JPH052244A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide an inexpensive silver halide color photosensitive material excellent in sharpness, graininess and color reproducibility. CONSTITUTION:This silver halide color photosensitive material has at least one photosensitive silver halide emulsion layer. Besides, the material contains a compd. liberating a photographic useful group or its precursor through a timing group by the coupling reaction with a developing agent oxidant. The timing group has plural photographic useful groups or their precursor on the different constituent atoms. However, the timing group does not utilize the electron transfer through a conjugated system. The desorbed timing group liberates plural photographic useful groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a coupler capable of releasing a plurality of photographically useful groups from a released timing group.

[0002]

2. Description of the Related Art In recent years, in a silver halide light-sensitive material, particularly in a color photographic material for photographing, an ISO400 photographic material (SuperHG-400) having an image quality as high as an ISO sensitivity of 100 is obtained.
There has been a demand for a sensitive material having high sensitivity, excellent graininess, sharpness, and excellent storability of the sensitive material as represented by No.

As a material for improving image quality, a photographically useful group is bonded to a coupling position of a coupler through a timing group so that the photographically useful group is released imagewise during photographic processing and at an appropriate timing. Methods are known and are disclosed, for example, in U.S. Pat. No. 4,409,323 and JP-A-60-218645.

The methods disclosed therein release one molecule of photographically useful group from one molecule of coupler.

However, when a large amount of these couplers are added to the film, a problem arises that the film thickness increases, the sharpness deteriorates, and the cost increases.

Further, US Pat. No. 4,861,701 describes a coupler having two photographically useful groups on different atoms of an electron transfer timing group, and is disclosed in JP-A-1-154057. Describes couplers having two photographically useful groups on the same carbon atom on a timing group, but these couplers are stable in that they also release the photographically useful groups by hydrolysis, for example. Was inferior in terms of.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to propose a silver halide photographic light-sensitive material excellent in sharpness, graininess, color reproducibility and inexpensive.

[0008]

It is an object of the present invention to have at least one light-sensitive silver halide emulsion layer on a support, and a photographic group via a timing group by a coupling reaction with an oxidized product of a developing agent. A silver halide photographic light-sensitive material containing a compound releasing a functionally useful group or a precursor thereof, characterized by having a plurality of functionally useful groups or a precursor thereof on different atoms constituting the timing group. Was achieved by a silver halide color photographic light-sensitive material.

The silver halide color photographic light-sensitive material of the present invention preferably contains a compound represented by the general formula (I) shown in Chemical formula 1 below.

In the general formula (I), A represents a coupler residue, and L ₁ and L ₃ represent a divalent timing group. L
_{Although 2} represents a timing group having a trivalent or higher valence bond, it does not utilize electron transfer through a conjugated system. PUG represents a photographically useful group. k and n each independently represent 0, 1 or 2, and m is 1 or 2
And S is a number obtained by subtracting 1 from the valence of L ₂ and represents an integer of 2 or more. When a plurality of L ₁ , L ₂ or L ₃ are present in the molecule, they may all be the same or different. Further, the plurality of PUGs may be the same or different.

Here, L ₂ which is a timing group for releasing a plurality of photographically useful groups or precursors thereof does not utilize electron transfer via a conjugated system, and a plurality of (L ₃ ) _n -PUG binds to different atoms on the L _2.

The compound represented by formula (I) will be described below.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, acylacetanilide and malondianilide open-chain ketomethylene type coupler residues) and magenta coupler residues (for example, 5-pyrazolone type and pyrazolotriazole type residues). Or an imidazopyrazole type coupler residue), a cyan coupler residue (eg phenol type, naphthol type, European Patent Publication No. 24)
The imidazole type described in No. 9,453 or the same 304,
No. 001 pyrazolopyrimidine type coupler residues) and non-color-forming coupler residues (for example, indanone type or acetophenone type coupler residues).
Also, U.S. Pat. Nos. 4,315,070 and 4,18
3,752, 4,174,969, 3,96
1,959, 4,171,223 or JP-A-5
It may be a heterocyclic type coupler residue described in No. 2-82423.

The redox group is a group which can be cross-oxidized by an oxidized product of a developing agent. Examples of the redox group represented by A include, for example, hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,
2-naphthohydroquinones, sulfonamide phenols, hydrazides or sulfonamide naphthols can be mentioned. Specific examples of these groups include, for example, JP-A Nos. 61-230135, 62-251746, 61-278852, and U.S. Pat. No. 3,364,022.
Nos. 3,379,529, 3,639,417
No. 4,684,604 or J. Org. Che
m. , 29, 588 (1964).

Preferred examples of A include general formulas (Cp-1), (Cp-2), (Cp-3), and
(Cp-4), (Cp-5), (Cp-6), (Cp-
7), (Cp-8), (Cp-9), (Cp-10) or (Cp-11) is a coupler residue.
These couplers are preferred because of their high coupling speed.

In the general formulas (Cp-1) to (Cp-11), the * mark derived from the coupling position represents the bonding position with L ₁ or less of the general formula (I).

In the general formulas (Cp-1) to (Cp-11), R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ ,
R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ or R ₆₅
If contains a non-diffusion group, it is selected to have a total carbon number of 8 to 40, preferably 10 to 30; otherwise, a total carbon number of 15 or less is preferred.

R _{51 to} R ₆₅ , k, d, e and f will be described in detail below. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group or an aromatic group. Represents a group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₂ . k is 0 or 1
Represents R ₅₄ represents a group having the same meaning as R _41, R ₄₁ CON (R
₄₃ ) -group, R ₄₁ R ₄₃ N-group, R ₄₁ SO ₂ N (R ₄₃ )-
Group, R ₄₁ SO- group, R ₄₃ O- group, R ₄₅ N (R ₄₃ ) CON
(R ₄₄ )-group or ::: C-group (::: represents a triple bond). R ₅₅ has the same meaning as R ₄₁ .
R ₅₆ and R ₅₇ are each 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, or R ₄₁
It represents a SO ₂ N (R ₄₃ )-group. R ₅₈ has the same meaning as R ₄₁ . R ₅₉ is a group of the same meaning as R _41, R ₄₁ CON
(R ₄₃ ) -group, R ₄₁ OCON (R ₄₃ ) -group, R ₄₁ SO ₂
N (R ₄₃ )-group, R ₄₃ R ₄₄ NCON (R ₄₅ )-group, R ₄₁
O-group, R ₄₁ S-group, halogen atom, or R ₄₁ R ₄₃ N
Represents a group. j represents 0 or 1. d is 0 to 3
Represents When d is plural, plural R _59's represent the same substituent or different substituents. Further, each R ₅₉ may be connected as a divalent group to form a cyclic structure. For example,
Examples of forming a cyclic structure include a pyridine ring and a pyrrole ring. R ₆₀ has the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is a group of the same meaning as R _41, R ₄₁ OCONH- group, R ₄₁ SO ₂
NH-group, R ₄₃ R ₄₄ NCON (R ₄₅ ) -group, R ₄₃ R ₄₄ N
SO ₂ N (R ₄₅₎ - represents group R ₄₃ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ R ₄₃ N- group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R ₄₅ ) -group, R ₄₃ R ₄₄ NC
O-group, R ₄₁ SO ₂ N (R ₄₄ ) -group, R ₄₃ R ₄₄ NSO ₂
- group, R ₄₁ SO ₂ - group, R ₄₃ OCO- group, R ₄₃ O-SO
₂ -group, halogen atom, nitro group, cyano group or R ₄₃
Represents a CO-group. e represents an integer of 0 to 4. When a plurality of R ₆₂ or R ₆₃ are present, they represent the same or different. R ₆₄ and R ₆₅ are each R ₄₃ R ₄₄ N
CO- group, R ₄₁ CO- group, R ₄₃ R ₄₄ NSO ₂ -group, R ₄₁
It represents group, a nitro group or a cyano group - OCO- group, R ₄₁ SO _2. Z ₁ is a nitrogen atom or a ═C (R ₆₆ ) group (R ₆₆
Represents a hydrogen atom or a group having the same meaning as R ₆₃ ). Z ₂ represents a sulfur atom or an oxygen atom. f is 0
Or represents 1.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group. Representative examples are methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl, (t) -amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,
Examples include 3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

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

The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, has a hetero atom selected from a nitrogen atom, an oxygen atom or a sulfur atom, and is preferably a 3- to 8-membered ring. It is a substituted or unsubstituted heterocyclic group. Typical examples of the heterocyclic group are 2-pyridyl, 2-furyl,
2-imidazolyl, 1-indolyl, 2,4-dioxo-1,3-imidazolidin-5-yl, 2-benzoxazolyl, 1,2,4-triazol-3-yl or 4-pyrazolyl can be mentioned. .

When the aliphatic hydrocarbon group, aromatic group or heterocyclic group has a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CO.
N (R ₄₈ )-group, R ₄₇ N (R ₄₈ ) CO- group, R ₄₆ OCO
N (R ₄₇ )-group, R ₄₆ SO ₂ N (R ₄₇ )-group, R ₄₇ R ₄₈
NSO ₂ - group, R ₄₆ SO ₂ - group, R ₄₇ OCO- group, R ₄₇
R ₄₈ NCON (R ₄₉₎ - group, a group having the same meaning as R _46, R ₄₆
COO- group, R ₄₇ OSO ₂ - group, a cyano group or a nitro group. Here, R ₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄₇ , R _48, and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom.
The meaning of an aliphatic group, an aromatic group or a heterocyclic group has the same meaning as previously defined.

Next, preferred ranges of R _{51 to} R ₆₅ , k, d, e and f will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ and R ₅₅ are preferably aromatic groups. R ₅₃ is preferably an aromatic group or a heterocyclic group.

In the general formula (Cp-3), R ₅₄ is R ₄₁
CONH- group or R ₄₁ R ₄₃ N-group, are preferred. R ₅₆
And R ₅₇ is an aliphatic group, an aromatic group, R ₄₁ O-group, or R ₄₁ S- groups are preferred. R ₅₈ is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R ₅₉ is preferably a chlorine atom, an aliphatic group or an R ₄₁ CONH-group. d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group. In general formula (C-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), e is preferably 0 or 1. R ₆₂
Is preferably an R ₄₁ OCONH- group, an R ₄₁ CONH- group or an R ₄₁ SO ₂ NH- group, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ CONH-group, R ₄₁ SO ₂ NH.
-Group, R ₄₁ R ₄₃ NSO ₂ -group, R ₄₁ SO ₂ -group, R ₄₁ R
₄₃ NCO- group, nitro group or cyano group is preferred, e
Is preferably 1 or 2. In the general formula (Cp-10), R ₆₃ is preferably a (R ₄₃ ) ₂ NCO— group, an R ₄₃ OCO— group or an R ₄₃ CO— group, and e is preferably 1 or 2. In formula (Cp-11), R ₅₄ is preferably an aliphatic group, an aromatic group or an R ₄₁ CONH-group, and f is preferably 1.

Further, A preferably has a diffusion resistant group.

In the general formula (I), L ₁ preferably includes the following. (1) Group utilizing cleavage reaction of hemiacetal, for example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A or L ₁ of the compound represented by the general formula (I), and the ** mark represents the position of bonding with L ₁ or L ₂ .

[0030] Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ Represents a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups shown in Chemical formulas 6 to 8 below. (2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction, for example, a timing group described in US Pat. No. 4,248,292. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, Nu Link is a group that can be more nucleophilically attacked to cleave the bond with **, and Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction.
Specific examples of the group represented by formula (T-2) include those shown in Chemical formulas 9 to 10 below. (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
No. 9737 and No. 58-209738 and is a group represented by the general formula (T-3) shown in Chemical formula 11 below.

In the general formula (T-3), *, **, W,
R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). However, R ₁₁ and R ₁₂ may be bonded to each other to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y are 0.
Or represents 1. When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and when t is 2, two-[Z
_{1 (R 11) x = Z} 2 (R 12) y] - may be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

Specific examples of (T-3) are shown in Chemical formulas 12 to 15 below. (4) A group utilizing a cleavage reaction by hydrolysis of an ester, for example, a linking group described in West German Laid-Open Patent No. 2,626,315, which has the following general formulas (T-4) and (T-
Examples thereof include groups shown in 5). In the general formulas (T-4) and (T-5), * mark and ** mark represent the general formula (T-
It has the same meaning as described in 1).

General formula (T-4) * -OCO-** General formula (T-5) * -SCS-** (5) A group utilizing the cleavage reaction of imino ketal, for example, US Pat. No. 4,546,073. And a group represented by the general formula (T-6) shown in Chemical formula 16 below.

In the general formula (T-6), *, ** and W have the same meanings as described in the general formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . General formula (T-
Specific examples of the group represented by 6) are shown below.
The groups shown in are listed.

L ₁ is preferably (T-1) to (T-
5), particularly preferably (T-
1), (T-3) and (T-4).

The group represented by L ₂ in the general formula (I) represents a timing group which does not utilize electron transfer through a trivalent or higher valent conjugated system, and preferably represented by the following general formula (T-L ₁ ). Is.

In the general formula (T-L ₁ ) *-N- (R _x -**) ₂ formula, * indicates A or L ₁ , L ₂ in the general formula (I).
The position where it bonds to L ₂ or the position where it binds to L ₂ or PUG. The R _x group represents a substituted or unsubstituted methylene group, and the two R _x groups may be the same or different. Further, two R _x groups may combine to form a ring.

Substituents on the R _x group include, for example, alkyl groups (eg, methyl, ethyl, isopropyl, t-
Butyl, hexyl, methoxymethyl, methoxyethyl,
Chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl), aryl groups (for example, phenyl, naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methoxyphenyl, 2,6-dimethylphenyl, 4-carboxyphenyl, 4-sulfophenyl), heterocyclic group (for example, 2-
Pyridyl, 4-pyridyl, 2-furyl, 2-thiethyl,
2-pyrrolyl), a halogen atom (eg, chloro, bromo), a nitro group, an alkoxy group (eg, methoxy, ethoxy, isopropoxy), an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, isopropylthio, t-butylthio), arylthio groups (eg phenylthio), amino groups (eg amino, dimethylamino, diisopropylamino), acylamino groups (eg acetylamino, benzoylamino), sulfonamide groups (eg methanesulfonamide, benzene) Sulfonamide), cyano group, carboxyl group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (eg, phenoxycarbonyl) or carbamoyl group (eg, - ethylcarbamoyl, N- phenylcarbamoyl). These substituents may be further substituted.

Specific examples of (T-L ₁ ) are shown in Chemical Formulas 18 to 20 below, but these groups may have a substituent, and the present invention is not limited thereto. .

In the general formula (I), L ₃ has the same meaning as L ₁ .

In the general formula (I), k is preferably 0 or 1. m is preferably 1. n is preferably 0 or 1, and particularly preferably 0.

The photographically useful group represented by PUG in the formula (I) is, for example, a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator or a fixing accelerator. Examples of preferable photographically useful groups include those described in U.S. Pat. No. 4,248,962 (the ones represented by the general formula PUG in the patent) and JP-A-62-49353. Dyes described (wherein the leaving group part released from the coupler), US Pat.
477,563, and the bleaching accelerators described in JP-A-61-201247 and JP-A-2-55 (the part of the leaving group released from the coupler in the specification). Can be mentioned. In the present invention, a development inhibitor is particularly preferable as the photographically useful group.

Preferred development inhibitors are groups represented by the general formulas (INH-1) to (INH-13) shown in Chemical formulas 21 to 26 below.

General formulas (INH-1) to (INH-13)
In the above, * indicates the position at which the compound represented by the general formula (I) is bonded to the group represented by L ₂ or L ₃ .

Further, ** represents a position to be bonded to a substituent, and examples of the substituent include a substituted or unsubstituted aliphatic group, an aryl group and a heterocyclic group, which are used in a processing solution during photographic processing. It is preferable that a decomposable group is contained in these substituents.

In the general formula (INH-6), R ₂₁ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group (eg methyl, ethyl, propyl, phenyl).

Specific examples of the aliphatic group include methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl, 2-methylthioethyl, benzyl, 4-methoxybenzyl, phenethyl, 1-methoxycarbonylethyl, propyloxycarbonylmethyl, methoxycarbonyl, phenoxycarbonyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2-cyanoethyloxycarbonylmethyl, 2,2-dichloroethyloxy Carbonylmethyl, 3-nitropropyloxycarbonylmethyl, 4-
Nitrobenzyloxycarbonyl methyl, 2,5-dioxo-3,6-Jiokisadeshiru, -CO ₂ CH ₂ CO ₂
Examples thereof include groups represented by R ₁₀₀ .

Here, R ₁₀₀ represents an unsubstituted alkyl group having 1 to 8 carbon atoms. As the aryl group, phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-
Examples thereof include ethoxycarbonylphenyl, 2-methylthiophenyl, 3-methoxycarbonylphenyl, 4- (2-cyanoethyloxycarbonyl) -phenyl and the like.

Examples of the heterocyclic group include 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl and 2
-Tetrahydropyranyl.

Of these, INH is preferably (I
NH-1), (INH-2), (INH-3), (IN
H-4), (INH-9) and (INH-12), particularly preferably (INH-1), (INH-2) and (INH-3).

The substituent that binds to INH is preferably an aliphatic group or a substituted or unsubstituted phenyl group.

Specific examples of the compounds used in the present invention are shown in Chemical formulas 27 to 34 below, but the present invention is not limited thereto.

The compound used in the present invention can be synthesized by various methods. For example, US Pat. No. 446
-OC (= O)-synthesized by the method described in 9773.
Using a compound having an NH ₂ group as a leaving group as a raw material, the following chemical formula 3
It can be synthesized as shown in Reaction Pathway 1 shown in FIG.

See also Tetrahedron, Vol. 47, 2
It is also possible to synthesize a precursor by a method similar to the method described on page 683 (1991) and to synthesize it by the route shown in the reaction route 2 shown in the following Chemical formula 36.

Hereinafter, as a typical example of the compound used in the present invention, a synthesis example of Exemplified compound (1) carried out according to reaction route 3 shown in the following Chemical formula 37 is shown.

Synthesis Example Synthesis of Exemplified Compound (1) Compound 1a (10.7 g) was reacted with 37% aqueous formalin solution (30 ml) in acetic acid (100 ml) at 70 ° C. for 5 hours, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-hexane 2: 1) to give 6.4 g of compound 1b (yield 53
%)Obtained.

Then, compound 1b (3.2 g) and compound 1
c (2.1 g) in chloroform (40 ml),
Zinc iodide (5.7 g) was added thereto and reacted at room temperature for 2 hours. After stopping the reaction with 1N hydrochloric acid and diluting with 40 ml of chloroform, the reaction solution was washed twice with water. The organic layer was dried over sodium sulfate and concentrated, and the obtained residue was subjected to silica gel column chromatography (ethyl acetate-hexane 1: 4).
4.1 g of Exemplified Compound (1)
(Yield 25%) was obtained. The structure is NMR, mass spectrum,
Confirmed by elemental analysis.

The light-sensitive material of the present invention is provided with at least one layer of blue-sensitive layer, green-sensitive layer, silver halide emulsion layer of red-sensitive layer and non-photosensitive layer on a support. If you have. A typical example is a silver halide photographic light-sensitive material having on a support a light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer having color sensitivity to blue light, green light, and red light, respectively. In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are arranged in this order from the body side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Between the above silver halide photosensitive layers and between the uppermost layer and the lowermost layer, for example, various non-photosensitive layers such as intermediate layers may be provided.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, for example, a coupler and a DIR compound may be contained, and a color mixing inhibitor may be contained as is commonly used. .

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
For example, JP-A-57-112751, JP-A-62-200.
No. 350, No. 62-206541, No. 62-20654
As described in No. 3, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

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

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

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

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

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

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

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

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
The grain size of twin plane silver halide may be fine grains of about 0.2 μm or less or large grains with a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pp. 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628
No. 3,655,394 and British Patent No. 1,41
The monodisperse emulsions described in 3,748 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, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photog.
radical Science and Engine
ering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure is uniform, and the inside and the outside may have different halogen compositions, and may have a layered structure. Also, silver halides having different compositions are joined by epitaxial joining. Or may be bonded with a compound other than silver halide of rhodan silver or lead oxide, for example. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
A shell type internal latent image type emulsion can be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-133.
No. 542. The thickness of the shell of this emulsion varies depending on, for example, the development treatment, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the corresponding portions are summarized in Table X below.

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

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

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

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

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

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating 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 preferably contained in this fine grain silver halide grain-containing layer.

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

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the related portions are shown in Table X below.

Table X Additive types RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in U.S. Patents 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

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

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

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers other than those represented by the general formulas (1) and (2) of the present invention include, for example, US Pat. Nos. 3,933,501 and 4,022,62.
No. 0, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10
739, British Patent Nos. 1,425,020 and 1,
476,760, U.S. Pat. No. 3,973,968,
No. 4,314,023, No. 4,511,649
And those described in European Patent 249,473A are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-55.
No. 4, No. 64-555 and No. 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,6.
The imidazole coupler described in No. 72 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282 and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A.

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

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in No. 46,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are, in addition to those of the present invention, RD17643, VII-F and N.
o. 307105, the patents described in the section VII-F, JP-A-57-151944, and JP-A-57-154234,
No. 60-184248, No. 63-37346, No. 6
Those described in 3-37350, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

For example, R. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Also preferred are compounds that release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in US Pat. No. 4,427, for example, multiequivalent couplers described in US Pat. Nos. 4,283,472, 4,338,393, and 4,310,618, such as JP-A- 60-185950, JP-A-62-242
No. 52 DIR redox compound releasing coupler,
DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent Nos. 173,302A and 313,
308A, a coupler which releases a dye that recolors after release, for example, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, a coupler which releases a leuco dye described in JP-A-63-75747, US Patent No. 4,7
The couplers which release the fluorescent dyes described in JP-A-74,181 can be exemplified.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- - ethylhexyl phenyl phosphonate), benzoic acid esters (e.g., 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amic acid (e.g., N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N) -Dibutyl-2
Examples thereof include butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide are mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,1.
99,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

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

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

Suitable supports which can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

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

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

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, 651 left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

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

The color developing solution is, for example, a pH buffering agent such as an alkali metal carbonate, boric acid solution or phosphate,
It generally contains a development inhibitor or an antifoggant such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as aminos, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black and white developer,
Dihydroxybenzenes such as hydroquinone, 3 such as 1-phenyl-3-pyrazolidone
The known black-and-white developing agents of pyrazolidones or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The pH of these color developer and black-and-white developer is 9
Generally, it is -12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per 1 square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, The slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is not limited to both color development and black and white development,
Subsequent steps, such as bleaching, bleach-fixing, fixing, washing,
It is preferably applied in all steps of stabilization.
Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Declosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-208.
32, 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40, 943 and 49-59, 644.
No. 53-94, 927, 54-35, 727.
No. 55, No. 55-26, 506, No. 58-163, 940.
Compounds described in the above publication; bromide ions can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat.
Compounds described in Japanese Patent No. 93,858, West German Patent No. 1,290,812 and JP-A No. 53-95,630 are preferable.
Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching agent and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. It is also preferable to use a thiosulfate solution in combination with, for example, a thiocyanate salt, a thioether compound, or thiourea. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or EP 29476.
The sulfinic acid compounds described in No. 9A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution.

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

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

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

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

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), the use, and further, for example, the rinsing water temperature, the number of rinsing tanks (number of stages), countercurrent, forward replenishment method, etc. It can be set in a wide range according to various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the
Society of Motion Pictu
re and Television Vision
rs vol. 64, p. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, for example, bacteria propagate, and the produced suspended solids adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, Japanese Patent Application Laid-Open No.
The method for reducing calcium ion and magnesium ion described in 2-288,838 can be used very effectively. In addition, for example, isothiazolone compounds, siabendazoles, chlorine-based bactericides of chlorinated sodium isocyanurate described in JP-A-57-8,542, and others, such as benzotriazole, by Horiguchi "The Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing,
Hygiene Technology Association, “Microbial Sterilization, Sterilization, and Antifungal Technology” (19
1982) It is also possible to use the bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on, for example, the characteristics of the light-sensitive material and the intended use, but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably at 25-40 ° C. for 30 seconds-5 minutes. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

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

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

For example, in processing using an automatic processor,
When each of the above treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, for example, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. .

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

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

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

[0131]

【Example】

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material composed of each layer having the composition shown below, was prepared.

[0132] represents the amount coating amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for Harogenha halide and colloidal silver, also couplers, for additives and gelatin in the unit of g / m ² The amount is shown, and for the sensitizing dye, it is shown in mol per mol of silver halide in the same layer.
The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye, ExS; sensitizing dye, ExC; cyan coupler; ExM; magenta coupler, ExY; yellow coupler, Cpd; additive first layer (halation) Prevention layer) Black colloidal silver 0.15 Gelatin 1.50 ExM-2 0.11 UV-1 3.0x10 ^-2 UV-2 6.0x10 ^-2 UV-3 7.0x10 ^-2 Solv -1 0.16 Solv-1 0.10 ExF- 1 1.0 × 10 -2 ExF-2 4.0 × 10 -2 ExF-3 5.0 × 10 -3 Cpd-6 1.0 × 10 - ³ .

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.25 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain, Diameter / thickness ratio 6.0) Coating amount 0.35 Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.45 μm, coefficient of variation of sphere equivalent diameter) 23%, plate-like particles, diameter / thickness ratio of 2.0) Coating silver amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-5 2. 3 * 10 < ^-4 > ExS-7 4.1 * 10 < ^-6 > ExC-1 0.09 ExC-2 4.0 * 10 ^<-2 > ExC-3 8.0 * 10 ^<-2 > ExC-5 0.88.

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter) 13%, cubic particles, diameter / thickness ratio of 1.0) Coating silver amount 0.55 Gelatin 1.05 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-5 2.4 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 2.0 × 10 ^-2 ExC-3 0.10 ExC-5 0.19 ExC-6 2.0 × 10 ^{-2 ExM-3 2.0 × 10 -2} C-1 3.5 × 10 -2 UV-2 5.7 × 10 -2 UV-3 5.7 × 10 -2.

Fourth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (9.3 mol% of AgI, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 24,0.6 mol% from the inside) , Equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 18%, plate-like particles, diameter / thickness ratio 5.5) Coating amount of silver 1.49 Gelatin 1.10 ExS-1 2.0 × 10 ^-4 ExS -2 1.1x10 ^-4 ExS-5 1.9x10 ^-4 ExS-7 1.4x10 ^-5 ExC-1 8.0x10 ^-2 ExC-4 9.0x10 ^-2 ExC −6 2.0 × 10 ⁻² C-1 1.0 × 10 ⁻² Solv-1 0.20 Solv-2 0.53.

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.03 Cpd-9 0.07 Solv-1 8.0 × 10 ^-2 .

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.33 μm, variation coefficient of sphere equivalent diameter 17%, plate-like grain, Diameter / thickness ratio 5.0) Amount of coated silver 0.19 Gelatin 0.44 ExS-3 1.5 × 10 ^-4 ExS-4 4.4 × 10 ^-4 ExS-5 9.2 × 10 ^-5 ExM- 1 0.17 ExM-3 3.0 * 10 ^<-2 > Solv-1 0.13 Solv-4 1.0 * 10 ^<-2 >.

Seventh Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain, Diameter / thickness ratio 4.0) Amount of coated silver 0.24 Gelatin 0.54 ExS-3 2.1 × 10 ^-4 ExS-4 6.3 × 10 ^-4 ExS-5 1.3 × 10 ^-4 ExM- 1 0.15 ExM-3 4.0 × 10 -2 ExY-1 3.0 × 10 -2 Solv-1 0.13 Solv-4 1.0 × 10 -2.

Eighth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.8 mol%, multi-structured grains having a silver amount ratio 3: 4: 2, AgI content of 24,0,3 mol from inside) %, Equivalent sphere diameter 0.60 μm, variation coefficient of equivalent sphere diameter 14%, cubic particles, diameter / thickness ratio 1.0) Coating amount of silver 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS -5 8.6 x 10 ^-5 ExS-8 2.8 x 10 ^-5 ExM-1 8.0 x 10 ^-2 ExM-2 3.0 x 10 ^-2 ExY-1 3.0 x 10 ^-2 ExC -1 1.0 x 10 ^-2 ExC-4 1.0 x 10 ^-2 Solv-1 0.23 Solv-2 5.0 x 10 ^-2 Solv-4 1.0 x 10 ^-2 Cpd-8 1. ^{0x10 -2} .

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2 .

10th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, internal high AgI type having a core-shell ratio of 1: 2, sphere equivalent diameter 0.50 μm, sphere equivalent diameter) Variation coefficient of 15%, tabular grains, diameter / thickness ratio of 7.0) Coating silver amount 0.67 Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.25 μm, sphere equivalent diameter) Variation coefficient of 20%, plate-shaped particles, diameter / thickness ratio of 7.0) Coating amount of silver 0.20 Gelatin 0.87 ExS-3 6.7 × 10 ^-4 ExS-4 0.16 Solv-1 0.30 Solv-6 3.0 x 10 ^-2 .

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ⁻² gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 8.0 × 10 ⁻² Cpd-6 2.0 × 10 ⁻³ H-1 0.25.

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain, Diameter / thickness ratio 7.0) Coating amount 0.50 Silver iodobromide emulsion (AgI 3.0 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain, Diameter / thickness ratio 7.0) Coating silver amount 0.30 Gelatin 2.18 ExS-6 9.0x10 ^-4 ExC-1 0.14 ExY-2 0.17 ExY-3 1.09 Solv-10 .54.

[0145]     13th layer (middle layer)   Gelatin 0.40   ExY-4 0.19   Solv-1 0.19.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, spherical equivalent diameter 1.0 μm, variation coefficient of spherical equivalent diameter 25%, multiple twins Plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.40 Gelatin 0.49 ExS-6 2.6 × 10 ⁻⁴ ExY-2 1.0 × 10 ⁻² ExY-3 0.20 ExC− 1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2 .

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, spherical equivalent diameter 0.07 μm) Coating silver amount 0.12 Gelatin 0.63 UV-40 .11 UV-5 0.18 Solv-5 2.0x10 ^-2 Cpd-5 0.10 polyethyl acrylate latex 9.0x10 ^-2 .

Sixteenth Layer (Second Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.36 Gelatin 0.85 B-1 ( Diameter 1.5 μm) 8.0 × 10 ⁻² B-2 (diameter 1.5 μm) 8.0 × 10 ⁻² B-3 2.0 × 10 ⁻² W-4 2.0 × 10 ⁻² H− 1 0.18.

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (200 ppm on average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. . Furthermore, B-4, B-5, F-1, F-2, F-3,
F-4, F-5, F-6, F-7, F-8, F-9, F
-10, F-11, F-12 and iron salt, lead salt, gold salt,
It contains platinum salt, iridium salt and rhodium salt.

In addition to the above components, each layer contains a surfactant W.
-1, W-2, and W-3 were added as a coating aid or an emulsifying dispersant.

The emulsion has been chemically sensitized by gold-sulfur sensitization or gold-sulfur-selenium sensitization. (Samples 102 to 113) Third Layer and Fourth Layer of Sample 101
Replacing coupler C-1 added to the layers with the comparative coupler and the coupler of the invention, samples 102-113
Was produced. Coupler type and amount added (C in molar ratio
The value obtained by setting -1 to 1.0) is shown in Table 1. The amounts of these additions were determined so that the cyan color density was almost the same.

These samples 101 to 113 were exposed to a pattern for MFF measurement, subjected to color development processing shown in Table A below, and a value of 25 cycles / mm of cyan image was determined by a conventional MTF method. Red filter (Fujifilm SC-
62) through imagewise exposure, followed by a uniform exposure of 0.05 CMS with a green filter (BPN-45 manufactured by Fuji Film) for development processing, and the value obtained by subtracting the magenta density at cyan fog density from the magenta density at cyan density 1.5 The degree of color turbidity is shown in Table 1 below.

Also, 500 μm × 4 cm and 15 μm ×
Irradiation with soft X-rays was carried out through an opening having a size of 4 cm, and the cyan density ratio at each center was obtained as an edge effect.

Table A Processing Method Method Processing time Processing temperature * Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 20ml 10 liters Bleach 45 seconds 38 ℃ 5ml 4 liters Bleach fixing (1) 45 seconds 38 ℃ -4 L bleach-fixing (2) 45 seconds 38 ℃ 30 ml 4 liters Water wash (1) 20 seconds 38 ℃ -2 liters Water wash (2) 20 seconds 38 ℃ 30 ml 2 liters Stability 20 seconds 38 ℃ 20 ml 2 liters Dry 1 minute 55 ℃ * Replenishment amount is 35mm width 1m per length. Each step of bleach-fixing and washing is from (2) to (1).
And the overflow of the bleaching solution was all introduced into the bleach-fixing (2).

In the above processing, the amount of the bleach-fixing solution brought into the washing step was 2 ml per 1 m length of the light-sensitive material having a width of 35 mm. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 0.5 Iodine Potassium iodide 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-4.7 6.2 hydroxyethylamino] -2-methylaniline sulphate Water was added 1. 0 liter 1.0 liter pH 10.00 10.15 (bleaching solution) mother liquor (g) replenishing solution (g) 1,3-diaminopropanetetraacetic acid 144.0 206.0 ferric ammonium monohydrate 1, 3-Diaminopropane tetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Aqueous ammonia (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Add water 1.0 liter 1.0 liter pH 4.3 3.4 (bleach-fix) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric iron 50.0-ammonium dihydrate Salt Ethylenediaminetetraacetic acid 5.0 25.0 Disodium salt Ammonium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution 290.0 ml 320.0 ml (700 g / liter) Ammonia water (27%) 6.0 ml 15.0 ml Add water 1.0 liter 1.0 liter pH 6.8 8.0 (washing water) mother liquor, replenisher common tap water with H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas), OH -Type strongly basic anion exchange resin (Amberlite IRA-400) filled with mixed bed column to pass calcium and magnesium ions Processing the degrees below 3 mg / liter, followed by the addition of sodium isocyanurate dichloride 20mg / liter. The pH of this liquid was in the range of 6.5-7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 [C ₁₀ H ₂₁ —O— (CH ₂ CH ₂ O) ₁₀ —H] Ethylene Glycol 1.0 Water added 1.0 liter pH 5.0-7.0 From Table 1, Samples 110 to 113 containing the compound used as the coupler in the present invention are color reproducibility represented by color turbidity. , MTF value and the sharpness represented by the edge effect are excellent.

Example 2 The EX-10 added to the third layer of the sample 116 of JP-A-3-2866 was removed, and the sample 201 was converted into the following chemical formula 27.
Compounds (1) and (2) used as a coupler in the present invention shown in the above are added to the fourth layer at 0.030 g / m ² respectively.
Samples 202 and 203 were prepared by adding.

When these samples 202 to 203 were evaluated in the same manner as in Example 1, the samples 202 and 20 of the present invention were evaluated.
It was confirmed that 3 was excellent in sharpness and color reproducibility.

The compounds used in the examples are those shown in
This is as shown in Chemical Formula 58.

[0160]

According to the silver halide color photographic light-sensitive material of the present invention, since it contains a coupler which releases a plurality of photographically useful groups from the separated timing group, sharpness, graininess and color reproducibility are improved. Notable effects such as further improvement and economic efficiency can be achieved.

[0161]

[Chemical 1]

[0162]

[Chemical 2]

[0163]

[Chemical 3]

[0164]

[Chemical 4]

[0165]

[Chemical 5]

[0166]

[Chemical 6]

[0167]

[Chemical 7]

[0168]

[Chemical 8]

[0169]

[Chemical 9]

[0170]

[Chemical 10]

[0171]

[Chemical 11]

[0172]

[Chemical 12]

[0173]

[Chemical 13]

[0174]

[Chemical 14]

[0175]

[Chemical 15]

[0176]

[Chemical 16]

[0177]

[Chemical 17]

[0178]

[Chemical 18]

[0179]

[Chemical 19]

[0180]

[Chemical 20]

[0181]

[Chemical 21]

[0182]

[Chemical formula 22]

[0183]

[Chemical formula 23]

[0184]

[Chemical formula 24]

[0185]

[Chemical 25]

[0186]

[Chemical formula 26]

[0187]

[Chemical 27]

[0188]

[Chemical 28]

[0189]

[Chemical 29]

[0190]

[Chemical 30]

[0191]

[Chemical 31]

[0192]

[Chemical 32]

[0193]

[Chemical 33]

[0194]

[Chemical 34]

[0195]

[Chemical 35]

[0196]

[Chemical 36]

[0197]

[Chemical 37]

[0198]

[Chemical 38]

[0199]

[Chemical Formula 39]

[0200]

[Chemical 40]

[0201]

[Chemical 41]

[0202]

[Chemical 42]

[0203]

[Chemical 43]

[0204]

[Chemical 44]

[0205]

[Chemical formula 45]

[0206]

[Chemical formula 46]

[0207]

[Chemical 47]

[0208]

[Chemical 48]

[0209]

[Chemical 49]

[0210]

[Chemical 50]

[0211]

[Chemical 51]

[0212]

[Chemical 52]

[0213]

[Chemical 53]

[0214]

[Chemical 54]

[0215]

[Chemical 55]

[0216]

[Chemical 56]

[0217]

[Chemical 57]

[0218]

[Chemical 58]

[0219]

[Table 1]

Claims (3)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer on a support and releasing a photographically useful group or its precursor through a timing group by a coupling reaction with an oxidized product of a developing agent. A silver halide color photographic light-sensitive material comprising a compound, wherein the silver halide photographic light-sensitive material has a plurality of photographically useful groups or precursors thereof on different atoms constituting the timing group. However, the timing groups that release a plurality of photographically useful groups or their precursors do not utilize electron transfer through a conjugated system. 2. A silver halide color photographic light-sensitive material containing the compound according to claim 1 having two timing groups. 3. A silver halide color photographic light-sensitive material comprising the compound according to claim 1 having a timing group utilizing cleavage of acetal.