JPH0220864A - Silver halide photographic sensitive material containing novel coupler - Google Patents

Abstract

PURPOSE:To improve the graininess of the title material by incorporated at least one kind of coupler selected from two kinds of specified phenol type cyan couplers and at least one kind of specified colorless cyan couplers in at least one layer of the photosensitive material, respectively. CONSTITUTION:At least one kind of the phenol type cyan coupler selected from the group comprising said coupler having a group shown by formula I at 2-position and R1-SO2-R2-CONH- group at 5-position of a benzene nucleus and said coupler having a group shown by formula II at 2-position and a group shown by formula III at 5-position of a benzene nucleus, and at least one kind of the colorless cyan coupler shown by formula VI, are incorporated in at least one layer of the photosensitive material. In formulas I-IV, R1 is alkyl group, etc., R2 is alkylene group, R3 is a substituting group, (n) is an integer of 1-4, R11 is alkyl group, etc., R15 is alkyl group, etc., R16 and R17 are each hydrogen atom, etc., R12 is trivalent straight chain hydrocarbon group, R13 is a branched alkyl group, etc., R14 is alkyl group, etc., R4 is alkyl group, etc., R5 is hydrogen atom, etc. Thus, the graininess of the photosensitive material is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material U It with improved graininess.

[Prior Art] Generally, a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material) consists of a red-sensitive silver halide emulsion layer containing a cyan coupler and a green-sensitive silver halide emulsion containing a magenta color-forming coupler on a support. It has a blue-sensitive silver halide emulsion layer containing a yellow coloring coupler and an antihalation layer, an intermediate layer, a filter layer, a protective layer, etc. as required.

With regard to recent photosensitive materials, on the one hand, users' demands for image quality have increased, and on the other hand, progress has been made toward smaller formats. For this reason, higher quality images are desired than ever before, and many efforts have been made to achieve this goal.

To improve graininess, for example, German patent 1.12
No. 1470 and British Patent No. 923.045 disclose that the silver halide emulsion layer is separated into a high-speed silver halide emulsion layer and a low-speed silver halide emulsion layer containing a dye image-forming coupler that develops substantially the same hue. It is stated that sensitivity can be increased without deteriorating graininess by applying multilayer coating and further adjusting the maximum coloring density of the high-sensitivity silver halide emulsion layer to a low value.

However, in the above method, the oxide of the para-phenylenediamine color developing agent generated by the development of coarse silver halide grains in the exposed high-sensitivity silver halide emulsion layer is The dye does not remain there and diffuses to the adjacent low-speed silver halide emulsion layer with a higher coupler density, forming conspicuously granular dye masses there, resulting in a drawback that the effect of improving graininess is reduced.

Also, Japanese Patent Publication No. 49-15495 and Japanese Unexamined Patent Publication No. 53-1989
No. 7230 discloses that a medium-sensitivity silver halide emulsion layer having a low coloring density and a medium-sensitivity silver halide emulsion layer containing a DIR compound are provided between a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer. It describes how to apply the coating.

However, this method has the disadvantage that the film becomes thicker and the amount of silver inevitably increases, resulting in poor sharpness, poor desilvering performance, and higher cost.

Furthermore, JP-A-57-155536 discloses a non-photosensitive silver halide emulsion layer containing a dye image-forming coupler between a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer that are sensitive to substantially the same spectral region. By providing an intermediate layer,
It is stated that a photosensitive material with high sensitivity and excellent graininess can be obtained.

However, even with this method, deterioration in sharpness cannot be avoided due to the increased film thickness.

As mentioned above, various efforts have been made to improve graininess, but the current situation is that they are still insufficient.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material with improved graininess.

[Structure of the Invention] The above object of the present invention is that at least one of the photosensitive silver halide emulsion layers on the support has R+ -3○2 at the 2-position.
Phenolic cyan coupler having an R2-CONH- group and a phenol having an R+4-802-R+2CONH- group at the 2-position
13 At least one of at least one monoru cyan coupler
The present invention has been achieved by providing a silver halide photographic material containing at least one colorless cyan coupler represented by the following formula [I].

(In the above groups, R1 is an alkyl group, aryl group or heterocyclic group, R2 is an alkylene group, R3 is a substituent, n
represents an integer of 1 to 4, and when n is 2 to 4, each R3 may be the same or different.

R11 is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, -OR+6
, -SR+s, -00OR+s, -NR+sC
OR+s, -(NR+e)1-8O2R1s, -Co(
0) I R+s, -3O2NR+sR+7:11. or a nitro group, R15 is an alkyl group, alkenyl group, cycloalkyl group, or aryl group, R16 and R17 are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and RI2 is a trivalent chain. RI3 is a branched alkyl group or alkenyl group, R14 is an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, IIG, t
represents an integer from o to 3, and when l is 2 or more, each R11 may be the same or different. Further, 2 represents O or 1. ) [wherein R4 represents an alkyl or aryl group,
R5 represents a hydrogen atom or an alkyl group. The total number of carbon atoms of R4 and R5 is 10 or more.

2 represents a phenyl group. ] The present invention uses a combination of specific cyan couplers to improve cyan graininess, which cannot be predicted from the performance of each coupler alone.

The present invention will be explained in more detail below.

A phenolic cyan coupler having the following and having an R+ -802R2-CONH- group at the 5-position will be described.

Examples of the alkyl group represented by R1 include linear or branched polygroups such as methyl, propyl, t-amyl, octyl, dodecyl, hexadecyl, octadecyl, and 1-methyl-heptadecyl, preferably carbon atoms. Numbers 1 to 20. The alkyl group represented by R1 is
Examples of such substituents include hydroxyl groups, carboxyl groups, cyano groups, aryl groups (such as tolyl groups), alkoxycarbonyl groups (such as hexadecyloxycarbonyl groups), and aryloxycarbonyl groups (such as hexadecyloxycarbonyl groups). For example, 1-lyloxycarbonyl group,
naphthyloxycarbonyl group), alkylsulfonamide group (e.g., methanesulfonamide group, etc.), acylamino group (e.g., acetamide group, etc.), alkoxy group (e.g., methoxy group, benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, etc.) , a sulfonyl group (methanesulfonyl group, etc.), and the like. Examples of the aryl group represented by R1 include phenyl group and naphthyl group, with phenyl group being preferred.

The aryl group represented by R1 includes those having a substituent, such as halogen atom (e.g. chlorine atom, bromine atom, etc.), hydroxyl, nitro, cyano, carboxyl, alkyl (e.g. methyl, ethyl,
t-butyl, t-amyl, dodecyl, octadecyl, etc.), alkoxy groups (e.g., methoxy, butoxy, dodecyloxy, etc.),
Alkylcarbonylamino groups (e.g., undecylcarbonylamino groups, etc.), arylcarbonylamino groups (e.g., benzoylamino groups, etc.), alkylsulfonamide groups (e.g., dodecylsulfonamide groups, etc.), arylsulfonamide groups (e.g., benzenesulfonamide groups, etc.) ),
Alkylaminosulfonamide group (e.g. dimethylaminosulfonamide group etc.), arylaminosulfonamide group (e.g. anilinosulfonamide group etc.), alkylcarbamoyl group (e.g. hexadecylcarbamoyl group etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group etc.) etc.), sulfonyl groups (eg, methylsulfonyl group, etc.), alkoxycarbonyl groups (eg, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group, etc.), and the like. Preferably, the heterocyclic group represented by R1 is a 5- or 6-membered heterocyclic group, and examples of the 5-membered ring group include a thienyl group, a pyrrolyl group, a furyl group, a thiazolyl group, an imidazolyl group, and a pyrazolyl group. , succinimide group, triazolyl group, tetrazolyl group, etc. Examples of the six-membered ring group include pyridyl group, pyrimidinyl group, triazinyl group, thiadiazinyl group, dithiazinyl group, and the like. These heterocyclic groups further include those forming a condensed ring with another ring (for example, benzene ring), such as purinyl group, imidazolyl group,
Examples include a benzoxacylyl group, a benzimidazolyl group, a quinolyl group, an indolyl group, and a phthalimide group.

These heterocyclic groups include those having a substituent, and examples of the substituent include the same substituents as those of the group when R1 is an alkyl group or a phenyl group.

The alkylene group represented by R2 preferably has 1 carbon atom.
~24 alkylene groups (e.g. -CH2--(CH2)
3- -CH-12H25 CH3 also included.

Specific examples of this substituent include halogen atom, cycloalkyl, aryl, heterocycle, sulfonyl, sulfinyl, carbamoyl, sulfamoyl, cyano, hydroxyl, alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, nitro, and alkyl. Eight groups include carbonyl, arylcarbonyl, acylamino, amino, sulfonamide, imide, sulfo, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, and aryloxycarbonylamino.

Among them, preferred substituents are an alkylcarbonyl group and an alkoxycarbonyl group.

Among these combinations of R1 and R2, R1 has 1 carbon atom
It is an alkyl group having 2 to 18 carbon atoms, and R2 has 2 to 1 carbon atoms.
It is preferable that it is a branched alkylene group with R2
It is preferable that 10HR- (R is an alkyl group having 1 to 9 carbon atoms).

Examples of the substituent represented by R3 include a halogen atom (
(e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups having 1 to 20 carbon atoms (e.g., methyl, hexyl,
8 groups such as dodecyl, octadecyl, and eicosyl groups), aryl groups (e.g., 8 groups such as phenyl and naphthyl groups),
Alkoxy groups (e.g. 8 groups such as methoxy, ethoxy, dodecyloxy, etc.), aryloxy groups (e.g. 8 groups such as phenoxy, 2,4-di[-aminophenoxy, naphthoxy), alkylthio groups (e.g. ethylthio groups), arylthio groups (e.g., phenylthio groups, etc.)
, alkylcarbonyl group (e.g., acetyl group, etc.), arylcarbonyl group (e.g., 4-me-1-xybenzoyl group, etc.), alkylsulfonamide group (e.g., methanesulfonamide group, etc.), arylsulf, phonamide group (
For example, p-tolylsulfonamide group, etc.), alkylsulfamoyl group (for example, dimethylsulfamoyl group, etc.), arylsulfamoyl group (for example, phenylsulfamoyl group, etc.), acylamino group (for example, acetamide group, etc.), 8 groups such as benzamide group), alkylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulf, inyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxyl group, carboxyl group, amino group, nitro group, cyan group, heterocyclic group, etc.

The substituent represented by R3 is preferably a chlorine atom, particularly preferably when it is bonded to the p-position with respect to the ureido group. In this case, the cyano group is preferably bonded to the l-position with respect to the ureido group.

group and R14-S O2R120ON H at the 5th position
In the phenolic cyan coupler having - group, R
The alkyl group and alkenyl group represented by lt, Rn, Rye, Rye, and R+7 may be linear or branched, and are preferably alkyl groups having 1 to 20 carbon atoms (for example, methyl, isopropyl, )-butyl, octadecenyl, dodecyl, eicosyl, etc. 8 groups)
It is.

R++, R++, RI5. The cycloalkyl group represented by each of Rye and R17 is preferably 5- to 6-membered.

Examples of the aryl group represented by Rlt, R14, Rls, Rls and R17 include phenyl and naphthyl groups, with phenyl being preferred.

The heterocyclic group represented by each of R11 and R14 preferably has at least one nitrogen atom as a ring constituent atom, and also includes a fused ring with another ring such as a benzene ring.

The halogen atom represented by R11 is preferably a chlorine atom or a bromine atom.

R11, R++, Rye, Rye or R1? The alkyl group, alkenyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R3, and the 8 groups represented by R3 include those having a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, Halogen atom such as bromine atom: Alkyl group; Alkoxy group such as methoxy group; Carbamoyl group such as nidodecylcarbamoyl group; Sulfonyl group such as dodecylsulfonyl group Sulfamoyl group such as dimethylsulfamoyl group: Oxycarbonyl group such as methoxycarbonyl group M: carboxyl group: nitro group; sulfonamide group such as m-hydroxybenzenesulfonamide group: ureido group such as N,N-dimethylureido group, and the like.

Rlt is preferably a halogen atom or -8O2R15, and most preferably an alkylsulfonyl group.

The trivalent chain hydrocarbon group represented by R12 preferably includes those having 1 to 3 carbon atoms, especially -〇H
- is preferred.

The branched alkyl group represented by R+3 preferably has 1 to 20 carbon atoms, and is particularly preferably an isopropyl group.

Rn is preferably an alkyl group.

In the present invention, preferably the cyan coupler represented by the following formula [I-1] or [I-2] is a cyan coupler represented by the general formula [I-1].
] In the formula, R+, R2, Ra and n have the same meanings as those described above, and the same types are exemplified.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent.

- Formula [I-2] In the formula, Rlt, R+2. R+3. R14 and m have the same meanings as those described above, and the same ones can be exemplified.

X has the same meaning as shown in formula [1-11].

In the above-mentioned formulas [l-11 and [l-21], specific examples of 8 groups such as arylamino), azo groups, aryloxy groups (e.g. p-
methoxyphenoxy, p-butanesulfonamidophenoxy, p-carboxyphenoxy, etc.), alkoxy groups (e.g., methoxy, 2-methoxyethoxy, etc.), arylthio groups (e.g., phenylthio, p-carboxyphenylthio, etc.) ), alkylthio groups (e.g. 8 groups such as methylthio and 2-hydroxyethylthio), heterocyclic thio groups (e.g. 8 groups such as 1-ethyltetrazole-5-thioyl and 2-pyridylthio), heterocyclic groups (e.g. 1 -pyrazolyl, 1-imidazolyl, 2,5-pyrazolinedione-1-yl, etc.), a carboxyl group, a sulfo group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, and the like.

Next, specific examples of the phenolic cyan coupler according to the present invention are shown below, but the present invention is not limited thereto.

The following margins The above phenolic cyan couplers are, for example,
Patent WA (5) filed by the present applicant on June 29, 1988, title of invention "Silver halide color photographic light-sensitive material" 1 Inventor: Norio Miura (and 2 others) and filed on July 1, 1986 It can be synthesized based on the description in the specification attached to Patent Application (2) 2 Invention Title: "Silver Halide Color Photographic Light-sensitive Material" 9 Inventor Shuji Nikita (and 2 others) filed by the present applicant.

The colorless cyan coupler represented by the general formula [II] is one in which the coupler itself is colorless.

In the general formula [II], R4 represents an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.) or an aryl group (e.g., phenyl group, naphthyl group, etc.). The group represented by R4 above includes those having a substituent, and preferred substituents include the following groups.

That is, halogen atoms (e.g. atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyano groups, alkyl groups (e.g. methyl groups, ethyl groups, propyl groups, 1so-
Propyl group, butyl group, is.

-butyl group, 5ec-butyl group, tert-butyl group,
Pentyl group, 1so-pentyl group, 5ec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1so-
dodecyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.), fluorinated alkyl group (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group (For example, methoxy group, ethoxy group, propyloxy group, 1so-propyloxy group, butoxy group, 1so-
Butoxy group, 5ec-butoxy group, tert-butoxy group, pentyloxy group, 1so-pentyloxy group,
tert-pentyloxy group, dodecyloxy group, etc.),
Aryloxy groups (e.g., phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxycarbonyl group (e.g., ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g. acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.), alkylamino group (e.g., ethylamino group, dimethylamino group, jetanolamino group, dodecylamide LL hexadecylamino group, etc.), aryl Amino groups (e.g., anilino group, naphthylamino group, etc.), alkylcarbamoyl groups (e.g., ethylcarbamoylcarbamoyl group (e.g., phenylcarbamoyl group, etc.)
, acylamino group (e.g. methanamide group, dodecanamide group, hexadecaneamide group, penzamide group, etc.),
Acyl groups (e.g. benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio groups (e.g. methylthio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl groups (e.g. methylsulfonyl group, ethyl sulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.), alkylsulfamoyl group (e.g. ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N.N-dimethylsulfamoyl group, etc.)
, an alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, 0-dodecylphenylsulfonamide group, etc.),
Examples include arylsulfonyl groups (eg, phenylsulfonyl groups, etc.).

R4 is preferably an alkyl group, more preferably an alkyl group substituted with a phenoxy group. R5 represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, an octyl group, a dodecyl group, etc.), and the alkyl group represented by R5 includes those having a substituent, and is preferable. As a substituent, the above-mentioned R
4 substituents are mentioned. R5 is preferably a hydrogen atom. However, the total number of carbon atoms including the substituents of R4 and R5 is 10 or more.

2 represents a phenyl group, and the phenyl group represented by Z includes those having substituents as shown below.

That is, halogen atoms (for example, chlorine atoms, etc.), nitro groups,
Acylamino group (e.g. methanamide group, ethanamide group, propaneamide group, butaneamide group, hexaneamide group, octaneamide group, dodecanamide group, benzamide group, etc.), alkylsulfonamide group (e.g. methanesulfonamide group, ethanesulfonamide group) , propanesulfonamide group, hexane sulfonamide group, octane sulfonamide group, dodecane sulfonamide group, etc.),
Arylsulfonamide groups (e.g. benzenesulfonamide group, naphthalenesulfonamide group, etc.), carbamoyl groups (e.g. methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoylurbamoyl group, etc.), sulfamoyl groups (e.g. Nmethylsulfamoyl group, N -ethylsulfamoyl group, N-
Butylsulfamoyl group, N-octylsulfamoyl group, N. N-dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylureido groups (e.g. methylureido group, ethylureido group, etc.), arylureido groups (e.g. phenylureido group, naphthylureido group, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, octyl group, dodecyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, propyloxy group, butyloxy group, octyloxy group, dodecyloxy group, etc.),
Amino M (e.g. methylamim L ethylamino group, propylamino group, butylamino L octylamino group, dodecylamino group, dimethylamino group, diethylamino group,
anilino group, acetylamino group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonylcarbonyl group, etc.), or aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), arylsulfonyl group (for example, phenylsulfonyl group, etc.), and formyl group.

In the present invention, it is preferable that the phenyl group represented by Z is 4-substituted with at least one acylamim L° alkylsulfonamide group or arylsulfonamide group, and furthermore, at least one of the 8 groups listed above is Particularly preferred is the case where the compound is substituted with 2 carboxyl groups.

A preferred embodiment of the naphthol-based cyanobyl compound represented by the general formula [II] of the present invention is as follows - Formula % Formula % In the formula, R4 is substituted (preferably replaced with a phenoxy group) or unsubstituted. represents an alkyl group having 10 or more carbon atoms, Rb represents an acylamino group, an alkylsulfonamide group, or an arylsulfonamide group; R'bG
．． Represents the same group as tRb or the group shown below.

That is, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, nitro group, cyano group, alkyl group (e.g. methyl group, ethyl group, propyl group,
iso-propyl group, butyl group, SO-butyl group, se
c-butyl group, tert-butyl group, pentyl group, is
o-pentyl group, sec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, iso-dodecyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group) etc.), fluorinated alkyl groups (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl groups (e.g.)
alkoxy groups (e.g. methoxy group, ethoxy group, progyloxy group, iso-prooxyl group, butoxy group, iso-butoxy group, se
c-butoxy group, tart-butoxy group, pentyloxy group, iso-pentyloxy group, tert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxy group Carbonyl groups (e.g., ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl group, etc.), alkylacyloxy groups (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy groups (e.g., benzoyloxy group, etc.) groups), alkylamino groups (e.g. ethylamino group, dimethylamino group, jetanolamino group, dodecylamino group, hexadecylamino group, etc.), arylamino groups (e.g. anilino group, naphthylamino group, etc.), alkylcarbamoyl group (e.g. ethylcarbamoyl group, carboxyethylcarbamoyl group, dodecylcarbamoyl group, etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group, etc.),
Acylamino group (e.g. methanamide group, dodecanamide group, hexadecanamide group, penzamide group, etc.), acyl group (e.g. benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.)
, alkylthio groups (e.g. methylthio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl groups (e.g. methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, decylsulfonyl group,
dodecylsulfamoyl group, etc.), alkylsulfamoyl group (e.g., ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.) ,
Alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-dodecylphenylsulfonamide group, etc.), arylsulfonyl group (e.g. phenylsulfonyl group, etc.)
etc. can be mentioned.

n represents an integer of 0 to 4, and when n is an integer of 2 to 4, R
' b may be the same or different.

Preferably, at least one group among R4, Rb N R' b contains at least one carboxyl group, and more preferably, Rb contains at least one carboxyl group. .

The cyan coupler represented by the general formula [I] is
It can be synthesized by the method described in No. 5239 and the like.

Specific compounds of the cyan coupler represented by the above-mentioned formula [I[] are illustrated below.
CHt(:OOH NHCH,(,"0(JH NO6 NH8O, CH3 NHCOCH, COOH (II-28) CsHo('1 NHCOCR.

(n-381 (It-41) (II-42) OCH, CI, C○0H NHCH,C(J(Jl-1 II CH.

[1 43] C2゜11□.

[1-55) Within the following margin "51.j" 1 NHCOCH, CH, Coo) I In the present invention, the phenolic cyan coupler according to the present invention and the naphthol cyan coupler represented by the general formula [II] are combined with silver halide. In order to incorporate it into the emulsion layer, a conventionally known method is used, for example, a mixture of a high boiling point solvent such as known dibutyl phthalate, tricresyl phosphate, dinonylphenol, etc. and a low boiling point solvent such as butyl acetate, propionic acid, etc. The couplers according to the present invention are dissolved individually or in combination, and then mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer, a colloid mill, or an ultrasonic dispersion machine. After that, it may be directly added to the emulsion, or the emulsified dispersion may be set, shredded, washed with water, and then added to the emulsion.

The content of the phenolic cyan coupler according to the present invention is usually 1.0 x 10 -3 mol to 1.0 mol, preferably 5.0 x 10 -3 mol per mol of silver halide. OX 10'mol-8
, OX 1Q' moles, and the above phenolic cyan couplers may be used alone or in combination of two or more.

The content of the cyan coupler represented by the general formula [I[] is usually 1.0×10 −5 mol to 1.0 mol, preferably 1.0×10 −5 mol to 1.0 mol per mol of silver halide. OX 10-4 mol ~ 8
．． It is in the range of 10-1 mol of OX. The cyan couplers represented by the general formula [I[] may be used alone or in combination of two or more.

The ratio of the phenolic cyan coupler according to the present invention to the cyan coupler represented by the general formula [I[] is 5/9.
The ratio is preferably 5 to 99.5/0.5, more preferably 15/85 to 99/1.

In the present invention, the phenolic cyan coupler according to the present invention and the cyan coupler represented by the general formula [II] are usually contained in a red-sensitive silver halide emulsion layer, but if necessary, other color-sensitive silver halide emulsion layers are included. It may be contained in the photosensitive hydrophilic colloid layer and/or the non-photosensitive hydrophilic colloid layer. In addition, when the red-sensitive silver halide emulsion layer consists of two or more layers, the number of layers (
If it is contained in both layers, the effects of the present invention can be obtained.

The phenolic and naphthol based cyan couplers of the present invention may be used in combination with other cyan couplers. That is, the red-sensitive silver halide emulsion layer containing the cyan coupler of the present invention may contain a cyan coupler and/or a colored cyan coupler other than the present invention. The layer containing cyan couplers and/or colored cyan couplers other than those of the present invention preferably accounts for less than 90 mol%, more preferably less than 70 mol%, of the total amount of cyan couplers in the emulsion layer.

The cyan coupler according to the present invention can be used together with a compound represented by the following formula [A].

- Formula [A] coup Ne(J-)-N=N-R In the formula, coup represents a cyan coupler residue, book represents a coupling site of the cyan coupler, J represents a divalent linking group, m represents O or 1, and R1 represents an aryl group.

The cyan coupler residues represented by coup include phenol couplers and differential coupler residues, and naphthol coupler residues are particularly preferred.

A preferable divalent linking group represented by J can be represented by the following general formula [8].

- Formula [8] represents -0-C-O-. R2 represents an alkylene group having 1 to 4 carbon atoms or an arylene group, R3 represents an alkylene group having 1 to 4 carbon atoms, and R2 and R3
The alkylene group represented by each of these may be substituted with J-substituted by an alkyl group or a sulfo group.

Z is -c-, -o-, -s-, -so--302
-, -302 NH-, -CONH - -COO-
-NHCO-, -NHSO2- or -OCO-, and R5 and R6 each represent an alkyl group or an aryl group.

R4 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonyl group,
It represents an alkoxy group, an aryloxy group, a carboxy group, a sulfo group, a halogen atom, a carbonamide group, a sulfonamide group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group.

p represents O or a positive integer, q represents 0 or 1, and r represents an integer from 1 to 4. When p is 2 or more, R
2 and 2 may be the same or different. When r is 2 or more, R4 may be the same or different.

The aryl group represented by R1 is preferably a phenyl group or a naphthyl group when m=Q. The phenyl group and naphthyl group can have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, and a 7J
Examples include ruboxyl group, alkoxycarbonylnyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group, alkylsulfonyl group, acyl group, acylamino group, sulfonamide group, carbamoyl group, and sulfamoyl group.

In Ill-1, the aryl group represented by R1 is preferably a naphthol group represented by the following formula [C].

In the formula, R7 is a linear or branched alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, S-butyl group, t-butyl group, etc.) , M is a photographically inert cation,
For example, hydrogen atoms, alkali metal cations such as sodium atoms and potassium atoms, ammonium, methylammonium, ethylammonium, diethylammonium,
It represents triethylammonium, ethanolammonium, jetanolammonium, pyridinium, piperidium, ammonium, toluidinium, D-nitroanilinium, anisidium, etc.

Next, specific examples of typical colored couplers represented by the above-mentioned formula [A] will be shown, but the invention is not limited thereto.

C-1 C-2 Margin below C-3 C-7 SO, Na C-9 H cc-t.

CC-13 CC-11 CC-14 CC-12 (77:'~ The following margin is "
No. 65957, No. 56-94347, Special Publication No. 1972-1
No. 1304, No. 44-32461, No. 48-1789
No. 9, No. 53-34733, U.S. Patent No. 3034.89
No. 2, British Patent No. 1,084,480, etc.

Examples of the high-boiling organic solvent used for dispersing the cyan coupler of the present invention include phenol derivatives that do not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, and fatty acid esters. An organic solvent having a boiling point of 150° C. or higher, such as trimesic acid ester or the like, is used.

In the present invention, U.S. Patent No. 2.322.027,
No. 2,533,514, No. 2,835,579, No. 3.287.134, No. 2.353.262, No. 2
, No. 852,383, No. 3.554755, No. 3.
676, No. 137, 3,676, 142, 3,
700.454, 3.748.141, 3
．． No. 779.765, No. 3,837,863, British Patent No. 958,441, No. 1.222753, OL 3
No. 2,538,889, Japanese Patent Application Publication No. 47-1031,
No. 49-90523, No. 50-23823, No. 51
-26037, 51-27921, 51-27
No. 922, No. 51-26035, No. 51-26036
No. 50-62632, No. 53-1520, No. 53-1521, No. 53-15127, No. 54
-119921, 54-119922, 55
-25057, 55-36869, 56-19
No. 049, No. 56-81836, Special Publication No. 48-290
High boiling point organic solvents such as those described in No. 60 can also be used.

Low-boiling or water-soluble organic solvents that can be used in conjunction with or in place of the above-mentioned high-boiling solvents include U.S. Pat.
, No. 171, No. 2,949,360, and the like. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol,
Acetonitrile, dioxane, dimethylformamide,
Examples include dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.

Examples of surfactants used as dispersion aids for couplers include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl sulfonates. Nonionic surfactants such as polyoxyethylene alkylphenyl ether, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids, and alkyl betaines. Preferred are amphoteric surfactants such as cationic surfactants such as quaternary ammonium salts, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in the “Surfactant Handbook” (Sangyo Tosho, 19
1966) and "Emulsifier, emulsifier research, technical data collection"
(Science Panronsha, 1978).

The silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention is a silver halide grain composed of two or more orders of magnitude different silver iodide content, and the average silver iodide A silver halide emulsion containing silver halide grains whose content is higher than the silver iodide content of the outer edge phase of the grains is preferred.

The fact that the average silver iodide content of the grains in the above silver halide emulsion is higher than the silver iodide content of the outer edge phase of the grains can be determined by the following method.

In other words, if the silver halide emulsion contains silver halide grains with an average value of grain size/grain thickness of less than 5, the average silver iodide content (Jl
) and the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship Jl>J2 is satisfied.

The particle size referred to here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

The above X-ray photoelectron spectroscopy was performed as follows.

XI! Prior to measurement by photoelectron spectroscopy, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and stirred at 40° C. for 1 hour to decompose gelatin. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions.

The sample is centrifuged again, the supernatant liquid is removed, and then distilled water is added to redisperse the emulsion particles in the distilled water, centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to use as a measurement sample.

For measurements using xsat photoelectron spectroscopy, a PH
Using ESCA/SAM 560 type manufactured by one company,
It is carried out under the conditions of M (J-K (X-ray), X-ray source voltage 15 KV, X-ray source current 4011 A, and pulse energy 50 eV.

A (13d) to determine the surface halide composition.

Br 3d , I 3d 3/2 electrons are detected. The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak. Aa 3d , Sr 3d , 13d3
/2 relative sensitivity coefficient of 5.10 respectively.

By using 0.81 and 4.592, the composition ratio is given in atomic percent.

When the silver halide emulsion used in the present invention contains grains having an average value of grain size/grain thickness of less than 5, it is preferable that the grain size distribution is monodisperse. A monodisperse silver halide emulsion is defined as ±20% around the average grain size γ.
The weight of silver halide contained within the grain size range is 60% or more of the total silver halide grains ff1ffi,
Preferably it is 70% or more, more preferably 80% or more.

Here, the average particle size γ is the frequency n of particles having particle size γi
It is defined as the particle size γ1 when the product nixγi3 of 1 and γi3 is the maximum (3 significant figures, the minimum digit is rounded down to 4 to 5).

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when its projected image is converted into a circular image of the same area.

The particle size can be obtained, for example, by enlarging the particle 10,000 to 50,000 times with an electron microscope, copying it, and actually measuring the particle diameter or projected area on the print (the number of particles measured is (Assume that there are at least 1000 items indiscriminately.)

Particularly preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

Here, the average particle diameter and particle diameter standard deviation shall be determined from γ1 defined above.

On the other hand, when the silver halide emulsion used in the present invention is a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more, the average silver iodide emulsion determined by the above-mentioned fluorescent X-ray analysis method is 80% from the center in the grain diameter direction of silver halide grains using the content (Jl) and X-ray microanalysis method.
When comparing the average value (J3) of the measured values of silver iodide content measured on silver halide crystals separated by more than % Jl > J3
It satisfies the following relationship.

The X-ray microanalysis method was performed as follows.

Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer in an electron microscope, and the magnification was set so that one particle entered the field of view of the CRT with liquid nitrogen cooling, and AgLα, AgLα, Integrate the intensity of 1mα rays. The silver iodide content can be calculated using the intensity ratio of ILα/AgLα and a previously prepared calibration curve.

In tabular silver halide emulsions in which the average value of grain size/grain thickness is 5 or more, the average value of grain size/grain thickness is more preferably 6 or more and 100 or less, particularly preferably 7 or more and 50 or less.

In a silver halide emulsion in which the average value of grain size/grain thickness is less than 5, the silver iodide content (J2) on the grain surface measured by X-ray photoelectron spectroscopy is preferably 6 to 0 mol%, and more preferably It is preferably 5 to 0 mol%, particularly preferably 4 to 0.01 mol%.

Silver halide grains separated from the center by 80% or more in the grain diameter direction as determined by X-ray microanalysis in a tabular silver halide emulsion with an average grain size/grain thickness of 5 or more. The average value (J3) of the silver iodide content measured on the crystal is preferably 6 to 0 mol%, more preferably 5 to 0 mol%, particularly preferably 4 to 0.01. It is mole%. The average thickness of the tabular silver halide grains is preferably 0.5 to 0.01 .mu.m, particularly preferably 0.3 to 0.05 .mu.m. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 30 μm, more preferably 1.0 to 20 μm.

The silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of less than 5 is preferably monodisperse, and is preferably of core/shell type. The tabular silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of 5 or more preferably has silver iodide localized in the center of the grains.

A core/shell type silver halide emulsion with an average value of grain size/grain thickness of less than 5 has a grain structure composed of two or more phase layers with different silver iodide contents. The phase having the highest content (referred to as the core) consists of silver halide grains other than the outermost layer (referred to as the shell).

The inner phase (core) having the highest silver iodide content may preferably have a silver iodide content of 6 to 40 mol%, more preferably 8 to 30 mol%, particularly preferably 10 to 20 mol%.
It is mole%. The silver iodide content of the outermost layer is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The ratio of the shell portion of the core/shell type silver halide grains is preferably 10 to 80% by volume, more preferably 1
It is 5 to 70%, particularly preferably 20 to 60%.

In addition, the core portion accounts for 10 to 80% of the total particle volume.
%, more preferably 20 to 50%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. Also preferably used is one having an intermediate layer between the core and the shell having a silver iodide content between the core and the shell.

In the case of core/shell type silver halide grains having the intermediate layer, the volume of the intermediate layer is preferably 5 to 60%, more preferably 20 to 55%, of the entire grain. The difference in silver iodide content between the shell, intermediate layer, and core is preferably 3 mol % or more, and the difference in silver iodide content between the shell and core is preferably 6 mol % or more.

The core/shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

Core/shell type silver halide emulsion is disclosed in JP-A-59-177.
535, 60-138538, 59-52238,
60-143331, 60-35726 and 60
It can be manufactured by a known method disclosed in Japanese Patent No.-258536 and the like.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A No. 60-138538, it is possible that the center of the grain has a halogen composition region different from that of the core. It's possible.

In such cases, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, silver chloride, etc., but if the silver iodide content is Silver iodobromide or silver bromide of 10 mol % or less is preferred.

The proportion of the seed grains in the total silver halide is 50% by volume.
% or less, particularly preferably 10% or less.

The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or using X-ray diffraction.

The core/shell type silver halide grains may be normal crystals such as cubes, tetradecahedrons, and octahedrons, may be composed of twin crystals, or may be a mixture of these, but it is preferable that they be normal crystals. preferable.

In a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more and silver iodide is localized in the center of the grain, the high iodine content phase in the center covers the entire grain volume. It is preferably 80% or less, particularly preferably 60% to 10%. The silver iodide content in the center is preferably 5 to 40 mol%, particularly 10 to 40 mol%.
30 mol% is preferred. The low iodine content phase (periphery) surrounding the high iodine content phase in the center has a silver iodide content of 0 to 10.
Preferably it consists of silver iodobromide in mole %, more preferably from 0.1 to 6.0 mole %.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method such as that disclosed in JP-A-59-99433.

In the silver halide color photographic material of the present invention, the average silver iodide content of all the silver halide emulsions in the silver halide photographic material is preferably 0.1 to 15 mol%, more preferably 0.5 to 12 mol%,
Particularly preferred is 1 to 6 mol%.

In the present invention, the average grain size of all the silver halide emulsions in the silver halide color light-sensitive material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm, particularly preferably 0.2 to 0.0 μm. .6 μm.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride as silver halides. Any emulsion commonly used in silver halide emulsions such as silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

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

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be added simultaneously at a pH of 1+1A (l) in a mixing pot. Silver halide grains are obtained that are regular in shape and nearly uniform in grain size.Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the grains.

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

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

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1
This can be carried out based on the method described in Section 2 of No. 17643 (hereinafter abbreviated as RD).

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (1oo) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

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

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

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

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

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

In the present invention, the lower limit of the total dry film thickness of all the hydrophilic colloid layers (hereinafter referred to as the film thickness on the emulsion side) of the silver halide color photographic light-sensitive material is the silver halide emulsion, coupler, oil agent, additives, etc. The preferred film thickness on the emulsion surface is 5 μm to 18 μm, more preferably 10 μm.
uffl~16 μm. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is different from the emulsion layer in color sensitivity and closest to the support is 10 μm. The following are preferred.

As a method for thinning a photosensitive material, there is a method of reducing the amount of hydrophilic colloid that is a binder. The purpose is to retain coupler minute oil droplets etc. dissolved in silver halide and high boiling point solvent, to prevent fog from increasing due to mechanical stress, and to prevent color turbidity due to diffusion of oxidized developing agent between layers. Because hydrophilic colloids are added, the amount can be reduced within a range that does not impair the purpose.

Another method for thinning the layer is to use highly chromogenic couplers.

As a highly chromogenic coupler advantageously used in the present invention, 2
Equivalent couplers are mentioned. For example, JP-A-52-115
2-equivalent yellow coupler described in No. 219 and No. 54-12338, JP-A-53-123129 and No. 55
2-equivalent magenta coupler described in JP-A-118034, JP-A-53-105226, JP-A-54-1473
A 2-arm Russian coupler described in No. 6 is used. Furthermore, examples of highly color-forming couplers that can be advantageously used in the present invention include polymer couplers.

For example, Japanese Patent Publication No. 46-22513, U.S. Patent No. 3,76
Polymer couplers described in US Pat. No. 7.412, US Pat.

Other methods for thinning the layer include reducing the amount of high-boiling solvent;
Examples include a method of thinning the intermediate layer by adding a scavenger of an oxidized developing agent to the intermediate layer between layers having different color sensitivities.

In the present invention, the total amount of silver halide contained in the light-sensitive silver halide emulsion contained in all the emulsion layers of the silver halide color photographic light-sensitive material is preferably 15 g/12 or less,
More preferably 2.5 to 12.01 J/12, more preferably 3.0 to io, o g7. ==1, particularly preferably 3.5 to 8.0 CI/l''.

The amount of silver halide can be determined by a fluorescent X-ray method, and the amount of silver halide is expressed in terms of silver.

In the present invention, the silver halide color photographic light-sensitive material is preferably stored at a relative humidity of 55% or less.

In the present invention, sealed packaging is preferred as a method for preserving the product at a relative humidity of 55% or less.

Sealed packaging as used in the present invention refers to moisture-proof packaging that is well known in the field of ordinary packaging.

Packaging materials include metals and metal foils such as aluminum plates, tin plates, and aluminum foils, glass or polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, and polyamide, various polymers, cellophane, and paper. , composite laminated materials (laminated materials in packaging terminology) made of materials such as aluminum foil are used.

Sealing methods include adhesive methods using various adhesives,
A thermal fusion method such as heat sealing, or a method using a cartridge case, which is common in the photographic industry, can be used. Details of these sealing methods are described in "Food Packaging Technology Handbook" edited by Japan Packaging Technology Association, pages 573 to 609.

The above-mentioned silver halide photographic light-sensitive material stored at a relative humidity of 55% or less is defined as the heavy IW+"" measured within 30 seconds after opening the silver halide photographic light-sensitive material at 25° C. and 55% relative humidity under the same conditions. Man constant L/ta weight f stored for days
fi W 255 (7) Difference ΔW 55= W 25
5-W155 is defined as being greater than or equal to zero.

The preferred conditions of the present invention are tl at 25°C and 30% relative humidity.
Ifi change ΔW30 becomes negative, and more preferable conditions are that weight change ΔW35 at 25°C and relative humidity 35%.
becomes negative.

In the present invention, a cartridge case made of a polymeric material such as polyethylene or polypropylene is preferable for a roll-type projection light-sensitive material, and a cartridge case made of a heat-sealed polyethylene or the like is preferable for a sheet-type photosensitive material.

These sealed packagings may be done in duplicate.

As a method of packaging by lowering the relative humidity as described above,
The silver halide photographic light-sensitive material may be packaged in a low-humidity room, the material may be dried more dry than usual, or a desiccant such as silica gel may be placed in the sealed container. The humidity may be lowered.

In the present invention, the total hydrophilic protective colloid layer coated on the emulsion layer side on the support of the silver halide color photographic light-sensitive material has a swollen film thickness during development of 180% to 350% of the dry film thickness. It is preferable that it is, particularly preferably 200
% to 300%.

Techniques for adjusting the swollen film thickness are well known to those skilled in the art, and can be achieved, for example, by appropriately selecting the range and type of hardening agent.

Hardeners used in the silver halide photographic light-sensitive material of the present invention include aldehyde-based and aziridine-based hardeners (for example, PB
Report, 19,921, U.S. Patent No. 2950197, U.S. Patent No. 2.964.404, U.S. Patent No. 2.983.611
No. 3.271.175, each specification, Special Publication No. 4
6-40898 and JP-A-50-91315), isoxazole-based (e.g., those described in U.S. Patent No. 331609), epoxy-based (e.g., U.S. Patent No. 3, No. 047,394, West German Patent Box No. 1.085663, British Patent Box No. 1,033,518
(described in the specifications of Japanese Patent Publication No. 4B-35495), vinyl sulfone type (for example, PB Report 1)
9.920, West German Patent No. 1,100,942, 2.
No. 337.412, No. 2, No. 545.722, No. 2,
No. 635,518, No. 2.742.308, No. 2.
No. 749.260, British Patent Box No. 1,251,091;
Patent application No. 45-54236, No. 48-110996,
U.S. Patent No. 3,539,644, U.S. Patent No. 3.490.9
11), acryloyl type (for example, Japanese Patent Application No. 48-27949, U.S. Pat. No. 3,64
0,720), carbodiimides (for example, U.S. Patent Nos. 2,938,892, 4,043,818, and 4,061,499), Special Publication No. 46-38715, Patent Application No. 1973
-15095), triazine-based (
For example, West German Patent No. 2,410,913, West German Patent No. 2.55
3.915, U.S. Patent No. 3.325.287, Mei IB books, and JP-A-52-12722)
, polymer type (for example, the specifications of British Patent Box No. 822,061, U.S. Patent No. 3.623878, U.S. Patent No. 3.396.029, and U.S. Patent No. 3,226,234, Japanese Patent Publication No. 1986-1
8578, No. 18579, and No. 47-48896), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and (N-methylol-based) hardening agents singly or in combination. Can be used. As a useful combination technique, for example, West German Patent Tube 2.44
7.587, 2.505γ46, 2,514,
No. 245, U.S. Patent No. 4.047.957, U.S. Patent No. 3.8
Specifications of No. 32.184 and No. 3.840.370,
Combinations described in JP-A No. 48-43319, JP-A No. 50-63062, JP-A No. 52-127329, and JP-A No. 48-32364 are exemplified.

In the present invention, the swollen film thickness during development is defined as the thickness after immersion for 3 minutes in the following solution kept at 38°C.

[Solution for measuring degree of swelling] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) Aniline/Sulfur M salt 4.75g Anhydrous sodium sulfite 4.25Q Hydroxylamine/1/21i Itl salt 2 ．． Oq anhydrous potassium carbonate 37.5 (sodium monobromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 [1
Potassium hydroxide 1.0g Add water to make 12.

The swelling film thickness can be measured by, for example, A. Green and G. I. B. Levenson, Journal on Photographic Science (J, Photo
, Sci, ), 20. 205 (197
2) Can be measured by the method described.

The dry film thickness means the film thickness measured at 23° C. and 55% humidity. Also, 11 each! Regarding the J thickness, the cross section of the dried sample is enlarged with an operating electron microscope and the film thickness of each layer is measured.

The above-mentioned total hydrophilic protective colloid layer includes at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, a protective layer coated as necessary,
It includes an antihalation layer, a yellow filter layer, an intermediate layer, etc.

The layer structure of a silver halide color photographic light-sensitive material that can particularly exhibit the effects of the present invention is as follows: from the support, a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate Ji), a green-sensitive layer (intermediate layer), and a colloidal silver yellow layer. Filter layer Blue-sensitive layer (intermediate layer) Coated with protective layer, and further sequentially from the support: Colloidal silver antihalation layer (intermediate layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (intermediate layer) Blue-sensitive layer (intermediate layer) layer) red-sensitive layer (
Intermediate rrz > green sensitive layer (colloidal silver yellow filter layer)
It has a layer structure in which a blue-sensitive layer (intermediate layer) and a protective layer are coated.

Note that the layers in parentheses may be omitted. It is preferable that each of the red-sensitive layer, green-sensitive layer and blue-sensitive layer is divided into a low-sensitivity layer and a high-sensitivity layer.

In addition, at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer as described in Japanese Patent Publication No. 49-15495 is
A layer structure divided into two partial layers, a layer structure separated into a high-sensitivity emulsion layer unit and a low-sensitivity emulsion layer unit as described in JP-A-51-49027, and 2.62 for West German Publication No.
No. 2.922, No. 2,622,923, No. 2, 6
22.924, 2.704.826 and 2
．． Examples include a layer structure as described in No. 704797.

In addition, in the present invention, JP-A No. 57-177551,
It is also possible to apply the layer configurations described in the respective publications of No. 59-177552 and No. 59-180555.

The silver halide photographic light-sensitive material of the present invention may contain, in addition to the cyan coupler according to the present invention, cyan couplers, magenta couplers, yellow couplers, etc. other than the present invention.

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

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

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Pat.
No. 5,057, same no.

3.265,506, 3.408.194, 3,551,155, 3.582.322,
No. 3,725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2,2
No. 19,917, No. 2,261,361, No. 2,41
4゜006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-73147, Japanese Patent Publication No. 50-6341, Japanese Patent Publication No. 50-8
No. 7650, No. 50-123342, No. 50-13
No. 0442, No. 51-21827, No. 51-102
No. 636, No. 52-82424, No. 52-11521
No. 9, No. 58-95346, etc.

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

Specific examples of magenta coloring couplers that can be used include, for example, U.S. Pat. Nos. 2,600,788 and 2,983,608
No. 3,062,653, No. 3,127,26
No. 9, No. 3.311.476, No. 3,419,3
No. 91, No. 3,519,429, No. 3,558,
No. 319, No. 3,582,322, No. 3.615
．． No. 506, No. 3,834,908, No. 3,89
No. 1,445, West German Patent No. 1.810.464, West German Patent Application (OLS) No. 2.408,665, West German Patent No. 2.41
No. 7,945, No. 2,418,959, No. 2,42
No. 4,467, Japanese Patent Publication No. 1973-6031, Japanese Patent Application Publication No. 1973-
No. 74027, No. 49-74028, No. 49-129
No. 538, No. 50-60233, No. 50-1593
No. 36, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 5
Examples include those described in Japanese Patent Application No. 3-55122 and Japanese Patent Application No. 110943/1983.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are made by using one or more hardeners to crosslink binder (or protective colloid) molecules and increase film strength. Can be hardened. The hardening agent can be added in an amount capable of hardening the light-sensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are A of Section X of RD 17643.
It is a compound described in .

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

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, Polymers containing combinations of methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. as the vehicle body components can be used.

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

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

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

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

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

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

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators include RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

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

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include bilayer silicon, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate. and styrene polymers and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount of water added is preferably 1 to 300 ma/f.

Slip a! for photosensitive materials! Lubricants can be added to reduce chafing.

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

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

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

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

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

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

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric esters, and phosphoric esters, and amphoteric surfactants such as sulfuric acid or phosphoric esters of amino acids, amino sulfonic acids, and amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process or a stabilization process.) Color development process - bleaching process Constant color fixing process ・Color development image process - bleaching and fixing Processing process / Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process - Fixing process - Washing process - Post-hardening process / Color development process - Washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Processing temperature is usually 1o. It is selected in the range of ℃~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

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

These compounds are generally about 0.0% per color developer.
A concentration of 1 to 30a is used, more preferably a concentration of about 1 to 15a for color developer 1y. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the above amine phenol developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-〇-phenylenediamine hydrochloride, 2- Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Lm M salt, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-
Examples include diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like.

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

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

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

E)H of the color developing solution used in the present invention is usually 7 or more, preferably about 9-13.

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

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

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

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

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches have a concentration of 5 to 450 (1/ffi, more preferably 20
Use at ~250Q/fl.

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

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349@, etc. can be added.

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

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with halogen and silver oxide to form water-soluble complex salts, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, and thiocyanic acid, are used as fixing agents. Typical examples include thiocyanates such as potassium, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5a/1 or more, within a range where they can be dissolved, but are generally used in an amount of 70 to 2500/ffi. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.1) H buffering agents may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as droxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols, nitrate M salts, and water-soluble aluminum salts. A hardening agent, an organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained.

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

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

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

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent, the I)H buffer that can be contained in the bleach-fixing solution, and other additives are the same as in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.0.
5, most preferably 6.5 to 8.5.

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

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

Example 1 Multilayer color photographic element sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) 1st layer: Antihalation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1
) 0.20 colored coupler (CC-1
) 0.05 colored coupler (CM-2)
0.05 high boiling point organic solvent (Oil -1)
0.20 gelatin 1.5
2nd layer; Intermediate layer (1, L, -1) U■ Absorbent (UV-1) 0.01 High boiling point organic solvent (ON-1) 0.01 Gelatin
1.5 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (En-1) Silver iodobromide emulsion (Ell-2) Sensitizing dye (S-1) 1.0 0.5 2.5X10-4 (mol/1 mole of silver) Sensitizing dye (S-2) 2.5x10-now (mol/1 mole of silver) Sensitizing dye (S-3) 0.5X10-4 (
mol/1 mol of silver) Cyan coupler (A-1) 0.8 cyan coupler (A-2) 0.2 colored cyan coupler (CC-1) 0.05 DIR compound (D-1) High boiling point solvent (Qil- 1) Gelatin 4th layer; High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) 0.002 0.5 1.5 (RH) 2゜0 2.0X10' (mol/1 mole of silver) 2, OX 10-gin (mol/1 mole of silver) 0, lX10-→ (mol/1 mole of silver) 0. 25 Cyan coupler (A-3) Colored cyan coupler (CG-1) DIR compound (D-2) High boiling point solvent (Oil-1> Gelatin 5th layer: Intermediate layer (1, L, -2) Gelatin 6th layer ;Low-sensitivity green-sensitive emulsion layer (GL) 0.015 0.05 0.5 1.5 0.5 Silver iodobromide emulsion (Em-1) Sensitizing dye (S-4) Sensitizing dye (S-5 > DIR compound (D-3) DIR compound (D-4) High boiling point solvent (Oil-2) Gelatin 7th layer: Intermediate layer (1,1').

Gelatin high boiling point solvent (Oil-1) No. 811; High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Ell-3) Sensitizing dye (S-6) = 3) Sensitizing dye (S-7) 1.0 X1O-4 (Mole/1 mole of silver) 1 x 10°→ (Mole/1 mole of silver) 0.4 0.05 0.015 0.020 0.5 1.0 Magenta coupler (M-1) Colored magenta coupler (CM-1 0.8 0.2 (GH) 1.3 1.5X 10-Dou (mol/1 mole of silver) 2.5X1G-now (mol/1 mole of silver) Sensitizing dye (S-8) 0 .5X 1O-
4 (mol/mol of silver) Magenta coupler (M-2) 0.05 Magenta coupler (M-3) 0.15 Colored magenta coupler (CM-2) 0.05 DrR compound (0-3) 0.01 High Boiling point solvent (Oil-3) 0.5 gelatin
1.0 9th layer: Yellow filter layer (YC) yellow colloidal silver 0
, 1 color stain inhibitor (SC-1) o, 1 high boiling point organic solvent (Oil-3) 0.1 gelatin
0.8 10th layer; low sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (Em -1)
0.25 silver iodobromide emulsion (Em-2)
0.25 sensitizing dye (S-10) 7x
10-4 (mol/silver 1 mol) Yellow coupler (Y-1> Yellow coupler (Y-2) DIR compound (D-2) High boiling point solvent (Oil-3) Gelatin 11th layer; High sensitivity blue-sensitive emulsion layer <8l-1) Silver iodobromide emulsion (Ell-4) Silver iodobromide emulsion (Ell-1) Sensitizing dye (S-9) O, SO 0,20 Xl0-4 (mol/III mol) 3× 10-Dou (mol/silver 1 mol) 0.30 0.05 0.07 1.1 0.1 0.01 0.15 1.0 Sensitizing dye (S-10) Yellow coupler (Y-1) Yellow Coupler (Y-2) High boiling point solvent (O11-3) Gelatin 12th layer: 1st protection 1st layer (PRO Fine grain silver iodobromide emulsion, average grain size 0.08μ, Agl UV absorber (UV-1) 0 .4 2 mol%) 0.10 UV absorber (tJV-2) High boiling point solvent (Oil-1 > 0.1 High boiling point solvent (Oil-4) 0.1 Formalin scavenger (+-(S-1) ) 0.05 0.5 Formalin scavenger (H8-2) 0.2 Gelatin 1.0 13th layer; 2nd protective layer (PRO-2) Surfactant (3u -1) 0.005 Alkali-soluble Matting agent 0.10 (average particle size 2 μm) Cyan dye (AI C-1) 0. (+0
5 Magenta dye (8 IM-1) (1,01 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, the elevated layer contains coating aid Su-2 and dispersion aid 5u-3. , Hardener H-1 and H-2, Preservative DI-1, Stabilizer 5tab
-1 and cuff 1J inhibitors AF-1 and AF-2 were added.

E-shin -1 Average grain size 0.46 μm, average silver iodide content 7.5%, monodisperse silver iodobromide emulsion m -2 Average grain size 0.32 μm, average silver iodide content 2.0 %, monodisperse silver iodobromide emulsion El! I-3 Monodisperse silver iodobromide emulsion with an average grain size of 0.78 μm and an average silver iodide content of 6.0% m −4 Average grain size of 0.95 μm and an average silver iodide content of 8.0% , Monodisperse surface low silver iodide content emulsion S-4 Below margin Comparative coupler A-1 Comparative coupler A-2 Comparative coupler A-3 ■ (C2H,), NH M-3 Below margin 1 M-1 M -2 CI! Below margin uv-i UV-2 C2Hs ((CH,=CH8O2CH2)3CCH2SOtCH
tCH2)INCH2CH2SO3KF-1 F-2 I-1 AX-1 1l-4 u-1 Na02S-CC00CH2(CF2CFri 3Hu-
2 Na0=S CC00C=H, t cH, -C00C,H,.

u-3 AICAL C-1AI In sample No. 1, the comparative couplers A-1, A-2, and A-3 of the third and fourth layers were changed as shown in Table-1 to create samples No. 082 to 13. did.

Margins below Each of the samples No. 1 to No. 13 prepared in this manner was subjected to wedge exposure using white light, and then subjected to the following development treatment.

Treatment process (38℃) For color development @ 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water 3 minutes 15 seconds fixing 6 minutes 30 seconds washing with water 3 minutes 15 seconds stabilization 1 minute 30 seconds drying Used in each processing step The composition of the treatment solution was as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75q anhydrous sodium sulfite 4.25g hydroxylamine 1/21a M salt 2.0 (] Anhydrous potassium carbonate 37.51: J Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.51 J Potassium hydroxide 1°0 g Add water to make 1 t.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 (1
Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 (1 Ammonium bromide 150.0 (1 Glacial acetic acid 10.0. Add water to make 11, use aqueous ammonia to make p) -1 = 6.0
Adjust to.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 12
and adjusted to I)H-6,0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1. hN Konidax (Konica Iu) 7.51Q Add water to make 12.

RMS was measured for each sample obtained using red light (W). The results are shown in Table-2.

The RMS value is the standard deviation of the variation in density value that occurs when scanning the minimum density +0.4 and +0.8 using a microdensitometer with an aperture scanning area of 250 μm2.
It is expressed as a relative value with 00.

Margin Table 2 Below: From the results in Table 2, it is clear that the graininess of cyan images is improved by the present invention.

Also, instead of compound ■-14 of sample 6, ■-1゜I-5
, l-11, l-16 or ■-24 in place of compound Ni-42 of sample 8, ■-25, l-28, l
The effect of the present invention was also observed when using either -31 to l-33 or 135 to knee 39.

[Example 2] In sample 4 of Example 1, the high boiling point organic solvent Oi1-1 used for the third and fourth layers was changed to Qil-2°Q if -
Samples 14 to 16 were prepared in the same manner except that Oif-3 and Oif-4 were used, and the same evaluation as in Example 1 was performed, and the effects of the present invention were obtained.

[Example 3] In sample 4 of Example 1, emulsion E1m-1°El-2
, El-3 into the following emulsions Ellll-5, Elll-
Sample 17 was prepared in the same manner as Sample 4 except for changing to Elf-7 and Elf-7, and the same evaluation as in Example 1 was performed. A 5% improvement was observed.

m-5 Average grain size 0.46 μm, average silver iodide content 7.5 mol%
9 Core/shell type silver iodobromide emulsion E+g-6 with distribution width 14%, core 25 mol%, shell 0.5 mol% Average grain size 0.32 μm, average silver iodide content 4.0 mol%
9 Distribution width 13%, core 30 mol%, shell 0 mol%
Core/shell type silver iodobromide emulsion m-7 Average grain size 0.80 μm, average silver iodide content 6.0 mol%
9 Distribution width 14%, core 20 mol%, shell 2 mol%
Example 4 Core/shell type silver iodobromide emulsion [Example 4] Sample No.
, 18 were created.

l-8 Average grain size: 1.48μ■, average silver iodide content: 6.0%2 Average value of grain size/grain thickness: 10.0, and silver iodide content of the outer edge phase: 0.5% It consists of tabular silver halide grains.

When sample No. 18 was evaluated in the same manner as in Example 1, the improvement effect of the present invention was recognized.

[Example 5] In sample 4 of Example 1, silver halide emulsion Em −
Sample No.
19 and 20 were created.

When these samples No. 19 and 20 were evaluated in the same manner as in Example 1, the improvement effect of the present invention was recognized.

[Example 6] In sample No. 4 of Example 1, silver halide emulsion E
The average particle diameter of l-1 to Em-4 was 0.5. 0
．． 8. 1.8. Sample No. 09 except that it was 2.0 μI.
Sample No. 21 was prepared in the same manner as in Example 4.

When this sample No. 21 was evaluated in the same manner as in Example 1, the improvement effect of the present invention was recognized.

[Example 7] In sample N014 of Example 1, by changing the gelatin content of each layer, the dry film thickness was changed to 15 or 1, respectively.
Samples Nos. 22 and 23 were prepared in the same manner as sample No. 0.4 except that the thickness was reduced to 3 μm.

When these samples No. 22 and 23 were evaluated in the same manner as in Example 1, the improvement effect of the present invention was recognized.

[Example 8] In Samples N011 and 4 of Example 1, m of the silver halide emulsion in each layer was changed to reduce the amount of photosensitive silver halide emulsion in all emulsion layers to 3.5 Q/f. Samples No. 0.24 and 25 were prepared in the same manner as samples No. 091 and 4, respectively, except for this.

When each of Sample Nos. 24 and 25 was evaluated in the same manner as in Example 1, it was found that Sample 25 of the present invention had a clear improvement in graininess compared to Comparative Sample 24.

[Example 9] Sample N 0.4 of Example 1 was stored for 3 months at relative humidity of 50 and 40% during packaging, respectively.
o, 26 and 27 were created.

When the same evaluation as in Example 1 was performed on each of Samples No. 0.26 and No. 27, the effects of the present invention were obtained.

[Example 10] Samples No. 0.28 and 29 were prepared by changing the amount of the hardening agent used in sample No. 0.4 of Example 1 and making the degree of swelling of the developed film thickness 220% and 250%, respectively. .

When the same evaluation as in Example 1 was performed on each of Samples No. 0.28 and No. 29, the effects of the present invention were recognized.

[Example 11] The following layers were coated sequentially from the support, and Sample No.

30 and 31 were created.

1st layer Antihalation layer 2nd layer Intermediate layer 3rd layer Low sensitivity red sensitive emulsion layer 4th layer 5th intermediate layer Low sensitivity green sensitive emulsion layer 6th layer 7th intermediate layer Low sensitivity blue sensitive emulsion layer 811 Intermediate layer 9th layer Highly sensitive red-sensitive emulsion layer 10th layer Intermediate layer 11th layer Highly sensitive green-sensitive emulsion layer 12th layer Intermediate layer 13th layer Highly sensitive blue-sensitive emulsion layer 14th layer 1st retention r! i-layer 15th layer Second protective layer Note that each layer of each of Samples N013/O and 31 had the same composition as that used in Samples N011 and 4, respectively.

That is, the 3rd layer, 5th layer, 7th layer, 9th layer, 11th layer, and 13M of sample Nos. 30 and 31 are respectively sample No.
01 and 4 3rd layer, 6th layer, 10th layer, 4th layer, 8th layer
This layer is made of the same constituent components as the 11th layer.

Further, the antihalation layer, first protective layer, and second protective layer of Samples 30 and 31 were made of the same components as those of Samples No. 1 and 4, respectively.

Samples Nos. 30 and 31 were each subjected to the same exposure and development treatment as in Example 1 and evaluated in the same manner. As a result, Sample 31 of the present invention was found to have the grain improvement effect of the present invention compared to Comparative Sample 30.

Claims (1)

[Scope of Claims] At least one of the photosensitive silver halide emulsion layers on the support has a ▲ mathematical formula, chemical formula, table, etc. ▼ group at the 2nd position, and R_1-SO_2-R_2- at the 5th position. A phenolic cyan coupler having a CONH- group and a ▲ formula at the 2nd position,
There are chemical formulas, tables, etc. ▼ having a group and in the 5th position ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ A halogenated compound characterized by containing at least one type of phenolic cyan coupler having a group and at least one type of colorless cyan coupler represented by the following general formula [II] Silver photographic material. (In the above groups, R_1 represents an alkyl group, aryl group or heterocyclic group, R_2 represents an alkylene group, R_3 represents a substituent, n represents an integer of 1 to 4, and when n is 2 to 4, each R_3 may be the same or different. R_1_1 is an alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, halogen atom, -OR
_1_6, -SR_1_6, -OCOR_1_5, -N
R_1_6COR_1_5, -(NR_1_6)_l-
SO_2R_1_5, -CO(O)_lR_1_6, -
SO_2NR_1_6R_1_7 or nitro group, R
_1_5 is an alkyl group, alkenyl group, cycloalkyl group or aryl group, R_1_6 and R_1_7 are each a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group or aryl group, R_1_2 is a trivalent chain hydrocarbon group, R_1_3 is a branched alkyl group or alkenyl group, R_1_4 is an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group,
m represents an integer from 0 to 3, and when m is 2 or more, each R_1
_1 may be the same or different. Further, l represents 0 or 1. ) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_4 represents an alkyl or aryl group, and R_
5 represents a hydrogen atom or an alkyl group. The total number of carbon atoms of R_4 and R_5 is 10 or more. Z represents a phenyl group. ]