JPS62170958A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve processing stability and heat resistance of a raw film at the same time by incorporating a specified colored cyan coupler in a red-sensitive emulsion layer in a specified ratio, and adding a compound to be allowed to release a diffusive development inhibitor by the coupling reaction with the oxidation product of a color developing agent. CONSTITUTION:A silver halide color photographic sensitive material is provided with at least one red-sensitive emulsion layer on a support, and this layer contains the colored cyan coupler represented by formula I in which COUP is a cyan coupler residue; * shows the coupling cite of the cyan coupler; J is a divalent bonding group; lis 0 or 1; and R3 is aryl. This colored cyan coupler is contained in the red-sensitive layer in an amount of 15-80% of all the couplers in this layer, and this layer contains the compound to be allowed to release a diffusive development inhibitor by the coupling reaction with the oxidation product of a color developing agent. This compound is represented by formula II in which A is a coupler component; n is 1 or 2; Y is a group to be allowed to release a development inhibitor high in diffusivity or its precursor by the coupling reaction of the component A with the oxidation product of a color developing agent. This compound of formula II is contained in an amount of 0.0005-0.05mol%, preferably, 0.001-0.01mol% of the silver halide in the emulsion.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, to high sensitivity, stability during development processing (hereinafter referred to as processing stability), and raw film stability. A silver halide photographic material (hereinafter referred to as heat resistance) with improved thermal stability (hereinafter referred to as heat resistance).
Hereinafter, it will be simply referred to as a photosensitive material. ) regarding.

[Background of the invention]

In recent years, there has been a demand for the development of photosensitive materials with high image quality and uniformity, and at the same time, the development process has become increasingly automated.
and faster. In other words, even if a photosensitive material has high image quality performance, if it does not have sufficient stability during processing, not only will the original performance of the photosensitive material not be brought out, but even a small amount of development will occur. Due to fluctuations in processing conditions, the resulting photosensitive materials have large variations in performance, making it impossible to meet the needs of users.

Methods for improving processing stability include, for example, controlling the developability of silver halide, using couplers with good developability, and adding substances that adsorb inhibitory substances such as fine grain silver halide and colloidal silica. methods, or methods of improving with various additives are known.

Although all of these techniques improve processing stability, they often result in a large decrease in sensitivity or deterioration in characteristics over time (especially heat resistance), and improvements are desired.

[Object of the present invention]

An object of the present invention is to provide a photosensitive material that has improved processing stability and raw film heat resistance.

[Structure of the invention]

As a result of studying various materials based on the above-mentioned technical background, the present inventors have found that, in a silver halide photographic light-sensitive material comprising at least one red-sensitive emulsion layer on a support, The proportion of colored cyan coupler contained in the red-sensitive emulsion layer is 15% of the total couplers in the red-sensitive emulsion layer.
It has been found that the object of the present application can be achieved by containing a compound which has an oxidized form of a color developing agent and releases a diffusive development inhibitor.

[Detailed description of the invention]

The colored cyan coupler of the present invention has the following general formula: , J represents a divalent linking group, Q represents 0 or l, and R3 represents an aryl group.

The cyan coupler residue represented by COυP includes a phenol coupler and a naphthol coupler residue, and a naphthol coupler residue is particularly preferred.

A preferred divalent linking group represented by J can be represented by the following general formula [2].

In the formula, Re represents an alkylene group having 1 to 4 carbon atoms or an arylene group, and R? represents an alkylene group having 1 to 4 carbon atoms, and the alkylene groups of R6 and R1 may be substituted with an alkyl group, a carboxy group, a hydroxy group, or a sulfo group.

Sow, 5OtNH, C0NH.

-COO+, -NHCO-, -NH9O,-.

-0CO-, and R11 and R-0 represent an alkyl group or an aryl group.

R8 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonyl group,
It represents an alkoxy group, an aryloxy group, a carboxy group, a sulfo group, a halogen atom, a carbonamide group, a sulfonamide group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group.

P represents 0 or a positive integer, q represents O or I, and γ represents an integer from 1 to 4.

When P is 2 or more, R6 and Z may be the same or different. When γ is 2 or more, R may be the same or different.

The aryl group represented by R3 is preferably a phenyl group or a naphthyl group when e=o.

The phenyl group and naphthyl group have a substituent +cy,
IJ+, -Ul, paleo-alkyl group, alkoxy group, aryloxy group, hydroxy group, acyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, etc.

When Q==1, the aryl group represented by R is preferably a naphthol group represented by the following general formula [3].

General formula [3] In the formula, R3 is a linear or branched alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, see-butyl group, butyl group, etc.), and M is a photographically inactive cation, such as a hydrogen atom, an alkali metal cation such as sodium or potassium atom, ammonium, methylammonium, ethylammonium, diethylammonium, triethylammonium, ethanol. Represents ammonium, jetanolammonium, pyridinium, viperinium, ammonium, toluidinium, P-nitroanilinium, anisidium, etc.

Next, specific examples of typical colored couplers represented by general formula (1) will be shown, but the invention is not limited thereto.

G-3 G-4 C-5 SIU3Ila C-6 G-7 C-9 C-10 C-11 cC-13 The above compounds are described in JP-A-50-123341 and JP-A-50-123341.
-65957, No. 56-94347, Special Publication No. 1977-
No. 11304, No. 44-32481, No. 48-178
No. 99, No. 53-34733, U.S. Patent No. 3,034
, 892 and British Patent No. 1,084,480.

When the red-sensitive emulsion layer is composed of at least two layers having different sensitivities, it is preferable to use the colored coupler of the present invention in the above-mentioned ratio in the red-sensitive emulsion layer having the highest sensitivity.
The preferred ratio of colored couplers of the present invention is 20% of the total couplers used in the emulsion layer.
% to 70%.

The total amount of coupler added to the most sensitive red-sensitive emulsion layer is generally from 0.001 mole to 0.2 mole, preferably from o,oos mole to 0.1 mole per mole of silver.

Cyan couplers used with the colored cyan couplers of this invention are generally colorless cyan couplers.

Colorless cyan couplers according to the present invention include phenol couplers and naphthol couplers, and preferred are couplers represented by the following general formulas [4], [5], or [6].

Δ General formula [5] OI ■ General formula [6] n.

^ In the above formula, A represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

RI, R2 and R3 each represent a group used in a typical phenol or α-naphthol coupler, and specifically R1 is a hydrogen atom, a halogen atom,
Alcoquine carbonylamino stores, aliphatic hydrocarbon residues,
N-arylureido, acylamino group, -0-R'
or -3-R" (where R4 is an aliphatic hydrocarbon residue), and when two or more R9s exist in the same molecule, two or more R1s may be different groups, Aliphatic hydrocarbon residues include those having substituents.

In addition, when these substituents contain an aryl group, the aryl group is an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group. group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group , alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group,
It may have a hydroxy group, a mercapto group, etc.

Examples of R2 and R3 include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
These groups also include those having substituents. Further, R1 and R3 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). .

Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, quinolyl, chenyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Ori-ruoxy, arylthio, arylazo, acylamino, carbamoyl, ester, decyl, acyloxy, sulfonamide, sulfamoyl,
Examples include groups such as sulfonyl and morpholino.

The leaving group represented by A includes any group known as a leaving group for 2-equivalent phenolic cyan couplers and 2-equivalent naphthol-based cyan couplers, but more preferably includes halogen atoms (e.g., fluorine, chlorine, etc.). ), substituted or unsubstituted alkoxy groups (e.g.
methoxy group, 2-methoxyethoxy group, 3-carboxypropoxy group, n-hexadecyloxy group), substituted or unsubstituted aryloxy group (e.g. phenoxy group,
l-naphthoxy group, 4-methoxyphenoxy group, 4-t
-octylphenoxy group, 4-methanesulfonylphenoxy group, 3-pentadecylphenoxy group), substituted or unsubstituted heterocyclic oxy group (e.g. 2-pyridyloxy group, 4.6-cymethoxy 1,3.5 -triazin-2-yloxy group, etc.), substituted or unsubstituted alkylthio groups (e.g., methylthio group, 2-methanesulfonylethylthio group, n-dodecylthio group, etc.), substituted or unsubstituted arylthio groups (e.g., phenylthio K, 4
-n-dodecylphenylthio group, 2-methoxy-5-t
-octylphenylthio group, etc.), substituted or unsubstituted alkylsulfonyl group (e.g. methylsulfonyl group, n
-decylsulfonyl group, 4-hydroxybutylsulfonyl group, etc.), substituted or unsubstituted heterocyclic groups (e.g.,
3-nitropyrazolyl group, morpholino group, l-benzyl-5-nitoxyhydantoin-3-yl group, etc.).

Among these, particularly preferable examples of X include a hydrogen atom, a chloro atom, a fluorine atom, an aryloxy group, a heterocyclic oxy group,
and an alkoxy group. Aryloxy groups are particularly preferred.

A particularly preferred cyan coupler according to the present invention is represented by the following general formula [7].

General formula [7] IJ In the formula, R1 represents an alkyl group which may have a substituent, an aryl group represents a heterocyclic group, Ar represents an aryl group which may have a substituent, and X is Represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidation product of a color developing agent.

In the general formula [7], R1 represents an alkyl group which may have a substituent, an aryl group, and a heterocyclic group. Preferably 1 to 30 carbon atoms (alkyl group of IJ,
It is an aryl group or a heterocyclic group. For example, straight-chain or branched alkyl groups (e.g., t-butyl, a-octyl, t-octyl, a-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and general formula [8 ] and the like.

General formula [8] In the formula, J is an oxygen atom or a sulfur atom, K is an integer from 0 to 4, a is 0 or l, and when K is 2 or more, two or more R1s are the same or different. R3
represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms, R3 represents a monovalent group, such as a hydrogen atom, a halogen atom (preferably chloro or bromo), an alkyl group (preferably a straight-chain or branched alkyl groups having 1 to 20 carbon atoms (e.g. methyl, tert-butyl, jert-pentyl, tert-octyl, dodecyl, pentadecyl, benzyl, phenethyl), aryl groups (e.g. phenyl), heterocyclic groups (preferably containing (heterocyclic group)
, an alkoxy group (preferably a linear or branched alkyloxy group having 1 to 20 carbon atoms (e.g. methoxy,
Ethoxy, Iert-butyloxy, octyloxy,
decyloxy, dodecyloxy)), aryloxy groups (e.g. phenoxy), hydroxy, acyloxy groups
(preferably an alkylcarbonyloxy group, an arylcarbonyloxy group, (e.g. acetoxy, benzoyloxy)), carboxy, an alkoxycarbonyl group (preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms), aryloxy Carbonyl group (
Preferably phenoxycarbonyl), alkylthio group (
Preferably C1 to C20) acyl group (preferably C1 to C20 linear or branched alkylcarbonyl group), acylamino group (preferably C1 to C20 linear or branched alkylcarboxamide), benzene carbamide), a sulfonamide group (preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms,
benzenesulfonamide group), carbamoyl group (preferably a straight-chain or branched alkylaminocarbonyl group having 1 to 20 carbon atoms, phenylaminocarbonyl group), sulfamoyl group (preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms) (aminosulfonyl group, phenylaminosulfonyl group), etc.

Ar represents an aryl group which may have a substituent, preferably a phenyl group or a naphthyl group, particularly preferably a phenyl group. Preferred examples of substituents include halogen atoms (fluorine, chlorine, bromine), cyano groups, nitro groups, alkyl groups that may have substituents such as hydroxyl groups, aryl groups, heterocyclic groups, alkylsulfonyl groups, and aryl groups. Examples thereof include a sulfonyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonamide group, an anrulamino group, an amino group, a sulfamoyl group, a carbamoyl group, and an acyloxy group. Among these, particularly preferred substituents include a halogen atom, a cyano group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfonamide group.

X represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidation product of the color developing agent. for example,
Halogen atoms (e.g. fluorine, chlorine, bromine), thiocyano groups, optionally substituted alkyloxy groups, aryloxy groups, such as heterocyclic oxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, acyloxy groups, sulfonamides group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a heterocycle, a phosphonyloxy group, and an arylazo group. More specific examples include U.S. Patent No. 3,476.563 and JP-A-47-374
No. 25, JP 4B-36894, JP 50-10
No. 135, No. 50-117422, No. 50-1203
No. 34, No. 50-130441, No. 51-10884
No. 1, No. 52-18315, No. 53-105226, No. 54-14736, No. 54-48237, No. 5
No. 5-32071, No. 55-65957, No. 56-1
No. 938, No. 56-12643, No. 56-27147
Examples include those described in each publication of the issue.

Among these, preferable examples of X include a hydrogen atom, a fluorine atom, a chlorine atom, an alkyloxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group. Particularly preferable examples of X include an alkyloxy group and an aryloxy group.

Some preferred specific examples of the cyan dye-forming couplers used in the present invention are shown below, but the present invention is not limited thereto.

C-55o■ C921125 C+J2s -57oH H The above cyan coupler according to the present invention is disclosed in Japanese Patent Application Laid-Open No. 1983-1989.
134, 57-204543, 57-204544
, 57-204545, 58-33249, 5g
-33253, 58-987311 58-1186
43, 58-179838, 58-187928,
59-65844, 59-71051, 59-8
6048, 59-105644, 59-11164
3, 59-111644, 59-131939, 59-165058, 59-177558, 59-
180559, -59-198455, 6G-35
73L 60-37557, 80-49335, 6
o-49336, 60-50533, 60-913
55, 60-107649, 60-107650,
61-2757, 53-105226, 53-1
09630゜50-10135, 50-11742
2, 54-66129, 55-32071, 55
-65957, 56-1938, 56-27143
, No. 59-166956, Japanese Patent Publication No. 49-11572, U.S. Patent No. 2,474,293゜No. 2,895,826. It can be synthesized by the method described in 3,476.563 and the like.

The diffusible DIR compound of the present invention is represented by the following general formula.

Diffusible DIR Compound General Formula (1) In the formula, A represents a strong coupler component, m represents 1 or 2, and Y is bonded to the coupling position of the coupler component A to form an oxidized form of a color developing agent. represents a group that leaves by the reaction of , and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling.

In the diffusible DIR compound general formula (1), Y represents the following general formulas (2A) to (5).

Diffusible DIR compound general formula (2A) Diffusible DIR compound general formula (2B) Diffusible DIR compound general formula (2C) Diffusible DIR compound general formula (2D) Diffusible DIr (compound general formula (2E) (X;O , S or Se ) Diffusible DIR compound general formula (3) Diffusible DIR compound general formula (4) Diffusible DIR compound general formula (5) % formula % In the above general formulas (2A) to (2D) and (3) ,
R is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, N
, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, heterocyclic group , a cyano group, an alkylsulfonyl group, and an aryloxycarbonylamino group. n represents 1 or 2; when n is 2, R1 may be the same or different; the total number of carbon atoms contained in n R's is 0 to 1O;

R7 in the above general formula (2E) is R in (2A) to (2D).

, X represents an oxygen atom, a sulfur atom, or a selenium atom, and in the general formula (4), R is an alkyl group,
Represents an aryl group or a heterocyclic group.

In general formula (5), R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. group, alkanesulfonamide group, cyano group, heterocyclic group, alkylthio group, or amino group.

When R1, R,, Rff or R4 represents an alkyl group, it may be unsubstituted, linear or branched, or may be a cyclic alkyl group. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group Or an arylthio group, etc.

When R3, R,, R1 or R4 represents an aryl group, the aryl group may be substituted. As substituents, alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups,
Examples include sulfamoyl group, hydroxy group, carbamoyl group, aryloxycarbonylamino group, alkoxycarbonylamino group, acylamino group, cyano group, and ureido group.

When R1, R1, R3 or R4 represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and a pyridyl group, selected from a quinolyl group, a furyl group, a benzothiazolyl group, an oxacylyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group, an oxanone group, etc., which are further substituted with the substituents listed for the above aryl group. may be done.

In general formulas (2E) and (4), the number of carbon atoms contained in R9 is! -15.

In the above general formula (5), the total number of carbon atoms contained in R3 and R4 is 1-15.

In the above general formula (1), Y represents the following general formula (6).

Diffusible DIR compound general formula (6) % formula % In the formula, the TIME group is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and is a group that can release an INHIBIT group in an appropriately controlled manner after being cleaved from a coupler. The INHIBIT group is a development inhibitor. In general formula (6) -TIME-IN old and old T
The groups represent the following general formulas (7) to (13).

Diffusible DIR compound general formula (7) Diffusible DIR compound general formula (8) Diffusible DIR compound general formula (9) % formula %) Diffusible DIR compound general formula (1o) Diffusible DIR compound general formula (11) Diffusion Diffusible DIR compound general formula (12) Diffusible DIR compound general formula (13) 'General formula (
In 7) to (13), R5 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group,
Alkoxy bracket, alkoxycarbonyl group, anilino group,
Represents an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, and an alkanesulfonyl group, and has general formulas (7) and (8) , (9), (11) and (13
), Q represents 1 or 2; in general formulas (7), (11), (12) and (13), (represents an integer from O to 2; general formulas (7), ( 10) and (11), R8
teeth? represents an alkyl group, an alkenyl group, an aralkyl group, a cyphcoalkyl group or an aryl group, and is represented by the general formula (12)
In (13), B represents an oxygen atom terminal. )
and the INIIIBIT group has the general formula (2A), (2B),
It represents the same aroma as the general formula defined in (3), (4)b and (5) except for the number of carbon atoms.

However, in general formulas (2A), (2B) and (3), the total number of carbon atoms contained in R1 in each molecule is l~
32, and in the general formula (4), the number of carbon atoms contained in R2 is 1 to 32, and in the general formula (5), the total number of carbon atoms contained in R3 and R4 is 0-32. be.

When R5 and R6 represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R3-R4 are alkyl groups.

When R5 and R11 represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R2-R4 are aryl groups.

Among the above diffusible DIR compounds, the general formula % formula % Particularly preferred are those having a leaving group.

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocycle included in U.S. Pat. No. 3,841,880 Coupler residues derived from substituted acetamides or heterocyclic substituted acetates or US Pat. No. 3,770,446, British Patent No. 1,459,171, West German Patent (OLS)
Coupler residues derived from acylacetamides described in 2.503,099, JP-A-50-139738, Research Disclosure No. 15737, etc., or heterocyclic type described in U.S. Pat. No. 4,046,574. Examples include coupler residues.

The magenta image-forming coupler residue represented by A includes 5-oxo-2-pyrazoline nucleus, pyrazolo-[1,5-
a] Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, or an indacylon or pyrazolotriazole coupler residue.

Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. This type of coupler residue represented by A is described in US Pat. ．． 05
No. 2,213, No. 4,088,491, No. 3,632
．． ．． No. 345, No. 3,958,993 or No. 3,96
Examples include the coupler residues described in No. 1,959.

Specific examples of the diffusible DIR compound of the present invention will be listed below, but the invention is not limited thereto.

[Exemplary compounds]

D-7 Shida teeth ll D-18 N=N Shit C1dl, 5OcOcHcOOc+tHts-N D-31 D-33 D 40 CzL teeth D-43C+zHts ShiV No.

OI 0H These compounds are U.S. Pat. No. 4,234,678;
．． No. 227.554, No. 3,617,291, No. 3.
No. 958,993, No. 4.149.886, No. 3,9
No. 33.500, Japanese Patent Publication No. 57-56837, Special Publication No. 5683
1-13239, British Patent No. 2,072,363, British Patent No. 2,070°266, Research Disclosure-1
It can be easily synthesized by the method described in No. 21228, December 981, etc.

The diffusible DIR compounds of the present invention can be used in any light-sensitive emulsion layer, but preferably in low-speed silver halide emulsion layers.

Use of a diffusible DIR compound in the silver halide photographic material according to the present invention! i is preferably in the range of o, oos to 0.05 mol per mol of silver halide in the emulsion. Particularly preferably 0.0 old to 0.0 old. One mole of O is one river.

The cyan coupler (colorless coupler, colored coupler, ITR coupler, etc.) used in the present invention can be added by a dispersion method well known in the art. For example, it is dissolved in a mixed solvent of a high boiling point solvent such as dibutyl fuculate, dioquidyl phthalate, tricresyl phosphate, etc. and a low boiling point solvent such as ethyl acetate or acetone, and the solution is mixed with alkylnaphthalene soda, benzenesulfonate sodium etc. In addition to an aqueous solution of a surfactant and gelatin, it can be emulsified using a colloid mill, and the emulsion can be added to a hydrophilic colloid solution.

The object of the present invention can only be achieved by combining the colored cyan coupler described above and the diffusive DIR compound described above, but the following silver halides can be used in the light-sensitive material of the present invention.

Silver halide emulsions include silver bromide, silver halide,
Silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride can be used, although any of those used in conventional silver halide emulsions can be used, especially silver bromide, Silver iodobromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while considering the critical growth rate of silver halide crystals, the formation may be carried out by sequentially and simultaneously adding halogenide ions and silver ions while controlling the pr-i and pAg in the mixing pot. . By this method, silver particles with a regular crystalline shape and a nearly uniform particle size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the /%logen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( By adding metal ions using at least Ti selected from complex salts), these metal elements can be contained inside the particles and/or on the particle surface, and by placing the particles in an appropriate reducing atmosphere. Reduction sensitizing nuclei can be provided inside and/or on the particle surface.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Disc.
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter abbreviated as RD).

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core 7-well grains in which the silver halide composition differs between the inside and surface layer of the grain.

The silver halide grains may be grains in which latent images are mainly formed on the surface, or grains in which latent images are mainly formed inside the grains.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of (100) and (111) planes can be used. Further, particles having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

The grain size of silver halide grains is 0.05 to 30
[mu], preferably 0.1 to 20 [mu].

Silver halide emulsions having any grain size distribution may be used. Emulsions with wide particle size distribution (
An emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). In some cases, the value is 0.20 or less.In the case of spherical silver halide, the particle size is the diameter, and in the case of particles of a shape other than spherical, the projector is used to measure the diameter of a circle of the same area. ) may be used alone or in combination. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
It is advantageous to use gelatin, including gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single or copolymers may also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane.

The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 -Triacryloyl-hexahydro-3-triazine, 1.
3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section 2, A.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or with acrylic acid. , methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-synthesizing couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

As the yellow dye-forming coupler, known decyl acetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3.265.506, No. 3,4
No. 08.194, No. 3,551,155, No. 3,
No. 582,322, No. 3.725,072, No. 3
, 891°445, West German Patent No. 1,547,868,
West German Application No. 2,219.917, No. 2,261,3
No. 61, No. 2,414,006, British Patent No. 1,42
No. 5,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 5G-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 5-21827, No. 51-102636, No. 52-82424, No. 52
-115219, 5g-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta coloring couplers that can be used include U.S. Pat. Nos. 2,600,788 and 2,983,608.
No. 3,062,653, No. 3,127,26
No. 9, No. 3,311,476, No. 3.419,3
No. 91, No. 3,519,429, No. 3゜558.
No. 319, No. 3,582,322, No. 3.61'
No. 5,506, No. 3,834,908, No. 3,8
91,445, West German Patent No. 1゜810.464, West German Patent Application (OLS) No. 2,408.665, West German Patent Application No. 2゜41
No. 7.945, No. 2,418,959, No. 2,424
, No. 467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 49-7
No. 4027, No. 49-74028, No. 49-1295
No. 38, No. 50-60233, No. 50-159336
No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 53-
55122, Japanese Patent Application No. 55-110943, and the like.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 3,730, No. 2,474,293, No. 2,8
No. 01,171, No. 2,895,826°, No. 3
, 476.563 No. 1. 3,737,326, 3,758,308, 3゜893.044, JP-A-47-37425, JP-A-50-10135
No. 50-25228, No. 50-112038,
Shinoya, which is described in Japanese Patent Publications No. 50-11'7422, No. 50-130441, etc., Japanese Patent Application Laid-Open No. 58-98731
The couplers described in the above publication are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. You can choose accordingly. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, and use a stirrer, homogenizer, etc. using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing it using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point solvents include phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. It can also be incorporated into hydrophilic colloids.

Anionic surfactants are used as dispersion aids when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves.
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the toning agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant may be used to prevent graininess from becoming noticeable.

The color anti-capri agent may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers, and one intermediate layer may be included.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section (■) J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of photosensitive materials, a formalin scavenger can be used in photosensitive materials.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the development properties such as development accelerators and development retardants, and bleaching accelerators can be added to the halogen film emulsion layer and/or the water-developable colloid layer of the light-sensitive material. A compound that can be preferably used as a development accelerator is R0176.
The compound is a compound described in Section XX1+3-D of No. 41, and the development retardant is a compound described in Section XXI and E of No. 17643. . A black and white developing agent and/or its precursor may be used for development acceleration and other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imiguzole derivatives, and the like.

Optical brighteners can be used in photosensitive materials to emphasize the whiteness of the white background and to make the coloration of the white background less noticeable. Compounds which can be preferably used as optical brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed away from the photosensitive material during development or are bleached. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, melonanine dyes, noanine dyes, and azo dyes.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material can be used to reduce the gloss of the light-sensitive material, improve the ease of writing,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

Any matting agent can be used, such as silicon dioxide, titanium dioxide, magnesium dioxide,
aluminum dioxide, barium sulfate, calcium carbonate,
Examples include polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and styrene polymers and copolymers thereof. The particle size of the matting agent is preferably 0.05 μ to 10 μ.

The amount added is preferably 1 to 300 mg/m''.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion decoy on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers provided on these films. flexible support, glass, metal,
Includes pottery etc.

The photosensitive material can be used directly or after subjecting the surface of the support to corona treatment, ultraviolet irradiation, flame treatment, etc. as necessary, or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, and hardness of the support surface. ,
It may be applied through more than one subbing layer to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which are so reactive that if added to the coating solution in advance will cause gelation before coating, should be mixed using a static mixer etc. immediately before coating. is preferred.

As a coating method, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as Zabonin, noniono surfactants such as alkylene oquinodo, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. heterocycles, cationic surfactants such as phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Furthermore, it is possible to use a fluorine-containing surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing.

Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. In addition, it is also possible to carry out bleach-fix processing using a 1-bath bleach-fix solution, and monobath processing using a 1-bath bleach-fix solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do the process.

In combination with these processing steps, a mole hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Process/Pre-film treatment process - Color development process - Stop fixing process - Water washing process - Bleaching process Constant fixation process - Water washing process - Post hardening process/Color development process - Water washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Processing temperature is usually 10°C ~ The temperature is selected within the range of 65℃,
The temperature may exceed 65°C. Preferably 25°C
Processed at ~45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as salt-like acids, sulfates, p-)luenesulfonates, sulfites, oxalates, benzenesulfonates, etc. I can do it.

These compounds are generally about 0.0% for color developer tg.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color developer IQ.

If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

As the aminophenol developer, for example, 0-
These include aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-fuynylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N.

N'-dimethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, N.

N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, etc., a moderating agent such as evacitrazic acid, and a preservative such as hydroquinolamine or sulfite, etc. May contain. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The p I-1 of the color developing solution used in the present invention is usually 7 or more, preferably about 9 to 13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid, l
-Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraacetic acid, oxycarboxylic acids such as citric acid or glyconic acid, 2-phosphonobutane1. Examples include phosphonocarboxylic acids such as 2',4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As the bleaching agent, a metal complex salt of an organic acid is used, and for example, one in which a metal ion such as iron, cobalt, or copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxydiethyl).
-N, N', N'-) diacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches have a content of 5 to 450 g/Q, more preferably 20 to 2
Use at 50g/Q.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Bleaching solutions used in the present invention include JP-A No. 46-280, JP-A-45-8506, JP-B No. 46-556, Belgian Patent No. 77 (1,910), JP-A No. 45-3836, JP-B No. 53. Various bleaching accelerators described in Japanese Patent Application Laid-open No. 71634-1987 and Japanese Patent Application Laid-Open No. 49-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 9/Q or more, within a range that can dissolve it, but it is generally used in an amount of 70 to 250 g/Q. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may include various PT- such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. The tl buffer may be contained alone or in combination of two or more. Furthermore, u-shimero products containing various optical brighteners, antifoaming agents, or surfactants are also available. or,
Preservatives such as hydroquinolamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardeners such as water-soluble aluminum salts, methanol , dimethylsulfamide, dimethylsulpoquinide, and other organic solvents may be appropriately contained.

The I)H of the fixer is used at 3.0 or more, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9.

As the bleaching agent used in the bleach-fixing solution, there may be mentioned the metal complex salts of organic acids described in the above bleaching process, and the preferred compounds and concentrations in the processing solution are the same as in the above bleaching process.

The bleach-fix solution should contain a silver halide fixer in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a halide such as ammonium bromide may be used. A bleach-fix solution containing a large amount of iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate)
III) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide may also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. You can do it.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 95, preferably 6.0 to 8.5.
and most preferably 6.5 to 8.5.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is per 1 m' unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side.
Multilayer color photographic element Sample 1 was prepared.

Sample-1 (comparison) 1st layer; Halenoyon prevention retainer (HC-1) Gelatin layer containing black colloidal silver.

Second layer; intermediate layer (r, L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Average particle size (r) 0.30 μm, Agl 6 mol%
Monodispersed emulsion (emulsion I) consisting of AgBr I containing...Silver coating ff11.8g/m
'Sensitizing dye ■... 6 X to 5 moles of sensitizing dye for 1 mole of silver...
- 1.0% per mole of silver. OX IF' Morcian coupler (C-41)... 0.06 mol per mol of silver Colored cyan coupler (CC-1)... 0003 mol per mol of silver 4th layer; High sensitivity red Sensitive silver halide emulsion layer (R11-1
) Monodisperse emulsion (emulsion ■) consisting of A g B r I with an average grain size (r) of 0.5 μm and containing 17.0 mol% of Ag...Silver coating (lit 1.3 g
/ tn2 sensitizing dye I... 3 x 10-5 mol sensitizing dye ■... per 1 mol of silver
- 1.0% per mole of silver. OX 10-'Morsian coupler (C-41)... 0.02 mol per mol of silver Colored cyan coupler (CC-1)... 0.0015 mol per mol of silver 5th layer; Middle layer (1, L,) Same as the second layer, gelatin layer.

Dry film thickness 0.5 μm 6th layer: Low sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion-1: Coated silver amount: 1.5 g/m' Sensitizing dye ■
... 2.5X 10-5 mole sensitizing dye for 1 mole of silver.
... 1.2X 10-5 mole magenta coupler (M-1) per 1 mole of silver... 0°050 mole colored magenta coupler (CM-1) per 1 mole of silver... 0.009 mol for the 7th layer, high-sensitivity green-sensitive silver
-1) Emulsion-II ... Coated silver amount 1.4 g/m'
Sensitizing dye ■... 1.5x to-' mol per 1 mol of silver, sensitizing dye ■
... 1 mole of silver. OX 10-' mol Magenta coupler (Ml)... 0.020 mol per mol of silver Colored magenta coupler (OM 1)... 0.002 mol per mol of silver 8th layer: Yellow filter FA (Y C-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2.5-G-1-octylhydroquinone.

9th layer: Low-speed blue-sensitive silver halide emulsion layer (BL-1)
Average particle size 0.48μm, ^g+ 8g containing 6 mol%
Dispersion emulsion (emulsion ■) consisting of Brl...Silver coating amount: 0.9 g/m" Sensitizing dye V...1.3X 10-' mol yellow coupler (Y-1) per 1 mol of silver. ... 0.29 mol per mol of silver 1st O layer; high sensitivity blue sensitive emulsion layer (Bl-1-1) average grain size 0.8 μm, AgBr1 containing 15 mol% Agl
Monodispersed emulsion (emulsion ■) consisting of...silver coating ff10.5g/m
'Sensitizing dye V... 1.0% per mole of silver. OX 10-' mol Yellow coupler (Y-1)... 0.08 mol per mt mol 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Agl 1 mol% Average grain size 0 .07μm)・
・Silver coating amount 0.5 g/m' Gelatin layer 12 layer containing ultraviolet absorbers UV-L and UV-2; 2nd protection layer (Pro-2) polymethyl methacrylate particles (diameter 15 μm) and formalin scavenger Gelatin layer containing (H5-1) In addition to the above composition, each layer contains a gelatin hardening agent ()i-
1) and a surfactant were added.

The compounds contained in each layer of sample 1 are as follows.

Sensitizing dye I: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarponoanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'- Anhydro-5,5'-diphenyl-9-
Ejiru 3.3'-no(3-sulfopropyl)oxacarbonanine hydrokid sensitizing dye ■; Anhydro 9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5'.

6'-dihenzoxacarponanine hydroquine sensitizing dye ■; Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine V-2 In this way Sample-1 was prepared, but as shown in Table 2, a DIR compound was added or a cyan coupler was added.
Samples 2 to 15 were prepared by changing the couplers (including colored and colorless couplers).

Compound DIR-■ contained in Sample-2 to Sample-15
(For comparison) 11'N, C, The following margins are for each sample obtained in this way at 65℃ and relative humidity 20℃.
% for 3 days, green exposure was applied through a wedge in the usual manner, and the following development process was performed, and the red density of each fog was measured.

Here, the difference in fog values is the value obtained by subtracting the fog value of the untreated sample from the fog value of the sample after the high temperature treatment.

The larger this value is, the worse the thermal stability is.

In addition, for samples that have not been subjected to high-temperature treatment, the ratio γa of the gamma value (γ0) under the following development conditions and the gamma value (γa) under the development time 20 seconds shorter (2 minutes 55 seconds)
/γox 100 (%) was measured. The ratio is 100 (%
) indicates that the stability of the phenomenon is better.

The results are shown in Table 2.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
3 minutes V 5 seconds fixed
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-edyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.259 Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate Z'l , 5g sodium bromide 1.39 nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make lQ
shall be.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt too,og ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Hydroxylic acid
Add 10.0mf7 water and
Q and adjusted to plI-60 using aqueous ammonia.

[Joseki liquid]

Ammonium thiosulfate 175.0gjH
(Water III! Sodium sulfate 8.5g
Sodium metasulfite2. Add 2.3g water to make IQ, adjust to pll-6,0 using acetic acid 4
-ru.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1, 5
mQ Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add n+Q water to make +12.

As is clear from Table 2, it is clear that the samples according to the present invention have excellent processing stability and heat resistance.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Tekasu 1 and AiT, iE 'nee 1F (Method) % formula % 2 Name of invention Silver halide photographic light-sensitive material 3, relationship to the hli correction case Patent applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact address 1-1 Sakuracho, Hino-shi, Tokyo 191 Konishiroku Photo Industry Co., Ltd. (0425-83-1521)
Patent Department 5, Specification subject to amendment 6, Contents of amendment

Claims (1)

[Claims] In a silver halide photographic light-sensitive material comprising at least one red-sensitive emulsion layer on a support, the ratio of the colored cyan coupler contained in the red-sensitive emulsion layer is greater than the total proportion of the red-sensitive emulsion layer. A silver halide photographic light-sensitive material, characterized in that it contains a compound which is 15% to 80% of the coupler and which reacts with an oxidized form of a color developing agent to release a diffusive development inhibitor.