JP2000321731A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve various performances such as graininess, color reproducibility and bleach ability and to enhance the fastness of a color image in dark preservation and under irradiation with light by incorporating at least one photographically useful group releasing compound into at least one of layers chiefly containing a yellow or magenta dye forming coupler and incorporating at least one of specified compounds into the same layer. SOLUTION: The silver halide color photographic sensitive material contains at least one photographically useful group releasing compound of the formula COUP1-B1 or COUP2-A-E-B2 forming a compound which does not substantially contribute toward a color image after coupling with the oxidized body of a developing agent in at least one of layers chiefly containing a yellow or magenta dye forming coupler and at least one of compounds of formulae I-III in the same layer. In the above formulae, each of COUP1 and COUP2 is the residue of a specified coupler, each of B1 and B2 is a specified photographically useful group or its precursor, E is an electron withdrawing part and A is a specified divalent combining group or a single bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a color photographic light-sensitive material having remarkably improved image fastness during dark storage and under light irradiation. .

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, for example, a photographically useful group-releasing coupler is generally used for improving graininess, improving color reproducibility, improving desilvering properties, and many other purposes. Dye-forming type photographically useful group-releasing couplers cannot separate the effect of the photographically useful group released from its own color development, and require a coupler mother nucleus to generate a dye corresponding to each layer with different spectral sensitivity. In addition, the development of the coupler and the design of the light-sensitive material were greatly burdened. In addition, sometimes the stability of the generated dye is poor, so that the image fastness in dark storage after processing may be deteriorated, and if the coloring dye is different from the color of the corresponding layer, the amount used is naturally limited. Will be done. In order to overcome these problems, compounds which do not substantially contribute to a color image even when coupled with an oxidized aromatic amine-based developing agent are disclosed, for example, in Japanese Patent Publication No. 1-527.
42 etc. However, instead of overcoming the above problems with dyeless couplers, US5,
258,271 and Japanese Patent Publication No. 9-2676284. In some cases, the effect of stabilizing the image storability under light irradiation by a formed dye known in JP-B-9-2676284 or the like may be sacrificed.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to improve various properties such as granularity, color reproducibility and desilverability by a coupler which functions in a light-sensitive material without substantially contributing to a color image, and An object of the present invention is to provide a color photographic light-sensitive material having excellent color image fastness during dark storage and under light irradiation.

[0004]

The objects of the present invention have been attained by the following silver halide color photographic materials.

(1) In a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, a yellow or magenta dye is used. Photographically useful to form a compound which does not substantially contribute to a color image after coupling with at least one of the layers mainly containing a coupler and an oxidized developing agent represented by formula (I) or (II). A color photographic light-sensitive material containing at least one group-releasing compound and containing at least one of the compounds represented by formulas (CI) to (C-III) in the same layer.

Formula (I) COUP1-B1 In the formula, COUP1 represents a coupler residue which releases B1 by a coupling reaction with an oxidized developing agent and forms a water-soluble or alkali-soluble compound. B1
Represents a photographically useful group linked at the coupling position of COUP1 or a precursor thereof.

Formula (II) COUP2-A-E-B2 In the formula, COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents
In the coupling product of COUP2 and oxidized developing agent, an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and the electrophilic site E results in 4
Represents a divalent linking group or a single bond capable of releasing B2 with an 8-membered ring, and may be bonded to COUP2 at the coupling position of COUP2;
It may be bonded to COUP2 at a position other than the coupling position of COUP2. B2 represents a photographically useful group or a precursor thereof.

[0008]

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Wherein R ₁ ^c is —CONR ₄ ^c R ₅ ^c ,
SO ₂ NR ₄ ^c R ₅ ^c , -NHCOR ₄ ^c , -NHCOOR
^{_{6 c, -NHSO 2 R 6 c}} , the -NHCONR ₄ ^c R ₅ ^c or ^{_{-NHSO 2 NR 4 c R 5 c}} , the R ₂ ^c is displaceable group to the naphthalene ring, m is an integer of 0 or 1 , K is an integer of 0 to 3, R ₃ ^c is a substituent, X ₁ ^c is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developing agent, a photographically useful group or a precursor thereof. Express. However, R ₄ ^c and R ₅ ^c may be the same or different,
Independently, a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ ^c represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R ₂ ^c may be the same or different, and may combine with each other to form a ring. R ₂
^c and R ₃ ^c or R ₃ ^c and X ₁ ^c may combine with each other to form a ring. R ₁ ^c , R ₂ ^c , R ₃ ^c or X ₁ ^c
May form a dimer or a multimer which bonds to each other via a divalent or divalent or higher valent group. )

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[0010]

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Wherein R ₂₁ ^c is an alkyl group, an aryl group or a heterocyclic group, R ₂₂ ^c is an alkyl group, and R ₂₃ ^c is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryl group. An oxy group, a carbonamide group or a ureido group, R ₂₄ ^c represents an alkyl group, an aryl group, an alkoxy group, a heterocyclic group, an aryloxy group, or an amino group;
X ₂ ^c represents a hydrogen atom or a coupling-off group, and n represents 0 or 1, respectively. (2) A photographically useful group-releasing compound that does not substantially contribute to a color image after coupling with an oxidized developing agent is represented by the general formula (I)
The silver halide color photographic light-sensitive material according to (1), which is I).

(3) The halogen according to (1), wherein the color-sensitive layer containing the photographically useful group-releasing compound is one or both of a blue-sensitive layer and a donor layer that gives a multilayer effect to the red-sensitive layer. Silver halide color photographic material.

(4) The halogen according to (2), wherein the color-sensitive layer containing the photographically useful group-releasing compound is one or both of a green-sensitive layer and a donor layer giving a multilayer effect to the red-sensitive layer. Silver halide color photographic material.

Hereinafter, the photographically useful group releasing compound represented by the formula (I) will be described in more detail.

General formula (I) COUP1-B1 (where COUP1 reacts with an oxidized developing agent to release B1 and generates a water-soluble or alkali-soluble compound. B1 represents COUP1.
Represents a photographically useful group linked at the coupling position of or a precursor thereof. ).

The photographically useful group-releasing compound represented by the formula (I) will be described.

More specifically, the photographically useful group releasing compound represented by the general formula (I) is represented by the following general formula (Ia) or (Ib).

Formula (Ia) COUP1- (TIME) _m -PUG Formula (Ib) COUP1- (TIME) _i -RED-PUG In the formula, COUP1 is (TIME) _m by a coupling reaction with an oxidized form of a developing agent. -PUG or (TIME) _i
Represents a coupler residue that releases a RED-PUG and generates a water-soluble or alkali-soluble compound, and TIME represents a timing group that cleaves a PUG or a RED-PUG after being released from COUP1 by a coupling reaction; Represents a group capable of cleaving PUG by reacting with an oxidized developing agent after release from COUP1 or TIME, PUG represents a photographically useful group, m represents an integer of 0 to 2, and i represents 0 or 1. . When m is 2, the two TIMEs represent the same or different.

When COUP1 represents a yellow coupler residue, for example, pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, A benzooxazolylacetamide type, benzimidazolylacetamide type, quinazolin-4-one-2-ylacetoanilide type or cycloalkanoylacetamide type coupler residue is exemplified.

When COUP1 represents a magenta coupler residue, for example, 5-pyrazolone type, pyrazolo [1,5-
a) Benzimidazole type, pyrazolo [1,5-b]
[1,2,4] triazole type, pyrazolo [5,1-
c] [1, 2, 4] triazole type, imidazo [1, 2
-B] pyrazole type, pyrrolo [1, 2-b] [1, 2,
4] Triazole-type, pyrazolo [1,5-b] pyrazole-type or cyanoacetophenone-type coupler residues.

When COUP1 represents a cyan coupler residue, for example, phenol type, naphthol type, pyrrolo [1,
2-b] [1,2,4] triazole type, pyrrolo [2,
1-c] [1,2,4] triazole type or 2,4-
And diphenylimidazole type.

Further, COUP1 may be a coupler residue which does not substantially leave a color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues.

A preferred example of COUP1 is represented by the following formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), (Cp-9), (Cp-10), (Cp-11)
Or a coupler residue represented by (Cp-12). These couplers are preferable because of their high coupling speed.

[0024]

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[0025]

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[0026]

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In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.

In the above formula, R₅₁, R₅₂, R₅₃, R₅₄,
R₅₅, R₅₆, R₅₇, R₅₈, R₅₉, R ₆₀, R₆₁, R₆₂, R
₆₃, R₆₄, R₆₅And R₆₆Has at least 10 carbon atoms
Below is preferred.

The coupler residue represented by COUP1 is R ₇₁
OCO- group, HOSO ₂ - group, HO- group, R ₇₂ NHCO
- group, or R ₇₂ NHSO ₂ - It is preferred to have at least one substituent group. That is, the formula (Cp-1)
In at least one of R _{51 and} R ₅₂ is a group represented by the formula (C
In p-2), at least one of R ₅₁ , R ₅₂ or R ₅₃ , and in the formula (Cp-3), at least one of R ₅₄ or R ₅₅ is a group represented by the formulas (Cp-4) and (Cp-5). )), At least one of R _{56 and} R ₅₇ has the formula (Cp
In -6), at least one of R _{58 and} R ₅₉ is
In the formula (Cp-7), at least one of R ₅₉ or R ₆₀ , and in the formula (Cp-8), at least one of R ₆₁ or R ₆₂ is a group represented by the formulas (Cp-9) and (Cp-10)
In formula (Cp-11), at least one R ₆₃ represents a group represented by the formula (Cp-11)
And (Cp-12), R ₆₄ , R ₆₅ or R ₆₆
At least one of R ₇₁ OCO—, HOSO ₂ —,
HO- group, R ₇₂ NHCO- group, or R ₇₂ NHSO ₂ - It is preferred to have at least one substituent group. R
₇₁ is a hydrogen atom, an alkyl group having 6 or less carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, t-
Butyl) or a phenyl group, and R ₇₂ is a group represented by R ₇₁ , an R ₇₄ CO— group, an R ₇₄ N (R ₇₅ ) CO— group, an R ₇₃ S
Represents an O ₂ — group or an R ₇₄ N (R ₇₅ ) SO ₂ — group, wherein R ₇₃ is an alkyl group having 6 or less carbon atoms (eg, methyl, ethyl,
Propyl, isopropyl, butyl, t-butyl) or a phenyl group, and R ₇₄ and R ₇₅ each represent a group represented by R _71, which may further have a substituent.

Hereinafter, R _{51 to} R ₆₆ , a, b, d, e and f will be described in detail. In the following, R ₄₁ is an alkyl group,
Represents an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . a represents 0 or 1. R ₅₂ and R ₅₃ each have the same meaning as R ₄₃ . When R ₅₂ in formula (Cp-2) is not hydrogen atom, it may form a ring of 5-7 members by bonding R ₅₂ and R _51. b represents 0 or 1. R ₅₄ represents a group having the same meaning as _{R 41, R 41 CON (R} 43) - _{group, R 41 SO 2 N (R} 43) -
A R ₄₁ N (R ₄₃ ) — group, an R ₄₁ S— group, an R ₄₃ O— group, or an R ₄₅ N (R ₄₃ ) CON (R ₄₄ ) — group. R ₅₅ is R
Represents a group having the same meaning as ₄₁ .

R ₅₆ and R ₅₇ are each independently a group having the same meaning as the R ₄₃ group, R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CON (R
₄₃ ) -group, R ₄₁ OCON (R ₄₃ ) -group or R ₄₁ SO ₂
Represents an N (R ₄₃ )-group.

R₅₈Is R₄₃Represents a group having the same meaning as R₅₉Is
R₄₁A group having the same meaning as₄₁CON (R₄₃) -Group, R₄₁O
CON (R₄₃) -Group, R₄₁SO_TwoN (R₄₃) -Group, R₄₃
N (R₄₄) CON (R₄₅) -Group, R₄₁O-group, R₄₁S-
Group, halogen atom or R₄₁N (R₄₃)-Represents a group.
d represents 0 to 3. When d is plural, plural R₅₉Is
Represents the same or different substituents. R₆₀Is R₄₃Same as
Represents a group having the same meaning. R₆₁Is R₄₃A group having the same meaning as₄₃O
SO_Two-Group, R₄₃N (R₄₄) SO_Two-Group, R ₄₃OCO-
Group, R₄₃N (R₄₄) CO-, cyano, R₄₁SO_TwoN
(R₄₃) CO-group, R₄₃CON (R₄₄) CO-group, R₄₃
N (R₄₄) SO_TwoN (R₄₅) CO-group, R₄₃N (R₄₄)
CON (R₄₅) CO-group, R₄₃N (R₄₄) SO_TwoN (R
₄₅) SO_Two-Group, R₄₃N (R₄₄) CON (R₄₅) SO_Two−
Represents a group.

R₆₂Is R₄₁A group having the same meaning as₄₁CONH
-Group, R₄₁OCONH- group, R₄₁SO_TwoNH- group, R₄₃
N (R₄₄) CONH- group, R₄₃N (R₄₄) SO_TwoNH-
Group, R ₄₃O-group, R₄₁S-group, halogen atom or R₄₁
N (R₄₃)-Represents a group. In the formula (Cp-8), e is 0
And e is an integer of 4 or more, and when e is 2 or more,
₆₂Represents the same or different.

R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON
(R ₄₄₎ - _{group, R 43 N (R 44)} CO- group, R ₄₁ SO ₂ N
(R ₄₃ ) —, R ₄₁ N (R ₄₃ ) SO ₂ —, R ₄₁ SO ₂ —
Represents group, a halogen atom, a nitro group, a cyano group, or R ₄₃ CO- group - group, R _{4 3} OCO- group, R ₄₃ OSO _2.
In the formula (Cp-9), e represents an integer of 0 to 4,
When e is 2 or more, each of a plurality of R ₆₃ represents the same or different. In the formula (Cp-10), f is 0
Represents an integer of 3 to 3, and when f is 2 or more, a plurality of R
₆₃ represents the same or different.

R₆₄, R₆₅And R₆₆Are each independently R₄₃
A group having the same meaning as the group, R₄₁S-group, R ₄₃O-group, R₄₁CO
N (R₄₃) -Group, R₄₁SO_TwoN (R₄₃) -Group, R₄₁OC
O-group, R₄₁OSO_Two-Group, R₄₁SO_Two-Group, R₄₁N (R
₄₃) CO-group, R₄₁N (R₄₃) SO_TwoGroup, nitro group
Or a cyano group.

In the above, R ₄₁ , R ₄₃ , R ₄₄ or R ₄₅
Is an alkyl group having 1 to 10 carbon atoms, preferably 1
To 6 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Representative examples include methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, n
-Hexyl, cyclohexyl, 2-ethylhexyl, n
Octyl, 1,1,3,3-tetramethylbutyl, n
-Decyl.

The aryl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is an aryl group having 6 to 10 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl. Naphthyl.

The heterocyclic group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is a heteroatom having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, derived from a nitrogen atom, an oxygen atom or a sulfur atom. It is a selected, preferably a 3- to 8-membered substituted or unsubstituted heterocyclic group. Representative examples of heterocyclic groups include 2-pyridyl, 2-benzoxazolyl, and 2? −
Imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2,2
A 4-triazol-2-yl group or 1-indolinyl is exemplified.

The above alkyl group, aryl group and heterocyclic ring
When the group has a substituent, a typical substituent is halo
Gen atom, R₄₃O-group, R₄₁S-group, R₄₃CON
(R₄₄) -Group, R₄₃N (R₄₄) CO-group, R₄₁OCON
(R₄₃) -Group, R₄₁SO_TwoN (R₄₃) -Group, R₄₃N (R
₄₄) SO_Two-Group, R₄₁SO_Two-Group, R₄₃OCO- group, R₄₁
SO _TwoO-group, R₄₁A group having the same meaning as₄₃N (R₄₄)-
Group, R₄₁CO_Two-Group, R₄₁OSO_Two-Group, cyano group or
A nitro group.

Next, R _{51 to} R ₆₆ , a, b, d, e and f
A preferred range will be described. R ₅₁ is preferably an alkyl group or an aryl group. a is particularly preferably 1. R
₅₂ and R ₅₅ are preferably an aryl group. R ₅₃ is preferably an aryl group when b is 1 and a heterocyclic group when b is 0. R
₅₄ is preferably an R ₄₁ CON (R ₄₃ )-group or an R ₄₁ N (R ₄₃ )-group. R ₅₆ and R ₅₇ are preferably an alkyl group, an aryl group, an R ₄₁ O-group or an R ₄₁ S-group. R ₅₈ is preferably an alkyl group or an aryl group.

In the formula (Cp-6), R ₅₉ is preferably a chlor atom, an alkyl group or an R ₄₁ CON (R ₄₃ ) — group, and d is preferably 1 or 2. R ₆₀ is preferably an aryl group. In the formula (Cp-7), R ₅₉ is R ₄₁ CON (R
₄₃ ) -group is preferred, and d is preferably 1.

R₆₁Is R₄₃OSO_Two-Group, R₄₃N (R₄₄)
SO_Two-Group, R₄₃OCO- group, R₄₃N (R₄₄) CO-
Group, cyano group, R₄₁SO_TwoN (R₄₃) CO-group, R₄₃C
ON (R_{Four Four}) CO-group, R₄₃N (R₄₄) SO_TwoN
(R₄₅) CO-group, R₄₃N (R₄₄) CON (R₄₅) CO
-Groups are preferred. In the formula (Cp-8), e is 0 or
1 is preferred, and R₆₂As R₄₁OCON (R₄₃)-
Group, R₄₁CON (R₄₃) -Group or R ₄₁SO_TwoN
(R₄₃)-Group, and these substitution positions are naphtho.
Position 5 of the ring is preferred.

In the formula (Cp-9), R ₆₃ is R ₄₁
CON (R ₄₃ ) — group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R ₄₁
N (R ₄₃ ) SO ₂ — group, R ₄₁ SO ₂ — group, R ₄₁ N (R ₄₃ )
CO-, nitro or cyano groups are preferred. e is 1
Or 2 is preferred.

In the formula (Cp-10), R ₆₃ is R ₄₃ N
(R ₄₄₎ CO- group, R ₄₃ OCO- group or R ₄₃ CO- group. f is preferably 1 or 2.

In the formulas (Cp-11) and (Cp-12), R ₆₄ and R ₆₅ are R ₄₁ OCO— groups, R ₄₁ OSO
_2- , R ₄₁ SO ₂ —, R ₄₄ N (R ₄₃ ) CO—, R ₄₄
N (R ₄₃₎ SO ₂ - is preferably a group or cyano group, R ₄₁
OCO- _{group, R 44 N (R 43)} CO- group or a cyano group is particularly preferable. R ₆₆ is preferably a group having the same meaning as R ₄₁ .
Each of R _{51 to} R ₆₆ preferably has a total carbon number of 18 or less including a substituent, and more preferably 10 or less.

Next, the photographically useful group represented by PUG will be described.

The photographically useful group represented by PUG may be any PUG known in the art.

Examples thereof include a development inhibitor, a bleach accelerator, a development accelerator, a dye, a bleach inhibitor, a coupler, a developing agent, a development aid, a reducing agent, a silver halide solvent, a silver complex forming agent, and a fixing agent. Agents, image toners, stabilizers, hardeners, tanning agents, fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers, desensitizers, and fluorescent brighteners But are not limited to these.

Preferably, PUG is a development inhibitor (eg, US Pat. Nos. 3,227,554 and 3,338,465).
No. 7, No. 3615506, No. 3617291,
No. 3,733,201, No. 5,200,306 and British Patent No. 1,450,479), bleaching accelerators (for example, Research Disclosure 1973, Item No. 1973).
Bleaching accelerators described in JP 11449 and EP 193389, JP-A-61-201247, JP-A-4-350
848, 4-350849 and 4-350853), development aids (for example, US Pat. No. 4,895,595)
No. 78 or JP-A-10-48787), a development accelerator (for example, a development accelerator described in U.S. Pat. No. 4,390,618 or JP-A-2-56543), a reducing agent (for example, JP-A-63-109439). Id 63-1283
42), a fluorescent color enhancer (for example, US Pat.
Fluorescent color enhancers described in 774181 and 5236804)
And the pKa of the conjugate acid of PUG is preferably 13 or less, more preferably 11 or less.

PUG is more preferably a development inhibitor or a bleach accelerator.

Preferred development inhibitors are mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptothiadiazole derivatives, mercaptooxadiazole derivatives, mercaptoimidazole derivatives, mercaptobenzimidazole derivatives, mercaptobenzthiazole derivatives, mercaptobenzoxazole derivatives,
Tetrazole derivatives, 1,2,3-triazole derivatives, 1,2,
Examples thereof include a 4-triazole derivative and a benzotriazole derivative.

A more preferred development inhibitor is represented by the following general formula DI-1
~ DI-6.

[0054]

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In the formula, R ₃₁ is a halogen atom, an R ₄₆ O- group,
R ₄₆ S— group, R ₄₇ CON (R ₄₈ ) — group, R ₄₇ N (R ₄₈ )
CO— group, R ₄₆ OCON (R ₄₇ ) — group, R ₄₆ O
₂ (R ₄₇₎ - _{group, R 47 N (R 48)} SO 2 group, R ₄₆ SO ₂ -
Group, R ₄₇ OCO— group, R ₄₇ N (R ₄₈ ) CON (R ₄₉ ) —
Group, R ₄₇ CON (R ₄₈ ) SO ₂ — group, R ₄₇ N (R ₄₈ ) C
ON (R ₄₉ ) SO ₂ — group, group having the same meaning as R ₄₆ , R ₄₇ N
(R ₄₈₎ - group, R ₄₆ CO ₂ - group, R ₄₇ OSO ₂ - group, a cyano group or a nitro group.

R ₄₆ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an alkyl group, an aryl group, a heterocyclic group or a hydrogen atom. R
_The alkyl group represented by ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is a saturated or unsaturated group having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms;
It is a linear or cyclic, linear or branched, substituted or unsubstituted alkyl group. Representative examples include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl,
i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,
3-tetramethylbutyl and n-decyl.

The aryl group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is an aryl group having 6 to 32 carbon atoms, preferably substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl. .

The heterocyclic group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is a heteroatom having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, selected from a nitrogen atom, an oxygen atom or a sulfur atom. It is preferably a 3- to 8-membered substituted or unsubstituted heterocyclic group. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl,
1,3,4-thiadiazol-2-yl, 1,2,4-
Examples include a triazol-2-yl group or 1-indolinyl.

R ₃₂ represents a group having the same meaning as R ₄₆ . k is 1
G represents 0 or 1; h represents 1 or 2; V represents an oxygen atom, a sulfur atom or -N ( _R46 )-. R ₃₁ and R ₃₂ may further have a substituent.

Preferred bleaching accelerators are shown below.

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Next, the group represented by TIME will be described.

The group represented by TIME is the CO
Any cleavage group that can cleave PUG or RED-PUG after cleavage from UP1 may be used. For example, U.S. Patent Nos. 4,146,396, 4,652,516 or
No. 4,698,297, a group utilizing a hemiacetal cleavage reaction described in U.S. Pat.Nos. 4,248,962, 4,847,185 or 4,857,440 A timing group for causing a cleavage reaction using an intramolecular nucleophilic substitution reaction described in 4,857,440. U.S. Pat.No. 4,409,323 or 4,421,845, a timing group for initiating a cleavage reaction by utilizing an electron transfer reaction described in U.S. Pat.No. 4,409,323, and a cleavage reaction utilizing a hydrolysis reaction of an imino ketal described in U.S. Pat.No.4,546,073. And a group which causes a cleavage reaction by utilizing an ester hydrolysis reaction described in West German Patent Application No. 2626317. TIME binds to COUP1 in the general formula (Ia) or (Ib) at a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom. Preferred TIMEs include the following general formulas (T-1) and (T-
2) or (T-3).

Formula (T-1) * -W- (X = Y) _j -C (R ₂₁ )
R ₂₂ - ** Formula (T-2) * -W- CO - ** Formula (T-3) * -W- LINK-E1 - **.

In the formula, * represents the general formula (Ia) or (Ib)
** represents a position binding to COUP1, ** represents PUG,
TIME (when m is plural) or RED (of general formula (Ia)
W) represents the position where it is bonded to
Child or> N-R_{twenty three}X and Y each represent methine or
Or j represents 0, 1 or 2;
R _{twenty one}, R_{twenty two}And R_{twenty three}Represents a hydrogen atom or a substituent, respectively.
You. Here, when X and Y represent substituted methine,
Substituent, R_{twenty one}, R_{twenty two}And R_{twenty three}Any two permutations of each of
Groups are linked to form a cyclic structure (eg, benzene ring, pyrazole
Ring) or not.
There may be. In the general formula (T-3), E1 is an electrophilic
LINK represents an intramolecular nucleophilic substitution reaction between W and E1
List the linking groups that relate sterically so that
You.

Specific examples of the TIME represented by the general formula (T-1) include the following.

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Specific examples of TIME represented by the general formula (T-2) include the following.

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Specific examples of TIME represented by formula (T-3) include the following.

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(TI) when m is 2 in the general formula (Ia)
ME) Specific examples of _m include, for example, the following.

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The group represented by RED in formula (Ib) will be described below. RED is COUP1 or TIM
It is a group that can be cross-oxidized by an oxidizing substance existing during development, such as an oxidized developing agent, by being cleaved from E to form RED-PUG. RED-PUG becomes PU when oxidized
Any substance that cleaves G may be used. Examples of the RED include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides and sulfonamidonaphthols. These groups are specifically described in, for example, JP-A-61-23.
No. 0135, No. 62-251746, No. 61-278
No. 852, U.S. Pat. Nos. 3,364,022 and 3,3
79,529, 4,618,571, 3,63
9,417, 4,684,604 or J.Org.C
hem., vol. 29, p. 588 (1964).

Preferred RED among the above are hydroquinones, 1,4-naphthohydroquinones,
(Or 4) -sulfonamidophenols, pyrogallols or hydrazides. Among them, the redox group having a phenolic hydroxyl group binds to COUP1 or TIME at the oxygen atom of the phenol group.

The compound represented by the general formula (Ia) or (Ib) was added until the silver halide photographic light-sensitive material containing the compound represented by the general formula (Ia) or (Ib) was developed. For the purpose of fixing the compound to the photosensitive layer or the non-photosensitive layer, the compound represented by the general formula (Ia) or (Ib) preferably has a diffusion-resistant group.
It is particularly preferred that it is included in E or RED. In this case, a preferable diffusion-resistant group is an alkyl group having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms, an alkyl group (3 to 20 carbon atoms), an alkoxy group (3 to 20 carbon atoms) or an aryl group (6 carbon atoms). To 20), and an aryl group having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms, having at least one of

For the method of synthesizing the compound represented by the general formula (Ia) or (Ib), a known patent or literature cited for explanation of TIME, RED and PUG,
JP-A-61-156127 and JP-A-58-160954.
No. 58-162949, No. 61-249052
No. 63-37350, U.S. Pat. No. 5,026,6
No. 28, EP-A-443530A2 and EP-A-444501A2.

Next, the photographically useful group releasing compound represented by formula (II) will be described.

Formula (II) COUP2-A-E-B2 In the formula, COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents C
In a coupling product of OUP2 and an oxidized developing agent, a nitrogen atom derived directly from the developing agent and directly bonded to the coupling position and an electrophilic site E undergo an intramolecular nucleophilic substitution reaction to form a 4- to 8-membered ring. Represents a divalent linking group or a single bond capable of releasing B2, and may be bonded to COUP2 at the coupling position of COUP2;
You may couple | bond with COUP2 other than the coupling position of OUP2. B2 represents a photographically useful group or a precursor thereof.

The coupler residue represented by COUP2 includes yellow coupler residues generally known as photographic couplers (for example, open-chain ketomethine-type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues. (Eg, coupler residues such as 5-pyrazolone type or pyrazolotriazole type), cyan coupler residues (eg, phenol type, naphthol type or pyrrolotriazole type coupler residues), and US Pat. No. 5,681.
No. 689, JP-A-7-128824, JP-A-7-128823, JP-A-6-222526
Nos. 9-258400, 9-258401, 9-269573, 6-
It may be a coupler residue for forming a yellow, magenta or cyan dye having a novel skeleton described in No. 27612 or the like, or may be other coupler residues (for example, US Pat. Nos. 3,632,345 and 3,280,41). A coupler residue that forms a colorless substance by reacting with an oxidized aromatic amine-based developing agent described in, for example, by reacting with an oxidized aromatic amine-based developing agent described in U.S. Patent Nos. 1,923,231 and 2,181,944. (A coupler residue that forms a black or neutral colored substance).

The coupler residue represented by COUP2 may be a monomer or a part of a dimer coupler, oligomer or polymer coupler, in which case the coupler contains more than one PUG. It may be.

Preferred examples of COUP2 of the present invention are shown below, but are not limited thereto.

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In the formula, * represents the bonding position to A. X ′ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chloro atom, a bromine atom, an iodine atom), R ₁₃₁ —, R ₁₃₁ O—, and R ₁₃₁ S
_{-, R 1 31 OCOO-, R} 132 COO-, R 132 (R 133) NCOO-, R 132 CON (R
₁₃₃ )-, and Y 'represents an oxygen atom, a sulfur atom, R ₁₃₂ N = or R ₁₃₂ ON =. Here, R ₁₃₁ represents an aliphatic group (the aliphatic group represents a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group, hereinafter referred to as an aliphatic group having the same meaning). Used), an aryl group or a heterocyclic group.

The aliphatic group represented by R ₁₃₁ is preferably an aliphatic group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms, and specific examples include methyl, ethyl, vinyl, ethynyl, propyl, and isopropyl. , 2-propenyl, 2-propynyl,
Butyl, isobutyl, t-butyl, t-amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,
1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl and octadecyl. Here, the “carbon number”, when the aliphatic group is a substituted aliphatic group, refers to the total carbon number including the carbon number of the substituent. Similarly, a group other than an aliphatic group refers to the total carbon number including the carbon number of the substituent.

The aryl group represented by R ₁₃₁ is preferably a substituted or unsubstituted aryl group having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms, and specific examples include phenyl, tolyl and naphthyl. .

The heterocyclic group represented by R ₁₃₁ is preferably a substituted or unsubstituted heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms, and specific examples thereof include 2-furyl and 2-furyl. Pyrrolyl, 2-thienyl, 3-tetrahydrofuranyl, 4-pyridyl, 2-pyrimidinyl, 2- (1,3,4-thiadiazolyl), 2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselena Zolyl, 2-quinolyl, 2-oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl and 2- (1,3,4 oxadiazolyl), 2-imidazolyl and the like.

R ₁₃₂ and R ₁₃₃ each independently represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. R ₁₃₂
And the aliphatic group, aryl group and heterocyclic group represented by R ₁₃₃ have the same meanings as R ₁₃₁ .

Preferably, X ′ is a hydrogen atom, an aliphatic group,
Aliphatic oxy group, aliphatic thio group or R ₁₃₂ CON (R ₁₃₃ )-
And Y ′ represents an oxygen atom.

Examples of the substituent suitable for the groups described above and below and the “substituent” described below include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom), hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, alkyl group (eg, methyl, ethyl, hexyl), fluoroalkyl group (eg, trifluoromethyl), aryl group (eg, phenyl, tolyl) , Naphthyl), a heterocyclic group (for example, the heterocyclic group described for R ₁₃₁ ), an alkoxy group (for example, methoxy,
Ethoxy, octyloxy), aryloxy groups (eg, phenoxy, naphthyloxy), alkylthio groups (eg, methylthio, butylthio), arylthio groups (eg, phenylthio), amino groups (eg, amino, N-methylamino, N, N-dimethylamino, N-phenylamino), acyl groups (eg, acetyl, propionyl, benzoyl), alkyl or arylsulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups (eg, acetylamino, benzoylamino), Alkyl or arylsulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), carbamoyl group (eg, carbamoyl, N-methylaminocarbonyl, N, N-dimethylaminocarbonyl, N-phenylaminocarbyl) Bonyl), sulfamoyl group (eg, sulfamoyl, N-methylaminosulfonyl, N, N-dimethylaminosulfonyl, N-phenylaminosulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl), aryloxy Carbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl), acyloxy groups (eg, acetyloxy,
Benzoyloxy), an alkoxycarbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), an alkoxycarbonylamino group (for example, methoxycarbonylamino,
Butoxycarbonylamino), an aryloxycarbonylamino group (eg, phenoxycarbonylamino),
Examples include an aminocarbonyloxy group (eg, N-methylaminocarbonyloxy, N-phenylaminocarbonyloxy) and an aminocarbonylamino group (eg, N-methylaminocarbonylamino, N-phenylaminocarbonylamino).

R ₁₁₁ and R ₁₁₂ are each independently R ₁₃₂ CO-, R
₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₁ SO _n- , R ₁₃₂ (R ₁₃₃ ) NSO _2-
Or represents a cyano group. Where R ₁₃₁ , R ₁₃₂ and R ₁₃₃
Has the same meaning as described above, and n represents 1 or 2.

R ₁₁₃ represents the same group as R ₁₃₁ described above. R ₁₁₄
Is R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₂ (R ₁₃₃ ) N-, R ₁₃₁ SO ₂ N (R
₁₃₂ )-, R ₁₃₁ S-, R _{1 31} O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ )
NCON (R ₁₃₄ )-, R ₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO- or a cyano group. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ have the same meaning as described above, and R ₁₃₄ represents the same group as R ₁₃₂ .

R ₁₁₅ and R ₁₁₆ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N
(R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R
_{133) NCON (R 134) -} , R 131 OCO-, R 132 (R 133) NCO-, a halogen atom or a cyano group, more preferably a group represented by R _131. Where R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R
₁₃₄ is as defined above.

R ₁₁₇ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 to 3. Preferred substituents of _{R 117, R 131 -, R} 132 CON (R 133) -, R 131 OCON
(R ₁₃₂ )-, R _{1 31} SO ₂ N (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
_{And 131} S-, R ₁₃₁ O-, and a halogen atom. Where R
₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When p and q are 2 or more, each R ₁₁₇ may be the same or different, or adjacent R ₁₁₇ may be bonded to each other to form a ring. Formulas (II-1E), (II-
In a preferred embodiment of 2E), at least one of the ortho positions of the hydroxyl group is R ₁₃₂ CONH-, R ₁₃₁ OCONH- or R ₁₃₂ (R ₁₃₃ ) NCONH-
Is replaced by

R ₁₁₈ represents a substituent, r represents an integer of 0 to 6, and s represents an integer of 0 to 5. Preferred substituents for R ₁₁₈ include R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ OCON (R ₁₃₂ )-, R
₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₁ S-, R
₁₃₁ O-, R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-,
Examples include a cyano group or a halogen atom. Where R
₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When r and s are 2 or more, each R ₁₁₈ may be the same or different, or adjacent R ₁₁₈ may be combined with each other to form a ring. General formula (II-1F), (II-2F), (I
In a preferred embodiment of I-3F), the ortho position of the hydroxyl group is R ₁₃₂ CONH
-, R ₁₃₂ HNCONH-, R ₁₃₂ (R ₁₃₃ ) NSO ₂ -or R ₁₃₂ NHCO-.

R ₁₁₉ represents a substituent.
_132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R
₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₂ (R ₁₃₃ ) NCO-, a halogen atom or a cyano group, more preferably a group represented by R ₁₃₁ . Where R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄
Is as defined above.

R ₁₂₀ and R ₁₂₁ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N
(R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R
_{133) NCON (R 134) -} , R 132 (R 133) NCO-, R 132 (R 133) NSO 2 -,
R ₁₃₁ OCO-, a halogen atom and a cyano group, more preferably R ₁₃₂ (R ₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , a trifluoromethyl group, R ₁₃₁ OCO- and a cyano group Represents Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above.

E is -CO-, -CS-, -COCO-, -SO-, -SO _2- , -P
_{(= O) (R 151)} -, - P (= S) (R 151) - {R 1 51 is an aliphatic group, an aryl group, an aliphatic oxy group, an aryloxy group, an aliphatic thio group, an arylthio group Represent.電子 or other electrophilic group or -C (R
₁₅₂ ) (R ₁₅₃ )-{R ₁₅₂ and R ₁₅₃ each represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. Each aliphatic group, aryl group, and heterocyclic group have the same _meanings as those described for R131. Represents｝, preferably -CO-.

A is obtained by an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent in the coupling product of COUP2 and an oxidized developing agent and directly bonded to the coupling position with the electrophilic site E (preferably 4). Represents a divalent linking group or a single bond capable of releasing B2 together with a ring formation of from 2 to 8 members, more preferably 5 to 7 members, and still more preferably 6 members.

Examples of the linking group represented by A include the following.

× − (CO) _n1 − (Y ′) _{n2 −ΔC} (R
₁₄₁ ) (R ₁₄₂ ) 4 _n4 − ×× × − (CO) _n1 − ｛N (R ₁₄₃ )｝ _n3 − ｛C (R ₁₄₁ ) (R
₁₄₂ ) { _n4 − ××× − (Y ′) _n2 − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )}
_n4 − ×× × − {N (R ₁₄₃ )} _n3 − (CO) _{n1 −ΔC} (R ₁₄₁ ) (R
₁₄₂ )｝ _n4 − ×× × − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − (Y ′)
_n2 − ×× × − (CO) _n1 − ｛C (R ₁₄₁ ) (R ₁₄₂ )｝ _n4 − ｛N (R
₁₄₃ )｝ _n3 − ××× − (Y ′) _n2 − ××, × − {N (R ₁₄₃ )} _n3 − ××.

In the formula, × represents a site binding to COUP2, xx represents a site binding to E, Y ′ represents an oxygen atom or a sulfur atom, and R ₁₄₁ , R ₁₄₂ and R ₁₄₃ are each hydrogen. Represents an atom, an aliphatic group, an aryl group, or a heterocyclic group (each of the aliphatic group, aryl group, and heterocyclic group has the same _meaning as described for R ₁₃₁ ), and represents R ₁₄₁ , R _142, and R ₁₄₃ are each other or COUP
It may combine with 2 to form a ring.

R ₁₄₁ and R ₁₄₂ are preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom. R
₁₄₃ is preferably a hydrogen atom or an aliphatic group.

N1 and n3 represent an integer of 0 to 2,
n2 represents 0 or 1; n4 represents an integer of 1 to 5 (when n3 and n4 represent an integer of 2 or more, each of N (R ₁₄₃ ) and C (R ₁₄₁ ) (R ₁₄₂ ) is the same; And a coupling product of COUP2 and an oxidized developing agent, and an intramolecular nucleophilic reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and an electrophilic site E. N1 + n2 + n4, n1 + n3 + n4, and n1 + n2 + n4 to form a 4- to 8-membered ring by the substitution reaction.
n2 and n3 are chosen. However, -N ( _R143 )-
When R is directly bonded to E, R ₁₄₃ is preferably not a hydrogen atom. When the linking group A is linked at the coupling position of COUP2, the portion directly linked to COUP2 is-
It cannot be Y'-.

The bonding position between COUP2 and the linking group A was determined after the coupling reaction between the coupler and the oxidized developing agent.
By an intramolecular nucleophilic substitution reaction between the nitrogen atom derived from the developing agent and the electrophilic site E in the coupling product (preferably 4 to 8 members, more preferably 5 to 7 members, and still more preferably 6 members) Any method can be used as long as B2 can be released with ring formation, but C2 is preferably used.
OUP2 is at or near the coupling position (the atom next to the coupling position or the atom next to it).

The present invention wherein the linking group A is bonded to 1) the coupling position, 2) the atom adjacent to the coupling position and 3) the adjacent atom adjacent to the coupling position of the coupler residue represented by COUP2. And the coupler of the present invention and A
The reaction of an aromatic amine-based developing agent represented by rNH ₂ with an oxidized form (Ar ′ = NH) can be represented by the following formula.

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Formula (II-1) wherein COUP2 is preferably (II-1A), (II-1B), (II-1
-1C), (II-1D), (II-1E), (II-1)
F) or (II-1G). Preferred examples of A with respect to｝ include the following: x-CO-C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ )-
××, × −C (R ₁₄₁ ) (R ₁₄₂ ) −C (R ₁₄₁ ) (R ₁₄₂ ) − ××, × −C (R ₁₄₁ ) (R ₁₄₂ ) −C (R ₁₄₁ ) (R ₁₄₂ ) − C (R
₁₄₁ ) ( _R142 ) -xx, x-C ( _R141 ) ( _R142 ) -N ( _R143 ) -xx, x-C ( _R141 ) ( _R142 ) -C ( _R141 ) (R ₁₄₂ ) -O-x
×, × −C (R ₁₄₁ ) (R ₁₄₂ ) −C (R ₁₄₁ ) (R ₁₄₂ ) −S− ×
×, × -C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R
₁₄₃ ) -xx, more preferably, -C ( _R141 ) ( _R142 ) -N ( _R143 ) -xx, -C ( _R141 ) ( _R142 ) -C ( _R141 ) (R ₁₄₂ ) -O-x
×, × -C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R
₁₄₃ ) -xx.

In the formula, x, xx, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ are as defined above (two or more -C in one linking group).
_{(R 141) (R 142)} - or each of R ₁₄₁ and R _{1 42} be different even in the same time it is present. ).

Formula (II-2) wherein COUP2 is preferably (II-2A), (II-2B),
(II-2C), (II-2D), (II-2E), (II
-2F) or (II-2G). Preferred examples of A for｝ include the following: x-C (R ₁₄₁ ) (R ₁₄₂ ) -xx, x-C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) ( _R142 ) -xx, x-O-xx, x-S-xx, x-N ( _R143 ) -x
X, x-C ( _R141 ) ( _R142 ) -O-xx, x-C ( _R141 ) ( _R142 ) -S-xx, x-C ( _R141 ) ( _R142 ) -N ( _R143 ) -xx, more preferably, -O-xx, -N ( _R143 ) -xx, -C ( _R141 ) ( _R142 ) -O-xx, -C (R ₁₄₁ ) ( _R142 ) -N ( _R143 ) -xx.

In the formula, X, XX, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ are as defined above (two or more —C in one linking group)
_{(R 141) (R 142)} - or each of R ₁₄₁ and R _{1 42} be different even in the same time it is present. ).

General formula (II-3) Here, preferably, COUP2 is represented by (II-3F). For｝, preferred A is x-C (R ₁₄₁ ) (R ₁₄₂ ) -xx, x-O-xx, x-S
-Xx, x-N ( _R143 ) -xx, more preferably x-O
-Xx, x-N ( _R143 ) -xx, x-N
( _R143 ) -xx is particularly preferred.

In the formula, x, xx, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ have the same _meanings as described above.

B2 represents a photographically useful group or a precursor thereof. A preferred embodiment of B2 is represented by the following general formula (III).

#-(T) _k -PUG (III) In the formula, # represents a site linked to E, T represents a timing group capable of releasing PUG after being released from E, and k represents 0. Represents an integer of 1 to 2, preferably 0 or 1.
PUG represents a photographically useful group.

As a timing group represented by T, for example, a group which releases PUG by utilizing a hemiacetal cleavage reaction described in US Pat. Nos. 4,146,396, 4,625,516 and 4,692,297, JP-A-9-14058 U.S. Pat.No. 4,424,962
No. 5,719,017 or 57,09987, a group which releases PUG using an intramolecular ring closure reaction described in JP-B-54-39727.
No., JP-A-57-136640, JP-A-57-154234, JP-A-4-2615
No. 30, 4-411246, No. 6-324439, No. 9-14058, U.S. Pat.No. 4,409,323 or a group which releases PUG by electron transfer via π electrons described in 4,421,845, etc. Akira
57-179842, JP-A-4-61530, 5-313322, etc., a group that releases PUG by generating carbon dioxide as described in the United States
Patent No. 4560773 describes a group capable of releasing PUG by a hydrolysis reaction of imino ketals.
And a group which releases PUG by utilizing a reaction with sulfite ion described in EP-A-572084.

Preferred examples of the timing group represented by T in the present invention include, but are not limited to, the following timing groups.

[0119]

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In the formula, # represents a site binding to the electrophilic site E or ##, and ## represents a position binding to PUG or #. Z represents an oxygen atom or a sulfur atom, and preferably represents an oxygen atom. R ₁₆₁ represents a substituent, preferably R
_131- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R
₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R
₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, a halogen atom, a nitro group and a cyano group. Where R ₁₃₁ ,
R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. R ₁₆₁
It may combine with any of R ₁₆₂ , R ₁₆₃ and R ₁₆₄ to form a ring. n ₁ represents an integer of 0-4. When n ₁ represents an integer of 2 or more, each R ₁₆₁ may be the same or different, and R ₁₆₁ may combine with each other to form a ring.

R ₁₆₂ , R ₁₆₃ and R ₁₆₄ represent the same groups as R _132, and n ₂ represents 0 or 1. R ₁₆₂ and R ₁₆₃ may combine to form a spiro ring. R ₁₆₂ and R ₁₆₃ are preferably a hydrogen atom or (C 1-20, preferably 1-10)
It is an aliphatic group, more preferably a hydrogen atom. R
₁₆₄ is preferably (having 1 to 20, preferably 1 to 10 carbon atoms)
Aliphatic group or (C6-20, preferably C6-10)
An aryl group. R _{16 5} is _{R 132 -, R 132 (R} 133) NCO-, R
₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, and R ₁₃₂ CO-. Where R
₁₃₁ , R ₁₃₂ and R ₁₃₃ are as defined above. R ₁₆₅ preferably represents R ₁₃₂ , more preferably an aryl group having 6 to 20 carbon atoms.

The photographically useful group represented by PUG has the same meaning as described above.

A preferred embodiment of the coupler of the present invention is represented by the above formula (II-2) or (II-3),
(II-3) is more preferred (in the general formulas (II-2) and (II-3), A, E, B2 and their preferred ranges are the same as those described above).

A more preferred embodiment of the formula (II-3) is represented by the following formula (II-3a), more preferably the following formula (II-3b), and particularly preferably the formula (II-3b) 3c)
It is represented by The structure of the cyclized product obtained by the reaction of the general formula (II-3c) with the oxidized form of the developing agent represented by ArNH ₂ (Ar ′ = NH) can be represented by the general formula (IV).

[0125]

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In the formula, Q ₁ and Q ₂ each represent a 5- or 6-membered ring, and a nonmetallic atom group necessary for causing a coupling reaction with an oxidized developing agent at the base atom of X ′. And X ′, T, k, PUG, R ₁₁₈ , s, and R ₁₃₂ are as defined above. R ₁₄₄ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, preferably represents an aliphatic group, an aryl group or a heterocyclic group, more preferably represents an aliphatic group (each aliphatic group, aryl group The group and the heterocyclic group have the same _meanings as those described for R _131. ).

In the present invention, at least the following groups are not B1 and B2.

[0128]

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In the formula, *** represents a site linked to the electrophilic site represented by E or the timing group represented by T; R ₇₁ represents a substituted or unsubstituted aliphatic group; R ₇₂ represents an unsubstituted aliphatic group.

Specific examples of the coupler used in the light-sensitive material of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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The method for synthesizing the compound represented by the general formula (I) is described in, for example, JP-A-58-162949, JP-A-63-37350, and JP-A-4-35604.
2, JP-A-5-61160, JP-A-6-130594, and US5234800.

Examples of the synthesis of the compound represented by formula (II) are shown below.

[0173]

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Dicyclohexylcarbodiimide (41.3 g) was added to a solution of compound 62a (50 g) and o-tetradecyloxyaniline (51.1 g) in N, N-dimethylacetamide (250 ml (hereinafter referred to as “mL”) at 30 ° C. ) Was added dropwise, and the reaction solution was stirred at 50 ° C. for 1 hour, and ethyl acetate (250 mL) was added, and the mixture was cooled to 20 ° C. After suction filtration of the reaction solution, 1N hydrochloric acid solution (25
(0 mL). Hexane (100 mL) was added to the organic layer, and the precipitated crystals were filtered, washed with acetonitrile, and dried to obtain Compound 62b (71 g).

Synthesis of Compound 62c An aqueous solution of sodium hydroxide (30 g) (150 mL) was added dropwise to a solution of Compound 62b (71 g) in methanol (350 mL) / tetrahydrofuran (70 mL), and the mixture was stirred at 60 ° C. for 1 hour under a nitrogen atmosphere. . After cooling the reaction solution to 20 ° C., concentrated hydrochloric acid was added dropwise until the system became acidic. The precipitated crystals were collected by filtration, washed with water, washed with acetonitrile, and dried to obtain Compound 62c (63 g).

Synthesis of Compound 62d Compound 62c (20 g), a succinimide (5.25 g) and a 37% aqueous solution of formalin (4.3 mL) in ethanol (150 mL) were stirred and refluxed for 5 hours. After cooling to 20 ° C, the precipitated crystals were filtered,
Drying yielded compound 62d (16 g).

Synthesis of Compound 62e A solution of Compound 62d (7 g) in dimethyl sulfoxide (70 mL) was added
After sodium borohydride (1.32 g) was slowly added at 70 ° C. so as not to exceed 70 ° C., the mixture was stirred at that temperature for 15 minutes. The reaction solution was slowly added to 1N aqueous hydrochloric acid (100 mL), and then extracted with ethyl acetate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. After removing the origin component with a short path column (developing solvent: ethyl acetate / hexane = 2/1), the compound 62e (3.3 g) was obtained by recrystallization from an ethyl acetate / hexane system.

Synthesis of Compound (62) To a solution of bis (trichloromethyl) carbonate (1.98 g) in dichloromethane (80 mL) was added phenoxycarbonylbenzotriazole (4.78 g) and N, N-dimethylaniline (2.42 g) in dichloromethane (100 mL). / Ethyl acetate (200 mL) solution was added dropwise,
Stirred at C for 2 hours (Solution S).

Compound 62e (2.0 g) and dimethylaniline
(0.60 g) tetrahydrofuran (20 mL) / ethyl acetate (20 mL)
After 120 mL of the above solution S was added dropwise to the solution at 10 ° C, the mixture was stirred at 20 ° C for 2 hours. The reaction solution was slowly added to 1N aqueous hydrochloric acid (200 mL), and then extracted with ethyl acetate (200 mL). Wash the organic layer with water,
After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. After purifying the column (developing solvent: ethyl acetate / hexane = 1/5), recrystallization from the ethyl acetate / hexane system yielded 1.3 g (m.
p. = 138-140 ° C.) was obtained (the compound was identified by elemental analysis, NMR and Mass spectrum).

The compound represented by formula (C-I) will be described in detail below.

R ₁ ^c is —CONR ₄ ^c R ₅ ^c , —SO _{2
^{NR 4 c R 5 c, -NHCOR}} 4 c, -NHCOOR 6
^c, represents ^{_{-NHSO 2 R 6 c, -NHCONR 4}} c R 5 c or ^{_{-NHSO 2 NR 4 c R 5 c}} , R 4 c, R
₅ ^c and R ₆ ^c are each independently the total number of carbon atoms (hereinafter C
Represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. R ₄ ^c
And R ₅ ^c it can also be a hydrogen atom.

[0182] _R ^{2 c} represents a group substitutable on a naphthalene ring (including atoms. Hereinafter the same), a halogen atom as a representative example (F, Cl, Br, I), hydroxyl group, carbonyl group, amino group, sulfo Group, cyano group, alkyl group,
Aryl group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group , A sulfamoylamino group, an alkoxycarbonylamino group, a nitro group, and an imide group. Examples of the case where k = 2 include a dioxymethylene group and a trimethylene group.
The C number of (R ₂ ^c ) k is 0 to 30.

[0183] _R ^{3 c} represents a substituent, represented by preferably the following formula (II'-1).

Formula (II′-1) R ₇ ^c (Y ^c ) _{m ′} − In the formula (II′-1), Y ^c is>NH,> CO or>
The SO _2, m 'is 0 or 1 _{integer, R} ^{7 c} is hydrogen atom, an alkyl group having a C number of 1 to 30, C number of 6 to 30 aryl group, a heterocyclic group having a C number of 2 to 30, - COR ₈ ^c

[0185]

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Or —SO ₂ R ₁₀ ^c , respectively.
Here, R ₈ ^c , R ₉ ^c and R ₁₀ ^c are the same as those of the above R ₄ ^c , R ₅ ^c
And R ₆ ^c have the same meaning.

R₁ ^cOr R₇ ^cIn the formula, -NR₄ ^c
R₅ ^cR₄ ^cAnd R₅ ^cAnd -NR ₈ ^cR₉ ^cR₈ ^c
And R₉ ^cAre bonded to each other to form a nitrogen-containing heterocyclic ring (eg,
(Pyrrolidine ring, piperidine ring, morpholine ring)
You may.

[0188] X ₁ ^c represents the (same.. Or less including that. Leaving atom leaving group) removable group upon coupling reaction with hydrogen atom or an aromatic primary amine developing agent oxidized form, the leaving group Representative examples include a halogen atom,

[0189]

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A thiocyanate group, a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom and bonded to a coupling active site (for example, a succinimide group, a phthalimide group, a pyrazolyl group, a hydantoinyl group, a 2-benzotriazolyl group). Can be mentioned. Here, R ₁₁ ^c has the same meaning as R ₆ ^c .

In the above, the alkyl group may be linear, branched or cyclic, and may contain a substituent (for example, a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group) even if it contains an unsaturated bond. , An alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and as typical examples, methyl, isopropyl, isobutyl, t-butyl, 2- Ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-
There is t-pentylphenoxy) propyl.

The aryl group may be a condensed ring (for example, a naphthyl group) or a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group).
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

Heterocyclic groups are represented by O, N, S, P, Se, T
e is a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom in the ring, and has a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), Representative examples include 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
There are 1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

The preferred examples of the substituent in the present invention are described below.

[0195] preferably -CONR ₄ ^c R ₅ ^c or -SO ₂ NR ₄ ^c R ₅ ^c is as _R ^{1 c,} carbamoyl Examples, N-n-butylcarbamoyl, N-n--dodecylcarbamoyl, N- ( 3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3- (2,4-di-t-pentylphenoxy) propyl] carbamoyl, N-hexadecylcarbamoyl, N- [4- (2, 4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methylpropyl) carbamoyl, N- [3-
(4-t-octylphenoxy) propyl] carbamoyl, N-hexadecyl-N-methylcarbamoyl, N-
(3-dodecyloxypropyl) sulfamoyl, N-
[4- (2,4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ ^c is particularly preferably -
CONR ₄ ^c R ₅ ^c .

As R ₂ ^c and k, k = 0, that is, unsubstituted one is most preferable, and then k = 1 is preferable. R ₂
^c is preferably a halogen atom, an alkyl group (eg, methyl, isopropyl, t-butyl, cyclopentyl), a carbonamide group (eg, acetamido, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (eg, methanesulfonamide, toluenesulfonamide) ) Or a cyano group.

R₃ ^cIs preferably in formula (II'-1)
M ′ = 0, and more preferably R₇ ^cIs -COR
₈ ^c[For example, formyl, acetyl, trifluoroacetate
Chill, 2-ethylhexanoyl, pivaloyl, benzoy
Pentafluorobenzoyl, 4- (2,4-di-t
-Pentylphenoxy) butanoyl], -COOR_Ten ^c
 [For example, methoxycarbonyl, ethoxycarbonyl,
Isobutoxycarbonyl, 2-ethylhexyloxyca
Rubonyl, n-dodecyloxycarbonyl, 2-methoxy
Siethoxycarbonyl] or -SO_TwoR_Ten ^c[For example
Methylsulfonyl, n-butylsulfonyl, n-hexa
Decylsulfonyl, phenylsulfonyl, p-tolyls
Ruphonyl, p-chlorophenylsulfonyl, trifluoro
Romethylsulfonyl], and particularly preferably R₇ ^cBut
-COOR_Ten ^cIt is. Further, m = 1 is preferable.

X ₁ ^c is a photographically useful group represented by B1 or B2 or a precursor thereof or a hydrogen atom, a halogen atom, —OR ₁₁ ^c [eg, ethoxy, 2-
Hydroxyethoxy, 2-methoxyethoxy, 2- (2
-Hydroxyethoxy) ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy, 2-methanesulfonamidoethoxy,
Alkoxy groups such as 2- (carboxymethylthio) ethoxy, 2- (1-carboxytridecylthio] ethoxy, for example, 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t-octylphenoxy, 4- Aryloxy groups such as nitrophenoxy, 4- (3-carboxypropanamido) phenoxy, and 4-acetamidophenoxy]] or -SR ₁₁ ^c
[For example, carboxymethylthio, 2-carboxymethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2-
Alkylthio group such as (N, N-dimethylamino) ethylthio, for example, arylthio group such as 4-carboxyphenylthio, 4-methoxyphenylthio, 4- (3-carboxypropanamido) phenylthio],
Particularly preferred are a photographically useful group, a hydrogen atom, a chlorine atom, an alkoxy group and an alkylthio group.

[0199] Couplers represented in general formula (C-I) of 2 to bind to each other via a respective bivalent or divalent or more group substituents ^{_R 1} _{c, R} 2 _c, the _R ^{3 c} or _X ^{1 c} Multimers of the body or higher may be formed. In this case, the number of carbon atoms may be out of the range specified for each substituent.

When the coupler represented by the general formula (CI) forms a polymer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (typically a homo- or copolymer of a cyan-color-forming monomer) This is an example, and is preferably represented by the formula (II′-2).

Formula (II'-2)-(Gi) _gi- (Hj) _{hj- In the} formula (II'-2), Gi is a repeating unit derived from a chromogenic monomer, and is represented by the formula (II'-3). Hj is a repeating unit derived from a non-color-forming monomer and is a group represented by the formula (II'-3), i is a positive integer, and j is 0 or a positive integer. , Gi and hi represent the weight fraction of Gi or Hj, respectively. Here, if i or j is plural, Gi
Or, Hj indicates that a plurality of types of repeating units are included.

Formula (II'-3)

[0203]

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In the formula (II'-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom;
A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms at both terminals such as a substituted or unsubstituted alkylene group, phenylene group, and oxydialkylene group. L represents -CONH-, -NHCONH-, -NHCOO-,-
NHCO-, -OCONH-, -NH-, -COO-,
-OCO -, - CO -, - O -, - SO 2 -, NHSO 2
— Or —SO ₂ NH—. a, b, and c represent an integer of 0 or 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ ^c , R ₂ ^c , R ₃ ^c or X ₁ ^{c of the} compound represented by the general formula (CI).

Examples of the non-color-forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developer giving the repeating unit Hj include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid ( Amides or esters derived from these acrylic acids (eg, methacrylic acid) (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n -Butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate Acrylates and β-hydroxyethyl methacrylates), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl) Acetophenone and sulfostyrene), itaconic acid, citraconic acid,
There are crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

In particular, acrylates, methacrylates and maleates are preferred. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula (II'-3) is in the form of a copolymer to be formed, for example, Solid, liquid, micellar and physical properties and / or chemicals such as solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility It can be selected so that the properties, thermal stability, coupling reactivity with an oxidized developer and diffusion resistance in a photographic colloid are favorably affected. These copolymers may be random copolymers or copolymers having a specific sequence (eg, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of several thousand to several million, but oligomeric polymer couplers having a molecular weight of 5,000 or less can also be used.

The cyan polymer coupler used in the present invention may be a lipophilic polymer which is soluble in an organic solvent (eg, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) even if it is an aqueous gelatin solution. The polymer may be a hydrophilic polymer that is miscible with a homocolloid or a polymer having a structure and properties capable of forming micelles in the hydrocolloid.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color-forming ethylene-like monomer (for example, acrylate, methacrylate, maleate, vinylbenzene, etc.) is mainly used as a copolymer component. It is preferable to select

A solution obtained by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by the above formula (II'-3) in an organic solvent is emulsified in the form of a latex in an aqueous gelatin solution. It may be made by dispersion or directly by an emulsion polymerization method.

The method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and the method of emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,080. 370,952
Can be used.

In order to obtain a hydrophilic polymer coupler soluble in neutral or alkaline water, N- (1,1
-Dimethyl-2-sulfonatoethyl) acrylamide, 3-sulfonatopropyl acrylate, sodium styrenesulfonate, potassium styrenesulfinate, acrylamide, methacrylamide, acrylic acid,
It is preferable to use a hydrophilic non-color-forming ethylene-like monomer such as methacrylic acid, N-vinylpyrrolidone and N-vinylpyridine as a copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and a water-miscible organic solvent such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide, and dimethylacetamide can be used. It can also be dissolved and added to a mixed solvent of water and water. Further, it may be added by dissolving in an aqueous alkali solution or an organic solvent containing alkaline water. Further, a small amount of a surfactant may be added.

Specific examples of each substituent in the formula (C-I) and the cyan coupler represented by the formula (C-I) are shown below.

Examples of R ₁ ^c

[0219]

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[0218]

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[0219]

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[0220]

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Examples of R ₂ ^c

[0222]

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Examples of R ₃ ^c NH—

[0224]

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[0225]

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[0226]

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[0227]

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[0228]

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Examples of X ₁ ^c

[0230]

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[0231]

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[0232]

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[0233]

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Specific examples of the cyan coupler represented by formula (C-I)

[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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[0250]

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Other specific examples of the cyan coupler represented by the formula (C-I) and / or methods for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, JP-A-60-237448, and JP-A-60-237448. 61-153640, 6
1-1145557, 63-208042, 64
No. 31,159 and West German Patent No. 3,823,049A.

The following formula (C-II) or (C) is contained in the silver halide color photographic light-sensitive material of the present invention.
The cyan coupler of -III), that is, the phenolic cyan coupler will be described in detail.

Formula (C-II) or (C-III)
In the formula, R ₂₁ ^C is the total number of carbon atoms (hereinafter referred to as C number) 1
To 36 (preferably 1 to 24) alkyl groups which may contain or be substituted with a linear, branched or cyclic unsaturated bond, and are substituted with 6 to 36 (preferably 6 to 24) C atoms. Or a substituted or unsubstituted heterocyclic group having 2 to 36 (preferably 2 to 24) C atoms.
Here, the heterocyclic group means at least one N, O,
5 having a hetero atom selected from S, P, Se, and Te
It is a 7-membered heterocyclic group which may be condensed, and examples thereof include 2-furyl, 2-thienyl, 4-pyridine, 2-imidazolyl and 4-quinolyl. Examples of the substituent of R ₂₁ ^C include a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, a heterocyclic group,
An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, Examples thereof include an alkoxycarbonylamino group and a sulfamoylamino group (hereinafter, referred to as substituent group A).
As the substituent, a halogen atom (F, C
l, Br, I), a cyano group, an alkyl group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group,
Examples include a carbonamido group or a sulfonamido group.

In the general formula (C-II), R ₂₁ ^C is preferably an alkyl group, and in the general formula (C-III), R ₂₁ ^C is preferably an alkyl group or an aryl group.

In the general formula (C-II), R ₂₂ ^C is
It is a linear, branched or cyclic alkyl group having 1 to 36 (preferably 1 to 24) C atoms. R ₂₂ ^C is preferably an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl,
Propyl, isopropyl, t-butyl, cyclopentyl).

Formula (C-II) or (C-III)
In the formula, R ₂₃ ^C represents a hydrogen atom, a halogen atom (F, C
l, Br, I), a linear, branched or cyclic alkyl group having 1 to 16 (preferably 1 to 8) C atoms, 6 to 6 C atoms
24 (preferably 6 to 12) aryl groups, having 1 to 2 carbon atoms
4 (preferably 1 to 8) alkoxy groups, 6 to 24 carbon atoms
(Preferably 6 to 12) aryloxy group, having 1 to 1 carbon atoms
It is a 24 (preferably 2 to 12) carbonamide group or a ureido group having 1 to 24 (preferably 1 to 12) C atoms. Here, when R ₂₃ ^C is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carbonamide group or a ureido group, it may be substituted with a substituent selected from the above-mentioned substituent group A.

In the general formula (C-II), R ₂₃ ^C is
Preferable is a halogen atom, and is represented by the above general formula (C-II
In I), R ₂₃ ^C is preferably hydrogen, a halogen atom,
An alkoxy group or a carbonamide group, particularly preferably hydrogen.

In the formula (C-II), R ₂₂ ^C and R
₂₃ ^C may combine with each other to form a ring. In formula (C-III), R ₂₃ ^C and R ₂₄ ^C may be bonded to each other to form a ring. At this time, R ₂₃ ^C may be a single bond or an imino group and may be a ring component.

In formula (C-III), R ₂₄ ^C has the same meaning as R ₂₁ ^C, and has 1 to 36 C atoms (preferably 1
To 24) alkoxy group having 6 to 36 C atoms (preferably 6
To 24), or an alkyl or aryl-substituted amino group having 1 to 36 (preferably 1 to 24) C atoms. R ₂₄ ^C is preferably the same as R ₂₁ ^C, and is more preferably an alkyl group.

The formula (C-II) or (C-III)
In the formula, X ₂ ^c represents a photographically useful group represented by B1 or B2 or a coupling-off group capable of leaving by a coupling reaction with a precursor thereof, a hydrogen atom or an oxidized form of a developing agent. Examples of the coupling-off group include a halogen atom (F, Cl, Br, I), a sulfo group, an alkoxy group having 1 to 36 (preferably 1 to 24), and a C 6 to 36 (preferably 6 to 36). 24) an aryloxy group, a C2-C36 (preferably 2-24) acyloxy group, a C1-36 (preferably 1-24) alkyl or arylsulfonyloxy group, a C1-3
6 (preferably 1 to 24) alkylthio groups, C number 6 to
36 (preferably 6 to 24) arylthio groups, C number 4
To 36 (preferably 4 to 24) imide groups, C number 1 to 3
6 (preferably 1 to 24) carbamoyloxy group or a heterocyclic group (e.g., tetrazol-5-yl) bonded to the coupling active site with a nitrogen atom having 1 to 36 (preferably 2 to 24) C, pyrazolyl, Imidazolyl, 1,
2,4-triazol-1-yl). Here, the group below the alkoxy group may be substituted with a group selected from the substituent group A. X ₂ ^c is preferably a photographically useful group, a hydrogen atom, a fluorine atom, a chlorine atom, a sulfo group, an alkoxy group or an aryloxy group, and particularly preferably a hydrogen atom or a chlorine atom.

The formula (C-II) or (C-III)
In the formula, n represents an integer of 0 or 1, and is preferably 0.

In the following, formula (C-II) or (C-II)
Examples of R ₂₁ ^c , examples of R ₂₂ ^c , examples of R ₂₃ ^c , and R in I)
_{24 cases} of ^c (addition to the examples of the R ₂₁ ^c in) _and supra after each examples of _X ^{2 c.}

Specific examples (IIC-1 to IIC-10) of the coupler represented by the general formula (C-II) and the couplers represented by the general formula (C-II)
Specific examples of the couplers represented by I) (IIIC-11 to IIIC-2)
6) will be described later.

The formula (C-II) or (C-III)
Specific examples of the substituents other than those described above, and a method of synthesizing a cyan coupler containing these, for example, US Pat.
No. 369,929, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 4,327,173, No. 4,333,999,
Nos. 4,334,011 and 4,430,423
No. 4,500,635 and No. 4,518,68
No. 7, No. 4,564,586, No. 4,609,6
No. 19, No. 4,686,177, No. 4,746,
602 and JP-A-59-164555.

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The amount of the photographically useful group-releasing compound represented by formulas (I) and (II) used in the light-sensitive material is 5 × 10 ^-4.
The coating amount is in the range of ~ ² g / m2. Preferably, 1 × 10 ⁻³ or more
In the range of 1 g / m ^2, more preferably ^{5 × 10 -3 ~5 × 10 -1} g
/ m ² .

For the use of the photographically useful group-releasing compound represented by formulas (I) and (II) in a light-sensitive material, any known dispersion method can be adopted depending on the compound. For example, in the case of alkali solubility, a method of adding an aqueous alkali solution or a solution dissolved in an organic solvent miscible with water, an oil-in-water dispersion method using a high-boiling organic solvent, a solid dispersion method, or the like is used. Can be added.

The photographically useful group releasing compounds represented by formulas (I) and (II) may be used alone or in combination of two or more. Further, the same compound can be used in two or more layers.

The amount of the (quenching) couplers represented by formulas (C-I) to (C-III) depends on the amount of the compound represented by formula (I) or the compound represented by formula (II) Is preferably 0.05 to 50 mol% with respect to the coupler mainly contained in the layer containing at least one compound selected from the group consisting of: It is more preferably 0.1 to 30 mol%, particularly preferably 0.5 to 15 mol%.

Further, instead of adding the (quenching) couplers represented by formulas (C-I) to (C-III), a cyan dye produced by coupling these with an oxidized developing agent may be added. good.

The light-sensitive material of the present invention may be provided with at least one light-sensitive layer on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-206
As described in 541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH.

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

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

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

To improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange a donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from that of the main photosensitive layer such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or close to the main photosensitive layer. .

A preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and
No. 18716 (November 1979), p. 648, No. 307105 (November 1989)
Pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et.
Phisique Photographiques, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal
Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention.

Tabular grains are described in Photographic Science and Engineering (Gutof).
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226; 4,414,310;
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

In the light-sensitive material of the present invention, the grain size, grain size distribution, halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

Silver halide grains having a fogged surface described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-214852.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. , Its preparation method is described in US Pat.
It is described in 214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide.

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

The coated silver amount of the light-sensitive material of the present invention was 6.0 g / m ^2.
Or less, and most preferably 4.5 g / m ² or less.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23 648 page right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, page 23-24 page 648, right column 866-868 superstrong sensitizer ~ page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column page 876 Lubricant 8. Coating aid, pages 26 to 27 page 650 right column page 875 to 876 surfactant 9. Static 27 page 27 page 650 right column 876 to 877 Inhibitor 10. Matting agents 878 to 879.

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred.

Yellow coupler: Formula (I) of EP 502,424A,
Coupler represented by (II); Formulas (1) and (2) of EP 513,496A
(Especially Y-28 on page 18); EP 568,037A
A coupler of the formula (I) of claim 1 of US Pat.
6,576, column 45, line 45 to 55, couplers represented by the general formula (I); JP-A-4-74425, paragraph 0008, couplers represented by the general formula (I); EP 498,381 A1, page 40, claim 1 Couplers (especially D-35 on page 18); EP 447,969A1-4
Couplers represented by the formula (Y) on the page (especially Y-1 (page 17), Y-54
(Page 41)); US Pat. No. 4,476,219, column 7, lines 36 to 58, formula (II)
~ (IV) (especially II-17,19 (column 1
7), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257, [A-4] -63 (p. 134), [A-4] -73, -75 (p. 139); EP 486,
965 M-4, -6 (p. 26), M-7 (p. 27); EP 571, 959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A 4-43345 C-
7,10 (p. 35), 34, 35 (p. 37), (I-1), (I-17) (pp. 42-43);
A coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385.

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

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

Couplers for correcting unnecessary absorption of a coloring dye are described in formulas (CI), (CII) and (CI) described on page 5 of EP 456,257A1.
II), yellow colored cyan couplers represented by (CIV) (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX- 7 (2
Magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) described in US 4,833,069, US 4,83
7,136 (2) (column 8), formula (A) of claim 1 of WO92 / 11575
Colorless masking coupler represented by (especially 36 to 45
Is preferred.

Examples of the compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds represented by the formula (I) described on page 7 of 6,938A2 (particularly D-49 (page 51)), compounds represented by the formula (1) of EP 568,037A (particularly (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly, (60),
(61)) and the compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7));
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; fluorescent dye releasing compound: of claim 1 of US 4,774,181
Compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
Compounds represented by the formulas (1), (2) and (3) in column 3 of 4,656,123 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only after leaving: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

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

Dispersion medium for oil-soluble organic compound: JP-A-62-215
272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,93
Latex for impregnating oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Compound represented by formula (I) in column 2, lines 54 to 62 of US 4,978,606 Especially I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: disclosed in JP-A-62-168139.
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially FI on page 33 to 55 of V-1, EP 445627A
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
III-1 to 36 on page 8, especially III-1,3, 8 to 26 in WO 88/04794
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, 2-26,315 and 3,
It is suitable for a film unit with a lens described in -39784.

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

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a value obtained by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

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

The light-sensitive material of the present invention can be obtained by the method described in RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

Next, the processing solution for a color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-121739, page 9, upper right column, line 1 to
The compounds described in page 11, lower left column, line 4, can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

These color developing agents are preferably used in an amount of 0.01 to 0.08 mol per liter (hereinafter also referred to as “L”) of a color developing solution, particularly preferably 0.015 to 0.1 mol.
It is preferably used in an amount of 06 mol, more preferably 0.02 to 0.05 mol. Also, the replenisher of the color developing solution has this concentration.
It is preferable to contain 1.1 to 3 times the color developing agent, particularly preferably 1.3 to 2.5 times.

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

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

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

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

The replenishing amount of the color developing solution is 80 to 1300 ml per m ² of the photographic material (hereinafter also referred to as “mL”).
However, from the viewpoint of reducing the environmental pollution load, it is preferably smaller, specifically 80 to 600 mL, more preferably 80 to 4
00 mL is preferred.

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

C = A−W / V C: bromide ion concentration in the color developing replenisher (mol / L) A: target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure When the material is color-developed, the amount of bromide ion eluted from the light-sensitive material into the color developer (mol) V: Replenishment of color-developing replenisher (L) for 1 m ² of light-sensitive material, and when replenishment amount is reduced In addition, when a high bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 may be used as a method for increasing sensitivity.
It is also preferable to use a development accelerator such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

Compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312 is preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a liquid having bleaching ability, and particularly preferably 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. When the liquid having bleaching ability is a bleaching liquid, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, especially 0.3 to 0.8 mol.
It is preferable to include a mole.

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

C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : concentration of component in replenisher C _T : concentration of component in mother liquor (treatment tank solution) C _P : during treatment the concentration of consumed components V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (mL) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
L).

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferable to use known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat. No. 3,893,858.

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

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

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

In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309590. The replenishment rate of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 mL, preferably from 150 to 700 mL, particularly preferably from 200 to 600 mL, per m ² of the light-sensitive material.

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

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

The bleach-fixing solution and the fixing solution preferably contain a free chelating agent which is not in the form of a metal complex from the viewpoint of improving the preservability. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

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

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

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

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

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

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

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

[0359] For the container for storing these treating agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm and are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the processing solution for the color reversal film used in the present invention will be described. Regarding the processing for the color reversal film, see page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

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

The color photographic light-sensitive material of the present invention is also suitable as a color negative film for an advanced photo system (hereinafter, referred to as APS).
F and NEXIA H (in the order of ISO 200/100/400), such as a film processed into APS format and stored in a special cartridge. These APS cartridge films are used by being mounted on an APS camera such as an Epion series represented by Fujion Epion 300Z. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim, which is a Fujicolor photograph run made by FUJIFILM.

[0364] The film photographed by the above is printed in the minilab system through the following steps.

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

[0366] These systems include Fujifilm's Minilab Champion Super FA-298 / FA-278 / FA-258.
/ FA-238 is preferred. FP92 as a film processor
2AL / FP562B / FP562BL / FP362B / FP3622BL, and the recommended treatment chemical is Fujicolor Justit CN-16L. PP3008AR / PP3008A / PP182 as a printer processor
8AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A are listed, and the recommended treatment chemical is Fujicolor Justit CP-47L
It is. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably Fujifilm's DT200 / DT100 and AT200 / AT100, respectively.

The APS system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with developed APS cartridge film, negative film, positive film,
Print image information from 35mm film scanner FE-550
Digital image data can be easily processed and edited by inputting data using a flat head scanner PE-550. The data can be output as a print by a digital color printer NC-550AL based on a light fixing type thermal color print system, a pictography 3000 based on a laser exposure heat development transfer system, or through an existing laboratory device through a film recorder. Also, Alad
The din 1000 can also output digital information directly to a floppy disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, a photograph can be enjoyed on a TV simply by loading the developed APS cartridge film into the Fuji Film Photo Player AP-1, or by loading it into the Fuji Film Photo Scanner AS-1. It is also possible to continuously capture image information at high speed in a personal computer.
To input a film, print, or three-dimensional object into a personal computer, a Fuji Vision PhotoVision FV-10 / FV-5 can be used. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using the photo factory application software of Fujifilm. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

To store the developed APS cartridge film, use the Fujicolor Pocket Album AP-5 Pop
L, AP-1 POP L, AP-1 POP KG or cartridge file 16 is preferred.

[0370]

EXAMPLES Example 1 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.170 Silver Iodobromide Emulsion P Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002.

Second layer (second antihalation layer) Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid dispersion dye ExF-2 0.015 Solid dispersion Dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion O 0.025 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.300 ExS-1 5.5 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.4 × 10 ^-4 ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 Gelatin 0.80 .

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion B Silver 0.300 Silver Iodobromide Emulsion C Silver 0.54 ExS-1 5.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D 1.47 ExS-1 3.7 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 1.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 gelatin 2.12.

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

Eighth Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Silver Iodobromide Emulsion 0.610 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F silver 0.39 silver iodobromide emulsion G silver 0.31 silver iodobromide emulsion H silver 0.35 ExS-4 2.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-2 0.36 ExM-3 0.045 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.42 ExS-4 5.3 × 10 ^-5 ExS-7 1.5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 Gelatin 0.44.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.21 Silver Iodobromide Emulsion J Silver 0.78 ExS-4 4.1 × 10 ^-5 ExS-7 1.1 × 10 ^-4 ExS-8 4.9 × 10 ^-4 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 polyethyl acrylate latex 0.099 gelatin 1.11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.020 Solid Disperse Dye ExF-6 0.020 Oil-soluble Dye ExF-7 010 HBS-1 0.082 gelatin 1.057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.16 silver iodobromide emulsion L silver 0.20 silver iodobromide emulsion M silver 0.09 ExS-9 4.4 × 10 ^-4 ExS-10 4.0 × 10 ^-4 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ⁻³ HBS-1 0.24 Gelatin 1.41.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.75 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.31 ExY-30 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91.

Fifteenth layer (first protective layer) Silver iodobromide emulsion O silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

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

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

Table 1 below shows the AgI content, grain size, surface iodine content and the like of the emulsions represented by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0390]

[Table 1]

In Table 1, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to O were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 below was dispersed by the following method. That is, water 2
1.7 mL and 5 mL of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonic acid 3 mL and 5 mL
A 0.5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed in a 700 mL pot mill, and 5.0 g of the dye ExF-2 and 500 mL of zirconium oxide beads (1 mm in diameter) were added. Was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents,
It was added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The solid dispersion of ExF-8 was dispersed by the following method.

70 g of water and W-2 were added to 1400 g of an ExF-8 wet cake containing 30% of water, and the mixture was stirred.
70 g of xF-8 was added and stirred, and the concentration of ExF-8 was 30%.
Slurry. Next, 1700 mL of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and crushed for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min through the slurry. did.

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

[0396]

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[0397]

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[0398]

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[0399]

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[0400]

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[0401]

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[0402]

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[0403]

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[0404]

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[0405]

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[0406]

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[0407]

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[0408]

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[0409]

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[0410]

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[0411]

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(Preparation of Sample 107 from Sample 102) Samples 102 to 107 were prepared in the same manner as Sample 101 except that the eighth layer of Sample 101 was replaced with a coupler as shown in Table 2 and an additional coupler was added.

(Preparation of Samples 108 to 114) Samples 108 to 114 were prepared in the same manner as Sample 101 except that the 10th and 11th layers of Sample 101 were replaced with couplers as shown in Table 3 and added with additional couplers. Was prepared.

(Production of Sample 121 from Sample 115) Samples 115 to 121 were produced in the same manner as in Sample 101 except that the 13th layer of Sample 101 was replaced with a coupler as shown in Table 4.

Samples 101 to 121 were prepared using a standard white light source and blackbody radiation 48.
Wedge exposure with a light source having an energy distribution of 00 ゜ K, the following development processing is performed, and after processing, the cyan, magenta, and yellow absorption densities of each sample are measured.
A characteristic curve was determined. Cyan, magenta, and yellow gradients γ _C , γ _M , and γ _Y were obtained from the obtained characteristic curves, and light fastness and wet heat fastness were evaluated by the methods described below.

Next, the method of developing each sample will be described.

[0417]

Next, the composition of the processing solution will be described. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate Water was added to adjust the pH to 1.0 L (adjusted with potassium hydroxide and sulfuric acid) 10.05.

(Bleach-fixing solution) (Unit g) Ferric ethylenediaminetetraacetate 100.0 Sodium trihydrate Disodium ethylenediaminetetraacetate 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 L water was added to 1.0 L pH (adjusted with ammonia water and nitric acid) 6.0.

(Fixing Solution) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Water is added to adjust the pH to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 .

(Stabilizing Solution) (Unit g) p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole) -1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 hydroxyethylcellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Water was added to 1.0 L pH 8.5.

The light fastness was determined by irradiating light with a fluorescent lamp (20,000 Lux) for one week and measuring the initial density (D0) = minimum density + 0.2 and 1.0 when measured with blue light or green light. Expressed as a percentage (%) of the concentration (D).

The wet heat fastness was stored at 60 ° C. and 70% for two months, and the percentage of the density (D) after storage relative to the initial density (D0) = minimum density + 1.0 when measured with blue light ( %).

[0424]

[Table 2]

[0425]

[Table 3]

[0426]

[Table 4]

As is clear from Table 2, each ExY-1
Was replaced with compound 106, it was possible to improve both the wet heat fastness (Y) and the effect of suppressing the development on the adjacent layer, but the light fastness of the low density part of the coloring dye (magenta) in the added layer was deteriorated. Let me do it. However, when a cyan dye-forming coupler is present, the light fastness is greatly improved, and the interlayer effect and the color image fastness can be sufficiently improved in total. Even when compound 12 is used, almost the same performance as compound 106 can be realized as a result.

As can be seen from Table 3, simply replacing ExC-6 with compound 12 or 106 does not provide an interlayer effect on the adjacent layer, but sacrifices light fastness. Also in this case, it can be seen that coexistence with a cyan dye-forming coupler makes it possible to achieve both an interlayer effect and light fastness.

From Table 4, it was confirmed that in the layer in which the cyan dye-forming coupler coexists, both the interlayer effect and the color image fastness can be improved in the same manner as seen in Tables 2 and 3.

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
In a silver halide color sensitive photographic material having a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer,
At least one of the layers mainly containing a coupler that forms a yellow or magenta dye contains a compound that does not substantially contribute to a color image after coupling with an oxidized developing agent represented by the general formula (I) or (II). A silver halide color comprising at least one photographically useful group-releasing compound to be formed and at least one compound represented by the general formulas (CI) to (C-III) in the same layer. Photosensitive material. Formula (I) COUP1-B1 In the formula, COUP1 represents a coupler residue that releases B1 by a coupling reaction with an oxidized developing agent and generates a water-soluble or alkali-soluble compound. B1
Represents a photographically useful group linked at the coupling position of COUP1 or a precursor thereof. In the formula, COUP2 represents a coupler residue capable of coupling with an oxidized developing agent, E represents an electrophilic site, and A represents
In the coupling product of COUP2 and oxidized developing agent, an intramolecular nucleophilic substitution reaction between a nitrogen atom derived from the developing agent and directly bonded to the coupling position and the electrophilic site E results in 4
Represents a divalent linking group or a single bond capable of releasing B2 with an 8-membered ring, and may be bonded to COUP2 at the coupling position of COUP2;
It may be bonded to COUP2 at a position other than the coupling position of COUP2. B2 represents a photographically useful group or a precursor thereof. Embedded image (Wherein, R ₁ ^c is —CONR ₄ ^c R ₅ ^c , —SO ₂ NR ₄ ^{c
_{R 5 c, -NHCOR 4 c,}} -NHCOOR 6 c, -NH
^{_{SO 2 R 6 c, -NHCONR 4}} c R 5 c or -NHSO ₂
NR ₄ ^c R ₅ ^c , R ₂ ^c is a group capable of being substituted on a naphthalene ring, m is an integer of 0 or 1, k is an integer of 0 to 3, R ₃ ^c is a substituent, X ₁ ^c Represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent, a photographically useful group or a precursor thereof. Where R ₄
^c and R ₅ ^c may be the same or different, independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₆
^c represents an alkyl group, an aryl group or a heterocyclic group. k
R ₂ ^c may be the same or different when
Further, they may combine with each other to form a ring. R ₂ ^c and R ₃ ^c , or R ₃ ^c and X ₁ ^c may be bonded to each other to form a ring. Further, a dimer or a multimer of R ₁ ^c , R ₂ ^c , R ₃ ^c, or X ₁ ^c may be bonded to each other via a divalent or divalent or higher valent group. ) Embedded image (Wherein, R ₂₁ ^c is an alkyl group, an aryl group or a heterocyclic group, R ₂₂ ^c is an alkyl group, R ₂₃ ^c is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, A carbonamide or ureido group is represented by R
₂₄ ^c represents an alkyl group, an aryl group, an alkoxy group, a heterocyclic group, an aryloxy group, or an amino group, X ₂ ^c represents a hydrogen atom or a coupling-off group, and n represents 0 or 1. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound capable of releasing a photographically useful group which does not substantially contribute to a color image after coupling with an oxidized developing agent is represented by the general formula (II). 3. The silver halide according to claim 1, wherein the color-sensitive layer containing the photographically useful group-releasing compound is one or both of a blue-sensitive layer and a donor layer which gives a multilayer effect to the red-sensitive layer. Color photographic light-sensitive material. 4. The silver halide according to claim 2, wherein the color-sensitive layer containing the photographically useful group-releasing compound is one or both of a green-sensitive layer and a donor layer that gives a multilayer effect to the red-sensitive layer. Color photographic light-sensitive material.