JPH02217846A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a preservable property by incorporating a DIR compd. and 5-pyrazolone 2-equiv. magenta coupler into a green photosensitive layer. CONSTITUTION:This photosensitive material is constituted by having at least the blue photosensitive, green photosensitive and red photosensitive silver halide emulsion layers respectively on a base. At least the green photosensitive layer is constituted of a single layer and contains the DIR compd. and the 5- pyrazolone 2-equiv. magenta coupler. The DIR compd. refers to a development restrainer or compd. which eliminates the compd. capable of releasing the development restrainer by reaction with the oxidant of a color developing agent. The silver halide color photographic sensitive which is low in the degradation in the density of the color development even under a gaseous formalin condition and has the excellent preservable property of the photosensitive material and the latent image preservable property is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide color photographic sensitizer 1111 suitable for full-color r-shading, and in particular to a negative-working halogen film in which at least one color-sensitive layer is a single layer. f! for silver chemical color photographic materials. fil-ru.

[Prior Art 1] Currently, the so-called negative-positive method is widely used for color photography, in which the photograph is printed using a color negative film and then enlarged onto color vapor to produce a color print.

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

"Having a wide exposure latitude" means that in the so-called characteristic curve where the horizontal axis is the exposure m and the vertical axis is the color density,
It means that the gradation is good over a wide exposure range from the shadow area where the exposure amount is low to the highlight area where the exposure amount is high.

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 range.For this reason, currently commercially available color negative films for photographic use have different chromatic sensitivities to blue, green, and red light. The layer 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 Wi tone but also the sharpness, graininess, and color reproducibility of dye images, and are essential in color negative films.

Incidentally, in recent years, general photographic materials have come into contact with formaldehyde gas more frequently. For example, furniture manufactured using formalin condensation adhesive,
Cameras or film loaded with film may be left in an atmosphere where formalin gas is generated, such as building materials, formaldehyde resin processed products, leather products tanned with formalin, and clothing using formalin as a sterilizing or bleaching agent. .

4-equivalent magenta couplers are affected by formaldehyde gas and cause problems such as decreased color development.
A method using a 5-pyrazolone 2 equim magenta coupler described in U.S. Pat. .

[Problems to be Solved by the Invention] As mentioned above, a color negative film has a multilayer structure using a plurality of emulsion layers containing silver halide grains with different grain sizes,
Furthermore, using a DIR compound, the gradation can be made denser.
1, the stagnation stability of the coating solution is poor, the storage stability of the photographic light-sensitive material before its breakthrough against external conditions such as temperature and humidity (hereinafter abbreviated as the storage stability of the light-sensitive material) is poor, and the stagnation stability of the coating solution is poor. It has disadvantages such as deterioration of gradation and deterioration of color reproducibility and tone reproducibility due to reasons such as poor storage stability against external conditions of later photographic light-sensitive materials (hereinafter referred to as latent image storage stability). There is.

Further, as a result of studies conducted by the present inventors, it has become clear that these drawbacks result in -ta deterioration when a 5-pyran 2 equivalent magenta coupler is used.

A technique for improving the stability of WAm is to chemically sensitize silver halide emulsions with equal average grain sizes, then add sensitizing dyes to each emulsion in different molar ratios, and mix again (
JP-A-60-244944) is known, but this remixed emulsion is undesirable because dye adsorption equilibrium occurs between particles during the stagnation period up to coating.

The present invention has been made in view of the above-mentioned conventional problems, and its purpose is to provide a silver halide color that has a small decrease in color density even under formalin gas conditions, and has excellent preservability of light-sensitive materials and latent image preservability. Our objective is to provide photographic materials.

[Means for Solving the Problems] In order to achieve the above object, the silver halide color photographic light-sensitive material of the present invention comprises at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsions on a support. In the silver halide color photographic light-sensitive material each having layers, at least the green-sensitive layer is composed of a single layer, and the green-sensitive layer contains a DIR compound and a 5-pyrazolone-based 2-equivalent magenta coupler. It is characterized by containing.

The present invention will be explained in more detail.

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 in an imagewise manner or may be one that releases the development inhibitor in a non-a-like manner.

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-(YI A represents a coupler residue, m represents 1 or 2,
Y represents a development inhibitor group or a group capable of releasing a development inhibitor by bonding with the coupling 1t of the coupler residue A and reacting with the oxidized product of the color developing agent.

- In the binding allowance (D-1), Y is typically as follows - the binding allowance (
D-2) to (D-20>).

- Tsuzuriyo (D-9) General formula (D-5) General formula (D-6) General formula (D-7) General formula (D-8) Rd.

In general formulas (D-2) to (D-7), Rdl is a hydrogen atom, a halogen atom, or alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy,
Carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthioaryl, heterocycle, cyano, alkylsulfonyl or aryl Represents 6 groups of oxycarbonylamino.

n represents O, 1 or 2, and when n is 2, each Rd+ may be the same or different.

The total number of carbon atoms contained in n Rdi is 0 to 10. Furthermore, the number of carbon atoms contained in Rdi in the binding margin (D-6) is 0 to 15.

X in the above-mentioned binding margin (D-6) represents an oxygen atom or a sulfur atom.

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

- In the binding margin (D-9), Rd3 is a hydrogen atom or 6 of alkyl, cycloalkyl, aryl or heterocycle
represents a group, Rdi is a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino,
Represents six groups: alkoxycarbonylamino, aryloxycarbonylaminosulfonamide, middlethio, or amino.

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

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

When Rdi, Rd2, Rd3 or Rdi represents a heterocyclic group, this heterocyclic group, Or! The A group includes those having a substituent, and is preferably a 5- or 6-membered monocyclic ring or a fused ring containing at least one hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, such as pyridyl, It is selected from the following six groups: quinolyl, furyl, benzothiazolyl, oxacylyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, and oxazine.

In general formula (D-8), the number of carbon atoms contained in Rd2 is 0 to 15.

In the above binding margin (D-9), the total number of carbons contained in Rd3 and Rdi is 0 to 15.

- Tsuzuriyo (D-10> -(TIME), -INHIBIT 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 the oxidized product of the color developing agent,
After being cleaved from the coupler, it is cleaved sequentially and finally INH
It is a group that can be released by appropriately converting the IBIT group. n is 1 to 3, and when 2°3, each TIME group may be the same or different. The INHIBIT group is a group that becomes a development inhibitor by the above-mentioned release (for example, the above-mentioned
) to (D-9).

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

General formula (D-11) General formula (D-14) General formula (D-15) General formula (D-16) υ General formula (D-17) General formula (D-12) - binding allowance (D-13
)〇 General formula (D-18) General formula (D-19) Kd, Kds In general formulas (D-11) to (D-15) and (〇-18), Rds is a hydrogen atom, a halogen atom or an alkyl, Cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonylanilino, acylamino,
Represents a polygroup of ureido, cyano, nitro, sulfonamide, sulfamoymoyl, aryl, carboxy, sulfo, hydroxy, or alkanesulfonyl, -Spelling (D-11) to (D-13), (D-15) (D-1
In 8), Rd5 may be bonded to each other to form a condensed ring;
15) and (D-19>, Rds is alkyl,
Represents a polygroup of alkenyl, aralkyl, cycloalkyl, heterocycle, or aryl, and in -spellings (D-16) and (D-17), Rdr is a hydrogen atom or alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle, or Represents a multiple group of aryl, -spelling allowance (D-19
Rda and Rds in > each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms),
k in 8) represents an integer of 0, 1 or 2, - binding margin (D-11) to (D-13), (D-15>, (D-
18) represents an integer from 1 to 4, - binding margin (D
-16), l represents an integer of 1 or 2, l-,
m is 2g. In the above case, each Rd5 and Rd7 may be the same or different, -n in the binding margin (D-19) represents an integer from 2 to 4, and the n Rdas and Rds may be the same or different, - Tsuzuriyo (D-16) ~ (D-18)
, B represents an oxygen atom or 1N- (Rds has the same meaning as Rda defined above), and - spelling margin (D = 16
) represents that it may be a single bond or a double bond, and in the case of a single bond, ■ is 2, and in the case of a double bond, m is 1.

-Tsuri allowance (D-20) ″'tT1TESR+T2+-I NH I B I 7
In the formula, T1 is SR+T2+rl N)-t 1B IT
The component that cleaves is S RG, t S R + T2 + r
After -I N HI B IT is generated, T2 is a component that generates (T2+-INHIBIT) by reaction with the oxidized form of the developing agent, and T2 is a component that cleaves rNl-11BIT after T is generated. , lNl-1
181 represents a development inhibitor, and 2 and m each represent O 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)-imidacylones, 5-isooquinacylones, uracils, homophthalimides, oxacylones, 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.

-+T 1”17 S R+ T 2 +rI N H
IBIT is preferably bonded to the active site of component A in general formula (D-1).

Moreover, when SR is a coupler component, SR is +T1−+−
After cleavage from , it is only coupled with +T1-+i- and +T2 squares INHIBIT to function as a coupler.

For example, when the coupler component is a phenol or naphthol, the oxygen atom of the hydroxyl group is
The l atom or the nitrogen atom at the 2nd position is also acetophenones,
In indanones, the oxygen atom of the hydroxyl group of the tautomer bonds with +T11, resulting in +T2+rI NH18
Preferably, the IT is attached to the active site of the coupler.

When SR is a redox component, examples thereof include hydroquinones, catechols, biogallols, aminophenols (e.g. (p-aminophenols,
0-aminophenols), naphthalene diols (e.g. 1,2-naphthalene diols, 1,4-naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (e.g. 1.2-7 minonaphthalene). 1,4-aminonaphthols, 2,6-aminonaphthols), etc.

Also, if SR is a redox component, SR is +T+ +2
It is first cleaved from - and then binds to +T1 and -+T2+rINHIBIT to function as a redox component.

Examples of the groups represented by T1 and T2 include those represented by the aforementioned general formulas (D-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 CD-
2), (D-3), (D-8), (D-10) or (D
-20), (D-10), (D
-20>1' in (7) is rNH[BIT with the general formula (D
-2), (D-3), (D-6) (especially - binding allowance (D-
When X in 6) 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: Exemplary Compound D-1 R-COCHCO-Rt (2) CH.

0 C14H2l -CON)ICH2CH,C0OH CON HCH! DI that can be used in the present invention, including these
Specific examples of R compounds are given in U.S. Pat. No. 4,234. f378,
No. 3,227,554, No. 3,617,291, No. 3.958.993, No. 4.149.88G%, No. 3
．． No. 933.500, patent rIi57-56837@,
51-132394, U.S. iW 2,072,363
No. 2,070,266, 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 where it can affect the development of silver halide in the single-layer emulsion layer.
Preferably, it is a silver halide emulsion layer, and more preferably a silver halide emulsion layer having a single layer structure and/or an emulsion layer having color sensitivity similar to that of the emulsion layer.

The 5-pyrazolone two-member magenta coupler used in the present invention is represented by the following general formula [I].

- Tsuzuriyo [I] Cp In the formula, Cp represents a 5-pyrazolone coupler residue, the umbrella represents the coupling position of the coupler, and Represents a group that leaves when a dye is formed.

Examples of the leaving group represented by 5 to 6 with at least one atom selected from
represents a group of atoms required to form a member ring), monovalent groups such as acylamino groups and sulfonamide groups, and divalent groups such as alkylene groups, and in the case of divalent groups, X forms a divalent group. .

Specific examples are given below.

Heron atom: salt, bromine.

Alkoxy group: Fluorine 10 CzHs -QC) (2CONHCH, CH20CH.

Heterocyclic oxy group Niacyloxy group Niaryloxy group: Alkylthio group 2-5CH2,-3C-Hs, 5CsH1tl
-8C12Hzs 1-9CH2COOCzHs 1 E3CH2CH20CxHs.

Arylthio group: heterocyclic thio group Azyl amitz group -NHe0(CFICFri, H -i Father 1: ′〜−)′ Pyrazolyl group.

imidazolyl group.

Triazolyl group.

Sulfonamide group: Alkylene group: As the 5-pyrazolone magenta coupler, those represented by the following general formulas [M-1] and [M-2] are preferred.

General formula [M-1] General formula [M-21] In the above-mentioned binding margins [M-11 to [M-2], R2 represents a hydrogen atom or a substituent, R3 represents a substituent, and X represents the general formula [I ], ri represents 1 to 5, and when 2 is 2 or more, each R2 may be the same or different.

2 [[ for example, a halogen atom,
Examples include 8 groups such as alkyl, cycloalkyl, aryl, and heterocycle bonded directly or via an atom or group of 21i1i.

Examples of the above divalent atoms or groups include oxygen atoms,
Examples include nitrogen atom, sulfur atom, carbonylamino, aminocarbonyl, sulfonylaminonosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonylleylene, thiocarbonylamino, sulfonyl, and sulfonyloxy.

Further, the alkyl, cycloalkyl, aryl, and heterocycle as examples of the substituent represented by R2 include those having an a12 substituent. Examples of the H substituent include halogen atom, nitro, cyan, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy,
Examples include alkoxycarbonylsulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide, acyl, and the like.

Examples of R3 include 8 groups such as alkyl, cycloalkyl, aryl, and heterocycle, including those having substituents, and examples of the substituents include the substituents possessed by the 8 groups listed as examples of R2. The following are examples.

The fflll12 group of X is particularly preferably an alkylthio group, an arylthio group, an aryloxy group, an acyloxy group, or a ren group.

Specific examples of the pyrazolone couplers used in the present invention are listed below, but they are not limited to these.
(Weight ratio) The addition m of magenta coupler is preferably 2
×10゛5 to IX10-3 mol/f, more preferably 5X10-5 to 1X10-3 mol/f.

The light-sensitive silver halide emulsion layer of the present invention contains a 2-power doubler, but a 4-power doubler can also be used in combination. In that case, m of the 2-power doubler contained is preferably:
It is preferable that 50 to 100 mol% of the total coupler m is made up of 4-equivalent coupler, with the remainder being 4-equivalent coupler, and more preferably 70 to 100% of the total coupler is 2-equivalent coupler.
Preferably 0 mole %, ie 2 equim of total coupler.

Note that the 4-equivalent coupler herein refers to a coupler that does not have a substituent at the coupling position, and examples of the magenta coupler include birazolones, cyanoacetyls, 5-virazolones, virazoloimidazole series, and vilazolotriazole series. Examples include zoroazoles, and 5-virazolones and virazoloazoles are preferred.

The color-sensitive layer is a single layer, which means that the color-sensitive layer is a single layer. It also includes the case where emulsion layers having the same color property are arranged as a continuous layer.

Here, "having the same color sensitivity" or "same color sensitivity" means, for example, that they are the same in terms of blue sensitivity, green sensitivity, and red sensitivity, but it is not necessary that the spectral sensitivity characteristics are exactly the same. There isn't.

In the present invention, the green-sensitive layer is a single layer, but it is more preferable that the blue-sensitive and green-sensitive silver halide emulsion layers are both single layers. Preferably, all of the photosensitive silver halide emulsion layers are each a single layer.

When the same color-sensitive layer has a single-layer structure, the number of coated shadows of the photosensitive material is reduced compared to the conventional multi-layer structure, and it becomes possible to form an i111l layer. Therefore, production efficiency and sharpness are improved,
Graininess is also improved. The film thickness after drying is preferably 20 to 3 μm, particularly preferably 15 to 5 μm.

Exposure latitude is the light reception m width at which a significant difference in exposure effect occurs, and is the exposure range from highlights to deep shadows in the characteristic curve, and is described in Photo Chemistry, p. 393 (
Shashin Kogyo Shuppansha, 1982).

In other words, the slope of the tangent at the foot and shoulder of the characteristic curve, where the horizontal axis is logH and the vertical axis is the transmission density, is 0.22.
This is the difference between points and oaH.

The light-sensitive material of the present invention preferably has an exposure latitude of 3.0 or more, as measured by the above method, and preferably 3.0 to 3.0.
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. Specifically, examples include a method in which silver halide grains having different grain sizes are mixed and used, 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 a combination having an intermediate average grain size of One or more types of 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, it is possible to reduce the difference in average grain size without changing the sensitivity of the silver halide grains, and furthermore, it is possible to mix and use silver halide grains having the same average grain size but 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 with a small coefficient of variation that are exposed to the same environment are preferable because their photographic performance is stabilized against changes over time and fluctuations in development processing. It is also possible to chemically sensitize a mixed system of silver particles 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 Ib group, mb group, lea group, mb group, rVb group in the periodic table of elements.
Examples include metal ions of the Group, VA group, and Group II. Preferred metal ions include Au, Zn, Cd, Tffi, S
c, Y, Bi, Fe.

RLI, Os, Rh, Ir, Pd, Pr, Sm.

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 DH of the AoX suspension system during doping is preferably 5 or less.

Also, the doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc., but A! lX
10-11-10-2 mol is preferable per 1 mol,
Furthermore, l Q-12 to 10-3 mol is preferable, especially 1 Q-12 to 10-3 mol.
0-9 to 10-4 mol is preferred.

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

If the doping amount is less than 10-2 mol/Ao III.

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 r:A degree difference and mixture ratio.

The antifoggants or stabilizers include azoles (e.g., benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, etc.), peterocyclic mercapto compounds (e.g., mercaptotetrazoles, mercaptothiazoles, mercapto Thiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) Azaindenes (e.g., tetraazaindenes, pentaazaindenes, etc.) vA acid decomposition products (e.g., adenine, guanine, etc.), benzenethiosulfonic acids, Examples include thioketo compounds.

Examples of desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hoporacyanine 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 light-sensitive material of the present invention, at least one green-sensitive layer preferably contains desensitizer-containing A (IX particles).

Preferably, the blue-sensitive layer and the green-sensitive layer, and most preferably all the color-sensitive layers, contain desensitizer-containing A (IX particles).

Further, the coefficient of variation defined by the ratio S/r of the standard deviation (S) of the grain size to the average grain size (') 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 (r) refers to the grain size (in the case of cubic silver halide grains, the length of the side thereof, or, in the case of grains with a shape other than a cube, the length of the grain converted into a cube having the same volume). When the number of particles of ri (length of one side) is 01, it is defined by the following formula.

-Σn1・ "i r -□ The relationship between 1-aperture particle size distribution is [Empirical relationship between sensitometric distribution and particle size distribution in photography" The Photographic Journal, LXX IX (1!1149) 330 This can be determined by the method described in the article by Tribel and Smith on page 338.

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 its S degree. The amount of iodine is 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 emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer, a dispersion (latex) of a water-insoluble or H-soluble synthetic polymer.

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

Furthermore, by coupling with colored couplers that have a color correction effect, competing couplers, and oxidized forms of developing agents, we can produce developers, silver halide solvents, toning agents, hardeners, antifoggants, and chemical sensitization. Compounds that release photographically useful fragments such as agents, 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 dyes and/or emulsion layers may contain dyes that flow out from the light-sensitive material during development or are bleached.

Formalin scavenge 11-1 optical brightener, matting agent, lubricant, image stabilizer, surfactant, color fog preventive agent, development accelerator, development retardant, bleach accelerator, etc. can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene 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.

Preparation of monodispersed emulsion A gelatin aqueous solution is charged into a reaction vessel, and the O in the reaction vessel is
While controlling AQ and pH, acid silver aqueous solution, potassium iodide aqueous solution and potassium bromide aqueous solution were added simultaneously while controlling the addition time, and then precipitation and desalting were performed using pF-1 coagulating gelatin to obtain gelatin. was added to prepare a seed emulsion. The obtained emulsion was designated as NE-1.

Seed emulsion NE-2 was also prepared in the same manner as above except that 3RhCffis was added to the reaction vessel.

The emulsion and its contents are not shown in Table-1.

Table-1 The above seed emulsion and gelatin aqueous solution were put into a reaction vessel, and while controlling the pAg 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 during grain growth. Add in proportion to the surface area,
Then, at the appropriate particle size, the solution was changed to potassium bromide solution and subsequently added. Similar to the seed emulsion, precipitation 11112j! Add gelatin and redisperse I) Afll 7.
An emulsion with pH 8, pH (i, o) 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 does not show the emulsion and its contents.

Table 2 Example 1 Preparation of sample N 0.101 (comparison) Multilayer color photosensitive material N 0.10 having a multilayer structure consisting of the following composition on a subbed cellulose acetate support.
1 was created.

For silver halide and colloidal silver, the coating amount is expressed in Q/f units in terms of silver, and for additives and gelatin, it is expressed in Q/f units, and sensitizing dyes,
The coupler and DIR compounds are expressed in moles per mole of halogenated Wi in the same layer. The emulsion contained in each color-sensitive emulsion layer is Thiotil! ! Optimal sensitization was performed using Mstorium and chloroauric acid.

ml NE-1 and NE-2 were used in equimolar amounts.

A surfactant was added to each layer as a coating aid in addition to the above ingredients.

C-3 C-1 IV-1 V-2 M-1 Shi II Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Hereinafter, each layer of the above composition will be described as the above-mentioned HC, IL -1, R-
1, R-2, 11-2, G-1, G-2゜YC, B-1
, B-2, Pro-1, Pro-2.

Next, samples N0.102 to l'40.113 were created.

Samples N0.102 to N0.104 are G-1, G-2
In place of MC-1 contained in EM-1 and EM-2 (
7) Used G) 1.0 (1/i' The others were prepared in the same manner as Sample No. 0.101. (G-1 sensitizing dye, coupler, DIR compound silver halide 1 mol) The winning bond is the same as sample No. 101.) Test 11 No.
, 105 to No., 107 are G- of sample NO, 101
Table 3 shows the emulsions contained in G-1 and MC-1 except for 2.
Sample No. except for the changes shown in .

It was produced in the same manner as No. 101.

In addition, samples N O, 108 to N O, 110 are sample N
o. Except for 8-2 and G-2 of 101, increase the amount of emulsion, gelatin and TCP contained in B-1 by 15% per mole of silver halide of the sensitizing dye and coupler of B-1. Sample No. 0.101 was prepared in the same manner as Sample No. 0.101, except that the emulsion and coupler contained in G-1 were changed as shown in Table 3. Furthermore, B-1
The same emulsion as G-1 was used for G-1.

Samples No. 0.111 to No. 0.113 contain the emulsion, gelatin, and T contained in R-1, except for R-2 with No. 0.108.
The amount of CP used was increased by 20% fnL, (G-1 sensitizing dye,
Sample No. 0.108 except that the coupler and DIR compound per mole of silver halide are the same as Sample No. 108), and the emulsion and coupler contained in G-1 are changed as shown in Table 3. Created in the same way. Furthermore, R-1 also has G.
The same emulsion as in -1 was used.

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

The emulsion mixing ratio of the green sensitive layer in Table Sample Nos. 105 to 112 was 1:1 (molar ratio).
Nos. 101 to 113 were used to evaluate the storage stability of photosensitive materials, gradation storage as latent image storage, and storage under formalin gas conditions (hereinafter referred to as formalin resistance) by the following methods. did. The results are shown in Table 4.

Un and standing and direct 1 Divide the sample into two, store one part in the refrigerator (5℃) and use it as a reference, and store the other part at 40℃ and 80% relative humidity for 7 days, and then divide it according to the usual method. After wedge exposure, the following processing steps were performed to evaluate the gradation preservation.

Latent image preservation After dividing the sample into two parts and exposing them to wedge light according to the usual method, one part was stored in a cold cup (5°C) as a reference, and the other part was stored at 25°C.
After being stored for 15 days under conditions of relative humidity of 80%, it was treated with the following processing steps to evaluate the storage stability of gradation.

1! A method for evaluating the storage stability of iml will be explained using figures.

FIG. 1 shows a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line). Minimum concentration +0 in Figure 1
．． From the exposure point that gives a density of 1, Δff1o! IIH-+
Each exposure point between the exposure points of 3.0 (Δff between each exposure point
The point gamma values of 10gl-1-0,15) are shown in FIG. From FIG. 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 is determined. The value obtained by multiplying the average value of Δγ by 1000 (
Δγ) and the standard deviation σ of Δγ multiplied by 1000, Σ, represent the gradation preservation.

That is, the larger the value of Δγ, the larger the difference in point gamma between the two characteristic curves, and the larger the value of Σ, the more uneven the change in gradation becomes, resulting in worse gradation preservation.

Divide the formalin-resistant sample into two parts, and add 35% glycerin aqueous solution to one part for 30 minutes.
W! A liquid containing 0CC was placed at the bottom and filled with air that was in equilibrium with this. It was left in a closed container at 30°C for 3 days, and the other part was left at 30°C for 3 days under the same conditions except that 5 cc of a 40% formaldehyde aqueous solution was added to the glycerin aqueous solution, and then wedge exposure was performed at the same temperature as above. The treatment was carried out and the concentration reduction under formalin conditions was evaluated.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4. ysg anhydrous sodium sulfite 4.2SQ hydroxylamine 1/2 iii! ! Acid salt 2.0g Anhydrous potassium carbonate 37.5 Q Potassium bromide 1°3g Nitrilotriacetic acid trisodium salt (monohydrate) 2. sg potassium hydroxide 1. Add OQ water to make 11. (+)H=10.02) Bleach solution Iron ethylenediaminetetraacetate (I
io, o g Add water and 1
1 and adjusted to pi-16.0 using ammonia water.

Fixer ammonium thiosulfate 175.0 (1
Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1
2 and adjusted to p)-16.0 using acetic acid.

stabilizing liquid Formalin (37% aqueous solution) Konidax (manufactured by Konica Corporation) Add water to make 11.

Table-4 1,5d y, snc ne1 Formalin resistance Determine the density of the sample stored under formalin conditions at the exposure amount that gives a green density of 1.0 for the sample stored under conditions without formalin gas, and calculate the density of the sample stored under formalin conditions. It was evaluated based on the size of Table 4 shows the decrease in concentration of sample N 0.101 by 10
It is shown as a relative value with the value set to 0.

The smaller the value, the smaller the decrease in concentration when stored under formalin conditions, and the better the formalin resistance.

As is clear from Table 4, the samples of the present invention show little density deterioration due to formalin, and are excellent in photosensitive material storage stability and latent image storage stability.

When the green sensitive layer has a multi-layer structure and a 4-coupler is used as a 2-coupler coupler, the storage stability of the photosensitive material and the latent image storage deteriorate (from a comparison of samples No. 0.101 and l'J O, 102-104). However, if this is made into a single layer structure, sample N 0.10
It can be seen that this is improved by more than 1. This was completely unexpected.

Comparing among the samples of the present invention, among the color-sensitive emulsion layers,
A single layer consisting of a blue-sensitive emulsion layer and a green-sensitive emulsion layer (sample No. 01108.109.110) is preferable because it greatly improves the storage stability of gradations in storage of light-sensitive materials and storage of latent images. Those in which all the color-sensitive layers are made into a single layer (samples Nos. 111 to 113) are preferable because they have an even greater improvement effect.

In addition, since samples No. 112, No. 113 contain emulsions doped with Rh ions inside one grain,
It can be seen that the grain size distribution of the silver halide grains in each color-sensitive layer is narrow, and the improvement effect is even greater, which is preferable.

In addition, samples No. 112 and No. 113 have stability against pH fluctuations and temperature fluctuations of the developer by about 30% compared to No. 0.111.
%, and it was found to be favorable also in terms of processing stability.

In addition, sample No. 0.113 is preferable in terms of production efficiency because physical ripening and chemical ripening can be carried out in one step compared to other samples in preparing the emulsion.

Furthermore, the effects of the present invention were also observed in samples in which coupler M-6, M-13, and M-14 were used instead of coupler M-2 used in samples No. 105.

Furthermore, each sample using D-6, D-2, 0=10 instead of D-23 of G-1 of sample N 0.106, sample No.
, each sample using 0.003 mol of D-23, D-29, D-10 per 1 mol of silver halide in 8-1 of 108,
D- instead of D-42 of R-1 of sample N 0.113
The effects of the present invention were also observed for each sample using No. 17, D-19, and D-21.

Also, instead of K3Rh Cri6, RIJ C13゜Os
C4! a, Pb(NO3)2'i-added seed emulsion was used instead of NE-2 to prepare emulsions as Sample No. 112, EM-3, and Sample No.
．． The effects of the present invention were also observed for each sample used in place of EM-4 in No. 113.

[Brief explanation of the drawing]

Figure 1 shows the characteristic curves of the standard (broken line) and evaluation target (solid line) photographic materials. Figure 1 shows the point gamma of the standard (broken line) and evaluation target (solid line) photographic light-sensitive materials. It is a diagram.

Claims (1)

[Claims] In a silver halide color photographic material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support, at least the green-sensitive layer is composed of a single layer; , and the green-sensitive layer contains a DIR compound and a 5-pyrazolone second equivalent magenta coupler.