JPH03184043A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material which is excellent in color reproducibility and sharpness by incorporating a specific compd. into the photosensitive material. CONSTITUTION:The compd. expressed by formula I is incorporated into the photosensitive material. In the formula I, A denotes a group which releases the part under (L)n by reacting with the oxidant of a developing agent; L denotes a group which further releases the part combined with L after elimination from A; X, Y respectively independently denote a carbon atom or nitrogen atom; R<1>, R<2> respectively independently denote 2 to 6C nitrogenous unsatd. heterocyclic groups of 5 to 7 members; R<3> denotes a development restrainer group or the precursor group thereof; R<4> denotes -OH, -NHSO2R<5>, -NHSO2NR<5> R<6>, -NH2, -NHR<5> or -NR<5>R<6>; R<5>, R<6> respectively independently denote an aliphat. group, arom. group or heterocyclic group; n denotes 0 to 2 integer. Thus, the production at an adequate cost is attained and the sharpness and color reproducibility are improved by using the compd. which can be used in such sufficient amt.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent sharpness and color reproducibility.

(Prior Art) Color photographic materials have conventionally used couplers that release development inhibitors (DIR couplers) for the purpose of improving image sharpness and color reproducibility. The above-mentioned improvement in color image quality by DIR couplers is remarkable, and various DIR couplers have been developed or proposed with the aim of further improvement.

DIR couplers such as U.S. Pat. No. 3,227.5
No. 54, No. 3,148,062, No. 3933.500
No. 4,477.563 discloses a coupler that releases a development inhibitor from the coupling position.

In these DIR couplers, a development inhibitor is bound to the coupling position of the coupler, and therefore, in some cases where a development inhibitor is used, a problem arises in that the cambring reaction between the coupler and the oxidized developer drug is delayed. In order to improve this, it was necessary to insert a linking group between the coupling position of the coupler and the development inhibitor. For example, US Pat. No. 4,1
These are couplers described in 46°396, 4,248,962, and 421.845. These couplers certainly show improvement in the speed of the coupling reaction and have a certain degree of performance. However, when compared with a DIR coupler in which a development inhibitor is directly bonded to the coupling position and which originally has high reactivity with the oxidized developing agent, it was found that there is almost no difference.

Furthermore, U.S. Patent No. 4.438,193;
No. 8,393, JP-A-62-291645 and JP-A-62-291645
No. 0-203943 discloses examples of couplers that emit DIR couplers. Although the couplers described in these patents show some performance in improving graininess or improving sharpness, further improvements were desired. In addition, in improving color reproducibility, it has been found that there is a problem in that a portion of the dye produced when the released DIR coupler diffuses and further reacts with the oxidized developing agent remains in the sensitive material.

Furthermore, U.S. Patent No. 4,618,571, 4.73
No. 7,451, JP-A-61-233741 and JP-A-61-233741
Coupler described in No. 1-238057 is known. The coupler described in this patent is a type of DIR coupler that releases a compound (DIR redox compound) that releases a development inhibitor through an oxidation-reduction reaction. The couplers described in these patents are
It exhibited excellent performance in improving sharpness due to the edge effect and color reproducibility due to the multilayer effect, with few of the above-mentioned drawbacks. However, these couplers have high base costs and have practical limitations, and further improvements have been desired.

(Problems to be Solved by the Invention) The object of the present invention is to provide a novel compound with excellent sharpness and color reproducibility by using a novel compound that can be manufactured at an appropriate cost and used in sufficient amounts. An object of the present invention is to provide a color photographic material.

(Means for Solving the Problems) The above object has been achieved by a silver halide color photographic material characterized by containing a compound represented by the following formula (1).

- Formula (1) In the formula, A represents a group that reacts with the oxidized developing agent to release a moiety of (L) 7 or less, and L is a moiety that is further bonded to L after being eliminated from A. represents a group that releases
each independently represents a carbon atom or a nitrogen atom,
R' and R'' each independently represent a 5- to 7-membered nitrogen-containing unsaturated heterocyclic group having 2 to 6 carbon atoms;
represents a development inhibitor group or its precursor group, R4 is -NH3O, R3, -NH3O, NR5R'-
NH,, ~NHR5 or -NR'R-, R5
, Rh each independently represents an aliphatic group, an aromatic group, or a heterocyclic group, n represents an integer from 0 to 2, and n is 2
may be the same or different, and R3 and R4 may be substituted on the same ring, or may be substituted on different rings.

In general formula (1), A is specifically a coupler residue or a redox group that can be oxidized to release a moiety of (L) 7 or less. L is a known timing group or linking group. The heterofused ring represented by R', Rχ, X and Y is
It has a structure that allows it to be oxidized by an oxidized developing agent after being cleaved from A-(L), - during development.

That is, in the heterocycle, the site bonding to A-(L), - and R4 are located at positions that satisfy the Kendall-Pelz rule.

By being oxidized in this way, the heterocycle becomes a structure capable of releasing the development inhibitor represented by R3 or its precursor. The release mechanism is nucleophilic addition-elimination of the oxidized heterocycle by a nucleophilic species, and therefore R3 to be eliminated must be substituted at the position to which the nucleophilic species is added.

Nucleophiles are, for example, hydroxylamine, sulfite ions or hydroxide ions. The development inhibitor or its precursor released during development by the above mechanism exhibits an edge effect and a multilayer effect, thereby improving image sharpness and color reproducibility.

The coupler described in JP-A-64-13548 has a heterofused ring similar to some of the compounds of the present invention as a leaving group, but it does not have a development inhibitor or its precursor as a substituent. The improvements in sharpness and color reproducibility as described above were completely inadequate.

The compound represented by the general formula (1) is particularly suitable for the following formula -i (
Compounds represented by II) to [■] are preferred.

General formula (II) - Numerical formula (III) RcoR' General formula (IV) General formula (V) General formula (Vr) General formula [■] In the formula, A reacts with the developing crude drug oxidized product (L), Represents a group that releases the following moiety, where L is released from A and then further L
R3 represents a development inhibitor group or its precursor group, R4 represents 1○H
-, -NH3O,R'NH30,NR'R", -NH
,, -NHR' or -NR'R', Rs, R
h each independently represents an aliphatic group, an aromatic group, or a heterocyclic group, n represents an integer of O to 2, and when n is 2, L may be the same or different, x, y,
z each independently represents -CR'= or N=, and R7 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group.

- In formulas (1) to [■], A is specifically a coupler residue or a redox group that can be oxidized to ~(L) to release the following moiety.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide),
Magenta coupler residues (e.g. coupler residues of the 5-pyrazolone type, pyrazolotriazole type or pyrazoloimidazole type), cyan coupler residues (e.g. phenol type, naphthol type or European Published Patent Application No. 24)
9453) and colorless coupler residues (eg coupler residues of the indanone or acetophenone type). Also, U.S. Patent No. 4315070, U.S. Patent No. 418375
It may be a hetero salt type coupler residue described in No. 2, No. 4174969, No. 3961959, or No. 4171223.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, such as hydroquinones, catechols, pyrogallols, 1.
Examples include 4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides, and sulfonamidonaphthols. Specifically, these groups include, for example, JP-A Nos. 61-230135, 62-251746, 61-278852,
US Pat. No. 3,364,022, US Pat. No. 3,379,529, US Pat. No. 3,639,417, US Pat. No. 4,684,604 or J, O
rg, Chew, 29.588 (1964).

In general formulas (1) to [■], A preferably represents a coupler residue.

When A represents a coupler residue in general formulas (1) to [■], preferable examples of A are as follows - Formula (Cp-1), (C
p-2), (Cp-3), (Cp-4), (Cp-5
), (Cp-6), (Cp-7), (Cp-8), (C
p-9) or (Cp-10). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3) General formula (Cp-4) S7 General formula (Cp 5) General formula (Cp-6) General formula (Cp-7) General formula (Cp-8) General formula (Cp9) General formula (Cp-10) 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, RS l + Rs z + Rs3+ R54+ RS S 1 Rat R5y, R5I+ Rsw+ Rie+ R
When &l+ R&ffi+ or R1 contains a diffusion-resistant group, it has a total number of carbon atoms of 8 to 40, preferably 10.
otherwise, the total number of carbon atoms is preferably 15 or less; in the case of bis-type, telomeric-type or polymeric couplers, any of the above substituents carries a divalent group; Represents, connects repeating units, etc. In this case, the range of carbon numbers may be outside the specified range.

R1 to R41%d and e will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group or a heterocyclic group, and Rat represents an aromatic group or a heterocyclic group,
Ras+ Raa and R4% are hydrogen atoms, aliphatic groups,
Represents an aromatic group or a heterocyclic group.

R5I represents the same meaning as Ra + aR5! and R
Each ss has the same meaning as Rat, R34 is R41
A group having the same meaning as R,, C0N- group, R□N- group, Ra
tRsR,, So, N- group, R□S- group, R430- group, 0 R43R44 Rss represents a group with the same meaning as R41 eR5& and R5'l each represent a group with the same meaning as R43 group, R41S - group, R430- group, R,, C0N- group, or 43 R4, SOχN- group *R5l has the same meaning as R□4
3 Represents a taste group, R2, has the same meaning as R41, R,
, C0N- group, RooCON- group, Ras
Ras R0〇- group, R,, S- group, halogen atom, or R4
1N- group; d represents 0 to 3;

When a plurality of 4ff d's are present, the plurality of Rsq's may represent the same substituent or different substituents, and each Rat may be connected as a divalent group to form a cyclic structure.

Examples of divalent groups for forming a cyclic structure include (R41
) r (R41) 42 R4! is cited as a typical example. Here f is O to 4
, g is an integer from O to 2, Ro is a group with the same meaning as R□, R1 is a group with the same meaning as R41, Rbt is a group with the same meaning as R□, R,, C0NH-
group, R410CONH- group, R44R45 R,, NSO, N- group, Rn5O- group, R-+S- group,
R44R4% Represents a halogen atom or Ra IN- group, Ro is 4
3 Group with the same meaning as R□, R,, C0N- group, R4% R43N GO O- group, R,, SO, N- group, Raa
Raa R,, NGO, - group, R,, So, N- group, 44 R,, 0CO- group, Ro〇-3ol- group, halogen atom, nitro group, cyano group or R4, Co- group,
e represents an integer from 0 to 4, a complex number R1 or R
63 each represents the same or different thing.

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

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

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

Representative examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-phthal, 1-imidazolyl, 1-indolyl,
Phthalimide, 1.3.4-thiadiazol-2-yl, 2-quinolyl, 2.4-dioxo-1,3-imidazolidin-5-yl, 2.4-dioxo-1,3-imidazolidine-3- yl, succinimide, 1,2.4-triazol-2-yl or 1-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R,, O- group, Rah S- group, RnffCR4m
R-・R4? R4? Examples thereof include R41 group, Rat○C○ group, R,, NC0N group, 4k R4@R't9 R,, Coo- group, R,, O20,- group, cyano group, and nitro group. Here, RAM represents an aliphatic group, an aromatic group, or a heterocyclic group, and R4.

RIB and R49 each represent an aliphatic group, an aromatic group, a heterogroup or a hydrogen atom, the meaning of aliphatic group, aromatic group or heterocyclic group having the same meaning as defined above.

Next, preferred ranges of RS l ''-R43, d and e will be explained.

R5I is preferably an aliphatic group or an aromatic group.

R5! + R53 and Rss are preferably aromatic groups.

R54 is preferably R1C0NH- group or R1-N- group is 0, R5 & and Rst are aliphatic groups, R410-
eRsm is preferably an aliphatic group or an aromatic group, - In formula (Cp-6), R59 is a chloro atom, an aliphatic group, or R,, C0N
H- group is preferable, d is preferably 1 or 2, Ro is preferably an aromatic group, - R% in formula (Cp-7)
% is R,, C0NH- group is preferable, - formula (Cp-7
), d is preferably 1, sR&+ is preferably an aliphatic group or an aromatic group, - in formula (Cp-8), e
is preferably 0 or 1, R1 is R,,0CON
H- group, R□C0NH- group or R41S Oz N
The H- group is preferred and the substitution position is 5 on the naphthol ring.
In formula (Cp-9), Rb2 is preferably R,, C0NH- group, R,, So! NH- group, group, nitro group or cyano group are preferred.

- In formula (Cp-10), R1 is preferably R1NC0-43 group, Ras CCO- group or R1C0- group. Next, typical examples of R8I to Rth3 will be explained.

Examples of Rs+ include (1)-butyl group, 4-methoxyphenyl, phenyl, 3-(2(2,4-di-monoamylphenoxy)butanamido)phenyl, or methyl. R%! and R%S is 2-chloro-5
-dodecyloxycarbonylphenyl, 2-chloro-5
-hexadecylsulfonamidophenyl, 2-chloro-
5-tetradecanamidophenyl, 2-chloro-5-(
4-(2゜4-di-L-aminophenoxy)butanamido)phenyl, 2-chloro-5-(2-(2,4-di-t)
-amylphenoxy)butanamido)phenyl, 2-methoxyphenyl, 2-methoxy-5tetradecyloxycarbonylphenyl, 2-chloro-5-(1-ethoxycarbonylethoxycarbonyl)phenyl, 2-pyridyl, 2-chloro5- Octyloxycarbonylphenyl, 2゜4-dichlorophenyl, 2-10rho5- (1
Mention may be made of dodecyloxycarbonylethoxycarponyl)phenyl, 2-chlorophenyl or 2-ethoxyphenyl.

R54 includes 3-(2-(2,4-di-t-amylphenoxy)butaneagodo)benzamide, 3-(
4-(2,4-di-t-aminophenoxy)butanamido)benzamide, 2-chloro-5-tetradecanamideaniline group, 5-(2,4-di-t-aminophenoxyacedeamide)benzamide, 2-chloro- 5-dodecenylsuccinimideaniline, 2-chloro-5-(2-
Examples of R5S include (3-butyl-4-hydroxyphenoxy)tetradecanamido)aniline, 2,2-dimethylpropanamide, 2-(3-pentadecylphenoxy)butanamide, pyrrolidino or N,N-dibutylamino. , 2,4゜6-dolichlorophenyl, 2-chlorophenyl, 2,5-dichlorophenyl,
2,3-dichlorophenyl, 2,6-dichloro-4-methoxyphenyl, 4-(2-(2,4-di-L-amylphenoxy)butanamido)phenyl or 2,6-
Dichloro-4-methanesulfonylphenyl is a preferred example. Rsh includes methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio, 3
-phenylureido, or 3-(2,4-di-t-amylphenoxy)propyl. R5? as 3-(2,4-di-t-amylphenoxy)propyl,
3-(4-(2-(4-(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamido)phenyl]
Propyl, methoxy, methylthio, ethylthio, methyl, 1-methyl-2-(2-octyloxy-5-(2-
Octyloxy-5-(1,1,3゜3-tetramethylbutyl)phenylsulfonamido]phenylsulfonamido)ethyl, 3-(4-(4-dodecyloxyphenylsulfonamido)phenyl)propyl, l, 1- Dimethyl-2-(2-octyloxy-5-(1,1,3
, 3-tetramethylbutyl)phenyl, sulfonamido]ethyl, or dodecyloxythio.

R□ is 2-chlorophenyl, pentafluorophenyl, heptafluoropropyl, 1-(2゜4-di-t
-amylphenoxy)propyl, 3-(2,4-di-t)
-amylphenoxy)propyl, 2,4-di-t-amylmethyl, or furyl phenoxy)
Butanamide, 2-(2,4-di-t-amylphenoxy)hexanamide, 2-(2,4-di-L-octylphenoxy)octanamide, 2-(2-chlorophenoxy)tetradecanamide, 2-(4 -(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamide, or 2-(2-(2°4-di-L-amylphenoxyacetamide)phenoxy)butanamide. R6° is 4-dinanophenyl, 2-cyanophenyl, 4-butylsulfonylphenyl, 4-propylsulfonylphenyl, 4-chloro-3-cyanophenyl, 4-ethoxycarbonylphenyl, or 3.
Examples of aR&1 include 4-dichlorophenyl, dodecyl, hexadecyl, cyclohexyl, 3-(2,4
-di-t-amylphenoxy)propyl, 4-(2,4
-di-t-amylphenoxy)butyl, 3-dodecyloxypropyl, t-butyl, 2-methoxy-5-dodecyloxycarbonylphenyl, or 1-naphthyl.

RhN includes isobutyloxycarbonylamino, ethoxycarbonylamino, phenylsulfonylamino,
Examples include methanesulfonamide, benzamide, trifluoroacetamide, 3-phenylureido, butoxycarbonyl alcohol, or acetamide. As Ro, 2,4-di-L-amylphenoxyacetamide,
2-(2゜4-di-t-amylphenoxy)butanamide, hexadecylsulfonamide, N-methyl-N-
Octadecylsulfamoyl, N, N-dioctylsulfamoyl, 4-L-octylbenzoyl, dodecyloxycarbonyl, chlorine atom, nitro, cyano, N-
[4-(2,4-di-t-arylphenoxy)butyl)
Mention may be made of carbamoyl, N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl, methanesulfonyl or hexadecylsulfonyl groups.

- In formulas (1) to [■], L is a known timing group or linking group 0 For example, U.S. Patent No. 414639
A group that utilizes the hemiacetal cleavage reaction described in No. 6, No. 4,652,516 or No. 4,698,297, a timing group that causes a cleavage reaction using an intramolecular nucleophilic reaction as described in U.S. Pat. No. 4,248,962, A timing group that causes a cleavage reaction using an electron transfer reaction as described in U.S. Pat. or a group that causes a cleavage reaction using an ester hydrolysis reaction described in West German Published Patent No. 2,626,317. A plurality of these groups may be used in combination, and L bonds to A at a heteroatom contained therein, preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

Preferred examples of the linking group represented by L include methyleneoxy, 4-methylene-3-pyrazolyloxy, 2 (or 4)-methylenephenoxy, and 2-carbonylaminomethylphenoxy.

In these oxygen atoms, -IC formula (I) or (I
Connect with A in I). These divalent groups can also be substituted at substitutable positions (e.g. in the methylene group or in the benzene ring).
may have a substituent, and typical substituents include alkyl groups (e.g. methyl, ethyl, isopropyl,
dodecyl), acyl groups (e.g. benzoyl, acetyl)
, alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), carbamoyl groups (e.g. ethylcarbamoyl), nitro groups, carboxyl groups, sulfonyl groups (
Examples include methanesulfonyl), aryl groups (eg, 4-nitrophenyl, 4-carboxyphenyl), halogen atoms (eg, chlorine atom, fluorine atom), and sulfamoyl groups (eg, octadecylsulfamoyl).

- R1 and R'' along with the nitrogen atom in formula (1)
Examples of the heterocycle constituted by include pyrrole, imidazole, pyrazole, 1,2,4-triazole, indole or α-pyridone. These heterocycles have A-(L
) n, and each bond to R3 and R4 at carbon atoms other than the hydrogen atoms of the two methine groups. The heterocyclic group may further have a substituent at a substitutable position, and examples of the substituent include those listed as the substituent for R41. Especially as the nitrogen-containing unsaturated heterocycle represented by R1 and R2, Preferred are nitrogen-containing unsaturated five-membered rings as represented by general formulas (n) to (■).

In general formulas (I[) to [■], x, y, z
each independently represents -COR'- or -N=, and R7 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group, or an aryloxy group. Examples of the aliphatic group include Methyl, ethyl, n-
Examples include propyl, i-propyl, t-butyl, cyclohexyl, 2-ethylhexyl, 1,1,3.3-tetramethylbutyl, decyl, and octadecyl groups. Examples of aromatic groups include phenyl, naphthyl, and anthracenyl groups, with phenyl being preferred. ? 3 [As a ring group, for example, 2-pyridyl,
Examples include 2-phthal, 1-imidazolyl, 1-morpholyl, succinimide, phthalimide, and 1-pyrazolyl. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms, and a particularly preferred one is chlorine atom. Examples of alkoxy groups include methoxy,
Examples include ethoxy, 2-ethylhexyloxy, and cyclohexyloxy groups. Examples of the aryloxy group include phenoxy and naphthoxy groups. still,
These groups represented by R7 may be further substituted with various substituents.

- In formulas (1) to [■], specific examples of the development inhibitor group represented by R3 include a heterocyclic thio group or a nitrogen-containing heterocyclic group bonded via a nitrogen atom.

Examples include tetrazolylthio, thiadiazolylthio, oxadiazolylthio, triazolylthio, benzimidazolylthio, benzthiazolylthio, tetrazolylseleno group, benzoxazolylthio, benzotriazolyl, triazolyl, or benzimidazolyl.

These groups are described, for example, in U.S. Pat.
No. 384657, No. 3615506, No. 361729
No. 1, No. 3733201, No. 3933500, No. 3
No. 958993, No. 3961959, No. 414988
No. 6, No. 4259437, No. 4095984, No. 4
No. 477,563 or British Patent No. 1,450,479.

- In the explanation of R4 in formula (13 to [■]), Rs,
The aliphatic group, aromatic group, and heterocyclic group represented by Rh are A
It has the same meaning as those represented by R 41 Ram and R6 used in the explanation section.

The compound of the present invention can be applied to a multilayer, multicolor photographic material having at least three different spectral sensitivities on a support, mainly for the purpose of improving sharpness, color reproducibility, or graininess. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary.

The compounds of the present invention can be added to any of these layers. It can be used not only in the light-sensitive emulsion layer but also in its adjacent layers, such as interlayers. Furthermore, the compound of the present invention can be added to layers of arbitrary sensitivity, such as high-sensitivity layers and low-sensitivity layers.

The amount of the compound of the present invention added varies depending on the structure of the compound, but is preferably 1 x 1 O-h to 0.5 mol per mol of silver present in the same layer or an adjacent layer, particularly preferably 1 x
10-' to l x 10-' moles.

When the compound of the present invention and a coupler for color image formation are mixed and used, the molar ratio used is 0.01/99.99 to 5.
0150 is preferably 1/99 to 30/To (compound of the present invention/color image type coupler).

(Compound Examples) Specific examples of the compounds of the present invention are listed below, but the invention is not limited thereto.

- Compounds co, cH included in formula (1) but not included in general formulas (II) to [■].

(3) O Compound contained in general formula (n) (4) 0 (5) (6) (7) H ■ (8) - Compound contained in formula (I[l) CHiSOtNH (10) 0 (11) Compounds contained in general formula (IV) (12) (13) (14) (15) Compounds contained in general formula (V) (16) H3 (17) 0H (18) Compounds contained in general formula (Vl) (19) (20) (21) Compound (22) 0 (23) 6H13 contained in -ta formula [■]
That is, it can be synthesized by a method similar to that of a heterocyclic dissociation type coupler.

For example, U.S. Pat. No. 4.146.369, U.S. Pat.
1.168, 4,076.533, 4.008
, No. 086, No. 4,046,575, No. 4,229,
No. 577, No. 4,326,024, No. 4,310,6
No. 19, No. 4,301,235, European Published Patent No. 87388A, or British Patent No. 2,132.78
It can be synthesized by a method similar to that described in No. 3A.

Next, a typical method of synthesizing the compound of the present invention will be described. Others can be synthesized in the same way.

Synthesis Example 1 Synthesis of Exemplary Compound (4) It was synthesized using the following synthetic route.

Exemplary Compound (4) 15.0 g of Compound 1, 29.51 g of Compound, and 3.06 g of triethylamine were mixed in 200 id of N,N-dimethylacetamide, and the reaction mixture was soaked for 5 hours. The reaction mixture was poured onto water and extracted with ethyl acetate. The organic layer was washed with water and then dried over magnesium sulfate. Filter off the desiccant,
Removal of the solvent gave a yellow oil. Ethyl acetate,
Crystallization was performed from a mixed solvent of n-hexane to obtain 16.2 g of the target exemplary compound (4) as pale yellow crystals.

Synthesis Example 2 Synthesis of Exemplary Compound (21) It was synthesized using the following platform route.

CIh5O□NH CH.

Synthesis of Exemplified Compound (21) 320.0 g of the compound and 417.2 g of the compound were heated under reflux for 5 hours in a mixed solvent of 100 m of methoxyethanol and 6011 f of acetic acid.The reaction mixture was poured onto water, and the precipitated solid was collected by filtration. By recrystallizing from a mixed solvent of acetonitrile and methanol, 31.0 g of the target exemplary compound (21) was obtained as colorless crystals.

The photosensitive +A material of the present invention has at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support.
There are no particular restrictions on the number or order of the silver halide emulsion layer and the non-light-sensitive layer. However, it is a silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having different photosensitivity, and the light-sensitive layer is one of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in order from the support side: a red-sensitive layer, a red-sensitive layer, a red-sensitive layer;
A green sensitive layer and a blue sensitive layer are installed in this order. 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 the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (1?L
), or BH/BL/GL/GH/RH/RL, or BH/BL/Gl(/GL/RL/RHO
They can be installed in any order.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of RH/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. One example is an arrangement in which a silver halide emulsion layer with a low density is disposed, and three layers with different photosensitivity are sequentially lowered toward the support. Even when the tank bottom is made up of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

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

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707.
No. 436, JP-A-62-160448, JP-A No. 63-89
It is preferable that a multilayer effect donor layer (CL) having a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, and RL as described in the specification of No. 850 is arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material 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 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) NIL17643
(December 1978), pp. 22-23, '1. Emulsion preparation
d types) ”s and the same Nα18716 (
November 1979), 648 Makoto, Grafkide, “Physics and Chemistry of Photography”, published by Paul Montell (P, GIaf
kids, Ches+ie et Ph1siqu
e Photograph-ique, Paul M.
1967), Duffin, "Photographic Emulsion Chemistry" 9, published by Focal Press (G, F, Duffio).

Photographic Emulsion Che
mistry (Focal Press.

1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikm)
anat al,, Making and
Coating Photographic Em
ul-sion, Focal Press, 196
It can be prepared using the method described in 4).

U.S. Patent Nos. 3,574.628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14 @ pp. 248-257 (1970); U.S. Pat.
, 433.048, 4,439.520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides of different compositions may be joined by epitaxial bonding. The particles may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide, or a mixture of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure NAI
It is described in L 17643 and Ceramics 18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. These are fine silver halide grains that are not substantially developed 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 necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0. O1 to 0.5μ is preferable, and 0.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same way as normal photosensitive silver halide! Ill can. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or zinc compound is added in advance (preferably).

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Riu5ALRwLIUfL■ Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity increasing agents
Same as above 3 Spectral sensitizer, pages 23-24
Page 648 right column - Super sensitizer Page 649 right column 4 Brightener Page 24 5 Anti-fogging agent Page 24-25 Page 649 right column - and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~Filter dye, page 650 left column UV vA @ collection agent 7 Stain inhibitor page 25 right column 8 page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Frame stop agent Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Ni117643, described in the patent described in ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022.620, No. 4.3
No. 26.024, No. 4.401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1.476.760, U.S. Patent No. 3.973,968, British Patent No. 4.314,
No. 023, No. 4,511,649, European Patent No. 24
No. 9,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4.351,897, European Patent No. 73,636, US Patent No. 3.061.432, US Patent No. 3.725,067, Research Disclosure N [L24220 (1984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, No. 4.540,654
No. 4,556.630, International Publication WO3810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146.396, No. 4,228.23
No. 3, No. 4.296,200, No. 2.369.9
No. 29, No. 2,801, No. 171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3.758, 308, No. 4,33
4.011, 4.327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121.365
No. A, No. 249°453A, U.S. Patent No. 3.446
．． No. 622, No. 4.333.999, No. 4,77
No. 5,616, No. 4.451.559, No. 4.4
No. 27.767, No. 4.690,889, No. 4,
Preferred are those described in No. 254.212, No. 4,296.199, and Japanese Patent Application Laid-Open No. 61-42658.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146,36
No. 8 is preferred, and also US Pat. No. 4,7
No. 74.181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96, 570, West German Patent (
The one described in Japanese Publication No. 3,234.533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4, No. 5764910, British Patent No. 2.102
．． It is described in No. 137, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
Those described in JP-A No. 2,131,188, JP-A-59457638, and JP-A No. 59-170840 are preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
LR coupler releasing redox compound or DIR redonx releasing redox compound, European Patent No. 173゜30
R, D, N1111449, a coupler that releases a dye that after separation is described in No. 2A, No. 313,308A.
, No. 24241, JP-A-61-201247, etc., bleach accelerator-releasing couplers, U.S. Patent No. 4.555.4
Ligand releasing coupler described in No. 11 etc., JP-A-63-
75747, a leuco dye-releasing coupler;
Examples include couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181.

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 U.S. Pat. No. 2,322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-sheet amyl phenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid II () Riphenyl phosphate, tricresyl phosphate, 2
-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoquine ethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides [(N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl)
sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-terL-octylaniline, etc.), hydrocarbons (paraffin, Examples include dodecylbenzene, diisopropylnaphthalene, etc.

Further, as the auxiliary solvent, 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 include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Nα17643, page 28, and Companion 18716, page 647 right column to page 648 left column.

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, even more preferably 18 μm or less, and 16 μm or less. is particularly preferable, and the membrane swelling rate T17! is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness is measured in days), and the film swelling rate TI/l is:
0, which can be measured according to techniques known in the art, e.g.
Photographic Science and Engineering (Photogr, Sci, Eng,)
+ 19@, No. 2, 124-129 It can be measured by using a swellometer (swelling membrane) of the type described in True. 90% of the maximum swelling film thickness reached is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate TI/l can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, 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>/H thickness).

The color photographic material according to the present invention includes the above-mentioned RD, N
ct 17643, pages 28-29, and same issue 1871
6, 615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amino color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 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-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

Color developers include pHWk buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitors. couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, alkylphosphonic acids,
Various calcinants such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylene glycol (O-hydroxyphenylacetic acid M) and salts thereof can be cited as a representative example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidone moieties such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

These color developing solutions and black and white developing solutions generally have a pn of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is less than 3i per square meter of -C light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than af. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, 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 surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, Aminopolycarbonate such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ethercyamine contagious acid, etc.! [Alternatively, complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Of these, iron ethylenediaminetetraacetate (I[[)i? iron(III) aminopolycarboxylic acids, including iron(III) it salts, and 1,3-diaminopropanetetraacetic acid iron(III) it salts! Salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acid iron (III) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. pH of bleach solution or bleach constant@ solution using these aminopolycarboxylic acid iron (lit) complex salts
is usually 4.0 to 8, but it is also possible to process at an even lower pH to speed up the process.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, No. 2,059,9813, JP-A No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95
No. 630, No. 53-95631, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. N1117129 (July 1978), etc. Compounds having a mercapto group or a disulfide group;
Thiazolidine derivatives described in JP-A-50-140/129; JP-A-45-8506, JP-A-52-2083
No. 2, No. 53-32735, U.S. Patent No. 3,706,
Thiourea derivatives described in No. 561; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2.748.
Polyoxyethylene compounds described in JP-A No. 430; polyamine compounds described in JP-A No. 45-8836; other JP-A Nos. 49-40,943, 49-59,644, 53-94,927, No. 54-35,727, same 5
Compounds described in Nos. 5-26.506 and 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. No. 3,893.
No. 858, West German Patent No. 1.290,812, JP-A-5
The compounds described in No. 3-95,630 are preferred, and further,
Also preferred are the compounds described in U.S. Pat. No. 4,552,834, these bleach accelerators may be added to the photosensitive material.
These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 2947698 are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable that the stirring be as strong as possible.Specific methods for strengthening the stirring include:
A method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material described in JP-A-62-183460, and JP-A-62-18
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there is a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface, and a method to increase the circulation flow rate of the entire processing liquid. can be mentioned. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the above-mentioned stirring improving means includes:
It is more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Te1e-vi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and suspended matter adheres to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Full volume of technology “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in (1986).

The pl+ of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Dye stabilizers that can be used include aldehydes such as formalin and glutaraldehyde.
, an N-methylol compound, hexamethylenetetramine, or an aldehyde sulfite adduct.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.9 For example, U.S. Pat. No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Ship base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, and U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various l-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at temperatures ranging from 10°C to 50"C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

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

Example I On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/r+ (units of silver) for silver halide and colloidal silver, and the amount expressed in g/rrf (units) for coupler additives and gelatin. For sensitive dyes, the number of moles per mole of silver halide in the same layer is indicated.The symbols indicating additives have the meanings shown below.However, if the additive has multiple effects, one of them is representative. I posted it.

U■; Ultraviolet absorber, 5olv; High boiling point organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler ExY: Yellow coupler, Cpd: Additive 1st layer (Haley silane prevention layer) Black colloid S 0.15 Gelatin 2.9UV=1
0.03UV
-20,06 UV -30,07 Solv-20,08 Ex F -10,01 Ex F -20,01 2nd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag! 4 mol %, uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8E x S
-12,3X10-' ExC-10,17 ExC-20,03 ExC-30,13 Third layer (medium-sensitivity red-sensitivity emulsion layer) Silver iodobromide emulsion (Ag+ 6 mol%, core-shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.65 Silver iodobromide emulsion (Ag1 4 mol) %, average-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.1 Gelatin 1.0ExS-1
zxto-' Ex S-21,2X10-'ExS-52xto-' ExS-77 Sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core-shell ratio 2:1
internal high AgI type, equivalent sphere diameter 0.7 pm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount 0.9 0.8 1.6X10-' 1. 6X10-'1.6X10"' 6 Xl0-' 0.07 0.05 0.07 0.20 4.6X10"' Gelatin ExS-I ExS-2 ExS-5 ExS-7 ExC-I XC-4 olv- I olv-2 Cpd-7 5th layer (intermediate layer) Gelatin V-4 V-5 Cpd-1 Polyethyl alcohol olv-1 0,6 0,03 0,04 0,1 Relay latex 0.08 0.05 6th Layer (Low-sensitivity green-sensitive emulsion FJ) Silver iodobromide emulsion (Ag1 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/IE ratio 2.0) Coated silver amount 0.18 Gelatin 0.4ExS-3
2X10-'ExS-47X10-' ExS -51XIO-' ExM-50,11 Ex M -70,03 Ex Y -80,01 Solv-10,09 S o 1 v-40,01 7th layer (medium Green sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core shell ratio 1:1
surface height Agl type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4. O) Coated silver amount 0.27 Gelatin 0.6EχS −
32X10-'ExS-47X10-'ExS-51XIO-' ExM -50,17 EχM -70,04 ExY-80,02 Solv-10,14 Solv-40,02 8th layer (high sensitivity green Sensitive emulsion layer) Silver iodobromide emulsion (Ag1 8.7 mol%, silver ratio 3:4
:2 multilayer structure particles, Agl content 24 mol from inside,
0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount 0.7 Gelatin 0.8E x
S -45,2X10-'ExS-51XIO"4 Ex S -80,3X10-' ExM-50,I EχM-60,03 Ex Y -80,02 Ex C-I Q,
02EχC-40,01 Solv-10,25 Solv-20,06 Solv-40,01 Cpd-? lXl0-
'9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate Latex 0.12Sol
v-10,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl 6 mol%, internal high AgI type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, equivalent to sphere) Coefficient of variation in diameter 25%, plate-like grains, diameter/W, ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, Coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/w, ratio 3.0) Coated silver amount 0.19 Gelatin 1.0ExS-3
6X10-' ExM-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8Cp d -2
0,13 Solv-10,13 Cp d -10,07 Cp d -60,002 H-10,13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter/thickness ratio 7.0) Coated silver amount 0.15 Gelatin 1.8ExS-6
9X10-' ExC-10,06 Ex C-40,03 Ex Y -90,14 EχY-110・89 Solv-10,42 13th layer (middle layer) Gelatin 0.7EχY-1
20,20 Solv-10,34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high Agl type,
Equivalent sphere diameter 1.0 am, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.
5 Gelatin 0.5ExS-6
1XIO-' E x Y -90,01 ExY-110,20 E
Mold, equivalent sphere diameter 0.07 pm) Coated silver amount 0.1
2 Gelatin 0.9UV-4
0,11 UV -50,16 Solv-50,02 H-10,13 Cp d -50,10 Polyethyl acrylate latex 0.09 No. 16
Layer (second protective layer) Fine grain silver iodobromide emulsion (Agl 2 mol%, homogeneous -Agl
Mold, equivalent sphere diameter 0.07 μm) Coated silver amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles (1.5 μm diameter) 0.2H-1
0,17 In addition to the above components, each layer contains an emulsion stabilizer c pa
-3 (o, o7g/bo), surfactant Cp, d-4 (
0.03 g/rd) was added as a coating aid.

V-1 H (Sushi, H9 UV-4 χ:y■70:30 (wt%) UV-5 olv-1 Tricresyl phosphate olv-2 Dibutyl phthalate olv-5 Trihexyl phosphate xF-1 EχS-1 xS -2 xS-3 xS-4 xS-5 xS-6 xS-7 (L;IhJxSOsH-N(CJs)sExS-8 ExC-1 0■ ExC-2 ExC-3 ExC-4 0) 1 xM-5 EχM -6 xM-10 xY-8 l ExY-9 (coupler described in US m, 4n, 563) ExY-11 pd-7 pd-1 CJ+old pd-2 υ p d-6 pd-5 pd-3 υH p d-4 -1 Preparation of samples 102 to 111 In sample 101, the 1211th layer, the 13th layer, and the 14th layer
Samples 102 to 108 were prepared in the same manner as sample 101 except that ExY-9 and ExY-12 added to the layer were changed to the couplers shown in Table 1.

The obtained sample was cut into a width of 350, and the following evaluations of Φ to ■ were performed.

(2) White imagewise exposure was applied, the following development process was carried out, and the relative sensitivity of the density of yellow image fog + 0.2 was determined.

(2) Exposure for MTF measurement was applied, the same development process was carried out, and the MTF value of the yellow color image was calculated by a conventional method.

(2) After uniform exposure to green light, imagewise exposure to blue light was performed and the same development process was performed. At this time, a value obtained by eliminating the magenta density in the area not exposed to blue light was determined as the interlayer effect from the magenta density at the exposure amount at which the yellow density was fogged +1.0.

Comparative compounds and color development processing steps are shown below.

Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Washing with water (1) 40 seconds Washing with water (2) 1 minute 00 seconds Stability 40 seconds Drying 1 minute 15 seconds Next, all the precepts of the processing liquid will be described.

(Color developing solution) Diethylenetriamine pentanotic acid l-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Treatment temperature 38°C 38°C 38°C 35°C 35°C 38°C 55°C (Unit g) 1.0 3.0 4.0 30.0 1.4 Potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β monohydroxyethylamino)-2-methylaniline sulfate was added to pH (bleach solution) 1 .5■ 1.01 10.05 (Unit g) Ethylenediaminetetranodic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator 120.0 10.0 100.0 10.0 o , oos mol Ammonia water (27%) Add water to pH (bleach-fix solution) L5.0R1 1,01 6,3 (Unit g) Ethylenediaminetetraacetic acid 50.〇Diferric ammonium trihydrate Ethylenediaminetetraacetic acid diacetate 5. O sodium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240. Od solution (70%) Ammonia water (27%) 6.0 d Add water 1.0 J pH 7,
2 (Washing liquid) Hotbed type tap water filled with H-type strongly acidic cation exchange resin D (Amberlite IR-120B manufactured by ROHM & BAR) and OH-type anion exchange resin (Amber-3 Lite TR-400) Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3/1 or less, and then 20/l of sodium isocyanurate dichloride and 150/It of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing liquid) (Unit: g) Formalin (37%) Polyoxyethylene-p-monononylphenyl nityl (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt solution to pH 2.0iif 0.3 0.05 1 .01 5.0-8.0 -4 Comparative coupler EXY-13 (Coupler described in U.S. Pat. No. 4.248.62) xY-14 (Coupler described in JP-A-60-203943) l xY-15 (same as above) xY-16 (coupler described in JP-A No. 62-291645) xY17 (same as above) *1) The amount of DIR coupler used in the sample qitot was set to 1.0
(The amount used was changed to match the approximate sensitivity and gradation.) *2) The exposure amount required to obtain a density of fog + 0.2 for sample 11hLOL is 100. It is shown as a relative value when

As is clear from Table 1, the samples using the coupler of the present invention were excellent in both sharpness and interlayer effect.

/ Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(!!Light layer admonition) The number corresponding to each component indicates the coating amount expressed in g/rd units, and for silver halide, it indicates the coating amount of silver conversion, but for sensitizing dyes, The amount of coating per mole of silver halide in the same layer is shown in moles.

(Sample 201) First layer (Haley silane prevention layer) Black colloid II iI O,
18 Gelatin 0.40 Second layer (middle layer) 2.5-di-t-pentadecylhydroquinone 0.18E
-10,07 EX-30/02 EX-12 U-1 -2 -3 B5-1 B5-2 Third layer of gelatin (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Increase Sensitizing dye ■ EX-2 EX-10 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I 0.002 0.06 0.08 0.10 0.10 0.02 1. 04 vAo, 25 11 O, 25 6,9X10-'1.8X10-' 3, lX10-' 0.335 0.020 0.060 0.87 Silver 1.0 5, lX10-' Sensitizing dye■ Sensitization Dye ■ EX-2 EX-3 EX-10 B5-1 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ EX-3 EX-4 EX-2 B5 -1 B5-2 Gelatin 6th layer (middle layer) EX-5 1,4X10-'2.3X10-' 0.400 o, os.

O,015 0, G60 1.30 °Silver 1.60 5.4X10-' 1.4X10-' 2.4X10-' o,oi.

o,os.

O,097 0,22 0,10 1,63 0,040 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX -1 EX-7 EX-14 B5-1 B5-3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 0.020 0.80 ii 0.15 11O,15 3,0X10-'1.0X10"'3.8X1G-' 0.260 0.021 0.030 G,012 0.100 0.010 0.63 g O,45 2, I X 10s7 , OX 10-'2.6X10-' EX-6 EX-14 EX-7 B5-1 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-13 E t!1 1.2 3.5X10-"8.0X10-'3.0X10-' 0.015 0.100 0.025 0.25 0.10 1.54 Silver 0.05 0.08 HBS-1 Gelatin 117th! ! (First blue emulsion N) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ X-9 X-8 B5-1 Gelatin 12th layer (Second blue emulsion layer) Emulsion G Sensitizing dye ■ X-9 X- 10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H 0.03 0.95 Silver 0.08 Silver 0.07 gl 0.07 3.5XIO-' 0.721 0.042 0.28 1.10 Silver 0.45 2, lX10-' 0.154 0.00? 0.05 0.78 Silver 0.77 Sensitizing dye■ 2.2X10-'E
X -90,20 HB S -10,07 Gelatin 0.69 No. 14
Layer (first protective layer) Emulsion I Silver 0.5U-4
0,11 0-50,17 HB S -10,05 Gelatin 1.00 No. 15
Layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 tt m) 0.
54S -10,20 Gelatin 1.20 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

X-1 X-2 X-3 0 ■ 0) 1 l X-4 0H X-5 C48th ω X-6 X X-8 X-9 1; l X-10 -13 -1 -2 -3 U-4 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ -1 -1 Lallz-Lrrl-tX LJIx L
;UNtl 1. :Hi comparative coupler EX-14 (a coupler similar to the coupler described in U.S. Pat. No. 4,338,393) Preparation of samples 202-203 EX added to the 7th and 8th layers in sample 201
Sample 20 except that -14 was changed to the coupler shown in Table 2.
Samples 202 and 203 were prepared in the same manner as in Example 1. Samples 202 and 203 using the coupler of the present invention were obtained by cutting the obtained sample into 351 cm wide pieces, exposing them to standard subject light, and performing the development process used in Example 1 or the development process described below. Even after processing, the sharpness and color reproducibility were extremely excellent.

Processing method Process Processing time Color development 2 minutes 30 seconds Bleach fixing 3 minutes 00 seconds Washing with water (11' 20 seconds Washing with water (2) 20 seconds Stability 20 seconds Dry 50 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Processing temperature: 40°C 40°C 35°C 35°C 35°C 65°C (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene, 1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium iodide Potassium hydroxylamine sulfate 4-[N-ethyl-N-(β-hydroxyethyl)amino]-2-methylaniline sulfate was added to H (bleach-fix solution) Ferric ethylenediaminetetraacetate 3.0 4.0 30.0 1.4 1.5■ 2.4 4.5 1.0L 10.05 (Unit g) 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate aqueous solution (70%) 5. 0 12.0 260, ml Acetic acid (98%) Bleach accelerator 5.0 L11 0.01 mol Add water 1. OLp H6
,0 (Washing liquid) Tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite F!A-400 manufactured by Rohm and Haas).
Water was passed through a hot bed column filled with 20% sodium chloride to reduce the concentration of calcium and magnesium ions to below 3μ/L, and then 20μ/L of sodium isocyanurate dichloride and 4.5 g of sodium sulfate were added.

The DH of this liquid is in the range of 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 liters Polyoxyethylene = p -0.3 Monononyl phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Add disodium salt water 1. OLp H5
,0-? -' Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in silver g/cd for silver halide, colloidal silver, and coupler, and the number of moles per 1 mole of halogenide in the same layer for sensitizing dye. Indicated.

1st layer: anti-halation layer black colloidal silver! ! Coating amount 0.2 gelatin 2.2 UV-10,1 V-2 pd-1 olv-1 olv-2 olv-3 2nd layer: Intermediate layer fine particle bromide l! (Equivalent sphere diameter 0.07μ) Silver coating amount Gelatin p d-2 3rd layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Aglto, o mol%, internal high Agl type, equivalent sphere diameter 0.7μ, Coefficient of variation of equivalent sphere diameter 14%, tetradecahedral particle) iIP! ! Placed silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral grains) 0.2 0.05 0.0I Oool 0, O8 0,15 0,26! ! Coating amount: 0.2 1.0 4.5 X 10-' mol x, 5xto-' mol 0.4 X 10-' mol 0.3 Gelatin xS-1 xS-2 xS-3 xS-4 ExC-1 ExC-2 Exemplary Compound (15) General formula (IVI XC-3 ExC-6 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion ( Agl 16 mol%, internal high Agl type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4.0) Gelatin xS-I xS-2 xS-3 1! Coating Amount 0.55 0.7 3X10-'lXl0'''0.3X10-' Ex S -40,3X10-' Ex C-30,05 Ex C-40,10 Ex C-60,08 5th Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (Ag 110.0 mol%, internal high Ag
L-type, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, 'diameter/thickness ratio 6.0) Silver coating amount 0.9 Gelatin 0.6ExS-1
2X10-' Ex S -20,6X10-' Ex S-30,2X10-' ExC-40,07 Ex C-50,06 Solv-10,12 S o I v-20,12 6th layer: Intermediate layer gelatin 1.0Cpd-
4 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (A g I 10.0 mol%, internal height A
GL type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 0.1 dodecahedral grains) Silver coating amount 0.2 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, sphere equivalent diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.1 Gelatin 1.2ExS-5
5X10-'ExS-62X10-'ExS-71XIO-' ExM-10,41 ExM-20,10 ExM-50,03 Solv-10,2 olv-5 8th layer: 2nd green-sensitive emulsion layer Odor Silveride emulsion (Ag 110 mol%, internally high iodine type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) m coating amount 0.4 0.35 3.5X10-'1.4X10-'0.7XlO-' 0.09 0.01 0.15 0.03 0.03 Gelatin xS-5 xS-6 xS-7 xM-1 xM-3 olv-1 olv -5 9th layer: Intermediate gelatin 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (AgllO, 0 mol%, internal high Agl type, equivalent sphere diameter 1.2μ, 0.5 equivalent sphere diameter) Coefficient of variation 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount Gelatin xS-5 xS-6 xS-7 xM-3 xM-4 xC-4 olv-1 11th layer: Yellow filter layer Cpd -3 Gelatin olv-1 12th layer; Intermediate layer gelatin Cpd-2 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Agno mol%, 1.0 0.8 2X10-'0.8X10-'0.8X10-' 0.01 0.04 o, oos O12 0,05 0,5 0,1 0,5 0,1 Internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14% , dodecahedral grains) 11 Coating amount 0.1 Silver iodobromide emulsion (Ag 14.0 mol%, internal high iodine type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, dodecahedral grains) Silver coating Amount 0.05 1.0 3X10-' 0.53 0.02 0,15 Gelatin xS-8 xY-1 xY-2 olv-1 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl19. 0 mol%, internal high Agl type, equivalent sphere diameter 1.0 μ Coefficient of variation of equivalent sphere diameter 16%, tetradecahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-8
2X10-' ExY-L O,22SoI
v-10,07 15th layer: Intermediate layer fine grain silver iodobromide (Ag 112 mol%, uniform type, equivalent sphere diameter 0.13μ) Silver coating amount 0.2 Gelatin 0.36 16th layer:
Third blue-sensitive emulsion layer silver iodobromide emulsion (A g I 14.0 mol%, internal height A
GL type, equivalent sphere diameter 1.5 μ Coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.0 0.5 1.5X10-' 0.2 0.07 Gelatin EχS-8 xY-I olv-1 17th layer: 1st protective layer Gelatin V-1 V-2 olv-1 olv-2 18th layer: 2nd protective layer Fine particle bromide t! (Equivalent sphere diameter 0.07μ) m Coating amount 1.8 0.1 0.2 0.01 0, Ol 0.18 Gelatin polymethyl methacrylate particles (diameter 1.5μ) -1 -1 pd-5 V-1 H3 O V-2 H2 COOCR.

ExC-1 OH ExC-3 ExC-6 OH ExC-4 OH ExC-5 IZH2S xM-1 Hx xM-2 xM-4 ExM-5 ExY-1 ExY-'1 xS-1 xS-2 xS-3 xS -4 tHs C2I(S xS-5 xS-6 tHs ” xS-8 (CH2)4S0,0 (CHz) 4SO3H-N (CJs) sxS-7 Solv-1 Solv-'1 Solv-3 5olv-5 Cpd- 1 Cpd-2 H Cpd-3 Cpd-4 CJ+, (n) Cpd-5 ■ ■ -1 CIH1?SOdenNHCHtCHt(HzOCHtCH
tN" (CHi)s-1 CIlzlIC1lSOzCLCONLCfhC1?,
, C11SO□CHxCONH-CL The color light-sensitive materials prepared as described above were processed using the development process of Example 1, the development process of Example 2, or an automatic processor using the following processing steps and processing solutions.

Processing step * Replenishment amount: per meter length of 35tm wide photosensitive material (color developer) Mother solution (g) Replenisher (g) Diethylenetriamine 5.0 6.0 Pentanotic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyl Amine sulfate 4-(N-ethyl-N-β-hydroxyethylamino-2-methylaniline sulfate Add water to pH (bleach solution) 4.0 30.0 1.3 1.21g 2.0 4.7 1.0L 10.00 37.0 1.0L 10,15 1.3 Diaminopropanetetraacetic acid ferric complex salt 1.3 Diaminopropanetetraacetic acid mother solution (g) Replenisher (g) 130 190 (0.36 mol/ f) (0.53 mol/j 3.0 ammonium bromide acetate ammonium nitrate Add water and adjust pH with acetic acid and ammonia (fixer) 1-hydroxyethythene-1,1-diphosphonic acid ethylenediamine tetranoic acid Disodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (700g/It) Rodan ammonium thiourea 3.6-cythia 1°5 0 0 1.01 pH 4,3 Mother liquor (g) 5.0 0.5 10.0 8.0 170.0m1 100.0 3.0 3.0 20 0 0 1.01 pH3.5 Replenisher (g) 7.0 12.0 10.0 200.0+51 150.0 8-Octanediol water Add 1. (M 1.ON acetic acid, ammonia and pH 6.5 6.7 (Stable solution) Mother liquor, replenisher common formalin (37%) 1.2■1 5-chloro-2-methyl- 6,0 ■ 4-isothiazolin 3-one 2-methyl-4-isothia 3.0 ■ Zoline 3
-on surfactant 0.4 ethylene glycol 1.0 water added
1.0L pH 5.0-7.0 Sample 301 was excellent in both color reproducibility and sharpness in any treatment method.

(Effects of the Invention) The silver halide color photographic material of the present invention is superior to conventional materials in terms of color reproducibility and sharpness. Furthermore, the compounds of the present invention (-formulas (1) to [■]) are easier to synthesize than conventional development inhibitor-releasing compounds, and can be provided at low cost.

Claims (4)

[Claims] (1) A silver halide color photographic material containing a compound represented by the following general formula [I]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, A represents a group that reacts with the oxidized developing agent and releases the moiety below (L)_n, and L represents the group released from A. rear,
Further represents a group that releases the moiety bonded to L, X,
Y each independently represents a carbon atom or a nitrogen atom, R^1 and R^2 each independently represent a 5- to 7-membered nitrogen-containing unsaturated heterocyclic group having 2 to 6 carbon atoms, and R^ 3 represents a development inhibitor group or its precursor group, R^4 is -OH-, -NHSO_2R^5, -NHS
Represents O_2NR^5R^6, -NH_2, -NH-R^5 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^
5, R^6 each independently represents an aliphatic group, an aromatic group, or a heterocyclic group, n represents an integer from 0 to 2, and n
When is 2, L may be the same or different, and R
^3 and R^4 may be substituted on the same ring, or may be substituted on different rings. (2) The silver halide color photographic material according to claim (1), wherein the compound represented by the general formula [I] is represented by the following general formula [II] or [III]. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. L represents a group that releases the moiety bonded to L after being separated from A, R^3 represents a development inhibitor group or its precursor group, and R^4 represents - OH-, -NHSO_2R^5, -NHSO_2NR
^5R^6, -NH_2, -NHR^5 or -NR^
3R^6, R^5 and R^6 each independently represent an aliphatic group, aromatic group or heterocyclic group, n represents an integer from 0 to 2, and when n is 2, L is They may be the same or different, and x, y, and z are each independently −
CR^7= or -N=, and R^7 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group. (3) The silver halide color photographic material according to claim (1), wherein the compound represented by the general formula [I] is represented by the following general formula [IV] or [V]. General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. L represents a group that releases the moiety bonded to L after being separated from A, R^2 represents a development inhibitor group or its precursor group, and R^4 represents - OH-,-NHSO_3R^5,-NHSO_2NR
^5R^6, -NH_2, -NHR^5 or -NR^
5R^6, R^5 and R^6 each independently represent an aliphatic group, aromatic group or heterocyclic group, n represents an integer from 0 to 2, and when n is 2, L is They may be the same or different, and x, y, and 2 are each independently -
CR^7= or -N=, and R^7 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group. (4) The silver halide color photographic material according to claim (1), wherein the compound represented by the general formula [I] is represented by the following general formula [VI] or [VII]. General formula [VI] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ General formula [VII] In the formula, A represents a group that reacts with the oxidized developing agent to release a portion of (L)_n or less, and L is from A. Represents a group that releases the moiety bonded to L after separation, R^3 represents a development inhibitor group or its precursor group, R^4 represents -OH-, -NHSO_2R^5, -NHSO_2NR
^5R^6, -NH_2, -NHR^5 or -NR^
5R^6, R^5 and R^6 each independently represent an aliphatic group, aromatic group or heterocyclic group, n represents an integer from 0 to 2, and when n is 2, L is They may be the same or different, and x, y, and z are each independently -
CR^7= or -N=, and R^7 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group.