JPS60128429A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the sensitivity of a photosensitive material and to reduce the influence of a change of a processing soln. by forming a layer contg. silver halide particles undergoing no development when the photosensitive material is developed on the outside of a photosensitive silver halide emulsion layer positioned farthest from the base. CONSTITUTION:At least one photosensitive silver halide emulsion layer and a layer contg. at least one kind of compound (FR compound) capable of releasing a fogging agent, a precursor thereof, a development accelerator or a precursor thereof in combination with the silver halide emulsion layer are formed on a base. At this time, it is required to form a layer contg. silver halide particles undergoing practically no development when the resulting photosensitive material is developed on the outside of a photosensitive silver halide emulsion layer positioned farthest from the base. A fogging agent, a silver sulfide forming agent or the like is used as the FR compound.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a silver halide photosensitive material with high sensitivity, improved graininess, uniform development quality, and reduced influence of processing solution fluctuations. Regarding materials.

(Background Art) In recent years, two major trends can be observed in silver halide photosensitive materials, particularly photographic photosensitive materials.

One is to increase sensitivity, as typified by films with ASA≠00, and the other is to increase image quality in response to smaller film sizes. Regarding the former, various methods have been studied, including increasing the size of silver halide grains, increasing coupler activation, and accelerating development.

Regarding increasing the size of silver halide, see G and C.

Farnell, J., B., Chanter, J., Pho.
As reported in Togr+Sc i, + Ta, 7j (/ri, 41), there is already a tendency for sensitivity to reach a plateau, and an increase in sensitivity cannot be expected even with increasing dog size.

Furthermore, increasing the size of silver halide grains is accompanied by various co-locations such as deterioration of graininess. Many studies have been conducted on increasing the activation of couplers, but they do not contribute enough to sensitivity and have the disadvantage of worsening graininess. To accelerate development, the addition of various development accelerators such as hydrazine compounds to the emulsion layer or developer has been considered, mainly for black-and-white photosensitive materials, but all of these methods are associated with increased fogging and deterioration of graininess. This is often not practical.

Therefore, a coupler that releases a development accelerator and caprase agent in an image-wise manner was proposed. For example, U.S. Patent No. 39.
21μ, No. 377, same! , 2! J.

No. 2, JP-A-11-74-37 discloses thiocyanate ion-releasing couplers that promote dissolution physical development. Furthermore, in JP-A-17-1.311, the principle of a coupler that releases a caprase agent such as acylhydrazine is disclosed in JP-A-17-1.311. Jt discloses couplers that release hydroquinone, aminophenol developers, and the like.

Furthermore, Tokugan Sho J-7-'/Is/j/j and Tokugan Sho!
I-J/l/l also discloses a coupler that releases a caplase agent, a silver sulfide nucleus forming agent, or its precursor, and has a high sensitivity effect and a high contrast effect by releasing a caplase agent imagewise. Alternatively, the development accelerating effect is described in detail.

However, when photosensitive materials containing these compounds are developed, the photographic properties may change due to fatigue of the processing solution, and depending on the development conditions, there may be serious defects such as uneven finish even within a single screen. has become clear.

This tendency is remarkable when high-temperature processing is performed at a development processing temperature of Jj0C or higher, and becomes a major practical obstacle.

(Object of the Invention) The first object of the present invention is to provide a silver halide photosensitive material which has high sensitivity, improved graininess, and further reduces the influence of processing solution fluctuations. The second purpose is to contain at least seven compounds that release capacitive agents or their precursors or development accelerators (or their precursors) such as silver sulfide formers and silver halide solvents, and that This improves the uniformity of the developed finish by preventing the fogging agent or development accelerator released in an image form from diffusing outside the sensitive material layer.
Another object of the present invention is to provide a silver halide photosensitive material in which the influence of developer fatigue is reduced.

(Structure of the Invention) An object of the present invention is to provide at least seven light-sensitive silver halide emulsion layers provided on a support and, in combination with the silver halide emulsion layers, a fogging agent or its precursor. or in a light-sensitive material containing at least one compound capable of releasing a development accelerator or its precursor, on the outside of the nine light-sensitive silver halide emulsion layers furthest from the support;
This has been achieved by a silver halide photosensitive material characterized by providing a layer containing silver halide grains that is not substantially developed by the development process of the photosensitive material.

The mechanism by which the structure of the present invention eliminates the non-uniformity of the development finish quality and the sensitization effect due to fluctuations in the processing solution is currently considered to be as follows.

A compound that releases a fogging agent or its precursor or a development accelerator or its precursor (hereinafter simply referred to as "rFR compound") in an image form corresponding to the amount of developed silver (hereinafter simply referred to as rFR-releasing compound) In a photosensitive material containing a compound (hereinafter referred to as ""), the FR compound released during development injects electrons into silver halogenide in the photosensitive material layer or forms silver sulfide. By increasing the number of starting points, the effect of promoting the development of hairlashes is brought about, and favorable effects such as increased sensitivity, increased contrast, improvement of graininess, and promotion of development are brought about. On the other hand, a part of the released FR compound passes through the photosensitive emulsion layers and oozes into the developer.
This promotes development over an unnecessarily wide range of the sensitive material, resulting in uneven development finish. 1fc, the FR compound leached into the developer accumulates in the processing solution as the amount of processed photosensitive material increases, and as a result, the photosensitive material challenged by this fatigued developer suffers from adverse effects such as increased fog and sensitivity fluctuations. receive.

This defect becomes more noticeable as the developing temperature increases, especially in Jj'C.
This is noticeable at higher temperatures.

In the present invention, in order to prevent the FR compound from diffusing from the photosensitive material layer into the developing solution, many additives and the like were investigated, but the side effects were large, and the method was ultimately discovered. That is,
The feature is that a layer containing silver halide grains that is not substantially developed even after the FR compound is deactivated is provided above the layer containing the PR-releasing compound, that is, on the developer side.

In order to be able to deactivate the PR compound, it is preferable to use silver halide with a large surface area, a high reaction frequency, or in other words, fine grains. Emulsions that are not developed by liquids, such as emulsions with low photosensitivity, especially those with internal a(11
Type 7 silver halide is preferred. Furthermore, as a result of extensive research, the present inventors found that -silver halogenide (as described in detail later) is particularly effective in deactivating FR compounds.
It has been found that the objects of the present invention can be achieved by providing a layer containing S silver halide grains on top of a layer containing an FR emitting compound.

The present invention will be specifically described below.

FR releasing compounds useful for use in the present invention include compounds that release at least seven of the following: fogging agents, silver sulfide formers, or silver halogenide solvents. These compounds release FR compounds through chemical reaction with the oxidized product of the developing agent generated when silver halogenide is reduced to silver during development. To illustrate the relevant reaction mechanism, (1) the FR compound is separated from the coupler by coupling with the oxidation product of the aromatic primary amine, which is a color developing agent; (11) the FR compound is separated from the coupler; The colored or colorless dye formed by coupling with the oxidation product is oxidized by the oxidized product of the developing agent, which functions as a FR compound. ,
The development accelerator is removed/Compounds (i), (ii) and (iii) of the present invention are represented by the following general formulas (1), (2) and (3), respectively.

(1) COUP-1-(TIME-1)n-FA(2
) (FOGC-0UP-2) BALL (3) RED-B In the general formula [1], C0UP-1 is a coupler residue that can cause a coupling reaction with the oxidation product of an aromatic primary amine developing agent. (TIME-1)n-FA represents a group released in a coupling reaction and has the ability to couple silver halide, or a residue containing a group having the ability to promote development, or a precursor thereof. represent.

The coupler residue represented by GOUP-1 can be any coupler residue known or already used in the art.

Examples of cyan coupler residues include phenol couplers and naphthol gablers. Examples of magenta coupler residues include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers. Yellow coupler residues include acylacetanilide couplers (e.g. benzoylacetanilide couplers, pivaloylacetanilide couplers, etc.),
Examples include malondianilide coupler. In addition, so-called colorless coupler residues whose coupling products with oxidized products of aromatic primary developers do not have significant visible absorption include open-chain or cyclic active methylene compounds (e.g. indanone,
cyclopentanone, cyclohexanone, malonic acid diester, acetophenone, imidazolinone, oxacillinone, thiazolinone, etc.). However, the hue of the coupling product produced by the reaction between GOUP-1 and the oxidized product of the aromatic primary amine developer is not limited to the above (it may be any hue).

Furthermore, the following can be mentioned as the coupler residue represented by GOUP-1.

General formula (1) In the formula, R1 represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylamino group, or an ani, lino group,
2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group; R3 is a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an aryloxy group, a sulfonyl group, a carbonamide group, a hydroxy group, a carboxy group, a sulfo group , a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a ureido group, or a halogen atom.

General formula (11) General formula [I[1] In the formula, R4 represents an alkoxy group, an alkylamino group, a dialkylamino group, an alkyl group, a carbonamide group, or a sulfonamide group, R5 represents an alkyl group or an aryl group, and A represents an alkyl group or an aryl group. Represents a group of nonmetallic atoms necessary to form a 5-membered azole ring (eg, imidazole ring, triazole ring, tet, and lazole ring). However, general formula (Iil) also includes its tautomer.

General formula (IV) General formula (V) OHOH system * In the formula, R6, R7 and R8 may be the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, ureido group, R9 represents a carbamoyl group or an alkoxycarbonyl group; RIO represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group;

General formula (VI) In the formula, R represents an alkyl group, an aryl group, aniso2 group, an alkylamino group, or an alkoxy group, and B represents an oxygen atom, a sulfur atom, or a nitrogen atom [■] 13 In the formula, R12 and R3 represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, or an acyl group, and R14 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

General formula [■] General formula - (iX, 1 ・pac = x heterocyclic group, cyano group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylamino group, dialkylamino group, anilino group, sulfonyl group, sulfamoyl group or ammoniamyl group, R16 is a hydrogen atom, an alkyl group, An aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group;

D together with l represents a 5- to 7-membered carbon ring (e.g., C-C-11R, Represents a group of nonmetallic atoms necessary to form a ring).

General formula (X) *N ■ R-C-R engineering.

8 In the formula, R and R19 may be the same or different, and may be an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group,
Represents a sulfinyl group, a sulfamoyl group, an ammonillamyl group, or -N"E.E\--77 together with -N forms a 5- to 7-membered heterocycle (for example, \talimide ring, triazole ring, tetrazole ring). Represents the necessary nonmetallic atomic group.

In general formulas CI) to (X), * represents the bonding position of X.

The timing group represented by TIME-1 is one that leaves C0UP by a coupling reaction and then leaves FA by an intramolecular substitution reaction, as described in US Pat. Patent No. 2072363A, Japanese Patent Application Publication No. 57-154234,
No. 57-188035, etc., which leaves FA by electron transfer via a conjugated system, JP-A No. 57-111
Examples include coupling components such as No. 536, which are capable of releasing FA through a coupling reaction with an oxidized product of an aromatic primary amine developer.

n represents 0 or 1.

When n is 0, FA becomes GOUP- by a coupling reaction.
A group that can be separated from 1, and when n is 1, TIME-
This is a group released from 1 and has a substantial fogging effect on silver halide grains or a group having a development accelerating effect.

FA is, for example, a group represented by (L)m-X. Here, L represents a divalent linking group, X is a reducing group or a group capable of forming silver sulfide during development, and m is 0.
Or 1. When FA is a group represented by (L)m-X, the bonding position with TIME may be any position in (L)m-X.

Even if it is X, it is due to a coupling reaction.

These may be bonded to the coupling carbon as long as they can be separated. Moreover, what is known as a so-called 2-equivalent dissociative group may be present between the coupling carbon and L or X. These groups include alkoxy groups (
methoxy group), aryloxy group (e.g. phenoxy group), alkylthio group (e.g. ethylthio group), arylthio group (e.g. phenylthio group), heterocyclic oxy group (e.g. tetrazolyloxy), heterocyclic thio group (e.g.
For example, there are pyridylthio) heterocyclic groups (e.g. hydantoinyl group, pyrazolyl group, triazolyl group, pacitriazolyl group, etc.), and others, British Patent Publication 2,011
．． 391 can be used as the FA.

The divalent linking group represented by in FA includes commonly used alkylene, alkenylene, phenylene, naphthylene, -〇-1-S-1-80-1-SO2-1-N=
It is composed of a ring selected from N-, carbonylamide, thioamide, sulfonamide, ureido, thioureido, heterocycle, and the like.

The group represented by X includes reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine,
1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt, quaternary salt carbazic acid represented by ethylene bispyridinium salt, etc.) or compounds that can form silver sulfide during development (thiourea, Examples include those having 11 -〇-N- partial structures, such as thioamide, dithiocarbamate, rhodanine, thiohydantoin, and thiazolidinethione.

Among the groups represented by X, some of those capable of forming silver sulfide during development have adsorption properties to silver halide grains and can also serve as adsorptive groups as described below.

An example of KL is shown below.

-CH2-1-CH2CH2-1-0CH2-1-OC
H2CH2-1-8c) (2- Examples of X are shown below.

-NHNHCHu, -NHNHCOCH3, -NHNH
It is particularly preferable that the group represented by 8(J2CH3, -NHNHC0CF3FA) contains a group capable of adsorbing silver halide.

These adsorption groups may be linked to either X or X in FA. As a group that can be adsorbed to silver halide, a nitrogen heterocycle having a dissociable hydrogen atom (
pyrrole, imidazole, pyrazole, triazole,
tetrazole, benzimidazole, benzopyrazole, benzotriazole, uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), containing at least one nitrogen atom and other heteroatoms (oxygen, sulfur, etc.) in the ring. Heterocycles with mercapto groups (2-mercaptobenzothiazole, 2-mercaptopyrimidine, 2-mercapto Baydioxazole,
1-phenyl-5-mercaptotetrazole, etc.), quaternary salts (tertiary amines, pyridine, quinoline, benzothiazole, benzimidazole, paidioxazole, etc. quaternary salts), thiophenols, alkylthiols S 1 (cysteine, etc.) ), a compound with a partial structure of N-C- (
Examples include those consisting of thiourea, dithiocarbamate, thioamide rhodanine, thiazolidinethione, thiohydantoin, thiobarbic acid, etc.).

Groups that connect these adsorption groups to L or X include alkylene, alkenylene, phenylene, naphthylene, -0-1-S-1-SO-1-s o 2-
Examples of these adsorption groups selected from 1-N=N-, carbonylamide, thioamide, sulfonamide, ureido, thioureido, heterocycle, etc. are shown below.

1 1 1 Ha Specific examples of the group represented by KFA are shown below.

Cloudy CH20H2CHU C)12 CECt-L Ha CH3 () N, N 0H CH2C=CH Specific examples of the compound represented by the general formula [I] among the compounds of the present invention are shown below, but the invention is not limited thereto. .

(1-1) (I-2) (1-3) (1-5) (1-6) (1-7) (I-9) ((-19) (1-21) Ct-ta (I -2°) CH3 ■ (1-22) (1-25) α (1-26) (1-32) 0H (1-33) (4-as) (1-37) (1-39) (I -38) H2 H0 (1-41) (1-43) (I-42) α (1-44) l 11 (1-45) α ('l-46) S-C=N General formula [ In the formula 2), CL) UP-2 is a group capable of causing a coupling reaction with the oxidation product of an aromatic primary amine developing agent, and BALL is bonded to the coupling position of COUP-2, and GOUP-2 and A group that can be separated from COUP-2 by reaction with an oxidized product of an aromatic primary amine developer, and represents a so-called ballast group having a size and shape that impart non-diffusivity to the coupler.

FOG represents a group that exhibits a fogging effect or a development accelerating effect in a developer after being released from BALL by reaction with an oxidized product of an aromatic primary amine developer.

The coupler residue represented by GOUP-2 can also be any coupler residue known or already used in the art.

Cyan coupler residues include phenol couplers, naphthol couplers, and the like. Examples of magenta coupler residues include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers. Yellow coupler residues include acylacetanilide couplers (e.g. pageylacetanilide coupler, pivaloylacetanilide coupler, etc.),
Examples include malondianilide couplers. In addition, so-called colorless coupler residues whose coupling products with oxidized products of aromatic primary developers do not have significant visible absorption include open-chain or cyclic active methylene compounds (e.g. indanone,
cyclopentanone, cyclohexanone, malonic acid diester, acetophenone, imidazolinone, oxacillinone, thiazolinone, etc.). However, the hue of the coupling product produced by the reaction between C0UP-2 and the oxidized product of the aromatic primary amine developer is not limited to the above, and may be any hue.

The so-called ballast group represented by BALL has a size and shape that imparts non-diffusivity to the coupler, and may be in the form of a polymer in which a plurality of releasing groups are linked, or an alkyl group that imparts non-diffusivity. and/or may have an aryl group. In the latter case, the total number of carbon atoms in the alkyl group and/or aryl group is preferably about 8 to 32. BALL is bonded to the coupling position of C0UP-2. It has a linking group for Typical linking groups are oxy(-0-), thio(-5-), azo(
-N=N-), carbonyloxy (-0CO-),
Sulfonyloxy (-0SO2-') and imino (-
N-), a preferable BALL has a total carbon number of 8 to
Alkoxy, aryloxy, heterocycleoxy, alkylthio, arylthio, heterocyclethio, arylazo, acyloxy, alkylsulfonyloxy, arylsulfonyloxy or heterocycle with 32 alkyl and/or aryl groups (pyrrole, pyrazole,
imidazole, triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, phthalimide, succinimide 1.2.4-imidazolidinedione, 2,4-oxacyridinedione,
2,4-thiazolidinedione, triacylidine-3,5
-dione, etc.).

FOG is a partial structure of a coupling product having appropriate diffusivity produced by the reaction of an aromatic primary amine developer with an oxidized product, and represents a group that does not exhibit a fogging effect in a developer. Specifically, these groups include reducing compounds such as hydrazine, hydrazide, hydrazone, enamine, polyamine, hydroquinone, aminophenol, phenylenediamine, acetylene, aldehyde, thiourea, thioamide, thiocarbamate, dithiocarbamate, rhodanine, thiocarbamate, etc. It is a group that has a partial structure of a compound capable of forming silver sulfide such as a thiocarbonyl compound such as hydantoin, or a quaternary salt compound such as a tetrazolium salt, and has the divalent structure necessary to connect to GOUP-2. Contains groups.

Appropriate diffusivity here varies depending on the purpose of use and the photosensitive material, but for example, in the case of color negative film, it may significantly reduce sharpness or have a significant effect on layers with different color sensitivities (for example, increased contrast). This means that it is diffusible to the extent that it does not cause any damage.

C0UP-2 and/or FOG contain commonly used substituents of appropriate size and shape (e.g. alkyl groups, alkoxy groups, halogen atoms, carbonamide groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups, carboxy groups, sulfo groups, sulfonyl groups, hydroxy groups, etc.) and groups that have adsorption properties for silver halides (e.g. triazole,
Azoles such as tetrazole, benzimidazole, indazole, and benzotriazole; heterocyclic rings containing other heteroatoms other than nitrogen atoms in the ring such as thiazole, thiadiazole, pagethiazole, and benzoxazole; 2-mercaptobenzothiazole; - Heterocyclic salts with mercapto groups such as mercaptobenzoxazole, 2-mercapto-1,3,4-thiadiazole, 1-phenyl-5-mercaptotetrazole, quaternary salts such as tetrazolium salts, thiourea, thioamide, rhodanine, etc. (a group having the structure of a thiocarbonyl compound) can be substituted.

A preferable example of C0UP-2 in the present invention is C0UP-
1, it is represented by general formulas (1) to (X).

General formulas (1) to [X]-* in general formula [2] are BA
Represents the bonding position of LL. FOG is general formula (1) ~
(X) R1-R19, A, B.

Substituted in any position of D. The sum of the molecular weights of C0UP and FoG is preferably 500 or less, more preferably 400 or less.

Preferred examples of BALL in the present invention are alkoxy groups,
Alkylthio group, acyloxy group and other general formulas (XI) ~
There are items indicated by [X■].

General formula (XI) General formula [X■] 1 S In the formula, R2 (1, R21 and R22 may be the same or different, hydrogen atom, halogen atom, alkyl group, ali, -l group, alkoxy represents an alkylthio group, a carbonamide group, a sulfonamide group, an acyl group, a sulfinyl group, a sulfonyl group, an alkoxycarbonyl group, an alkoxysulfonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, or a nitro group.

R23, R24 and R25 may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an acyl group, an acylamino group, an alkoxycarbonyl group or an aryloxy group.

General formula (Xll General formula (XII/) 1 OS In the formula, F and G are non-containing compounds necessary to form a 5- to 7-membered heterocycle (e.g., triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring). Represents a metal atom group, R and R2□ may be the same 6 or different; hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, alkylthio group, arylthio group, carbonamide group or sulfonamide group represents.

General formula (XV) General formula (XVI) 1 General formula [X■] ? 34 The nonmetallic atomic groups necessary to form a ring (e.g., hydantoin ring, oxazolidinedione ring, pyridone ring) are
is a group of nonmetallic atoms necessary to form an azole ring (e.g., pyrazole, imidazole, triazole, tetrazole) with 1N, a group of nonmetallic atoms necessary to form a ndazole, benzimidazole, or benzotriazole ring. represent. R211 and R
29 may be the same or different (hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group,
Represents an aryloxy group, alkylthio group, arylthio group, alkylamino group, dialkylamino group, anilino group, alkoxycarbonyl group, carbamoyl group, sulfinyl group, sulfonyl group, acyloxy group, carbonamide group or sulfonamide group, R and R3□・can be the same or different O. Hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, alkylthio group, alkoxycarbonyl group, carbamoyl group, cyano group, aryloxy group,
Represents a carbonamide group, a sulfonamide group or a ureido group, R8□ and R34 may be the same or different, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group. , arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, sulfonamide group, sulfamoyl group or ureido group. In general formulas (XI) to [X■], the total number of carbon atoms of each substituent is 8 to 32, preferably 12 to 24.

Preferred examples of R00 in general formula [2] are groups having partial structures represented by the following general formulas (X■) and (XIX).

General formula [X■] R3,H In the formula, 'R35 is an acyl group (formyl group, acetyl group,
represents a trifluoroacethio group, etc.), a sulfonyl group (methanesulfonyl group, ethanesulfonyl group, etc.), or an alkoxycarbonyl group (methoxycarbonyl group), and Ra
s represents a hydrogen atom, an alkoxycarbonyl group or an acyl group, and R37 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. In the general formula (X■),
The group to be converted is C-0UP- by a divalent group (e.g. alkylene, alkenylene, arylene, -〇-1-S+, carbonyl, sulfonyl, imino group) at any position of R35, R36, R37 or the phenyl ring. -N-N-R connected to 2 but directly to the aryl ring of C0UP-2
35 may be connected as 1 36H.

General formula [XIX] R38 ++ 1 -X-C-N- 1 In the formula, -C- represents a thiocarbonyl group, R3g represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and
represents alkylene, alkenylene, aryl, -〇-1-8- or 1.

N- This group is linked to C0UP-2 via a group-like divalent group of general formula [X■] or directly to C0UP-2.

Examples of compounds of general formula [λ] are shown below.

(II -!, ) <y-z) (II -3,) OOH (II -4,) (■-5,) (II -6,') 0OH (ll-7,) (ll-9,' ) -Ta (II -10,) (II -12-) SaH3 (II-13,) (In -14,) -= RED in the general formula [3] of the compound of the present invention is represented by the following general formula ( General formula [XX] represented by XXD ~ [XX■]
] ] General formula [XX■] General formula CXXIII ] General formula [XX■] ,,, [XXV] General formula [XXVD General formula [axl] R51°R in ~(XXVI)
52 and R53 may be the same or different and are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an alkoxycarbonyl group, a carbamoyl group, Represents a sulfamoyl group, carboxyl group, sulfo group, sulfonyl group, acyl group, cyano group, carbonamide group, sulfonamide group, or heterocyclic group, and R54 is an alkyl group, aryl group, acyl group, carbamoyl group, sulfonyl group, or It represents a sulfamoyl group, and R51 and R52 are combined to form a benzene ring or a 5- to
It may form a 7-membered heterocycle.

Zl and Z2 may be the same or different and each represents a hydrogen atom or a group that can be hydrolyzed and released under alkaline conditions, and B represents a group that exhibits a fogging effect in the developer after being released. , Y represents a group which exhibits a fogging effect in the developer after being separated as Y-5O2NH2 (or its anion).

Typical examples of Z or z2 include hydrogen atom, acyl group (e.g. acetyl group, chloroacetyl group, dichloroacetyl group, totafluoroacetyl group, benzoyl group, p-
nitrobeidiyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, benzenesulfonyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, phenoxycarbonyl group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, phenylcarbamoyl group, etc.) , oxalyl group (e.g. pyruvoyl group, methoxalyl group, phenyloxamoyl group, etc.), as well as the following general formula CXX■), (X
Mention may be made of the groups X and (XXIX).

General formula (XXW) -C)I-CH-R5s 1 R57R56 General formula (XX■) -C=C-R,5 1 57R5g In the formula, R5 is an acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group , represents an alkoxycarbonyl group, a nitro group, a carboxy group, a sulfo group, or an ammoniayl group, and Rss and R57 may be the same or different and each represents a hydrogen atom, an alkyl group, or a group listed for R55. R55 and R57 are combined to form the general formula 5-7 (XXDo 1 ・-CR2O,' \ I 9 N-CH- "-v, where R2O is a hydrogen atom, an alkyl group, or an aryl group. , ■ represents -C- or -S-, and Q represents a nonmetallic atomic group necessary to form a 5- to 1-membered ring.

Specific examples of the groups represented by the general formulas CXX■], [XX■] and [XXIX] are shown below.

-CHzCHzCOOCzHs -CH2CH2CNC
I-T3COOC2H5-CH2CHCN-CH2CHCOOC2HsX is preferably a group represented by the following general formula CXXXI.

General formula CXXX) (-TIME--Z+l LL(-L2→kA TI
ME□, 2ba After X is released -Lt(L2-), 1A
1□ represents the so-called timing group that releases O
or / represents an integer. Examples of timing groups are U.S. Patent ≠, 2≠, Ri-O-No., and JP-A-57-! ;1,1
Those utilizing intramolecular nucleophilic substitution reactions as described in No. 37, etc., British Patent λ, 072:3 Otsu No. 3A, JP-A-1989-37-
/J-≠, 23≠ issue, same j7-/♂ and 03 evening issue, same tag g
Examples include those that utilize electron transfer via an intramolecular conjugated system, as described in No. 7172♂. T
IME-λ also includes those involving multi-step reactions.

When l is θ, Ll has the general formula CXXI] ~ CXXVI
] Represents a group that can be separated from B by a redox reaction with the oxidized form of a developer under alkaline conditions, and when 1 is 1, the separated B can be separated from TIME-2. represents a group. Examples of these groups include aryloxy groups, heterocyclic oxy groups, arylthio groups,
Examples include a heterocyclic thio group and an azolyl group. Specific examples of Ll are given below. * is ÷ T'IME-2
The bonding position to +l is shown.

L2 is a divalent linking group, and k represents all integers of 0 or 1. Examples of L2 include alkylene, alkenylene, all-11-lene, covalent heterocyclic group, -〇-1-S-, imino, -COO-1-CONH-1-NHCONH-1-
N)(COO-1,5O2NH-1-CO-1-8O2
Examples include -1-80-1-NH8O2N)T-, etc., and composites thereof.

A is a group that substantially exhibits a fogging effect on the silver halide emulsion when B is present in the developing solution in the form of B- or B-H, and specifically, it is a reducing group. (e.g. hydrazine, hydrazide, hydrazone, hydroxylamine,
polyamine, enamine, hydroquinone, catechol,
p-aminophenol, 0-aminephenol, aldehyde, acetylene partial structure) or a group that can act on silver halide during development to form a developable silver sulfide nucleus (e.g. thiourea, thioamide, thiocarbamate) , dithiocarbamate, thiohydantoin, rhodanine, etc.) and quaternary salts (such as tetrazo1
1 um salt, etc.).

Particularly useful groups among the groups represented by A are those represented by the following general formula [XX
It is a group represented by XI:].

General formula CXXXT) In the formula, R59 is a hydrogen atom or alkoxy is a carbonyl group, Rso Iti acyl group, sulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group,
Represents all thioacyl groups, thiocarbamoyl groups, or heterocyclic groups. The benzene ring of the general formula (XXXI) is the general formula [X
XX] may overlap with the benzene ring of Ll.

A specific example of B is shown below.

CH3Y represents the same thing as described above, specifically, the same thing as specifically described for A.

Examples of compounds of the present invention are shown below.

■-1゜[1-3 H ■-6゜■-7゜[7-10゜■1-11 ■-14 ■-15 1 ■-16 Ill-17゜1 ■-18 11-19゜[ 1-'20° These compounds of the present invention are based on generally known compounds, and are disclosed in Japanese Patent Application Publication No. 2003-120002. z, Japanese Patent Publication No. 17-1a
ll, 34. U.S. Patent No. 3.21, No. 377, No. 3.2
j3. Octopus number, special application 1977-/A/j/t,
Special request! It can be synthesized by the method described in Japanese Patent Application No. 1-1116097 and Japanese Patent Application No. 1-1116097.

A silver halide emulsion that is substantially undeveloped (hereinafter referred to as "undeveloped silver halide") that can be effectively used in the present invention refers to a silver halide emulsion that is substantially undeveloped (hereinafter referred to as "undeveloped silver halide"), and is a silver halide emulsion that can be effectively used in the present invention. Usually refers to silver halide grains that are substantially undeveloped when processed under current conditions. moreover,
When the development accelerator of the present invention acts on the silver halide in the photosensitive layer, it brings about a development accelerating effect through the development process, whereas the development accelerator acts on the undeveloped silver halide provided outside the photosensitive layer. The difference is that, even after the accelerator has acted, it is still substantially undeveloped by development.

The halogen composition of the undeveloped silver halide grains that can be used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Preferably, the grains have a silver bromide content of 40 mole or more, a silver chloride content of 30 mole % or less, and a silver iodide content of 4 co mole or less.

Preferably, the silver iodide content is θ, since the developing activity is low.
Silver iodobromide having a silver iodide content of 0.3 to about J mol is more preferred in that it does not increase the visible light absorption of the silver heptahalide grains.

Regarding the grain size of the undeveloped silver halide of the present invention, a relatively small size is preferable in terms of low photosensitivity and low absorption in the visible region. Preferably, the average particle size is less than or equal to about O0λμ, with o. is μ or less, more preferably 00IOμ or less (hereinafter, undeveloped silver halide grains with an average grain size of about 0.2 μ or less are referred to as "fine grain silver halide").Undeveloped silver halide emulsion may have any particle size distribution. Preferably, the grain size distribution is narrower, and it is particularly preferred that the size range of grains that account for 0% of the total weight of silver halide grains is within ±4 AO% of the average grain size.

The fine grain silver halide used in the present invention can be prepared using known methods. That is, any method such as an acidic method, a neutral method, or an ammonia method may be used, and the method for reacting a soluble silver salt with a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. good.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, a controlled double jet method can be used. This method is preferred as a method for preparing the fine grain emulsion of the present invention because the grain size distribution is narrow.

The fine emulsion grains may have regular crystal shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons, or may have spherical or tabular crystal shapes. Even if the interior and surface of emulsion grains are composed of different halogen compositions,
It may have a uniform halogen composition. Fine grain emulsions contain impurities such as cadmium ions, lead ions, iridium ions,
Rhodium ions or the like may also be included. Those containing a desensitizer such as rhodium inside the particles are preferred. The fine grain emulsion may be of a surface latent image type or an internal latent image type, and may have turnip kernels inside. Internal latent image type emulsions are preferred for use as the undeveloped silver halide in the present invention because they are difficult to develop with surface developers commonly used in the present invention.

Fine-grain emulsions can be subjected to conventional chemical sensitization, including sulfur sensitization, gold sensitization, and reduction sensitization.

In the present invention, it is preferable to use a so-called unripened emulsion which is not subjected to chemical sensitization.

The fine grain emulsion may contain cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrene dyes, hemioxonol dyes, and the like. Desensitizing dyes that are undesirable in ordinary negative emulsions due to their large desensitization can also be preferably used. The fine particles may also contain antifoggants and stabilizers. For example, antifogging agents or stabilizers such as azoles, heterocycles, mercapto compounds, thioketo compounds, azaindenes, benzenethiosulfonic acids, and benzenesulfinic acids can be added.

The coating amount of undeveloped silver halide is 0003~λ, li'
/ m "Ashi, preferably O0O!~lfi/T
It is rL2. The binder for the undeveloped silver halide containing layer may be any hydrophilic polymer, but gelatin is particularly preferred. The amount of binder is silver halide 2!0
It is preferable to have less g.

The undeveloped silver halide grains according to the present invention are contained in a colloid layer, that is, a protective layer, outside the photosensitive silver halide layer. Providing a fine-grain emulsion on the outside of a light-sensitive silver halide is described, for example, in Japanese Patent Application Laid-Open No. 2003-31121.
2t or the same evening o-js 33.2, these inventions disclose that in a light-sensitive material containing an existing inhibitor-releasing compound in the light-sensitive emulsion layer, the inhibitor is released from the light-sensitive emulsion layer during development. In order to prevent the development inhibitor from diffusing into the developer, the physical property of adsorption of the development inhibitor to silver halide is utilized.

In the present invention, the PR released from the FR-releasing compound
It is thought that the compound is deactivated by a chemical reaction such as electron injection between it and the undeveloped silver halide, so the presence of an adsorption group in the FR compound is not an essential requirement at all. Even if the temporary KFR compound has an adsorption group and this may promote the subsequent chemical reaction through the physical effect of adsorption to silver halide, this does not mean that the chemical action of the PR compound is different from that of the FR compound. It is believed that the mechanism of action of the present invention is that FR is deactivated by interaction with developed silver halide. This is supported by experimental evidence that even FR compounds without adsorption groups are thought to be deactivated by undeveloped silver halide.

The compounds and couplers of the present invention can be introduced into the silver halide emulsion layer using known methods, such as U.S. Pat.
The method described in No. 27 is used.

Examples include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate). ), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. organic solvents with a boiling point of about JO'C to 110°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate;
Ethyl propionate% After being dissolved in λ-class butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokuko Shoj/-J Ritg No. 3, Tokukai Shoj/-! Tata 1
The dispersion method described in No. 3 can also be used for the polymers described in No. 3.

When the compound or coupler of the present invention has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into a hydrophilic colloid as an alkaline aqueous solution in addition to the above-mentioned emulsion dispersion wave.

Unexploded E! In addition to the compound of the present invention, the photographic emulsion layer of the photographic light-sensitive material prepared using A contains other dye-forming couplers, i.e., aromatic primary amine developers (for example, phenylene diamine derivatives, amino A compound that can develop color by oxidative coupling with a phenol derivative (such as a phenol derivative) may also be used. For example, magenta coupler and Lte, J--pyrazolone coupler, virazolobenzimidazole coupler, cyanoacetyl coumaron coupler 1
Open-chain acylacetonitrile couplers include amber, yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, piparoylacetanilides), etc., cyan couplers include naphthol couplers, phenol couplers, and the like. These couplers are preferably non-diffusible and have a hydrophobic group called a /ζ last group in the molecule, or are polymerized. The coupler may be either equivalent or bi-equivalent to the silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the coupling reaction product is colorless and releases a development inhibitor.
It may also contain a coupling compound.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

Two or more of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required for photosensitive materials,
Of course, the same compound may be added to two or more different layers.

The photographic color formers used are conveniently selected to provide intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan color former is about 400 to 77-2
0n, and the maximum absorption band of the magenta dye formed from the magenta color former is about 200 to j t 0 n'
Preferably, the maximum absorption band of the yellow dye formed from the yellow color former is between about ≠00 and ≠ronm.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, O-proteins such as casein:
Cellulose conductors such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Useful silver halides have a silver bromide content of t.

An emulsion in which the silver chloride content is 30 moles or more and the silver iodide content is not more than aO mole, and a silver iodobromide emulsion in which the silver iodide content is 2 moles or more and 1.2 j moles or less. is preferable, the silver iodide content is 1 molar or more, and λ! Particularly preferred are silver iodobromide emulsions having a lower modulus.

The average grain size of the light-sensitive silver halide grains in a photographic emulsion (the grain diameter is used for spherical or approximately spherical grains, the edge length is used for cubic grains, and the projected area is expressed as an average value). ) is not particularly limited, but the emulsion used in the same layer as the compound of the present invention preferably has a 0. Alt7
1 or more, more preferably /, 0 μm or more, particularly preferably l.

It is 34m or more.

The particle size distribution may be narrow or wide.

The light-sensitive silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or a hexagonal, or may have an irregular crystal structure such as a spherical or plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. A composite form of these crystal forms may also be used. It may also consist of a mixture of particles of moderate crystalline form.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy at least jOx of the total projected area.

The photosensitive silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle.

Two or more types of separately formed photosensitive silver halide emulsions may be used as a mixture.

In the process of photosensitive silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist. good.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Tardel water washing method, which involves gelling gelatin, may be used. inorganic salts such as sulfuric acid), anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin,
A sedimentation method (flocculation) using aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may also be used.

Photosensitive silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H, Fr1eser edition' D
ie GrundlagenderPhotograph
hischen Prozesse m1tS i:l
be r halogeniden “(Akad
emi 5cheVer lagsgesel 1sc
haft, /ritf) G7. The method described in pages t to 73≠ can be used. That is, sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines,
); reduction sensitization using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts as well as Pt.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Ir%Pd can be used alone or in combination.

The light-sensitive photographic emulsion used in the present invention has the following properties:
Alternatively, various compounds can be included for the purpose of stabilizing photographic performance.

Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-j-mercaptotetrazole); mercaptopyrimidines; mercaptopyrimidines; Zaindenes, tetraazaindenes (especially ≠-hydroxy substituted (/, J, 32%7) tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonic acid amide, and the like.

For more detailed examples of these and how to use them, see, for example, U.S. Pat. 12. Rihiro No. 7, Tokukosho,? Those described in Nos. 2-, 2r, and tto can be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as enhancement of contrast, enhancement of contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers 1; tpolJ ethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylconolate polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as alkyl carboxylates, alkyl sulfonates, alkylbenzene melfoonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurine kind,
Sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers.

Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates; amino acids, aminoalkylsulfonic acids, amino Ampholytic surfactants such as alkyl sulfates or phosphates, alkyl betaines, and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts - heterocyclic μ-class ammonium salts such as pyridinium and imidazolium , and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thiojl--thyl compounds, and thiomorpholine for the purpose of increasing sensitivity, increasing contrast, or promoting development. , quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Pat.
．． No. 132, 2. Hiro 23. ! ≠No. 2, same co, 716,
06λ No. 3. t/7, 21rO, same J, 77
2.

No. 0λ7, J, III, No. 003, British patent l.

11.221 etc. can be used.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 176 No. 2
Any of the known methods and known treatment liquids as described on pages t to 30 can be applied. This photographic processing may be any photographic processing that forms a dye image (color photographic processing) depending on the purpose. The processing temperature is usually selected between /1r0c and zo0ctv, but may be lower than 1t0C or higher than to'c.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and developed by processing the photosensitive material in an alkaline aqueous solution. Among the developing agents, hydrophobic ones are listed in Research Disclosure/
II of A, 9% US Patent No. 2.73, Jri No. 0, British Patent No. 1r/3゜233 or West German Patent No. 1. j4A
They can be incorporated into the emulsion layer by various methods such as those described in US Pat. No. 7,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When forming a dye image, conventional methods can be applied.

For example, the negative-positive method (e.g. 'XJournal of
the 5ociety of Motion Pic
tureand Te1evision Engine
ers' A/vol. (1913), 667-70/
) etc.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (Re5earchDI 5clos)
ure) / No. 76 whistle, pages II to 30 (RD-176
Any of the known methods and known treatment liquids as described in ≠3) can be applied. This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 1t0C and ro0c, but may also be below /r'c or above so0c. The effect of the photosensitive material having the non-developable silver halide layer of the present invention is particularly remarkable when it is developed at a high temperature of 30°C or higher. Further, the photosensitive material of the present invention can be effectively used when performing continuous processing using a replenisher.

The developer used in black-and-white photographic processing can contain known developing agents. As a developing agent, dihydroxybenzenes (e.g. hydroquinone)%3-
Pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p
-aminophenol), ascorbic acid, etc. can be used alone or in combination. The developing solution generally contains other known preservatives, Alka'J buffering agents, antifoggants, etc., and further contains solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. as necessary. , water softener,
It may also contain a hardening agent, a viscosity-imparting agent, and the like.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine'fA imager, such as phenylenediamines (e.g. ≠-amino-N, N-diethylaniline, 3-methyl-der-amino-N, N-diethylaniline, guamino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-μm amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N゛-ethyl- N-β-methoxyethylaniline, etc.) can be used.

In addition, Photogra by L, F, A, Mason
phicProcessing Chemistry
(P-226 of Focalp (ess, 1ytt)
~2 pieces of US patents, /93.01! No., same J, jri λ.

Those described in No. 36 Hiro, JP-A-Kokai Akihiro t-6φ233, etc. may be used.

Color developers may also contain pH buffering agents such as alkaline maple sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. etc. can be included. Also, if necessary, water softeners, preservatives such as human-90xylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers. , a fogging agent such as sodium borosonolide, an auxiliary developer such as l-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like.

Specific examples of these additives can be found in Research Disclosure/
No. 74 No. 174443, as well as US patents≠.

It is described in No. 013.7JJ, OLS, OLS, 6λ, No. 10, etc.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1),
Compounds of polyvalent metals such as cobalt (III), chromium (Vl), and copper (II), peracids, quinones, nitroso compounds, and the like are used.

For example, ferricyanide, dichromate, iron (III)
) or copal) (III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, l.

Complex salts of aminopolycarboxylic acids such as 3-diamino-coprobanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganate salts, and nitrosophenols can be used. . Among these, potassium ferricyanide, ethylene diamine ferric acetate (II)
I) Sodium and iron(III) ethylenediaminetetraacetate
) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3.0μ2.12
No. 0, same 3. -≠ノ, zjA, special public show gt-trot
In addition to the bleaching accelerator described in Japanese Patent Publication No. 4t7-1rJt, 1983, and the thiol compound described in JP-A-33-65732, various additives may be added.

The light-sensitive photographic emulsion used in the present invention includes methine dyes,
It may also be spectrally sensitized by other methods.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyridine nucleus, oxazinone nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a λ-thioxazoline nucleus, a μm dione nucleus, a thiazolidine nucleus, a ≠-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus as a nucleus having a ketomethylene structure. A j-4 membered heteroartic ring nucleus such as the following can be applied.

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

A typical example is the US patent 2゜tr♂! 4tj issue, same 2,
77, 2 Kota No. 3,327, 0zO, 43. J
Coco, No. 052, 3.127. Hiromu / No. 3.41
7.223, J, Jλ1. ri t≠ issue, same 3.7jJ
, No. 4tlrO, ibid., 772.

rye issue, J, 47F, 4121, 3.70j,
No. 377, No. 3, 76, No. 3O/, No. 3゜♂/! ,
No. 40, J, JrJ7.142, No. 4', 02t
, No. 707, British Patent/, 34AlA, No. 211, 1
．． No. 307.103, Special public Sho 4L3-μri No. 36, same 1
No. 3-12,371, Tokukai Sho! Co., Ltd., Titr No. 225, Jλ-10, No. 225.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Patent No. 33.30, U.S. Pat. No. 3.33.7)
2)), aromatic organic acid formaldehyde condensates (for example, those described in US Patent J, No. 7473.j10), cadmium salts, azaindene compounds, and the like. US Patent 3,1. /! , No. 413, same J
,t/! , t≠No., J, l, No. 17.22j, J
, 4.3! , No. 72 is particularly useful.

It is also applicable to dud BA/fi, multilayer, multicolor photographic materials with 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 back-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 growing emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2, J-dihydroxydioxane, etc.), activated vinyl compounds (/, 3. !-) lyacryloyl-hexahydro-S-) riazine, /,
3-vinylsulfonyl-cofluorohanol, etc.), active halogen compounds (2,1A-dichloro-6-hydroxy-S-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. Can be used alone or in combination.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

A light-sensitive material made using Fud 8A may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzo) IJ azole compounds substituted with aryl groups (e.g. those described in U.S. Pat. No. 3,633.72≠), Hiro-thiacylidone compounds (e.g. U.S. Pat. 332゜tri), benzophenone compounds (e.g., those described in JP-A No. 27J'μ), cinnamic acid ester compounds (e.g., those described in U.S. Pat.
．． 70! ,♂θ! No. 3,707,37j'), butadiene compounds (e.g., U.S. Pat.

O4L,? , 222), or benzoxidol compounds (e.g., those described in U.S. Pat. No. 3,7oo, t
t-ss) can be used. Additionally, U.S. Patent 3. ≠Tata, 7A2, Tokukai Akihiro-17
Those described in No. 1131 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

In the photosensitive material produced using the present invention, the hydrophilic colloid layer may contain a water-soluble dye as a filter dye for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Example 1 A non-developable silver halide emulsion of the present invention was prepared as follows.

〇 2 Tigelatin aqueous solution i' maintained at 'C' 000 (
1) while stirring lλ, aqueous silver nitrate solution f00 (1
) and %O0λ4, a 100σ aqueous solution containing potassium bromide, male, and jrqb was simultaneously added for 12 minutes, and the pAg was maintained at 7.7 during this time to obtain 2 mol tb of particle size o, orμm. Silver iodobromide emulsion A containing silver iodide was obtained.

Next, on the cellulose triacetate film support, an emulsion layer as shown below in which the coupler Cp-/ was dissolved and emulsified and dispersed in a silver halide emulsion and tricresyl phosphate was coated, and Sample 10/ shown below was prepared. Created.

(Sample 1oi) (1) Emulsion layer O negative silver iodobromide emulsion...silver coating amount t, 29/TrL'' 0 coupler CI) 1...-0-11i/m
”O tricresyl phosphe) ・・・−o、a Ji'/m2
゜Gelatin ...... o, 79/m" (2) Cough retention layer. 2.≠-dichloro-t-hydroxy-3-triazinna) Riu A ......0.019/, "O gelatin・・・・・・ /,! 9/1n'' (sample to2) Sample 10 was prepared in the same manner as sample 1oi, except that the coupler C-/ added to the emulsion layer of sample 10/ was replaced with the FR compound (I-/) of the present invention in equimolar amounts. .

(Sample 1O3) Sample 1O3 was prepared by adding 1 mol of the FR compound (I-/I) of the present invention to C-/Ic to the emulsion layer of sample ioi.

(Sample 1o4A-ion) While keeping the amount of gelatin in each of the protective layers of Samples 10/-103 constant, a silver iodobromide emulsion with an average grain size of 00 otrμ silver iodide λ morch was used as the coating amount of silver, / 9
Sample 10/-103 except that it was applied so that it was /m2
Samples ioμ to iot were created in the same manner.

These samples were cut into pieces of width -1, gel K and length 1.2 m, exposed to light for sensitometry, and 35 of the samples were passed through the following A treatment (6 liquids/l).

The liquid treated with sample 101 will be referred to as A-/treatment liquid, and the fatigue treatment liquid treated with sample IO, 2~/0 t will hereinafter be referred to as Aλ~A≦treatment liquid.

Samples 10/-104 were subjected to sensitometric exposure and then passed through the A/-A4 treatment solution for the same processing time as the A treatment. The photographic results are summarized in Table 7. The photographic quality of the book was determined by measuring the density through a red filter.

Process A The development process used here was carried out by Jff'C as described below.

t Color development...3 minutes is seconds 2
Bleaching・・・・・・・・・・・・・・・・・・6 minutes 3
0 seconds & wash with water・・・・・・・・・・・・・・・
3 minutes/j seconds table Fixing・・・・・・・・・・・・・・・
Hold ... for 30 seconds and wash with water...
...3 minutes/j seconds stable...
...... 3 minutes lj seconds The composition of the next treatment liquid used in each step is as follows.

Color developer (A) Sodium nitrilotriacetate 1.0g Sodium sulfite DA, OI Sodium carbonate SO, OP Potassium bromide 1. Reference g Hydroxylamine sulfate 2.4Ag potassium iodide i,
z■ San-(N-ethyl-N-βhydroxyethylamino)-1-methyl-aniline sulfate ≠, jp Add water ip Bleach solution Ammonium bromide / 10.09 Aqueous ammonia (Colti) Coz , omt Ethylenediamine-tetraacetic acid sodium iron salt i3og Glacial acetic acid ld Add water il Fixer Sodium tetrapolyphosphate s, og Sodium sulfite ゛ ≠, og Ammonium thiosulfate (70%) t 7 j, owa
Sodium bisulfite g, A& add water il stabilizer formalin r, oat add water /lj From Table 1 it is clear that: Sample 10/~
IOJ is the processing liquid (A-/~
When processed with A-J processing), a significant change in sensitivity is observed compared to A processing. However, samples to4c, toz and i
It is clear that there is almost no change in sensitivity when these samples 10≠, 101, and IOT are treated with the treatment solution (A-μ, A''% A').

In addition, samples 101 and 10 of the present invention are samples 10/ and l.
The sensitivity was significantly higher than that of 04A, and the graininess was also good.

Further, as another sample 107, only the protective layer of sample 70μ was coated on a cellulose acetate film so that the coating amount of silver was /,09/m2. After giving the same exposure as above, 114 (X, t, and B) of processing A was carried out, and when the amount of developed silver was examined, it was found that the emulsion of this example was non-developable. It was confirmed that this was the case.

The structure of cp-/ used in the present invention is as follows.

H Example 2 A sample of a multilayer color photosensitive material consisting of each layer of a cell 4-striacetate film support having the composition shown below.
7 was created.

The amount of emulsion coated was expressed as the amount of silver coated.

Misfire f! A non-developable silver halide emulsion according to AK was prepared as follows. ≠o While stirring the cochigelatin aqueous solution/100oc maintained OCK, add 100α of 20% silver nitrate aqueous solution. , 19! % potassium iodide and /J, 7
Silver iodobromide containing 1 mol of silver iodide with a grain size of 0.07 μm was added simultaneously for 7 minutes and 30 seconds to maintain pAg at 7.2. Emulsion B was obtained.

@/layer: antihalation layer black colloidal silver ......o, irg/z" UV absorber C-/ ...0./29/@2M CJ
-...-0.17117 m'' gelatin layer 2nd layer: Intermediate layer Ko,!
S ...... θ, //9/m'' Silver iodobromide emulsion, , , , 0, / 197 m 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion ...-o, 72g/m2 Sensitizing dye I...5 7,0X/0 moles per mole of silver Sensitizing dye ■...52.0X10 moles per mole of silver Sensitizing Dye ■...4 2.1rX10 mol for 7 moles of silver Sensitizing dye ■...5 for 1 mole of silver m
"Coupler C-j...0131.!II/
Gelatin layer containing WL2 coupler C6, 0,0109/m2 φ layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion 1.49/m2 Sensitizing dye I...Silver 7 5 against a mole! , 2×10 mol sensitizing dye ■... i, zxio mol per mol of silver Sensitizing dye ■... 4 ko, 1xio mol sensitizing dye ■... 1 mol of silver Against 5/,! X10 Molar coupler C-II...--0, / 09/@2 coupler C-7-,0, 04/ 9/m2 coupler (:'
4 ・0.00!9/1rL2 coupler C-7・0.
Gelatin layer containing 04Al, 9/rrL2 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion.../, t9/2 Sensitizing dye I...5 per 7 moles of silver ! T,! tX10 mol sensitizing dye ■...5 per mole of silver tXlo mole sensitizing dye ■...5 per 1-1 silver 2.2X10 mole sensitizing dye ■...1 mole of silver /, Axlo" molar coupler C-7-, 0, 04A4A9/1rL2 coupler C-4 0.004A9/1rL2 coupler C-
7...Gelatin layer containing Kawao, ltI/77L2: Intermediate gelatin layer 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion...0.1!9/lrt ” Sensitizing dye V...J, rxlo'%A per mole of silver.

Sensitizing dye ■... J, 0 x 10 mole per mole of silver Sensitizing dye ■... 1.2 x 10' mole coupler C-t, 9.2 per mole of silver 17m2 coupler C-2,,0,01t09/@2 coupler C-10
...0. O! ! p/2 cup face-C// ・-・0,
0119/m" 1st layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion.../#fl/m2 Sensitizing dye ■...4 λ, 7 x 10 mol per mol of silver Sensitizing dye ■...+2.7xlO mol per mole of silver Sensitizing dye ■...Z×i o mole per mole of silver Coupler C1, -0,2jjj/m2 Coupler C-
7,,0,0/3j; l/m2 coupler C-/θ ・
...0. ooori l/m2 coupler C-//--0
, 0/ / g/r Gelatin layer containing IL2 Second layer: Third green-sensitive emulsion layer Silver iodobromide emulsion...l, j9/m2 Sensitizing dye V...for 7 moles of silver 4 3.0X10 mole sensitizing dye ■...2 mols per mole of silver Sensitizing dye ■...5 per mole of silver! ×70 Molar coupler C-/2 -0.0709/milk coupler C
-//-0,00,29/y12 coupler C-ta
-o, gelatin layer containing oi3g/m2 1st O layer: yellow filter layer yellow colloidal silver...0.01A9/@2 pieces,
! -D-t-pemetadecylhydroquinone...0. Gelatin layer 1/layer containing o3/9/m2: first blue-sensitive emulsion layer silver iodobromide emulsion---0-0, j29/m2 coupler C-/J...0, 4111/wt
2 Gelatin layer containing coupler C-/lA-, 0.030 g/y12 12th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion...O0≠0 fi/m 2 coupler C-
/J-,,0,-2-2! ? /@2 sensitizing dye ■・
...4 2 per mole of silver. Gelatin layer containing 2X/0 mol Thirteenth layer: Fine grain emulsion layer Silver iodobromide emulsion Gelatin layer 1st layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion.../, 00g/@2 Coupler C-/3 -------0. ．． 2/9/m2 Sensitizing dye ■...2.3 x 10 mol per mol of silver 1st j layer: 1st protective layer UV absorber C-/...o, itt-g7y
2 UV absorber C-J...O1λλ, i;I
Gelatin layer containing /, 2: 2nd protective layer polymethyl methacrylate particles (diameter t, tμ,) - Gelatin layer containing 0.0zfi/m2 In addition to the above composition, each layer contains: gelatin hardener C-12 and a surfactant were applied to the surface.

(Sample 202, λo3) The FR compound of the present invention (l-3
2) Samples 202 and 203 were prepared in the same manner as sample 201, with the addition of f, 2197 m2, (i-22) /w9/ei2.

(Sample 20≠, KoO, 2ug) Samples aoi, Ko02 and 203F) Samples λ01S202.A, except that fine-grain silver iodobromide emulsion B with an average grain size of 0.07μ and 1 mol of silver iodide was added to the 16th layer. Same as 203, sample number O4! , 20j and Ko0t were created.

The sample aoi-xot obtained in this way has a width J −
j Cl11% length 1. The film was cut to a size of 2 m, and after being exposed to the J-limit necessary to give the maximum density at a ratio of 3 frames to 1 frame, it was developed according to the following developing process.

Processing process Temperature Time color development 310CJ minute bleach jl"c/min 30 seconds fixation jJr'c 3 minutes water washing Jt"CJ public stability Jf'C/min The development process using the above process is for each treatment with the following composition. Starting with two mother liquors each, and then continuously adding 2.1 T of each processing solution having the following composition each time 5 zones of color negative film was processed.
rL2 treated.

<Color developer> Mother solution replenisher Sodium nitrilotriacetate i, og i, i11 Sodium sulfite, 0g ≠, 4c11 Sodium carbonate JO, 0ji Jko, 0I Potassium bromide 1. ≠9
0.79 Hydroxylamine sulfate 2. -9 2.69 Reference-(N-ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate Reference, 19 1.09 Add water jl/1 <Bleach solution> Mother solution replenisher Ammonium bromide /40. Ofi 174g ammonia water (coli) Koz, om 1zR1 Ethylenediamine-tetraacetic acid sodium iron salt 130.077 /4AJ9 Glacial acetic acid 1u, oW41iu, add oyst water ll
ll <Fixer> Mother solution replenisher Sodium tetrapolyphosphate Co, 0,9 J, Co9 Sodium sulfite a, og Ammonium thiosulfate (709g) 171.0at IPJ, Otd Sodium bisulfite Co, 4,9 ! , /li add water j
l /ll <Stabilizing solution> Mother solution replenisher formalin r, am Add 2.0ml water jl /A! The above development process was performed with different samples to create a fatigued running process solution. That is, sample 20/~cot
Area of each 2. /@2 was treated, and the running treatment solution after treatment was designated as B-/-B-4, respectively. Next, film samples obtained by processing samples 201 to 0t using presh liquid B, which has not been subjected to any development processing, and running liquid 33-/~B-t, are subjected to sensitization using a real color filter. The photographic sensitivity results obtained are shown in Table 2.

From the results in Table 2, it can be seen that the conventional product 20/ containing neither FR compound nor fine grain emulsion, Fresh and running liquid B-
The sensitivity does not change with either of /, while the sensitivity of CoO, Co and No. 203, which contain an FR compound and do not have a fine grain emulsion, both have high sensitivity with Fresh processing solution B, but the sensitivity changes with running. On the other hand, a method according to the present invention which contains an FR compound and has a fine grain emulsion in the protective layer! and 204, both the fresh and running liquids showed high sensitivity. Also, for λ01, 2
O! Both samples of 20t and 20t had excellent graininess.

Q.
Title of the invention Silver halide photosensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment ``Detailed explanation of the invention'' column 5 of the specification, ``Details of the invention'' in the description of the contents of the amendment The description in the "Explanation" column has been amended as follows.

(1) Delete the ≠ page.

(2) Correct the page number of No. 1 Hiro J' page to read ``Hiro≠''.

(3) Insert a separate sheet before page 2 of Ko No. 2.

(4) Correct the structure 2 of compound (I-20) on page 50.

(5) Correct the structural formula of compound 1[-/co on page 100.

(6) th page, jth line rFOGcOUP-CoJBALLJ Correct as rFOG-(COUP-Co1-BALLJ.

(7) 2nd page line ``can live'' “It can happen.” and correct it.

(8) Page 10, line 2 "Gappler" [coupler" and correct it.

(9) After the first row of the first page, insert "Here, * represents the site that binds to (TIME-/) n-FA."

Kan, page 13, line 6 "Carbodiamide group" "Carbonamide group" and correct it.

al) 1st≠page/line rR12J rRx! j and correct it.

Sumita: Delete the description on page 17, lines 1 to 1.

a3 Page 1r, line 10 to line // rTIMEJ rTIME-/J and correct it.

a4 No. λ/Page Hironoto and correct it.

Clause a, page 23, line 6 and correct it.

U+ page 26, line 2 [ and correct it.

(1'rl 2nd line on page 1) "Beizo" "Benzo" and correct it.

Bet λth page μth line and correct it.

Sumi Yu 3rd O Sada 3rd line [ ■Page 30 [ and correct it.

(2B, page 37, line j [ and correct it.

@ Structural formula on page 33, line 7 and correct it.

(To) Structural formula on page 33, line λ Ha and correct it.

Q4 3rd≠Structural formula on page 1st line and correct it.

(c) The third is negative/the structural formula of the row is and correct it.

(b) Structural formula of page Vλ, line λ and correct it.

(5) Structural formula on the 3rd line of page ≠ "1 ” and correct it.

Shitaru page 113/line structural formula -1 and correct it.

c29+ Correct the structural formula of compound (I-5) on page V6.

(To) First, correct the structural formula of compound (I-za) on page 7.

Gυ Correct the structural formula of the compound (I-//I) on page 1≠r.

The compound on page 31 (the structural formula of 1-4'-21 is (
Corrected with ε.

(To) Page 3, line 3 [Basile] "Benzoyl" and correct it.

G4J page z3/line "General formula [X■]" 1-General formula (Xl[) j and correct it.

(39 page 69th line to 70th line 1-phenyl ring” [Benzene ring] and correct it.

(To) Structural formula on page 70, line λ and correct it.

0η Page 70, lines 3 to 6, and R39 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and Q is alkylene, alkenylene, arylene, -〇-1-S-13g Or represents -N-. ” he corrected.

□□□Page t3 ≠ line and correct it.

ci9 1st r! 1st line of page rXJt- rBJ and correct it.

(41st page tz, line j XJ t- I3J and correct it.

(AD @rz page jth line -L 1-4- L 2 +TA J [-L 1
+L2-)-yAJ.

(Page 42, t!, line 6 rmJ rmJ and correct it.

(The structural formula on page 43, page j, line λ is and correct it.

(Compound) on page 100 [Correct the structural formula of 1-/J.

(c) Compound [1-/! on page ioi] The structural formula of COC
H3” is corrected.

) on page 1O4A, line 6 after "etc." [re-,2t4! toB Insert.

1st/2nd page, line 1 "Hydrophobic group" "Hydrophobic group" and correct it.

(4) The structural formula of the i6ith compound C-10 is (ε and correct it.

Specific examples of the compound represented by the general formula (1) among the compounds of the present invention are shown below in the attached sheet, but the invention is not limited thereto.

(!-1) (1-2)

Claims (1)

[Claims] at least seven light-sensitive silver halide emulsion layers provided on a support, and in combination with the silver halide emulsion layers, releasing a Kazurashi agent or a precursor thereof or a development accelerator or a precursor thereof; In a light-sensitive material containing at least seven compounds, a layer containing silver halide grains that is not substantially developed by the development process of the light-sensitive material is provided outside the light-sensitive silver halide emulsion layer furthest from the support. A silver halide photosensitive material characterized by being provided with.