JPH04328743A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity, excellent graininess, sharpness and color reproducibility and excellent shelf stability of a yellow image by incorporating an acylacetamide type yellow dye forming coupler and to inhibit the deterioration of photographic performance during storage by using specified core-shell type silver halide particles. CONSTITUTION:This sensitive material has at least one photosensitive emulsion layer on the base and contains an acylacetamide type yellow dye forming coupler represented by formula I and chemically sensitized core/shell type silver halide particles each having the shell part at the outside of the core part.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, which contains a silver halide emulsion with a high silver iodide content and a novel yellow coupler, and has high sensitivity, graininess, and color reproducibility. The present invention relates to a silver halide color photographic light-sensitive material which has excellent properties, small changes in photographic performance during storage, and excellent color image storage stability after processing.

0002

[Prior Art] Silver halide color photographic light-sensitive materials, especially color light-sensitive materials for photography, have high sensitivity, good graininess, color reproducibility, and sharpness, little change in photographic performance during storage, and There is a demand for photosensitive materials with excellent image storage properties.

As a yellow coupler for forming color photographic images, T. H. James, The Theory
Of the Photographic Process” 4th edition, 3
As described on pages 54-356, benzoylacetanilide-type and hivaloylacetanilide-type couplers having active methylene (methine) groups are commonly used. However, these couplers have low color density,
It is very difficult to satisfy all of the requirements for dye formation speed, dye hue, and color image fastness, and if a dye with high color density or dye formation speed is used for high sensitivity, the hue may be unfavorable. This was a serious problem because the fastness of the color image was extremely low.

[0004] In addition, a sensitive material having a clear layered structure containing silver iodobromide with a high silver iodide content and containing silver halide grains with a high average silver iodide content was disclosed in Japanese Patent Application Laid-Open No. 1983-1999. -1433
No. 31, JP-A No. 1-186938, JP-A No. 1-26993
No. 5 and No. 2-28637, etc., and it has become possible to provide a sensitive material with high sensitivity and good graininess. However, when used in combination with a conventional yellow coupler, image storage stability and color reproduction after processing There was a problem with sexuality.

[0005]

[Problem to be Solved by the Invention] The purpose of the present invention is to
The second objective is to provide a photosensitive material with high sensitivity and excellent graininess, sharpness, and color reproducibility.The second objective is to provide a photosensitive material with excellent yellow image storage stability.The third objective is to provide a photosensitive material that has excellent granularity, sharpness, and color reproducibility.The third objective is to provide a photosensitive material with excellent yellow image storage stability. An object of the present invention is to provide a photosensitive material whose photographic performance changes little during its storage period.

[0006]

[Means for Solving the Problems] The objects of the present invention have been achieved by the following color photosensitive materials.

[0007] A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support contains an acylacetamide type yellow dye-forming coupler represented by the following general formula (I), and contains A silver halide color photographic light-sensitive material characterized by containing chemically sensitized core/shell type silver halide grains having a shell portion on the outside.

[0008]

[Formula 2] (In the formula, R1 represents a monovalent group. Q together with C,
Represents a group of nonmetallic atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. (However, R1 is not a hydrogen atom and does not combine with Q to form a ring.) The acylacetamide type yellow coupler used in the present invention is preferably represented by the following general formula (Y).

[0009]

[Image Omitted] In formula (Y), R1 represents a monovalent substituent other than hydrogen,
Q together with C is a 3- to 5-membered hydrocarbon ring or at least one
R2 is a hydrogen atom, a halogen atom (F, Cl, Br
,I. The same applies to the description of formula (Y) below. ), alkoxy group, aryloxy group, alkyl group or amino group,
R3 is a group that can be substituted on the benzene ring, X is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developer (hereinafter referred to as a leaving group), l
(L) represents an integer from 0 to 4, respectively. However, l
When (L) is 2 to 4, a plurality of R3's may be the same or different.

Here, examples of R3 include halogen atoms,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group,
There are ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, alkoxysulfonyl groups, acyloxy groups, nitro groups, heterocyclic groups, cyano groups, acyl groups, acyloxy groups, alkylsulfonyloxy groups, and arylsulfonyloxy groups. Examples of the group include a heterocyclic group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclicoxy group, and a halogen atom, which are bonded to the coupling active position through a nitrogen atom.

[0011] When the substituent in formula (Y) is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group is a linear, branched or cyclic, even if substituted Alkyl groups that may contain unsaturated bonds (e.g. methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethyl, methoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in formula (Y) is an aryl group or contains an aryl group, unless otherwise specified, the aryl group may be substituted with an optionally substituted monocyclic or fused ring aryl group (for example, phenyl, 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecyl phenyl,
2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

[0013] When the substituent in formula (Y) is a heterocyclic group or contains a heterocycle, unless otherwise specified, the heterocyclic group is at least one selected from O, N, S, P, Se, Te. A 3- to 8-membered optionally substituted monocyclic or fused-ring heterocyclic group containing 2 heteroatoms in the ring (e.g., 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide, 1
-benzyl-2,4-imidazolidinedione-3-yl).

The substituents preferably used in formula (Y) will be explained below.

In formula (Y), R1 is preferably a halogen atom, a cyano group, or a monovalent group with a total carbon number (hereinafter abbreviated as C number) of 1 to 30 that may be substituted (
For example, an alkyl group, an alkoxy group) or a C number of 6 to 3
0 monovalent groups (e.g. aryl group, aryloxy group)
Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamide group, a sulfonamide group, and an acyl group.

In formula (Y), Q is preferably 3-
A hydrocarbon ring having 3 to 30 carbon atoms which may be substituted with any of the 5 members, or a hetero atom having 2 to 30 carbon atoms containing at least one heteroatom selected from N, S, O, and P in the ring. ring as C
Represents a group of nonmetallic atoms necessary to form with. Further, the ring formed by Q together with C may contain an unsaturated bond within the ring. Examples of rings formed by Q together with C include cyclopropane, cyclobutane, cyclopentane, cyclopropene, cyclobutene, cyclopentene, oxetane, oxolane, 1,3-dioxolane, thietane, thiolane,
Contains pyrrolidine. Examples of substituents include halogen atoms, hydroxyl groups, alkyl groups, aryl groups, acyl groups, alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, alkylthio groups, and arylthio groups.

In formula (Y), R2 is preferably a halogen atom, each of which may be substituted, and has 1 to 3 carbon atoms.
0 alkoxy group, C6-30 aryloxy group,
It represents an alkyl group having 1 to 30 carbon atoms or an amino group having 0 to 30 carbon atoms, and its substituents include, for example, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In formula (Y), R3 is preferably a halogen atom, any of which may be substituted, and has 1 to 30 carbon atoms.
Alkyl group, C6-30 aryl group, C1-3
0 alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C
Carbonamide group having 1 to 30 carbon atoms, sulfonamide group having 1 to 30 carbon atoms, carbamoyl group having 1 to 30 carbon atoms, 0 to 30 carbon atoms
30 sulfamoyl group, C1-30 alkylsulfonyl group, C6-30 arylsulfonyl group, C1-30 ureido group, C0-30 sulfamoylamino group, C2-30 30 alkoxycarbonylamino group, C1-30 heterocyclic group, C1-30 acyl group, C1-30 alkylsulfonyloxy group, C6
~30 arylsulfonyloxy groups, and its substituents include, for example, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups,
Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, and arylsulfonyloxy group.

In formula (Y), l (L) preferably represents an integer of 1 or 2, and the substitution position of R3 is as follows:

[
0020

[C4] The meta or para position is preferred.

In formula (Y), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents a heterocyclic group, X is preferably an optionally substituted 5- to 7-membered monocyclic or condensed ring heterocyclic group, examples of which include succinimide, malein, etc. imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2
, 4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole,
imidazolidine-2,4-dione, oxazolidine-2
, 4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one,
Benzoxazoline-2-one, benzothiazoline-2
-one, 2-pyrrolin-5-one, 2-imidazoline-
5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-
Pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,
4-thiazolin-4-one, these heterocycles may be substituted. Examples of these heterocyclic substituents include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, sulfo groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and alkyl groups. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl It has an amino group. When X represents an aryloxy group, X preferably has 6 to 6 carbon atoms.
represents an aryloxy group of 30, and may be substituted with a group selected from the substituent groups listed above when X is a heterocycle. Substituents for the aryloxy group include a halogen atom, cyano group, nitro group, carboxyl group, trifluoromethyl group, alkoxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, and arylsulfonyl group. or cyano group is preferred.

Next, particularly preferably used substituents in formula (Y) will be explained.

R1 is particularly preferably a halogen atom or an alkyl group, most preferably a methyl group. Q is particularly preferably a group of nonmetallic atoms in which the ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example,

00
25]

[Chemical formula 5] Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, the plurality of R's may be the same or different.

[0026] Most preferably, Q forms a three-membered ring together with the bonded C.
|R It is R. R2 is particularly preferably a chlorine atom, a fluorine atom, a C1-6 alkyl group (e.g. methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), a C1-8 alkoxy group (e.g. methoxy,
ethoxy, methoxyethoxy, butoxy), or C6-24 aryloxy group (e.g. phenoxy group, p
-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

R3 is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group or an alkoxycarbonyl group. ,
It is a carbonamide group or a sulfonamide group.

X is particularly preferably represented by the following formula (Y-1), (
Y-2) or (Y-3).

[0029]

[C6] In formula (Y-1), Z is

[0030]

Represents [Chemical 7]. where R4, R5, R8, and R9
represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an amino group, and R6 and R7 represent a hydrogen atom, an alkyl group, an aryl group, an alkyl It represents a sulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R10 and R11 represent a hydrogen atom, an alkyl group or an aryl group. R10 and R11 may be combined with each other to form a benzene ring. R4 and R5, R5 and R6, R6 and R7, or R4 and R8 may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by formula (Y-1), particularly preferred are those in which Z is

003
2]

[Image Omitted] is a heterocyclic group. The heterocyclic group represented by formula (Y-1) has 2 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 5 to 16 carbon atoms.

[0033]

embedded image In formula (Y-2), at least one of R12 and R13 is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, or a carbamoyl group. The other group may be a hydrogen atom, an alkyl group, or an alkoxy group. R14 represents a group having the same meaning as R12 or R13, and m represents an integer of 0 to 2. Formula (Y-
The number of carbon atoms in the aryloxy group represented by 2) is 6 to 30,
Preferably it is 6-24, more preferably 6-15.

[0034]

embedded image In formula (Y-3), W represents a nonmetallic atom group necessary to form a pyrrole ring, pyrazole ring, imidazole ring or triazole ring together with N. Here, the formula (Y
The ring represented by -3) may have a substituent, and examples of the substituent are preferably a halogen atom, nitro group, cyano group, alkoxycarbonyl group, alkyl group, aryl group, amino group, alkoxy group, aryloxy group or carbamoyl group. The heterocyclic group represented by formula (Y-3) has 2 to 30 carbon atoms, preferably 2 to 24 carbon atoms, and more preferably 2 to 16 carbon atoms.

X is most preferably a group represented by formula (Y-1).

The coupler represented by formula (Y) has substituents R1, Q, X, or

[0037]

[Image Omitted] In the formula, a dimer or a multimer of more than two molecules may be formed which are bonded to each other via a group having a valence of two or more. in this case,
The number of carbon atoms in each of the above substituents may be outside the specified range.

Specific examples of the yellow coupler represented by formula (Y) are shown below.

[0039]

[Chemical formula 12]

[0040]

[Chemical formula 13]

[0041]

[Chemical formula 14]

[0042]

[Chemical formula 15]

[0043]

[Chemical formula 16]

[0044]

[Chemical formula 17]

[0045]

[Chemical formula 18]

[0046]

[Chemical formula 19]

[0047]

[C20]

[0048]

[C21]

[0049]

[C22]

[0050]

[C23]

[0051]

[C24]

[0052]

[C25]

[0053]

[C26]

[0054]

[C27]

[0055]

[C28]

[0056]

[C29]

[0057]

[C30]

[0058]

embedded image The yellow coupler represented by formula (Y) can be synthesized by the following synthetic route.

[0059]

[Image Omitted] Here, compound a is defined by J. Chem. Soc. (C
), 1968, 2584, J. Am. Che
m. Soc. , 1934, 56, 2710,
Synthesis, 1971, 258, J. O
rg. Chem. , 1978, 43, 1729
, CA, 1960, 66, 18533y, etc.

Compounds b, c, d, e and f can be synthesized by conventionally known methods. Below is the formula (
An example of synthesis of a coupler represented by Y) is shown below.

Synthesis Example 1 Synthesis of Exemplary Compound Y-28 Gotkis, D, et al, J. Am.
Chem. Soc. , 1934, 56, 27
38.1 g of oxalyl chloride was added dropwise to a mixture of 25 g of 1-methylcyclopropanecarboxylic acid synthesized by the method described in 10, 100 ml of methylene chloride, and 1 ml of N,N-dimethylformamide at room temperature over 30 minutes. . After the dropwise addition, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure using an aspirator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride.

6 g of magnesium and 2 ml of carbon tetrachloride
100 ml of methanol was added dropwise to the mixture at room temperature over 30 minutes, and after heating under reflux for 2 hours, 32.6 g of ethyl 3-oxobutanoate was added dropwise over 30 minutes under heating under reflux. After the dropwise addition, the mixture was further heated under reflux for 2 hours, and methanol was completely distilled off under reduced pressure using an aspirator. 100 ml of tetrahydrofuran is added to the reactant to disperse it, and the previously obtained 1-methylcyclopropanecarbonyl chloride is added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was diluted with 300ml of ethyl acetate.
l. Extracted with dilute sulfuric acid water, washed with water, dried the organic layer over anhydrous sodium sulfate, and distilled off the solvent to obtain 55.3 g of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate as an oil. I got it.

A solution of 55 g of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate and 160 ml of ethanol is stirred at room temperature, and 60 ml of 30% ammonia water is added dropwise thereto over 10 minutes.

[0064] After stirring for 1 hour, 300ml of ethyl acetate was added.
After extraction with diluted hydrochloric acid, neutralization, and washing with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain an oily product of ethyl (1-methylcyclopropanecarbonyl) acetate 43
I got g. 34 g of ethyl (1-methylcyclopropanecarbonyl)acetate and 44.5 g of N-(3-amino-4-chlorophenyl)-2-(2,4-di-t-pentylphenoxy)butanamide were added at the internal temperature of a reaction vessel. 100-1
Heat to reflux at 20° C. under reduced pressure using an aspirator. After 4 hours of reaction, the reaction solution was purified by column chromatography using a mixed solution of n-hexane and ethyl acetate to obtain Exemplified Compound Y-28.
49 g were obtained as a viscous oil. The structure of the compound is MS
Confirmed by spectrum, NMR spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Exemplified Compound Y-1 22.8 g of Exemplified Compound Y-28 was added to 300 m of methylene chloride.
5.4 g of sulfuryl chloride was added dropwise over 10 minutes under ice-cooling. After reacting for 30 minutes, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain Exemplified Compound Y.
-28 chloride was obtained. 1-benzyl-5-ethoxyhydantoin 18.7g, triethylamine 11.2ml
In a solution of 50 ml of N,N-dimethylformamide, add the chloride of the previously synthesized exemplary compound Y-28 to N,N-dimethylformamide.
A solution dissolved in 50 ml of N-dimethylformaldehyde was added dropwise over 30 minutes at room temperature.

Thereafter, the reaction was allowed to proceed at 40° C. for 4 hours, and the reaction solution was extracted with 300 ml of ethyl acetate, washed with water, washed with 300 ml of a 2% aqueous triethylamine solution, and then neutralized with diluted hydrochloric acid. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and dried to obtain crystals of Exemplary Compound Y-1 22.
8g was obtained.

The structure of the compound was confirmed by MS spectrum, NMR spectrum, and elemental analysis. Also, the melting point is 132
It was ~3°C.

It has been found that by using the novel yellow coupler represented by the general formula (I), high sensitivity, excellent color reproducibility, and image storage stability after processing can be greatly improved. However, when a photosensitive material containing this coupler is stored, especially in a relatively high temperature environment,
It has become clear that there is a problem in that the fog increases and therefore the effective sensitivity also decreases.

In order to improve this drawback, the present inventors conducted various studies and found that the emulsion layer containing the coupler of the present invention has a chemically sensitized core/layer having a shell portion outside the core portion. It has been found that the above drawbacks can be overcome by using shell-type silver halide grains.

The core/shell type silver halide grains will be explained below. These core/shell type silver halide grains are chemically sensitized core/shell type silver halide grains in which the average silver iodide content in the entire grain is 4 mol % or more.

In the core/shell structure of the core/shell type silver halide grains of the present invention, the silver iodide content in the shell portion existing outside the grain is higher than the silver iodide content in the core portion existing inside the grain. Although the content may be higher or lower than the content, preferably the content in the shell is lower than that in the core. Further, it is preferable that the difference in silver iodide content between the core part and the shell part is at least 1 mol % or more.

Furthermore, the core portion of the grain may be formed as two or more layers having different silver iodide contents. The silver halide grains of the present invention may have a sharp change in silver iodide content at the interface between a core portion and a shell portion having different silver iodide contents, or may have a continuous change in silver iodide content. There may be.

The distribution state of silver iodide in the above-mentioned silver halide grains can be detected by various physical measurement methods described below.

The core portion or shell portion of the core/shell type silver halide grains of the present invention does not necessarily have to be a continuous layer. For example, a shell part that covers the vicinity of the apex or the vicinity of the ridge of the cubic core part is also included.

The core/shell type silver halide grains of the present invention preferably have a substantially two distinct layered structure.

In particular, chemically sensitized silver iodobromide containing 15 to 45 mol% of silver iodide has a clear layered structure, and the silver iodide content of the entire grain exceeds 7 mol%. They discovered that the above drawbacks can be overcome by using silver halide grains.

The clear layered structure mentioned here can be determined by the method of X-ray diffraction. An example of applying the X-ray diffraction method to silver halide grains is given by H. Hirsch's Journal of Photographic Science Volume 10 (1962)
), page 129 onwards. When the lattice constant is determined by the halogen composition, Black's condition (2ds
A diffraction peak occurs at a diffraction angle that satisfies inθ=nλ).

The X-ray diffraction measurement method is described in detail in Basic Analytical Chemistry Course 24 "X-ray Diffraction" (Kyoritsu Shuppan) and "X-ray Diffraction Guide" (Rigaku Denki Co., Ltd.). The standard measurement method uses Cu as the target and
using Kβ rays as a radiation source (tube voltage 40kV, tube current 60m)
A) A method of determining the diffraction curve of the (220) plane of silver halide. In order to increase the resolution of the measuring machine, a slit (
Appropriately select the width of the divergent slit, light receiving slit, etc., the time constant of the device, the scanning speed of the goniometer, and the recording speed.
It is necessary to confirm measurement accuracy using a standard sample such as silicon.

In the present invention, a clear layered structure is defined by the diffraction intensity versus diffraction angle of the (220) plane of silver halide using the Kβ ray of Cu with a diffraction angle (2θ) in the range of 38° to 42°. When obtaining a curve of This refers to the case where a diffraction maximum and one minimum appear between them, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer. , more preferably the diffraction intensity ratio is 1/5 to
The ratio is 3/1, particularly preferably 1/3 to 3/1.

In the emulsion according to the present invention having substantially two distinct layered structures, it is more preferable that the minimum diffraction intensity between the two peaks is one of two or more diffraction maximums (peaks). The strength is preferably 90% or less, more preferably 80% or less, particularly preferably 60% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Publishing).

It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a curve analyzer manufactured by Du Pont.

Even in the case of an emulsion in which two types of grains having different halogen compositions, which do not have a clear layered structure, coexist, two peaks appear in the X-ray diffraction.

Such an emulsion cannot exhibit the excellent photographic performance obtained by the present invention.

In order to determine whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, E
PMA method (Electron-Probe Micro
This is possible by using the Analyzer method).

In this method, a sample is prepared in which the emulsion grains are well dispersed so that they do not come into contact with each other, and the sample is irradiated with an electron beam. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each lattice.

EPMA for at least 50 particles
By confirming the halogen composition by a method, it can be determined whether the emulsion is an emulsion according to the present invention.

In the emulsion of the present invention, it is preferable that the iodine content among grains is more uniform.

[0089] When the distribution of iodine content among particles is measured by the EPMA method, the relative standard deviation is preferably 50% or less, more preferably 35% or less.

Another preferred interparticle iodine distribution is
This is a case where the logarithm of particle size and iodine content show a positive correlation. In other words, the iodine content of large size particles is high and the iodine content of small size particles is low. Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is preferably 40% or more, more preferably 50% or more.

In the core part, silver halide other than silver iodide is
Either silver chlorobromide or silver bromide may be used, but a higher proportion of silver bromide is preferred. Silver iodide content is 15-45 mol%
The content is preferably 25 to 45 mol%, more preferably 30 to 45 mol%. The most preferred silver halide for the core portion is silver iodobromide containing 30 to 45% silver iodide.

The composition of the outermost layer is silver halide containing 8 mol % or less of silver iodide, more preferably silver halide containing 6 mol % or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. Particularly preferred for the outermost layer is silver iodobromide or silver bromide containing 0.5 to 6 mol % of silver iodide.

Regarding the halogen composition of the entire grain, it is necessary that the silver iodide content exceeds 7 mol %, but preferably 10 mol %.
~25%, more preferably 12-20 mol%.

One of the reasons why the silver halide emulsion used in the present invention has good graininess is that it can be highly iodized without reducing development activity, which increases light absorption. It is thought that this is because the latent image forming efficiency was improved because the particle had a clear layered structure including a high iodine layer in the core part and a low iodine layer in the outermost layer.

The size of the silver halide grains having a clear layered structure of the present invention is 0.05 to 3.0 μm, preferably 0.1 to 1.5 μm, more preferably 0.2 to 1 μm.
．． It is 3 μm, more preferably 0.3 to 1.0 μm.

The average grain size of silver halide grains in the present invention is defined by T.H.
``The Theory of the Photographic Process'' by James et al.
of the Photographic Process
ss) 3rd edition 39 pages, published by Macmillan (1966)
is the geometric mean value of particle size well known in the art as described in . In addition, particle size can be determined from "Introduction to Particle Size Measurement" by Masafumi Arakawa (Journal of Powder Engineering Society, Vol. 17, 299-31).
3 (1980), and can be measured by methods such as the Coulter counter method, single particle light scattering method, and laser light scattering method.

The types of silver halide grains having a clear layered structure of the present invention include those having regular crystal shapes (normal crystal grains) such as hexahedrons, octahedrons, dodecahedrons, and dodecahedrons. It may also have an irregular crystal shape such as spherical, potato-like, or tabular, especially with an aspect ratio of 1.2 to 8.
Among these, tabular twin grains of 1.5 to 5 are preferred.

In the case of normal crystal grains, grains having 50% or more (111) planes are particularly preferred. Even in the case of irregular crystal shapes, particles having 50% or more (111) planes are particularly preferred. The surface ratio of the (111) plane can be determined by the Kubelka-Munk dye adsorption method. This is a (111) plane or a (1
00) preferentially adsorbs to one of the faces, and (111)
A dye is selected in which the association state of the dye on the plane and the association state of the dye on the (100) plane are different spectrally. The surface ratio of the (111) plane can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

Although the emulsion of the present invention may be used in any layer in a silver halide light-sensitive material, it is preferably used in a red-sensitive emulsion layer. Further, in the present invention, it is preferable that the red-sensitive emulsion layer consists of two or more layers having different sensitivities;
It is particularly preferable to use it in layers other than those with the lowest sensitivity.

In the present invention, it is particularly preferable to use a compound represented by the following general formula (A).

General formula (A) G-SM1 In the formula, G represents a heterocyclic residue to which at least one selected from the group consisting of SO3 M2, -COOM2, -OH and -NR1 R2 is bonded directly or indirectly; , M1 and M2 are independently hydrogen atoms, alkali metals,
Represents quaternary ammonium or quaternary phosphonium, R1
, R2 represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Specific examples of the heterocyclic residue represented by G in general formula (A) include oxazole, thiazole, imidazole, selenazole, triazole,
Tetrazole, thiadiazole, oxadiazole, pentazole, pyrimidine, triazine, thiadiazine,
or rings bonded to other carbocycles or heterocycles, such as benzothiazole, benzotriazole, benzimidazole, benzoxazole, benzoselenazole, naphthoxazole, triazaindolizine, diazaindolizine, tetraazaindolizine. It will be done.

Among the mercapto heterocyclic compounds represented by the general formula (A), particularly preferred are the mercapto heterocyclic compounds represented by the general formula (B).
) and (C).

[0105]

In general formula (B), Y' and Z' independently represent a nitrogen atom or CR4 (R4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). and R3 is -SO3 M2, -C
An organic residue substituted with at least one selected from the group consisting of OOM2, -OH and -NR1R2, specifically an alkyl group having 1 to 20 carbon atoms (e.g.
methyl, ethyl, propyl, hexyl, dodecyl, octadecyl), an aryl group having 6 to 20 carbon atoms (e.g., phenyl, naphthyl), and L1 is -S-, -O-,
-N=, -CO-, -SO- and -SO2 -, and n is 0 or 1.

These alkyl groups and aryl groups are
Additionally, halogen atoms (e.g. F, Cl, Br), alkoxy groups (e.g. methoxy, methoxyethoxy), aryloxy groups (e.g. phenoxy), alkyl groups (e.g.
When R2 is an aryl group), an aryl group (when R2 is an alkyl group), an amide group (for example, acetamide,
benzoylamino), carbamoyl group (e.g., unsubstituted carbamoyl, phenylcarbamoyl, methylcarbamoyl), sulfonamide group (e.g., methanesulfonamide, phenylsulfonamide), sulfamoyl group (
For example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), sulfonyl groups (e.g.
methylsulfonyl, phenylsulfonyl), sulfinyl groups (e.g. methylsulfinyl, phenylsulfinyl), cyano groups, alkoxycarbonyl groups (e.g. methoxycarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl), and other groups such as nitro groups. It may be substituted with a substituent.

Here, the substituents of R3 -SO3 M, -C
When there are two or more OOM2, -OH or NR1R2, they may be the same or different.

M2 means the same thing as represented by general formula (A).

Next, in the general formula (C), X represents a sulfur atom, an oxygen atom or -N(R5)-, and R5
represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

L2 is -CONR6, -NR6CO
-, SO2 NR6 -, NR6 SO2 -, OCO
-, -COO-, -S-, NR6 -, -CO-, -S
O-, -OCOO-, NR6 CONR7 -, NR6
COO-, OCONR6- or NR6 SO2
NR7 −, R6 and R7 are each a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

R3 and M2 have the same meanings as those represented by general formulas (A) and (B), and n represents 0 or 1.

Furthermore, R4, R5, R6 and R
As substituents for the alkyl group and aryl group represented by 7, the same substituents as those listed for R3 can be mentioned.

In the general formula, R3 is -SO3 M2
and -COOM2 are particularly preferred.

Specific examples of preferred compounds represented by the general formula (A) used in the present invention are shown below.

[0115]

[C34]

[0116]

[C35]

[0117]

[C36]

[0118]

[C37]

[0119]

[C38]

[0120]

[C39]

[0121]

[C40]

[0122]

[C41]

[0123]

embedded image The compound represented by the general formula (A) is known and can be synthesized by the method described in the following literature.

[0124] US Pat. No. 2,585,388, 2,
No. 541,924, Japanese Patent Publication No. 42-21,842, Japanese Patent Publication No. 53-50,169, British Patent No. 1,275,70
No. 1, D. A. Burgess et al., “Journal of Heterocyclic Chemistry” (D.A. Ber
ges et. al. , “Journal of
the Heterocyclic Chemistry
y”) Volume 15, No. 981 (1978), “The Chemistry of Heterocyclic Chemistry”, Imidazole and Derivatives Part I (“T
he Chemistry of Haterocyc
lic Chemistry “Imidazole
and Derivativespart I), 3
pp. 36-9, Chemical Abstracts
al Abstract), 58, No. 7921 (196
3), 394 pages, E. Hogarth, “Journal of
Chemical Society (E. Hoggarth “J”
Internal of Chemical Society
y”) pp. 1160-7 (1949), and S. R. Saudler, W. Caro, “Organic Functional Group Preparation”, Academic Press (S. R. Saudler, W. caro)
, “Organic Functional Gro
up Preparation”Academic P
ress) pp. 312-5 (1968), M. M. Chamdon, et. al., Bretin de la Sochete Chimique de France (
Bulletin de la SocieteChi
Mique de Faance), 723 (195
4), D. A. Shirley, D. W. array,
Journal of the American Chemical Society (D.A. Shirley, D.W.A.
Lley, J. Amer. Chem. Soc.
), 79, 4922 (1954), A. Ball, W. Marchwald Berichte (A. Wohl, W.M.
Archwald, Ber. ) (Journal of the German Chemical Society),
22, p. 568 (1889), Journal of the American Chemical Society (J. Amer.
Chrm. Soc. ), 44, pp. 1502-10,
U.S. Patent No. 3,017,270, British Patent No. 940,
No. 169, Japanese Patent Publication No. 8,334, 1983, Japanese Patent Publication No. 55-5
No. 9,463, Advanced in Heterocyclic Chemistry
cyclic chemistry), 9, 165~
209 (1968), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds Imidazole and Derivatives (T
he Chemistry of Heterocyc
lic Compounds Imidazole a
nd Derivatives), Vol 1, 38
Page 4, Organic Synthesis
h. ) IV. , 569 (1963), Berichte (Bre.), 9, 465 (1976), Journal of the American Chemical Society (J.Am.
er. Chrm. Soc. ), 45, 2390 (19
23), JP-A-50-89,034, JP-A No. 53-28
, No. 426, No. 55-21,007, Japanese Unexamined Patent Publication No. 40-2
No. 8,496.

The compound represented by the general formula (A) can be used in silver halide emulsion layers, hydrophilic colloid layers (for example, intermediate layers,
(surface protective layer, yellow filter layer, antihalation layer).

It is preferable to include it in the silver halide emulsion layer or a layer adjacent thereto.

[0127] Further, the amount added is 1 x 10-7 to 1 x
10-3 mol/m2, preferably 5×10
-7 to 1 x 10-4 mol/m2, more preferably 1 x 10-6 to 3 x 10-5 mol/m2.

The emulsion of the present invention is preferably a monodisperse emulsion.

The monodisperse emulsion according to the present invention is one in which the coefficient of variation S/rAVE regarding the grain size of silver halide grains is 0.
．． The emulsion has a particle size distribution of 25 or less. Here rA
VE is the average particle size and S is the standard deviation regarding the particle size. That is, when the grain size of individual emulsion grains is ri and the number of emulsion grains is ni, the average grain size rAVE is

[0130]

[Math 1] is defined, and its standard deviation S is

[0131]

[Math 2] is defined as

[0132] The individual grain size as used in the present invention refers to the silver halide agent manufactured by T.H.
``The Theory of the Photographic Process'' by Mes) et al.
the Photographic Process
) 3rd edition, pp. 36-43, published by Macmillan (196
This is the diameter equivalent to the projected area, which corresponds to the area projected when a microphotograph is taken using a method well known in the art (usually electron microscopy), as described in 1996). Here, the diameter equivalent to the projected area of a silver halide grain is defined as the diameter of a circle equal to the projected area of the silver halide grain, as shown in the above-mentioned book. Therefore, even if the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, tetradecahedral, tabular, potato-like, etc.), it is possible to determine the average grain size rAVE and its deviation S as described above. be.

The coefficient of variation related to the grain size of silver halide grains is 0.25 or less, preferably 0.20 or less,
More preferably it is 0.15 or less.

The emulsion of the present invention may be used alone in the photosensitive emulsion layer, or it may be mixed with two or more emulsions having different average grain sizes or two or more emulsions having different average silver iodide contents to form the same emulsion. It may also be used in the photosensitive layer. As mentioned above, the use of a mixture of emulsions is useful for gradation control, graininess control from low to high exposure areas, and color development dependence (time and color developing agents, sodium sulfite salts, etc.). This is preferable from the viewpoint of controlling the composition dependence (dependence on developer solution, pH dependence), etc.

The light-sensitive material of the present invention only needs to be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the silveride emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in the multilayer silver halide color photographic light-sensitive material,
Generally, the unit photosensitive layers are arranged in the following order from the support side: a red sensitive layer, a green sensitive layer, and a blue sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

[0136] Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

[0137] The intermediate layer includes JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,
It may contain a coupler, a DIR compound, etc. as described in JP 61-20037 and JP 61-20038, and may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-speed emulsion layer, a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of sensitive emulsion layers can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-112751, JP-A No. 62-200350
As described in No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side away from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL
)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (R
L), or BH/BLGL/GH/RH/RL, or BH/BL/GH/GL/RL/RH, or the like.

Alternatively, as described in Japanese Patent Publication No. 55-34932, the layers may be arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side farthest from the support. Also, JP-A-56-25738, JP-A No. 62-6393
As described in No. 6, the layers may be arranged in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support.

Furthermore, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a middle layer. An example of such an arrangement is to arrange a silver halide emulsion layer having a lower photosensitivity than the above, and to have three layers each having a different photosensitivity, the photosensitivity of which is successively lowered toward the support. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer.

In addition, the layers may be arranged in the following order: high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer.

[0143] Also, in the case of four or more layers, the arrangement may be changed as described above.

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochloride containing about 30 mol % or less of silver iodide. It is chemical silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubic, octahedral, and tetradecahedral, those with irregular crystal shapes such as spherical and plate shapes, and those with regular crystal shapes such as spherical and plate shapes. It may be one having crystal defects such as crystal planes, or a composite form thereof.

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
tion and types)” and the same No.
18716 (November 1979), p. 648, No.
307105 (November 1989), 863-86
5 pages, and “Physics and Chemistry of Photography” by P. Glafkides, published by P. Glafkides Chem.
ie et Physique Photography
ique, Paul Montel, 1967),
"Photographic Emulsion Chemistry" by Duffin, published by Focal Press (
G. F. Duffin, Photography
cEmulsion Chemistry (Foca
Press, 1966), Zelikman et al.
"Production and Coating of Photographic Emulsions", published by Focal Press (V.
L. Zelikman et al. , Maki
ng and coating photography
c Emulsion, Focal Press,
(1964) and others.

[0149] US Patent No. 3,574,628, US Patent No. 3,
655,394 and British Patent No. 1,413,748
The monodispersed emulsions described in No. 1, etc. are also preferred.

[0150] Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
hic Science and Engineering
ng), Vol. 14, pp. 248-257 (1970)
; U.S. Patent No. 4,434,226, U.S. Patent No. 4,414,3
No. 10, No. 4,433,048, No. 4,439,52
0 and British Patent No. 2,112,157.

[0151] The crystal structure may be uniform, the inside and outside may have different halide compositions, it may be a layered structure, or silver halides of different compositions may be bonded by epitaxial bonding. You can also
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The above-mentioned emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grains, or a type in which a latent image is formed both on the surface and inside the grains. , it is necessary to be a negative emulsion. Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. The method for preparing this core/shell type internal latent image type emulsion is described in Japanese Patent Application Laid-Open No.
No. 133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643, same No. 18716 and the same No. 307105, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, and
Two or more types of emulsions differing in at least one characteristic such as grain shape and sensitivity can be mixed and used in the same layer.

Silver halide grains covered with the grain surface described in US Pat. No. 4,082,553, US Pat.
, 626,498, and JP-A-59-214852, silver halide grains whose interiors are covered with colloidal silver are coated with a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid. It can be preferably used for layers. Silver halide grains that are coated inside or on the surface are uniformly coated with (
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the grain surface is described in U.S. Pat.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, especially 0.05 to 0.6 μm is preferred. Also,
There are no particular limitations on the grain shape; regular grains may be used, or polydisperse emulsions may be used; however, monodisperse grains (at least 95% of the weight or number of silver halide grains are within ±40% of the average grain size) It is preferable that the particles have a particle size of .

[0157] In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. .

[0158] The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and silver chloride and/or silver bromide are optionally added.
It may also contain silver iodide. Preferably silver iodide is 0.
It contains 5 to 10 mol%.

[0159] The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. .

[0160] Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized;
Also, spectral sensitization is not required. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver.

[0161] The amount of coated silver in the photosensitive material of the present invention is 6.0 g.
/m2 or less is preferable, and 4.5g/m2 or less is most preferable.

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

[0163] In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
, 435,503, which can be immobilized by reacting with formaldehyde, is preferably added to the photosensitive material.

[0164] The photosensitive material of the present invention is disclosed in JP-A-1-1060.
As described in No. 52, it is preferable to contain a compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof, regardless of the amount of developed silver produced by the development process.

[0165] The photosensitive material of the present invention is disclosed in International Publication WO88/
No. 04794, dyes dispersed by the method described in Japanese Patent Publication No. 1-502912 or EP No. 317,308A,
U.S. Patent No. 4,420,555, Japanese Patent Publication No. 1-25935
It is preferable to contain the dye described in No. 8.

[0166] Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure No. 17643, VII-C to G, and the same No. 307105, VII-C-G.

[0167] In addition to those represented by the general formula (I) of the present invention, examples of yellow couplers include those shown in US Pat.
No. 933,501, No. 4,022,620, No. 4
, 326,024, 4,401,752, 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, 1,476,76
No. 0, U.S. Patent No. 3,973,968, U.S. Patent No. 4,31
Preferred are those described in European Patent No. 4,023, European Patent No. 4,511,649, European Patent No. 249,473A, and the like.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and are described in US Pat. Nos. 4,310,619 and 4,351,897.
European Patent No. 73,636, U.S. Patent No. 3,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
, Japanese Patent Publication No. 60-33552, Research Disclosure No. 24230 (June 1984), JP 60-43659, JP 61-72238, JP 60-
No. 35730, No. 55-118034, No. 60-18
5951, U.S. Patent No. 4,500,630, U.S. Pat.
, 540,654, 4,556,630, International Publication No. WO 88/04795, etc. are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308 ,
4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559, Same No. 4,427,767, Same No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred. Furthermore, JP-A-64-553, JP-A No. 64-554
No. 64-555, No. 64-556, and the pyrazoloazole couplers described in US Pat.
The imidazole couplers described in No. 72 can also be used.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820;
No. 0,211, No. 4,367,282, No. 4,4
No. 09,320, British Patent No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A, etc.

[0171] Couplers whose coloring dyes have appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570,
Preference is given to those described in German Patent No. 3,234,533.

[0172] Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, No. 307105
Section VII-G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,92
No. 9, No. 4,138,258, U.S. Patent No. 1,14
6,368 is preferred. In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774,181 and reacting with developing agents as described in U.S. Pat. No. 4,777,120 are also available. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds which release photographically useful residues upon coupling can also be preferably used in the present invention. In addition to those of the present invention, DIR couplers that release development inhibitors include the aforementioned RD17643, Item VII-F and No. RD17643. 307105, the patent described in Section VII-F, JP-A-57-151944, JP-A-57-154234
No. 60-184248, No. 63-37346,
Those described in US Pat. No. 63-37350, US Pat. No. 4,248,962, and US Pat. No. 4,782,012 are preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840 are preferred. Also, JP-A-60-107029, JP-A No. 60-107029,
No. 0-252340, JP-A No. 1-44940, JP-A No. 1-
Compounds described in No. 45687 that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents are also preferred.

Other compounds that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent coupler described in No. 618 etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173,302A and EP 313,308A. , R. D. No
．． No. 11449, No. 24241, JP-A-61-201
Bleach accelerator-releasing couplers described in US Pat. No. 247, etc., ligand-releasing couplers described in US Pat. , 774, 181, etc., which emit a fluorescent dye.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

[0178] Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate), phosphoric acid or Phosphonic acid esters (e.g. triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2 -ethylhexylphenylphosphonate), benzoic acid esters (e.g. 2
-ethyl-hexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or Phenols (e.g. isostearyl alcohol, 2,4-di-ter
t-amylphenol), aliphatic carboxylic acid esters (e.g., bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples include aniline derivatives (for example, N,N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). Further, as the auxiliary solvent, for example, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, -Ethoxyethyl acetate and dimethylformamide.

[0179] Latex dispersion process steps, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230, etc.

[0180] The color light-sensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A No. 62-
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- It is preferable to add various preservatives or fungicides such as (4-thiazolyl)benzimidazole.

[0181] The present invention can be applied to various color photosensitive materials, and typical examples include general or movie color negative film, color reversal film for slides or television, color paper, color positive film, and color reversal paper. can be mentioned.

Suitable supports that can be used in the present invention include, for example, the above-mentioned RD. No. 17643, page 28, same No.
．． 18716, page 647 right column to page 648 left column, and the same No. 307105, page 879.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less;
More preferably, the time is 0 seconds or less. The film thickness is 25℃ relative humidity 55
%, which means the film thickness measured under humidity control (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, A. Green (
A. Photographic Science and Engineering (Photogr. Green) et al.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-1
It can be measured using a swell meter (swell meter) of the type described on page 29, and T1/2 is 30% with a color developer.
9 of the maximum swelling film thickness reached when treated at ℃ for 3 minutes and 15 seconds.
0% is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (
It can be calculated according to the maximum swelling film thickness - film thickness)/film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers, lubricants, coating aids, surfactants, and the like. The swelling rate of this back layer is 150~
500% is preferred.

[0186] The color photographic material according to the present invention has the above-mentioned RD. No. 17643, pages 28-29, same No.
．． 651 left column to right column of 18716, and the same No.
307105, pages 880-881.

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

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant such as. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite solution, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as ethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Various chelating agents such as acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene- 1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-
Typical examples include hydroxyphenylacetic acid) and salts thereof.

[0189] When performing reversal processing, black-and-white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

[0190] pH of these color developing solutions and black and white developing solutions
is generally from 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 3 liters per square meter of light-sensitive material, and can be reduced to less than 500 ml by reducing the bromide ion concentration in the replenisher. You can also. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

[0191] The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

[0192] That is,

[0193]

##EQU00003## The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

[0194] The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include iron(III)
organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Aminopolycarboxylic acids such as methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid or complex salts such as citric acid, tartaric acid, malic acid can be used. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron(III) complex salts is usually 4.0 to 8, but the pH can be lowered to speed up the processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,127
, 715, and the iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,4
Polyoxyethylene compounds described in No. 30;
Polyamine compound described in No. 5-8836; other JP-A Nos. 49-40,943, 49-59,644, 5
No. 3-94,927, No. 54-35,727, No. 55
Compounds described in No. 26,506 and No. 58-163,940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,8
No. 58, West German Patent No. 1,290,812, JP-A-53
-95,630 is preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

[0198] Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, large amounts of iodide salts, etc., but the use of thiosulfates are common, with ammonium thiosulfate being the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixing solution or bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfanic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

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

[0200] The total time of the desilvering process is preferably as short as possible so long as desilvering failure does not occur. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 1 to 2 minutes. Further, the treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. In a preferable temperature range, the desilvering rate is improved and the generation of stain after treatment is effectively prevented.

[0201] In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the stirring include a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460, and a method of stirring using a rotating means as described in JP-A-62-183461. A method to improve the stirring effect, and a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution to create turbulence on the emulsion surface, and circulation of the entire processing solution. One method is to increase the flow rate. Such stirring improvement means can be used for bleaching solution, bleach-fixing solution,
It is effective for any fixer. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

[0202] The automatic developing machine used for the photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open No. 60-191257 and No. 60-19125.
It is preferable to have a photosensitive material conveying means described in No. 8 and No. 60-191259. The above-mentioned JP-A-60-1
As described in No. 91257, it is possible to significantly reduce the carrying of processing liquid from the front bath to the rear bath by such a conveying means, and it is highly effective in preventing performance deterioration after processing. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society
y of Motion Picture and T
elevision Engineers Volume 64,
P. 248-258 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of water used for washing can be significantly reduced, the increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In processing the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. In addition, JP-A-57
- Chlorine disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 8,542, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi (1986) "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by Sankyo Publishing, Hygiene Technology Society (198
2) It is also possible to use the fungicides described in the "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by the Society of Industrial Science and Technology and the Japan Society of Antibacterial and Antifungal.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally they are in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-
All known methods described in No. 14834 and No. 60-220345 can be used.

[0206]Furthermore, following the water washing treatment, a further stabilization treatment may be carried out, for example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. You can mention bathing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

[0207] Various chelating agents and antifungal agents can also be added to this stabilizing bath.

[0208] The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process.

[0209] When the above-mentioned processing liquids are concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3
, No. 3,342,599, Research Disclosure No. 14,850 and the same No. Examples include Schiff base type compounds described in No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

[0211] The silver halide color photosensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
No. 4547 and No. 58-115438.

[0212] Various processing solutions in the present invention can be used at temperatures ranging from 10°C to 50°C.
Used at ℃. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

[0213] The silver halide photosensitive material of the present invention is also disclosed in US Pat.
No. 49, No. 59-218443, No. 61-23805
The present invention can also be applied to heat-developable photosensitive materials such as those described in European Patent No. 6 and European Patent No. 210,660A2.

[0214]

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

Example 1 (Preparation of emulsion) Inert gelatin 2
0g, potassium bromide 2.4g, potassium iodide 2.05g
An aqueous solution in which 5.0 g of silver nitrate was dissolved was stirred at 58°C, and 150 ml of an aqueous solution in which 5.0 g of silver nitrate was dissolved was stirred at 58°C.
cc was added instantaneously, excess potassium bromide was further added, and the mixture was physically aged for 20 minutes. Additionally, U.S. Patent No. 4,
0.2 mol/l according to the method described in No. 242,445
, 0.67 mol/l, 2 mol/l silver nitrate and potassium halide aqueous solutions (mixed with potassium bromide 58 mol% and potassium iodide 42 mol%) at a flow rate of 10 cc/min, respectively. was added to grow 42 mol% silver iodobromide grains. The emulsion was washed with water for desalination to prepare emulsion a. The finished amount of emulsion a was 900 g. The average grain size of emulsion a is 0.61 μm. According to emulsion a, silver iodide content of 42 mol%, 0.59 μm, 0.56 μm, 0.
Prepare silver iodobromide grains of 52 μm and 0.46 μm,
Emulsions b, c, d and e were used.

[0216] Take 300g of emulsion a and add 850cc of distilled water.
and 30 cc of 10% potassium bromide were added, heated to 70°C, and stirred. Compound (18) shown in Chemical Formula 37 was added to this at 0.0%.
02g was added and the pAg was kept at 8.0.
300 cc of an aqueous solution containing 25 g of potassium bromide and 320 cc of an aqueous solution containing 25 g of potassium bromide were simultaneously added over 40 minutes.
Further, by simultaneously adding 800 cc of an aqueous solution containing 100 g of silver nitrate and 860 cc of an aqueous solution containing 75 g of potassium bromide for 60 minutes, the silver iodide content was 14 mol%.
Silver iodobromide emulsion 1 having a grain size of 0.88 μm was prepared. Emulsion 1 was a twin crystal with an aspect ratio of 2.0, and its (111) plane ratio was 80%. A silver iodobromide emulsion 2 having a silver iodide content of 12 mol % was prepared by taking 300 g of emulsion b and shelling it with a total amount of silver nitrate of 125 g in the same process as in the preparation of emulsion 1. Emulsions 3 to 5 were prepared according to this procedure.

In addition, in the method of preparing emulsions 1 to 4,
Emulsions 6 to 9 were prepared under the same conditions as in preparing Emulsions 1 to 4, except that the shelling conditions were changed to a temperature of 60 DEG C. and a pAg of 9.0, and compound (18) was removed.

Emulsion 10 was prepared by taking 133 g of emulsion b and 167 g of emulsion d and shelling them in accordance with the method for preparing emulsion 3 from 300 g of emulsion c. Also, 5 each of emulsions a and b
Emulsion 11 was prepared by taking 200 g of Emulsion C and shelling it in accordance with the method for preparing Emulsion 3 from 300 g of Emulsion C. Further, in the method for preparing Emulsion 1 and Emulsion 4, compound (18) was removed and the pAg was changed to 7.5 to prepare Emulsion 12 and Emulsion 13. Table A summarizes the characteristic values of these emulsions.

[0219]

[Table 1] On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/m2 of silver for silver halide and colloidal silver, and the amount expressed in g/m2 for couplers, additives and gelatin. For sensitizing dyes, the number of moles is expressed per mole of silver halide in the same layer. 1st layer (antihalation layer) Black colloidal silver
0.15 gelatin

1.90ExM-8
2.0×10-2 second
Layer (middle layer) Gelatin
2.10UV-1

3.0×10-2UV-2
6.0×1
0-2UV-3
7.0×10-2ExF-
1
4.0×10-3So1v-2
7.0×
10-2 Third layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%,
Normal crystal, twinned mixed particles, diameter/thickness ratio 2.5) Silver coating amount
0.50 Gelatin
1.50ExS-1

1.0×10-4ExS-2
3.0×10-
4ExS-3
1.0×10-5ExC-3

0.22ExC-4
3.0×10-
2SoIv-1
7.0×10-3 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%,
Normal crystal, twinned mixed particles, diameter/thickness ratio 2.5) Silver coating amount
0.85 Gelatin
2.00ExS-1

1.0×10-4ExS-2
3.0×10-
4ExS-3
1.0×10-5ExC-2

8.0×10-2ExC-3
0.3
3ExY-14
1.0×10-2Cpd-10

1.0×10-4So1v-1
0.10 5th
Layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed grains, diameter/thickness Ratio 2.0) Silver coating amount
0.70 Gelatin
1.60ExS-1

1.0×10-4ExS-2
3.0×10-
4ExS-3
1.0×10-5ExC-5

7.0×10-2ExC-6
8.0×10
-2So1v-1
0.15So1v-2

8.0×10-2 6th layer (middle layer) gelatin

1.10 P-2
0.17Cpd-1

0.10Cpd-4
0.17
So1v-1
5.0×10-2 7th layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28% , normal crystal, twinned mixed particles, diameter/thickness ratio 2.5) Silver coating amount
0.30 Gelatin
0.50ExS-4

5.0×10-4ExS-5
2.0×10-
4ExS-6
0.3×10-4ExM-8

3.0×10-2ExM-9
0.2
0ExY-14
3.0×10-2Cpd-11

7.0×10-3So1v-1
0.20 8th
Layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, mixed twin grains, diameter /thickness ratio 4.0) Silver coating amount
0.70 Gelatin
1.00ExS-4

5.0×10-4ExS-5
2.0×10-
4ExS-6
3.0×10-5ExM-8

3.0×10-2ExM-9
0.2
5ExM-10
1.5×10-2ExY-14

4.0×10-2Cpd-11
9.0×10-3S
o1v-1
0.20 9th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%,
Normal crystal, twinned mixed particles, diameter/thickness ratio 2.0) Silver coating amount
0.50 Gelatin
0.90ExS-4

2.0×10-4ExS-5
2.0×10-
4ExS-6
2.0×10-5ExS-7

3.0×10-4ExM-8
2.0×10
-2ExM-11
6.0×10-2ExM-12

2.0×10-2Cpd-2
1.0×10-
2Cpd-9
2.0×10-4Cpd-10

2.0×10-4So1v-1
0.20S
o1v-2
5.0×10-2 10th layer (yellow filter layer) Gelatin
0.60 yellow colloid

5.0×10-2Cpd-1
0.20S
o1v-1
0.15 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral grains ) Silver coating amount 0.40 Gelatin
1.00ExS-8

2.0×10-4ExY-13
0.25E
xY-15
0.60Cpd-2
1.
0x10-2So1v-1
0.20 12th layer (high sensitivity blue-sensitive emulsion layer) Emulsion 1
Silver coating amount 0.80 gelatin

0.60ExS-8
1.0×10-4Ex
Y-13
0.15ExY-15
0
．． 42Cpd-2
1.0×10-3So1v-
1
0.15 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, AgI type)
1 mol%)
0.20 gelatin
0.40UV-2

0.08UV-3

0.08UV-4
0.16So1
v-3
3.2×10-2P-2
9
．． 0x10-2 14th layer (second protective layer) Gelatin
0.40B-1 Polymethyl methacrylate particles (diameter 2.4 μm)
0.08B-2 Poly(methyl methacrylate-acrylic acid) copolymer Polymerization ratio 1:1 (diameter 2.4 μm
) 0.10H-1

0.40 Furthermore, in order to improve storage stability, processability, pressure resistance, anti-mold/bacterial properties, antistatic properties, and applicability, the following Cpd-3, Cpd-5, Cpd-6, Cpd- 7.C
pd-8, P-1, W-1, W-2, and W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. Furthermore, B-4, F-1, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-13 and iron salt, lead salt, gold salt,
Contains platinum salt, iridium salt, and rhodium salt.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

[0223]

[C43]

[0224]

[C44]

[0225]

[C45]

[0226]

[C46]

[0227]

[C47]

[0228]

[C48]

[0229]

[C49]

[0230]

[C50]

[0231]

[C51]

[0232]

[C52]

[0233]

[C53]

[0234]

[C54]

[0235]

embedded image (Samples 102-113) Emulsion 1 of the 12th layer of sample 101
Samples 102 to 113 were prepared by replacing emulsions 2 to 13.

(Samples 114-126) Samples 101-11
The acylacetamide type yellow dye-forming coupler (Y-1
Samples 114 to 126 were prepared by replacing 0) with an equimolar amount.

(Samples 127, 128) The first sample of sample 114
Half of Emulsion 1 in the two layers was replaced with Emulsion 3 and Emulsion 5 to form Sample 127 and Sample 128, respectively.

(Samples 129-132) Samples 123-12
The 11th layer of No. 6 and Y-10 of the 12th layer were also replaced with the aforementioned acylacetamide type yellow dye-forming coupler (Y-10).
Samples 129 to 132 were prepared by substituting equimolar amount of -40).

These samples were imagewise exposed to white light and subjected to the following color development process. The results of the photographic performance obtained are shown in Table B together with the RMS value (value of cyan image with an aperture of 48 μm diameter) indicating granularity. In addition, these samples were uniformly exposed to green light for 1 lux/second, then imagewise exposed to blue light, and the following color development was performed, with an exposure amount that gave a yellow density of (fog + 0.5). The value obtained by subtracting the magenta density at the yellow foggy density from the magenta density is shown in Table B as the color turbidity.

[0240] Furthermore, these samples were incubated at 45°C and relative humidity of 30°C.
% conditions for 7 days and the refrigerator for that period (
The same sample stored at 6°C) was subjected to the following color development, and the difference (ΔY) between the yellow fog density when stored at 45°C and that between the sample stored in the refrigerator is also shown in Table B.

[0241] This sample was also heated at 70°C and relative humidity 70%.
After being left for 4 weeks under these conditions, the density was measured again, and the change in yellow density is shown in Table B as color image fastness.

[0242] Table Treatment method Step Treatment time Treatment temperature
Refill amount Tank capacity Color development
3 minutes 15 seconds 38℃ 4
5ml 10L bleach
1 minute 00 seconds 38℃
20ml 4L bleach fixing
3 minutes 15 seconds 38℃ 3
0ml 8L Washing (1)
40 seconds 35℃ (2) to (1) 4 L
Countercurrent piping method to water washing (2) 1 minute 00 seconds 35℃
30ml 4L
Stability 40 seconds
38℃ 20ml 4
L drying 1 minute 15 seconds 5
The amount of replenishment at 5° C. is per 35 mm width and 1 m length.Next, the composition of the processing solution is described. (color developer)
Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0
1.1 1-Hydroxyethylidene-
3.0
3.2 1,1-Diphosphonic acid Sodium sulfite
4.0 4.4
potassium carbonate
30.0 37.
0 potassium bromide
1.4
0.7 Potassium iodide
1.5mg
- Hydroxylamine sulfate
2.4 2.8
4-[N-ethyl-N-β-hydroxy 4.5
5.5 Ethylamino]
-2-Methylaniline sulfate Add water
1.0 L 1.
0 L pH
10.05
10.10 (Bleach solution) Common to mother liquor and replenisher solution (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120
．． 0 Ethylenediaminetetraacetic acid disodium salt
10.0 Ammonium Bromide
100.0 Ammonium nitrate
10.0 Bleach accelerator

0.005 mole {
(CH3 )2 N-CH2 CH2 -S}2 ・2
HCl ammonia water (27%)
15.
Add 0ml water

1.0 L pH

6.3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt
5.0 Sodium sulfite

12.0 Ammonium thiosulfate aqueous solution (7
0%) 240.0m
l Ammonia water (27%)
6.0
Add ml water

1.0 L pH

7.2 (Water solution) Mother liquor and replenisher Common tap water was washed with H-type strongly acidic cation exchange resin (Amberlant I manufactured by Rohm and Haas).
R-120B) and an OH-type anion exchange resin (Amberlite IR-400), water was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/
20 mg/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were subsequently added. The pH of this solution was in the range of 6.5-7.5. (Stable solution) Common to mother solution and replenisher solution (Unit: g) Formalin (
37%)
2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.
3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt
0.05 Add water

1.0L

[0243]

[Table 2] From Table B, it is clear that the samples of the present invention have high sensitivity and are excellent in graininess, color reproducibility, change in fog during high temperature storage, and color image storage stability.

When the compound of general formula (A) is further included and the silver iodobromide grains are monodispersed, particularly high sensitivity and good results have been obtained.

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, which contains an acylacetamide-type yellow dye-forming coupler represented by the following general formula (I), and a core 1. A silver halide color photographic light-sensitive material comprising chemically sensitized core/shell type silver halide grains having a shell part on the outside of the part. [Formula 1] (In the formula, R1 represents a monovalent group. Q together with C,
Represents a group of nonmetallic atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. However, R1 is not a hydrogen atom and does not combine with Q to form a ring) 2. The silver halide color photographic material according to claim 1, which contains a compound represented by the general formula (A). General formula (A) G-SM1 (wherein G represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of -SO3M2, -COOM2, -OH and -NR1R2,
M1 and M2 independently represent a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium;
R2 independently represents a hydrogen atom or an alkyl group) 3. The silver halide according to claim 1 or 2, wherein the silver halide grains according to claim 1 are monodisperse emulsions having a coefficient of variation in grain size of 0.25 or less. Color photographic material. 4. A claim characterized in that two or more types of silver halide grains according to claim 1, or the silver halide grains and silver halide grains other than the silver halide grains according to claim 1 are contained in the same photosensitive layer. 1. The silver halide color photographic material described in 1. 5. A claim characterized in that two or more types of silver halide grains according to claim 2, or the silver halide grains and silver halide grains other than the silver halide grains according to claim 2 are contained in the same photosensitive layer. 2. The silver halide color photographic material described in 2. 6. A claim characterized in that two or more types of silver halide grains according to claim 3, or the silver halide grains and silver halide grains other than the silver halide grains according to claim 3 are contained in the same photosensitive layer. 3. The silver halide color photographic material according to 3.