1 represents 0 or 1. )