JPH02220045A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material wide in exposure latitude and superior in shelf life of a photosensitive material and a latent image by incorporating a DIR compound and an N-containing heterocyclic compound having a mercapto group in a photosensitive material. CONSTITUTION:It is preferred that blue- and green-sensitive silver halide emulsion layers both have single layer structure and especially each of all the blue- and gree- and red-sensitive silver halide emulsion layers has single layer structure. The DIR compound contained in some of them means a compound to be allowed to release a development inhibitor or its precursor by reaction with the oxidation product of a color developing agent and its typical structural formula is A-(Y)m in which A is a coupler residue and m is 1 or 2 and Y is a DIR group combined at the coupling site of A, and the N-containing heterocyclic compound having the mercapto group is, preferably, the one represented by general formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic material suitable for full-color photography.

[Prior art] Currently, color photography is possible only with color negative film! ! In recognition of this, the so-called negative-positive method, in which enlarged color prints are made on color paper, is widely used.

One reason for this is that color negative film has a very wide exposure latitude, and the probability of failure during shooting is extremely low, allowing even some users without specialized knowledge to easily take color photos. .

[Having a wide exposure latitude] means that in the so-called characteristic curve where the horizontal axis is the exposure amount and the vertical axis is the color density,
It means that iv4 is good over a wide exposure m range from a shadow part with a low exposure amount to a highlight part with a large exposure m.

If this gradation is poor, the color reproducibility and tone reproducibility of the dye image will deteriorate.

Color negative film is a photosensitive material that requires strict control of gradation throughout the color reversal film, and for this reason, currently commercially available color negative films for photography have different photosensitive layers for blue, green, and red light. d has a multilayer structure including a plurality of emulsion layers including a high-speed layer containing silver halide grains with a large grain size and a low-sensitivity layer containing silver halide grains with a small grain size, and further reacts with an oxidized product of a developing agent. So-called DIR compounds are used which result in the formation of development inhibitors.

This technology is unique to color negative film;
In particular, DIR compounds improve not only gradation but also the sharpness of dye images.
It also improves graininess and color reproducibility, and is essential for color negative films.

[Problem 1 that the present invention aims to solve Color negative film has a multilayer structure using multiple emulsion layers containing silver halide grains with different grain sizes, as described above.
Furthermore, since the gradation is strictly controlled using a DIR compound, the storage stability of the photographic light-sensitive material before photographing (hereinafter referred to as "sensitivity material storage stability") against external conditions such as temperature and humidity is poor.
It has disadvantages such as deterioration of gradation and deterioration of color reproducibility and tone reproducibility due to poor storage stability against external conditions of photographic light-sensitive materials after photography (hereinafter referred to as latent image storage stability). There is.

As a technique for improving the stability of such gradations, a method is proposed in which silver halide emulsions with equal average grain sizes are chemically sensitized, sensitizing dyes are added to each emulsion at different molar ratios, and then mixed again (Unexamined Japanese Patent Publication No. No. 60-244944) is known, but this remixed emulsion is undesirable because dye adsorption equilibrium occurs between grains during the stagnation period up to coating.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material that has a wide exposure latitude and is excellent in photosensitive material storage stability and latent image storage stability.

Means for Solving Problem E] The above-mentioned object of the present invention is to provide a silver halide color photographic photosensitive material having at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. In the material, the light-sensitive material contains a DIR compound and a mercapto nitrogen-containing heterocyclic compound, and at least two of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers are composed of a single layer. This is achieved by a silver halide color photographic light-sensitive material characterized by the following characteristics.

The present invention will be explained in more detail below.

In the present invention, the DIR compound refers to a compound that releases a development inhibitor or a compound capable of releasing a development inhibitor upon reaction with an oxidized product of a color developing agent.

The compound capable of releasing the development inhibitor described above may be one that releases the development inhibitor imagewise or non-imagewise.

Examples of those that release imagewise include those that result from a reaction with an oxidized product of a developing agent, and examples of those that release non-imagewise include those that utilize the TIME group described below.

Representative structural formulas are shown below.

General formula (D-1>A-(Y)I A represents a coupler residue, and the symbol represents 1 or 2,
Y represents a group that binds to the coupling position of the coupler residue mA and leaves by reaction with the oxidized product of the color developing agent, and represents a development inhibitor group or a group capable of releasing the development inhibitor.

In the general formula <D-1), Y is typically the following general formula C
It is represented by D-2) to (D-20).

General formula (D-22 General formula (D-5) General formula (D-8) General formula (D-7) General formula (D-8) General formula (D-9) R4 General formula (D-2) ~ In (D-7), Rd+ is a hydrogen atom, a halogen atom, or an alkyl, alkoxy,
Acylamino, alkoxycarbonyl, thiazolidinylideneamine, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N, N-
Represents eight groups: dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocycle, cyano, alkylsulfonyl, or aryloxycarbonylamino . n represents 0.1 or 2, and when n is 2, each Rd1 may be the same or different.

The total number of carbon atoms contained in n Rdt in (D-2) to (D-5> and (D-7) is 0 to 10.Also, the carbon number contained in Rdl in general formula (D-6) is 0 to 10. The number is O
~15.

X in the above general formula (D-6) represents an oxygen atom or a sulfur atom.

In the general formula (D-8>), Rd2 represents an alkyl group, an aryl group, or a heterocyclic group.

In general formula (D-9), Rda is a hydrogen atom or 8 of alkyl, cycloalkyl, aryl or heterocycle.
represents a group, Rd+ is a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino,
Represents eight groups of alkoxycarbonylaminocansulfonamide, cyanide, heterocycle, alkylthio, or amino.

When Rd+, Rd2, Rd3 or Rd+ represents an alkyl group, this alkyl group may have a substituent and may be either linear or branched.

When R1+, Rd2, Rd3 or Rd4 represents an aryl group, the aryl group includes those having a substituent.

When Rd+, Rd2, Rd3 or Rd+ represents a heterocyclic group, this heterocyclic group includes those having a substituent, the heteroatom is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and this heterocyclic group The group is preferably a 5- or 6-membered monocyclic ring or fused ring containing at least one of the above heteroatoms, such as pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido. , oxazine, etc.

In general formula (D-8), the number of carbon atoms contained in Rd2 is O to 15.

In the above general formula (D-9), the total number of carbon atoms contained in Rda and Rd is 0 to 15.

General formula (D-10) -(TIME), iN)-11BiT In the formula, the TIME group is a group that is bonded to the coupling position of A and can be cleaved by reaction with an oxidized product of a color developing agent,
After cleavage from the coupler, it is cleaved sequentially and finally IN)
-11BIT is a group that can be released in a controlled manner.
, n is 1 to 3, and when n is 2 and 3, each TIME
The groups may be the same or different. The INHABIT group is a group that becomes a development inhibitor by the above-mentioned release (for example, the above-mentioned general formula (D
-2) to (D-9).

In general formula (D.-10), the TIME group is typically represented by the following general formulas (D-11) to (D-19).

General formula (D-11) General formula (D-12) General formula (D-13) General formula (D-14) General formula (D-15) General formula (D-16) General formula (D-17) General formula (D-18) General formula (D-19) d1Eda In general formulas (D-11) to (D-15) and (D-18), Rd s is a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, Represents a polygroup of alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, humanOxy or alkanesulfonyl, and has the general formula (D-11 ) ~ (D-13), (D-1
5) In (D-18), R(!5 may combine with each other to form a condensed ring, and the general formula (D-11), (D-
14), (D-15) and (D-19), Rd
s represents a polygroup of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle, or aryl, and has the general formula (
In D-16) and (D-17), Rd7 represents a hydrogen atom or a polygroup of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle, or aryl, and R (La and Rd9 in general formula (D-19) Each has a hydrogen atom or an alkyl group (preferably 1 to 4 carbon atoms)
represents an alkyl group of general formula (D-11), (D-
15) to (D-18), \ represents an integer of 011 or 2, and general formulas (D-11) to (D-13), CD
-15), l in (D-18) represents an integer of 1 to 4, m in general formula (D-16) represents an integer of 1 or 2, and when l, , and rb are 2 or more, each Rds, Rdy
may be the same or different, 0 in general formula (D-19) represents an integer of 2 to 4, and Rda and Rd9 of nl
may be the same or different, and the general formula (D-16
) to (D-18), B is an oxygen atom or -N-(
Rds has the same meaning as Rda defined previously. ), and the general formula (D-16
> indicates that it may be a single bond or a double bond; - is 2 in the case of a single bond, and 1 is in the case of double bonding.

General formula (D-20) →T1−+iSR+T2+−INHIBITIn the formula, T1
is the component that cleaves S R+ T 2KINHIBIT, and SR is S R+72 +r-I N l-11B I
After T is generated, (T
2+-IN HI B I T
2 is (T2+1l-INHIBIT is generated, then IN
INHIBIT represents a component that cleaves HIBIT, INHIBIT represents a development inhibitor, and i and I each represent 0 or 1.

The component represented by SR may be one that produces the above-mentioned component by reaction with the oxidized form of the developing agent, such as a coupler component that reacts with the oxidized form of the developing agent and a coupler component that reacts with the oxidized form of the developing agent. Examples include redox components that undergo redox reactions.

Coupler components include acylacetanilides, 5-
Pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2 (5H)-imidazolones, 5-isoxacilones, uracils, homophthalimides, oxazolones, 2,5 -Thiadiazoline-
In addition to 1,1-dioxides, triazolothiadiazines, indoles, yellow couplers, magenta couplers, and cyan couplers, those that produce various dyes or those that do not produce dyes may be used.

+T1+-8R+T2+r-1NHIBIT is the general formula (
It is preferable that it binds to the active site of component A in D-1).

In addition, when SR is a coupler component, SR is cleaved from fT1\, and then the SR is fused to function as a coupler for the first time.
T1+i- and →T2 are coupled with INHIBIT.

For example, when the coupler component is a phenol or naphthol, the oxygen atom of the hydroxyl group is the oxygen atom of the hydroxyl group at the 5-position of the tautomer, or the nitrogen atom at the 2-position is the tautomer. , also, acetophenones,
In indanones, the oxygen atom of the hydroxyl group of the tautomer bonds with +T++, resulting in +T2+-INHIBI
Preferably, T is bound to the active site of the coupler.

When SR is a redox component, examples thereof include hydroquinones, catechols, pyrogallols, aminophenols (such as p-7 minophenols,
0-aminophenols), natuthalene diols (e.g. 1,2-naphthalene diols, 1,4-naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (e.g. 1,2-naphthalene diols) 1,4-aminonaphthols, 2,6-aminonaphthols), etc.

Also, if SR is a redox component, SR is + T I
Cleaved from M-, it first binds with +T+4- and +T2-)yyINHIBIT to function as a redox component.

Examples of the groups represented by T1 and T2 include those represented by the aforementioned general formulas CD-11) to (D-19).

Examples of the development inhibitor represented by INHIBIT include those represented by the aforementioned general formulas (D-2) to (D-9).

Among the DIR compounds, preferred are those in which Y has the general formula (D-
2>, (D-3), (D-8), (D-10) or (D
-20), (D-10), (D
-20), IN)-IIBIT has the general formula (D-
2), (D-3), <0-6) (especially general formula (D-6)
When X is an oxygen atom) or (D-8>) is preferable.

Examples of the coupler component represented by A in general formula (D-1) include yellow image-forming coupler residues, magenta image-forming coupler residues, cyan image-forming coupler residues, and colorless coupler residues.

Preferred DIR compounds used in the present invention include the following compounds, but these are limited to exemplified compounds R, -COC) (Co-R).

Y R,,R,Y's Cji CH.

Cji C) CI 4 Meeting H -CONHCH,CH,C00H -CONHCH, CH, C00CH.

CH.

(Specific examples of DIR compounds that can be used in the present invention are U.S. Pat. Nos. 4,234,678 and 3,227,5
No. 54, No. 3.617.291, No. 3.958.
No. 993, No. 4.149886, No. 3.933.5
No. 00, JP-A No. 57-56837, 51-13239
No. 2,072゜363, U.S. Patent No. 2,070,2
No. 66, Research Disclosure No. 21228, December 1981, etc.

DIR compound is 0,0001 per mole of silver halide
It is preferable to use ~0.1 mol, especially 0.001 mol.
It is preferable to use ~0.05 mol.

The DIR compound may be added at any place that affects the development of silver halide in a silver halide emulsion layer having a single layer structure, preferably in a silver halide emulsion layer, and more preferably in a single layer structure. and/or an emulsion layer having the same color sensitivity as the silver halide emulsion layer.

The mercap 1-based nitrogen-containing heterocyclic compound used in the present invention is preferably one represented by the following general formula [I].

General formula [I] In the formula, 2 is a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom,
Represents an atomic group necessary to form a 5- or 6-membered heterocycle consisting of selenium atoms, including fused heterocycles, and M represents a hydrogen atom, an alkali metal atom, or an ammonium group.

Examples of the heterocycle formed by 2 include pyridine,
Pyrimidine, imidazole, benzimidazole, naphthimidazole, oxazole, benzoxazole,
Examples include naphthoxazole, thiazolinthiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, triazole, oxadiazole, thiadiazole, 1-riazine, tetrazole, purine, azaindene, and the like. These heterocycles may have a substituent, and examples of the substituent include an aromatic group, an aliphatic group, a hydroxy group, an alkoxy group, an aryloxy group, an amino group, a nitro group, a halogen atom, and a carboxyl group. or a salt thereof, a sulfo group or a salt thereof, a mercapto group or a salt thereof, an alkylmercapto group, an acylamino group, a sulfamoyl group, a sulfoamide L
Examples include carbamoyl group.

Among the compounds of general formula [I], the following general formula [II]
], [I[] and [IV] are particularly preferred.

General formula [II] In the formula, Ar represents a phenylene group, a naphthylene group, or a cyclohexylene group, R1 represents a group or a hydrogen atom that can be substituted for the Ar group, and M is the same as M in the general formula [I] above. are synonymous.

General formula [1 [1] In the formula, zl is a sulfur atom, an oxygen atom, a selenium atom, or -
represents an N- group, R2 represents a substituent or a hydrogen atom, m
represents 1 to 4, and when m is 2 to 4, each R2 may be the same or different, or may be bonded to each other to form a condensed ring. Moreover, M has the same meaning as M in the general formula [I].

General formula [IV] represents -N+-1802R6, R5 represents an alkyl group, aryl group, cycloalkyl group, aralkyl group, or amino group, and R6 represents an alkyl group, aryl group, cycloalkyl group, or aralkyl group. , M is the general formula [I
] is synonymous with M.

Specific examples of mercapto nitrogen-containing heterocyclic compounds are listed below, but the present invention is not limited to the following compounds.

In the formula, z2 represents a sulfur atom, an oxygen atom, a selenium atom, R or -N-, and R3 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an acylamino group, or a sulfone. represents an amide group or a heterocyclic group, and R'' is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, -COR5-302R5-NHCOR6 or (Z-
12) (Z-14) (Z-16) (Z-1,8) (Z-20) (Z-7) (Z-9) (Z-13) (Z-22) (Z-15) ( Z-17) (Z-19) (Z-21) (Z-8) (,lI (Z-10) (Z-23) (Z-34) (Z-35) The above general formula [I[] The compound is disclosed in JP-A-56-1118
Publication No. 46, British Patent No. 1,275,701,
U.S. Pat. No. 3,266,897 and U.S. Pat. No. 2,403,
It can be synthesized by the method described in No. 927 or a method analogous thereto.

The compound of the above general formula [DI] is disclosed in U.S. Patent No. 2,824
．． Specification No. 001, Japanese Patent Publication No. 40-28496, Journal of Chemical Society 4237 (
1952) and 1723 (1951), or a method analogous thereto.

The compound of the above general formula [IV] is disclosed in U.S. Patent No. 2.843
No. 491, Specification No. 3,017,270, British Patent No. 940, No. 169 Mei II, JP-A-55-59463
It can be synthesized by the methods described in JP-A-51-102639, or methods similar thereto.

Although it is difficult to unconditionally define the amount of the mercapto nitrogen-containing heterocyclic compound used in the present invention, the desensitization range when added compared to when it is not added is within 0.20 in terms of Δ and loH, and even within 0. The amount added is preferably within .10.

Any known method can be used for adding the mercapto nitrogen-containing heterocyclic compound.

Further, the addition location is preferably in the silver halide emulsion layer.

The fact that the photosensitive silver halide emulsion layer is a single layer means that the type of coupler contained in the emulsion layer, the grain size of the silver halide grains, the halogen composition and crystal habit, and the ratio of coupler and silver halide are the same. This also includes the case where a plurality of emulsion layers having the same photosensitivity are arranged as a continuous layer.

Here, "having the same photosensitivity" or "same photosensitivity" may mean, for example, the same in terms of blue sensitivity, green sensitivity, and red sensitivity, and it is not necessary that the spectral sensitivity characteristics be exactly the same. .

In the present invention, it is preferable that both the blue-sensitive and green-sensitive silver halide emulsion layers are a single layer, and in particular, all of the blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers are each A single layer is preferred.

When the same photosensitive layer has a single layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional multilayer structure, making it possible to make the film thinner. Therefore, production efficiency, sharpness, and graininess are improved. The film thickness after drying is 20~
The thickness is preferably 3 μm, particularly preferably 15 to 5 μm.

One of the characteristics of the silver halide color photographic light-sensitive material of the present invention is that it has a wide exposure latitude.

Here, exposure latitude is the width of the amount of received light that produces a significantly different exposure effect, and is the exposure range from highlights to deep shadows in the characteristic curve.
93 (Shashin Kogyo Publishing, 1982).

In other words, it is the difference between two points of ffiogH where the slope of the tangent at the foot and shoulder of the characteristic curve where the horizontal axis is ffiogHS and the vertical axis is transmission density is 0.2.

The light-sensitive material of the present invention preferably has an exposure latitude of 3.0 or more, and preferably 3.0 to 3.0 or more, as measured by the above method.
8.0 is particularly preferred.

As a means for widening the exposure latitude of a single silver halide emulsion layer to 3.0 or more, a method of mixing and using silver halide grains having different sensitivities can be used. Examples of JA methods include a method in which silver halide grains having different grain sizes are used in combination, and a method in which a desensitizer is contained in at least a portion of the silver halide grains.

Silver halide grains with different grain sizes used in combination to obtain a wide exposure latitude have an average grain size of 0.2.
A combination of silver halide grains having a maximum average grain size of ~2□0 μm and silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferable, and further an intermediate average grain size is preferred. One or more silver halide grains may be combined.

Further, the average grain size of the silver halide grains having the maximum average grain size is 1.5 to 4% of the average grain size of the silver halide grains having the minimum average grain size.
Preferably, it is 0 times.

In order to obtain a wide exposure latitude, it is possible to mix and use silver halide grains with different average grain sizes. If used, the difference in average grain size can be reduced without changing the sensitivity of silver halide grains, and furthermore, it is possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, a wide exposure latitude can be obtained even if the coefficient of variation of the entire grain is made small.

Therefore, these silver halide grains having a small coefficient of variation that are exposed to the same environment are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing. Furthermore, from the viewpoint of production technology, it becomes possible to chemically sensitize a mixed system of silver halide grains having different sensitivities in the same batch.

Various desensitizers can be used, such as metal ions, antifoggants, stabilizers, and desensitizing dyes.

In the present invention, a metal ion doping method is preferred. Metal ions used for doping include Group Ib, Group ■b, Group ■a, Group ll1b, and Group IV in the periodic table of elements.
Examples include metal ions of group B, group VA, and group II. Preferred metal ions include Au, Zn, Cd, Tfl,
Sc, Y, Bi, Fe.

Ru, Qs, Rh, lr, Pd, Pr, SrQ.

Examples include Yb metal ions. Particularly preferably Rh
, Ru, Qs, lr. These metal ions can be used, for example, as halide complex salts, and the pH of the AgX suspension system during doping is preferably 5 or less.

In addition, the doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grain, the doping position of the metal ion, the desired sensitivity, etc.
It is preferably 17 to 10-2 mol, more preferably 12 to 10-3 mol, and particularly preferably 10-9 to 10-mol per 1 mol.

Furthermore, by selecting the type of metal ion, doping position and doping member, various different sensitivity qualities can be imparted to the silver halide grains.

When the doping amount is 10-2 mol/1 mol AQ
Silver halide grains with a narrow grain size distribution can be prepared even under the same grain growth conditions and even under the same batch growth.

It is also possible to prepare silver halide grains with different doping conditions to conditions suitable for practical use, mix them at a predetermined m ratio to form the same batch, and then chemically sensitize the grains. Each silver halide grain receives a sensitizing effect based on its properties, and an emulsion having a wide exposure latitude can be obtained depending on the sensitivity difference and mixture ratio.

The antifoggants or stabilizers include azoles (e.g., benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, etc.), heterocyclic mercapto compounds (e.g., mercaptotetrazoles, mercaptothiazoles, mercapto Thiadiazoles, mercap-1 benzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) Azaindenes (e.g., tetraazaindenes, pentaazaindenes, etc.) Nucleic acid decomposition products <r* e.g. adenine, guanine, etc.>, benzene Examples include thiosulfonic acids and thioketo compounds.

Examples of desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

The location of the desensitizer is preferably mixed inside the silver halide grains from the viewpoint of storage stability of the photosensitive material, stagnation stability of the coating solution, etc., and even if its distribution is uniform, , even if it is localized at the center or intermediate position of the particle,
It may gradually decrease from the center of the particle toward the outside.

From the viewpoint of production efficiency, it is preferable that the seed particles be localized in the center of the particles, and if a method using seed particles with a small coefficient of variation is used, the steps after particle growth can be performed in the same batch.

In the photosensitive material of the present invention, it is desirable that at least one photosensitive layer (for example, a blue-sensitive layer) contains XX particles containing a desensitizer. Preferably, the blue-sensitive layer contains the desensitizer-containing IX particles, more preferably the blue-sensitive layer and the green-sensitive layer, and most preferably all the color-sensitive layers contain desensitizer-containing IX particles.

Further, the coefficient of variation defined as the ratio S/ of the standard deviation (S) of the grain size to the average grain size (lower) of the entire silver halide grains contained in each silver halide emulsion layer is 0.4 or less. It is preferably 0.33 or less, more preferably 0.25 or less, and particularly preferably 0.20 or less.

The average grain size (D) is the grain size (in the case of cubic silver halide grains, the length of its side, or, in the case of grains with a shape other than a cube, the diameter when converted to a cube having the same volume). When the number of particles with side length ri is ni, it is defined by the following formula.

Σn1-ri r = Σn The standard deviation (S) is defined by the following formula.

The relationship between particle size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photography," The Photographic Journal, Vol. LXXIX (1949), 330-3.
In the method described in the paper by Tribel and Smith on page 38,
You can decide this.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any conventional silver halide emulsion can be used, but silver halide containing substantially iodine in the halogen composition (for example, silver iodobromide, silver iodochlorobromide) is preferred;
Silver iodobromide is particularly preferred in terms of sensitivity. As iosutan 1
It is preferably mol% or more and 20 mol% or less, particularly preferably 3.5 mol% or more and 12 mol% or less.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The milk, drug layer, and other hydrophilic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling with a colored coupler, which has the effect of color correction, and an oxidized form of a competing coupler and a developing agent, a developer, a silver halide solvent, a toning agent, a hardening agent, an antifoggant, a chemical sensitizer, etc. Compounds that release photographically useful fragments such as spectral sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or emulsion 1 may contain dyes that are washed out or bleached from the light-sensitive material during development.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retardant, a bleach accelerator, etc. can be added to the photosensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene non-terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The photosensitive material of the present invention is particularly useful as a negative photosensitive material.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Prior to the Examples, silver halide emulsions used in the Examples were manufactured.

P in the reaction pot was charged with L4 concentrated J and l gelatin aqueous solution.
While controlling Ag and DH, silver nitrate aqueous solution,
Seed emulsion NE was prepared by adding an aqueous potassium iodide solution and an aqueous potassium bromide solution simultaneously while controlling the addition time, and performing precipitation desalting using pH-coagulable gelatin and adding gelatin.
-1 was prepared.

Also, 3 RhCJ in the reaction pot! Seed emulsion NE-2 was prepared in the same manner as above except that s was added.

The seed emulsion and its contents are shown in Table-1.

Table-1 The above seed emulsion and gelatin aqueous solution were put into a reaction vessel, and while controlling the I)A (+) and pH in the reaction vessel, an ammoniacal silver nitrate aqueous solution, a potassium iodide aqueous solution, and a potassium bromide aqueous solution were added for grain growth. The IJ was added in proportion to the surface area at the time, and the potassium bromide solution was changed to an appropriate particle size, and then added.Similarly to the seed emulsion, precipitation and desalting were performed, and gelatin was added and redispersed.1) AQ 7 .8,
An emulsion with a pH of 6.0 was obtained.

In this way, the inside of the grain becomes a silver iodobromide emulsion EM with a relatively high content.
-1 to EM-4 were prepared.

Table 2 shows the emulsions and their contents.

Table 2 A multilayer color photosensitive material No. 1 having a type layer structure having the following composition was placed on a support to subbed cellulose acetate-1 (sample No. 101).
01 was created.

The coating amount is expressed in units of g/V converted to silver for silver halides and colloidal silver, and in units of g/12 for additives and gelatin, and sensitizing dyes, The coupler and DIR compounds are expressed in moles per mole of silver halide in the same layer. Incidentally, the emulsion contained in each photosensitive emulsion layer was prepared by using equimolar amounts of ml NE-1 and NE-2 using thioacid, storum and chloroauric acid.

In addition to the above components, a surfactant was added to each layer as a coating aid.

UV-t UV-2 C-1 M-2 Sensitizing dye ■ Sensitizing dye ■ M-1 Sl Sensitizing color I'll Sensitizing dye H Sensitizing dye m Below, each layer of the above composition is the above-mentioned HC, +L-1, R-
"l, R-2, 1L-2, G-1, G-2゜YC, B-
1, 8-2, Pro-1, Pro-2 (denoted with the abbreviation D.

Next, samples N0.702 to NO,116 were created.

First, sample No. 102 is sample N 0.1010Gl
Sample No. 101 was prepared in the same manner as Sample No. 101, except that the compounds shown in Table 3 were added to G-2.

Sample No. 103 and No. 104 are sample No. 101
Except for 0G-2, the emulsions contained in G-1 were EM-1 and E.
Instead of the equimolar mixture of M-2, an emulsion contained in G-1,
Increased usage of gelatin and TCP by 30% each,
Furthermore, Sample No. 104 was prepared in the same manner as Sample No. 101 except that the compounds shown in Table 3 were added to G-1. However, the amount per mole of halogenated G-1 sensitizing dye, coupler, and DIR compound is the sample NO, tQ.
Same as l.

Sample No. t05 to No. 114 is sample No.
Except for B-2 of 103, the emulsion contained in B-1 was EM-
Instead of an equimolar mixture of 1 and EM-2, the amounts of the emulsion, gelatin and TCP contained in B-1 were increased by 15%, and the emulsion and compound contained in G-1 were roughly shown in Table 3. It was prepared in the same manner as sample No. 103 except that . However, m per mole of silver halide of the sensitizing dye and coupler of B-1 is the same as that of sample No. 0.103.

Sample No. 115, No. 116 are sample No. 0.10
Except for R-2 in 5, the emulsion contained in R-1 was replaced with an equimolar mixture of EM-1 and EM-2, and the amounts of emulsion, gelatin, and DOP contained in R-1 were each increased by 25%. However, as shown in Table 3, the emulsion and compounds contained in G-1 were changed, and Sample No.

It was created in the same manner as No. 105. However, the amounts of the sensitizing dye, coupler, and DIR compound in R-1 per mole of silver halide are the same as in Sample No. 105.

The samples thus prepared and their contents are shown in Table 3.

-: In the blue photosensitive layer *: Green photosensitive layer L: Red photosensitive layer Table - 3 However, sample No., 105 to No., 113 and N 0.1
The emulsion contained in No. 15 G-1 is an equimolar mixture of two types of emulsions shown in Table 3.

In addition, the amount of each compound contained in the green photosensitive layer shown in Table 3 is 2 to 1 mole of silver halide in the green photosensitive layer.
×10→mol.

Compounds A-1 to A-3 shown in Table 3 each have the following structures.

■・I 11 The obtained samples N0.101 to 116 were cut and divided into appropriate sizes, and two of them were exposed to wedge light using white light according to a conventional method. A part of this exposed sample was kept in the refrigerator (temperature 5℃) (W standard), and the remaining part was kept in the refrigerator at a temperature of 25℃.
After being stored for 15 days at a relative humidity of 80%, it was developed using the following processing steps.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water
3 minutes 15 seconds stabilization 1 minute 3
0 second drying The composition of the treatment liquid used in each treatment step is shown below.

11 ri 11 4-amino-3-methyl-N-ethyl -N-(β-hydroxyethyl) Aniline/sulfate anhydrous sodium sulfite Hydroxylamine 1/2 sulfate Anhydrous potassium carbonate potassium bromide Nitrilotriacetic acid trisodium salt (monohydrate salt) potassium hydroxide Add water to make 1ft. (1) H-10 bleaching solution Iron ethylenediaminetetraacetate (m) ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water to make it 1, Adjust to DH6.0.

Ammonium thiosulfate 10.0 (] 150, Og 10.0 0 Using ammonia water 4°75g 4.25CI 2.0 g 37.5 (1 1,39 2.5g i, og 100, og 175.0 g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 11, and adjust the pH to 6.0 using acetic acid.

1 Formalin (37% aqueous solution) 1.5 Reviews (Konica Corporation tJ)? , 5iI
2 Add water to make 1 ft.

The temperature of the developed sample was measured in accordance with a conventional method, a characteristic curve was obtained, and the gradation preservation property related to the latent image preservation property was evaluated.

Hereinafter, a method for evaluating gradation preservation will be explained using figures.

Figure 1 shows the reference characteristic curve (dashed line) and the characteristic surface I! (solid line). Minimum concentration + in Figure 1
From the exposure point giving a density of 0.1 Δi0g)-1-+
Each exposure point between 3.0 exposure points (ΔIDQ between each exposure point
Figure 2 shows the point 1 to gamma box of H-0, 15).

From Figure 2, the absolute value Δγ of the difference in point gamma at each exposure point between the reference characteristic curve and the characteristic curve to be evaluated.
seek. The preservation of gradation was expressed by the value (Δγ) obtained by multiplying the average value of Δγ by 1000 and by the value Σ obtained by multiplying the standard deviation σ of Δγ by 1000.

That is, the larger the value of Δ is, the greater the point gamma of both characteristic curves is, and the larger the value of Σ is, the more uneven the change in gradation becomes, resulting in poor gradation preservation.

Example 2 The obtained samples NO, 101 to 116 were cut and divided into appropriate sizes, and two parts of them were used without exposing them to light.

A part of the unexposed sample was stored in a cold storage (temperature: 5°C) (based on
The remaining portion was stored for 7 days at a temperature of 40° C. and a relative humidity of 80%, and exposed using a wedge using white light according to a conventional method. This sample was developed in the same manner as when evaluating the gradation storage property related to the latent image storage property, and a characteristic curve was obtained to evaluate the gradation storage property related to the storage property of the photosensitive material.

The results for the green photosensitive layer are shown in Table 4.

Table 4 As is clear from Table 4 below, the sample of the present invention has a small gradation displacement from the highlight part to the shadow part of the characteristic curve.
It was found that the gradation stability related to photosensitive material storage stability and latent image storage stability was good. Also, the exposure latitude is ΔffiO
It was found that the gH value was 3 or more, and that the film had a wide exposure latitude.

When compared in the present invention, samples (112 to 116) containing emulsions doped with Rh ions inside the grains have a narrow grain size distribution of silver halide grains in each photosensitive layer, and have a large improvement effect, which is preferable. I understand.

In particular, samples No. 115 to 11 in which all the photosensitive layers were made into a single layer
It was found that sample No. 6 had a large improvement effect and was preferable.

Moreover, Samples Nos. 114 and 116 are preferable in terms of production efficiency, since physical ripening and chemical ripening can each be performed once in the preparation of the emulsion, compared to other samples.

In this example, a monodisperse emulsion with a coefficient of variation of 0.19 to 0.20 was used, but the effects of the present invention were also observed even when a polydisperse emulsion with a coefficient of variation of 0.28 was used. In this example, the green-sensitive layer was evaluated, but samples were similarly prepared using the blue-sensitive layer and the red-sensitive layer, and the gradation storage stability was evaluated, and the effect of the present invention was observed.

Furthermore, a larger improvement effect was observed in the system containing an emulsion in which Rh ions were doped in all layers and inside the grains.

Also, sample No. 109 (DZ-3 (7) substitute 1.:
Z-1゜2-4.2-6. Z-7, test No. 113
ICZ-8, 2-9, Z-1C
l, Sample FI No. 110 No. Z-1417) Substitute Z-12, Z-21, 2-23, Sample No. 111
f7) Z-3277) Z-24,2-27,2 instead
The effects of the present invention were also observed for each sample using -31.

In addition, each sample using (D-29), (D-4), and (D-2) instead of (D-42) in (B-2) of sample N01109, and (G- 1) (D-23)
(D-6), (D-2) instead.

Each sample using (D-10), sample N 0.116 (
(D-23) and (D-42) in R-1)
-2) and (D-17), also (D-19) and (D-
21), the effects of the present invention were observed in all samples.

Also, Ks Rh Cl! RIICffi3 instead of s
．． .

Os Cff13. A seed emulsion prepared by adding Pb (NO3)2 was used instead of NE-2, and the emulsions prepared were EM-3 for samples No. 112, 113, and 115, and EM-4 for samples No. 114 and 116. The effects of the present invention were also observed for each sample used instead of .

[Effects of the Invention] As is clear from the above results, the present invention has been able to provide a silver halide photographic material that has a wide exposure latitude and is excellent in photosensitive material storage stability and latent image storage stability. .

[Brief explanation of the drawing]

Figure 1 is a diagram showing the characteristic curves of the standard (broken line) and evaluation target (solid line) photographic light-sensitive materials, and Figure 2 is a diagram showing the point gamma of the reference (broken line) and evaluation target (solid line) photographic light-sensitive materials. be.

Claims (1)

[Claims] A silver halide color photographic light-sensitive material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support, the light-sensitive material comprising a DIR compound and a mercapto nitrogen-containing heterocycle. contains a compound, and
A silver halide color photographic light-sensitive material, wherein at least two of the blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers are composed of a single layer.