JPH02219056A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve shelf life of a photosensitive material and to prevent deterioration of gradation, color reproduction and tone reproduction by incorporating a DIR compound and at least one kind of organic high-boiling point solvent having a specified dielectric constant and forming at least two of blue-, green-, and red-sensitive layers having single layer structures. CONSTITUTION:The DIR compound and at least one kind of high boiling point organic solvent having a dielectric constant of >=4.00 (25 deg.C, 10kHz) are contained, and at least two of the blue-, green-, and red-sensitive silver halide emulsion layers has single layer structures, and the DIR compound means a development inhibitor or the compound to be allowed to release the development inhibitor by reaction with the oxidation product of the color developing agent, and the solvent is used for dispersing a coupler, thus permitting the obtained silver halide color photographic sensitive material to be superior in shelf life and good in gradation and color and tone reproduction performances.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material suitable for full-color photography, and particularly to a negative-working silver halide light-sensitive material in which at least two color-sensitive layers are a single layer. Concerning color photographic materials.

[Prior art]

Currently, color photographs are taken with color negative film and then enlarged and printed on color paper.
The positive method 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 a wide exposure range from shadow areas with low exposure to highlight areas with high exposure in the so-called characteristic curve where the horizontal axis is the exposure and the vertical axis is the color density. This means that the gradation is good compared to the other.

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

Unlike color reversal film and color paper, color negative film is a photosensitive material that requires strict control of gradation over a wider exposure range, and for this reason, color negative film currently on the market for photographic use is , each layer sensitive to blue, green, and red light is a plurality of emulsion layers including a high-sensitivity layer containing silver halide grains with a large grain size and a low-sensitivity layer containing silver halide grains with a small grain size. A so-called DIR compound is used which has a multilayer structure and further produces a development inhibitor by reaction with an oxidized product of a developing agent.

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

D used in recent silver halide color photographic materials
Various requirements are placed on IR compounds and couplers. For example, it has excellent chemical stability, excellent color development, and excellent hue of color images.

However, it is extremely difficult to completely satisfy all of these requirements. For this reason, in recent years, methods have been taken such as devising high boiling point organic solvents used for dispersing couplers.

As mentioned above, color negative film has a multilayer structure using multiple emulsion layers containing silver halide grains with different grain sizes, and furthermore, the gradation is strictly controlled using a DIR compound, so that the dielectric constant is 25. If a high boiling point organic solvent with improved color development of 4.00 or higher at °C is used, the storage stability of the photosensitive material against external conditions such as temperature and humidity (hereinafter referred to as photosensitive material storage stability) will be poor, resulting in poor gradation. It has the disadvantage that it deteriorates, resulting in poor color reproducibility and tone reproducibility.

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 (
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.

[Purpose of the invention]

Therefore, an object of the present invention is to provide excellent storage stability of photosensitive materials, and to improve gradation and
To provide a silver halide color photographic material with good color reproducibility and tone reproducibility.

[Structure of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers on a support, in which a DIR compound is used. contains and has a dielectric constant of 4.00 (25°C110
A silver halide color photographic light-sensitive material containing at least one kind of high-boiling point organic solvent having a boiling point of 1 KHz or higher, and at least two of the blue, green, and red color-sensitive layers have a single-layer structure. achieved by.

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)m A represents a coupler residue, m represents 1 or 2, and Y is bonded to the coupling position of the coupler residue A to form an oxidized product of the color developing agent. A group that leaves by reaction and represents a development inhibitor group or a group capable of releasing a development inhibitor.

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

-Formula (D-2) -Formula (D-3) -Formula (D-4) -Formula (D-5) -Formula (D-
6) General formula (D-7) General formula (D-8) - Mathematical formula (D-9) - Mathematical formula (
In 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, alkylthio, arylthio, aryl, heterocycle,
Represents cyano, alkylsulfonyl, or aryloxycarbonylamino layers.

n is 0. 1 or 2, and when n is 2, each Rd.

may be the same or different. The total number of carbons contained in n Rdl is 0-10.

Also, the number of carbon atoms contained in Rd in formula (D-6) is o-is.

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

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

- In formula (D-9), Rd represents a hydrogen atom or each layer of alkyl, cycloalkyl, aryl, or heterocycle; Rd4 represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, Represents each layer of aryloxycarbonylamino, alkanesulfonamide, cyano, heterocycle, alkylthio, or amino.

When Rdl, Rdt, Rd, or Rd4 represents an alkyl group, this alkyl group may have a substituent and may be either a straight chain or a branched chain.

When Rdl, Rd2, Rd, or Rd4 represents an aryl group, the aryl group includes those having a substituent.

When Rd, , Rd, , Rd, or Rd represents a heterocyclic group, this heterocyclic group includes those having a substituent, and the heteroatom is at least one selected from a nitrogen atom, an oxygen atom, and a sulfur atom. A 5- or 6-membered monocyclic ring or fused ring containing 5- or 6-membered rings is preferred, and is selected from, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, and oxazine layers.

- The number of carbon atoms contained in Rd in formula (D-8) is 0-15.

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

- Formula (D -10) -(TIME)n-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 Kazler, it is cleaved sequentially and finally IN
It is a group that can release the HIBIT group in a moderately controlled manner.

n is 1 to 3, and when 2.3, each TIME group may be the same or different.

The IN old and old T group is a group that becomes a development inhibitor by the above-mentioned release (for example, a group represented by the above-mentioned formulas (D-2) to (D-9>).

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

- Mathematical formula (D-11) General formula (D-12) General formula (D-13) - Mathematical formula (D-14) General formula (D-15) General formula (D-16) General formula (D-17) General Formula (D-18) General formula (D-19) General formula (D-11) to (D-15) and (D-1
In 8), Rds is a hydrogen atom, a halogen atom, or alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy,
Represents a polygroup of sulfo, hydroxy or alkanesulfonyl, - Formulas (D-11) to (D-13), (D
-15), (D -18), Rd may be combined with each other to form a condensed ring, and the formula (D -11)
, (D-14), (D-15) and (D-19)
, Rd & represents a polygroup of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle, or aryl, and in formulas (D-16) and t/(D-17), Rd is a hydrogen atom or alkyl, alkenyl, It represents a polygroup of aralkyl, cycloalkyl, heterocycle, or aryl, and Rcta and Rd in formula (D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms). , - formula (D -1
1), k in (o -15) to (D -18) is 0
．． Represents an integer of 1 or 2, - Formula (D -11) ~ (D
-13), (D -15), (D -18) a in i:: represents an integer of 1 to 4, - m in formula (D -16) represents an integer of l or 2, and <1. Each Rds when m is 2 or more.

Rd7 may be the same or different, - formula (D -19
), n represents an integer from 2 to 4, and n Rd and Rd may be the same or different, and - formula (D
B in -16) to (D-18) is an oxygen atom or S. ), and = in formula (D-16) indicates that it may be a single bond or a double bond, and in the case of a single bond, m is 2, and in the case of a double bond, m is l.

General formula (D -20) 1+T1st floor 5R-(T, TakeruINH-!-BIT formula, T
Is it SR? ,-) "The component that cleaves lNl1T,
SR is 5R ((!After the old INHIBIT is generated, it reacts with the oxidized form of the developing agent (T *fI N HI
The component that generates B I T is T2 (Tt and INHI
After BIT is generated, the component that cleaves INH is added to INH.
IBIT represents a development inhibitor, and α and m each represent 0 or l.

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-ynoxacilones, uracils, homo7thalimides, oxacilones, 2.5-Thiadiazoline-1
, 1-dioxides, diazolothiadiazines, indoles, etc., yellow couplers, magenta couplers
In addition to cyan couplers, those that generate various pigments,
It may be one that does not produce a pigment.

-fT1 piece 5RfT, ilN old and old T is general formula (D-
It is preferable that it binds to the active site of component A in 1).

, and when SR is a coupler component, SR is +T li
After cleavage from -, it is bonded to -(T, Kinuta and +T2 piece INHIBIT) so that it functions as a coupler.For example, when the coupler component is phenol or naphthol, the oxygen atom of the hydroxyl group is - In the case of pyrazolones, the oxygen atom of the 5-position hydroxyl group of the tautomer or the nitrogen atom of the 2-position is + r+-)-H,!: Bonds, -(-'
Preferably, the r w piece I N H is bound to the active site of the coupler.

When SR is a redox component, examples include hydroquinones, catechols, pyrogallols, aminephenols (e.g. (p-aminophenols,
O-aminophenols), naphthalene 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), and the like. In addition, when SR is a redox component, SR is cleaved from -(Tl) and functions as a redox component for the first time.
'r z) Combines with mlNHIBIT. T1 and T,
Examples of the group represented by the above-mentioned general formula (D-1
Examples include those represented by 1) 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> or (D-10) or (D-20), (D-10),
In (D-20), INHIBIT has the general formula (D-
2), (D-3), (D-6) (especially - formula (D-6)
(7) When X is an oxygen atom) or (D-8) is preferable.

The coupler component represented by A in general formula (D-1) includes a yellow image-forming coupler residue, a magenta image-forming coupler residue, a cyan image-forming coupler residue, and a colorless coupler residue. Can be mentioned.

Preferred DIR compounds used in the present invention include the following compounds, but these are limited to:

DI that can be used in the present invention, including these
Specific examples of R compounds are U.S. Pat. No. 4,234,678, U.S. Pat.
, No. 958.993, No. 4,149,886, No. 3,
No. 933,500, JP-A-57-56837, JP-A No. 51
-13239, U.S. Patent No. 2,072,363, No. 2
, No. 070,266, Research Disclosure (hereinafter abbreviated as RD), December 1981, No. 21,228, etc.

The DIR compound contains o, ooo per mole of silver halide.
It is preferable to use t~0.1 mol, especially o, oo
It is preferable to use t~0.05 mol.

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

The high boiling point organic solvent according to the present invention has a boiling point of 150°
Water-immiscible compounds of C or higher are preferred, such as those represented by the following formulas (A) to [D].

General formula (A) R+ C00R2 General formula (C) In the formula, R+, R* and R1 each represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R1 and R2 in the general formula CD) may form a fused ring. Also, R6 is R1+-OR, or -3RI
, where n is an integer from 1 to 5, and when n is 2 or more, R4 may be the same or different.

Examples of the alkyl group represented by R1-R3 include methyl, butyl, octyl, nonyl, octadecyl, etc., and the alkyl group includes those having a substituent. Examples of the substituent include halogen, cycloalkyl, aryl, ester, and the like.

Examples of the cycloalkyl group represented by R1-R1 include 5- to 6-membered ones, such as alkoxycarbonyl,
Including those with substituents such as aryloxycarbonyl. The alkenyl group represented by R1-R1 is C4
Examples include H7, C5H18, CaHssCJImH1@-, including those having substituents such as halogen, alkoxy, aryl, cycloalkyloxy, alkyl, and aryloxy.

The aryl group represented by R1-R3 includes phenyl,
Examples include naphthyl, and include those having substituents such as alkoxycarbonyl, aryloxycarbonyl, and cyclohexyloxycarbonyl.

In general formula CD), examples of the condensed ring formed by bonding R1 and R2 include oxane, oxirane, oxolane, and the like.

The dielectric constant of a high boiling point organic solvent can be measured, for example, by the transformer bridge method.

In the present invention, the dielectric constant is preferably 15.0 or less.

Examples of high boiling point organic solvents are shown below, but the invention is not limited to these. Dielectric constant is shown in parentheses.

B-1 B-2 B-3 CHsCOCH2COOC+2Hzs (6,4) B B-33 H B B-31 B-38 CHzCOOCHzCI(C2Ha)C*HsHB-4
2 HB-47 HB-43 CH, α loss C, H.

HB-48 (CsH+10)3PO (7,2) HB-49 HB-44 HB-45 COOC, H.

C, +HziCON(C211s)z
(13,5) The high-boiling organic solvent of the present invention is preferably used as a solvent for dispersing the coupler, and the amount used is preferably 0.05 to 20 times the weight of the coupler.

In the present invention, the color-sensitive layer being a single layer means that the type of coupler contained in the emulsion layer, the grain size of 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 color sensitivity are arranged as a continuous layer.

Here, "having the same color sensitivity" or "same color sensitivity" may mean, for example, the same blue sensitivity, green sensitivity, and red sensitivity, and it is not necessary that the spectral sensitivity characteristics be completely the same.

In the present invention, it is more 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 Preferably each is a single layer.

When the color-sensitive layer has a single-layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional multi-layer structure, making it possible to form a thin film. Therefore, production efficiency, sharpness, and graininess are improved. The film thickness after drying is 20
~3 μm is preferred, particularly 15-5 μm.

Exposure latitude is the width of the amount of received light that produces a significantly different exposure effect, and is the exposure range from the highlight to even darkness in the characteristic curve, as 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 QogH and the vertical axis is transmission density, is 0.22.
There is a difference of (2og H) between the points.

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. 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; 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, 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, and Group I1la in the periodic table of elements.

Examples include metal ions of group mb, group IVb, group Va, and group II. Preferred metal ions include Au, Zn, and Cd.
.

T12. Sc, Y, Bi, Fe, 'Ru, Os, Rh,
Examples include metal ions of Ir, Pd, Pr, Sm, and Yb. Particularly preferred are Rh, Ru, and Os.

1 “It is.

These metal ions can be used, for example, as halogen complex salts, and the pH of the AgX suspension system during doping is preferably 5 or less.

In addition, these metal ion doping amounts are f1 of metal ions.
AgX
IQ-I F to 10-2 mol is preferable, more preferably 10-th to 10-' mol, especially 10-' mol per 1 mol.
-' to 1O-4 mol is preferred.

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

If the doping amount is less than 1O-2 mol/AgX mol, it will not have a large effect on grain growth, so silver halide grains with a narrow grain size distribution are prepared under the same grain growth conditions and even under the same batch growth. be able to.

It is also possible to prepare silver halide grains with different doping conditions so that they can be put to practical use, then mix them in a predetermined 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 Thia diazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) Azaindenes (e.g. tetraazaindenes, pentaazaindenes, etc.) Nucleic acid decomposition products (e.g. adenine, guanine, etc.), benzenethiosulfonic acids , thioketo compounds, and the like.

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 light-sensitive material of the present invention, it is desirable that at least one color-sensitive layer (for example, a blue-sensitive layer) contains desensitizer-containing AgX particles. Preferably, the blue-sensitive layer contains desensitizer-containing AgX particles, more preferably the blue-sensitive layer and the green-sensitive layer, and most preferably all the color-sensitive layers contain desensitizer-containing AgX 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 (7) of the grain size as a whole including the silver halide grains contained in each silver halide emulsion layer is 0. 4
It is preferably 0.33 or less, more preferably 0.33 or less, and 0.33 or less is more preferable.
25 or less is more preferable, and 0.20 or less is the average particle diameter (
(lower) means grain size (for cubic silver halide grains,
(or, in the case of particles with a shape other than a cube, the length of one side when converted to a cube with the same volume) "When the number of particles of i is ni, defined by the following formula. It is what was done.

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 halides containing substantially iodine in the halogen composition (for example, silver iodobromide, silver iodochlorobromide) are preferred, especially silver iodobromide. is preferable because high sensitivity can be obtained.

The amount of iodine is preferably 1 mol% or more, 20 mol%,
Particularly preferred is 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 can be hardened and can 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. Colored couplers also have a color correction effect.By coupling with competing couplers and oxidized forms of developing agents, they can be used to improve the ability of developers, silver halide solvents, toning agents, hardeners,
Compounds that release photographically useful fragments such as antifoggants, chemical 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 the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

For photosensitive materials, formalin scavenger-fluorescent brightener,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, a bleaching accelerator, etc. can be added.

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 p in the reaction vessel is
While controlling Ag and pH, silver nitrate aqueous solution,
After adding an aqueous potassium iodide solution and an aqueous potassium bromide solution simultaneously while controlling the addition time, precipitation desalting was performed using pH coagulating gelatin, and gelatin was added to prepare a seed emulsion.

The obtained emulsion is called NE-1.

Seed emulsion NE-2 was also prepared in the same manner as above except that K and RhCQ were added to the reaction vessel.

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

Table 1: Put the above seed emulsion and gelatin aqueous solution into a cooking pot.
While controlling pAg and p) in the reaction vessel,
An ammoniacal silver nitrate aqueous solution, a potassium iodide aqueous solution, and a potassium bromide aqueous solution were added in proportion to the surface area during grain growth, and at an appropriate particle size, the solution was changed to a potassium bromide solution and subsequently added. In the same manner as the seed emulsion, precipitation and desalting were performed, gelatin was added, and redispersion was performed to give a pAg of 7.8. pH
A 6.0 emulsion was obtained.

In this way, the inside of the grain is a silver iodobromide emulsion EM with a high concentration of demons.
-1-EM-4 was prepared.

Table 2 shows the emulsions and their contents.

Table-2 Equimolar amounts of NE'NE-1 and NE-2 were used.

Example 1 Preparation of sample No. 101 (comparison) A multilayer color photosensitive material N having an upper and lower layer structure having the composition shown in the coating above was placed on a subbed cellulose acetate support.
o, lOl was created.

Coating amounts are expressed in g/m'' units for silver halide and colloidal silver, and g/m'' units for additives and gelatin. The dyes, couplers and DIR compounds are expressed in moles per mole of silver halide in the same layer.

The emulsion contained in each color-sensitive emulsion layer is optimally sensitized with sodium thiosulfate and chloroauric acid to UV-2 C, H.

In addition to the above ingredients, a surfactant is applied to each layer. CM-1 Sensitizing dye I Sensitizing dye■ Hereinafter, each layer having the above composition will be described as HC and IL-1.

R-1, R-2, IL-2, G-1, G-2, YCB
-1, B-2, Pro -1, Pro-2.

Next, samples Nos. 102 to 112 were created.

Samples Nos. 102 to 106 were prepared in the same manner as Samples No. 101, except that those shown in Table 3 were added instead of the high boiling point organic solvent HB-A contained in each layer.

Sample No. 107 is G-2 in sample No. 101,
Except for B2, the emulsions contained in G-1 and B-1 were converted into EM-2.
Sample No. 1 was prepared in the same manner as Sample No. 1O1 except that EM-3 was used in an equimolar amount.

Samples No. 108 to No. 112 were prepared in the same manner as Sample No. 107, except that those shown in Table 3 were added instead of the high boiling point organic solvent HB-A contained in each layer.

The sample No. 1O1-112 thus obtained was prepared in this way.
To check the storage stability of the photosensitive material, one part (standard) was dried and the other part was dried for 15 days at 25°C and 80% RH.
After being left for a day, wedge exposure was performed according to a conventional method, and the following processing steps were performed.

Processing process (38°C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3° minutes 15 seconds Fix
Wash 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.

Color developer 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine l/2 sulfate 2.0g anhydrous potassium carbonate 37.5 g potassium bromide
1.3 g nitrilotriacetic acid 3
Sodium salt (l hydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make IQ (pH = 10.02) Bleach solution Ethylenediaminetetraacetic acid Iron (II[) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and
Q and p using ammonia water.

Adjust to 6.0.

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite Sodium metasulfite 8.6g 2.3g Add water to adjust to IQ, and adjust to pH 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) l, 5m
ff Konidax (manufactured by Konica Corporation) 7.5+
Add nM water to obtain IQ.

In order to examine the storage stability of the sensitive materials for each sample processed in this way, the characteristic curves were compared, and the results of the green-sensitive layer evaluated in terms of gradation storage according to the evaluation method described below are shown in the table below.
4.

The evaluation method for gradation preservation will be explained using the attached figure.

FIG. 1 shows characteristic curves, where the broken line shows the characteristics of the reference sample and the solid line shows the characteristics of the sample to be evaluated.

Each exposure point between the exposure point giving the minimum density +0.1 and the exposure point ΔQogH=+3.0 in Figure 1 (points of Δ(2 layers gH-0-15) between each exposure point) The gamma values are shown in FIG.

From Figure 2, the absolute value Δ of the difference in point gamma at each exposure point between the reference characteristic curve and the characteristic curve to be evaluated.
The gradation preservation property was expressed as a value Σ obtained by multiplying the standard value difference σ of γ by 1000.

The larger the value of Σ, the less uniform the change in gradation, which indicates that gradation preservation is not excellent.

Table 4 As is clear from Table 4, the sample of the present invention has a small gradation variation from highlight to shadow in the characteristic curve during storage of the sensitive material, indicating good gradation storage stability. .

Sample No. when using a comparatively high boiling point organic solvent.

Comparison of lot and No. 107 and No. 102 and No.
, 108, although there is only a slight improvement even when the two color-sensitive layers are made into a single layer structure, when the high boiling point organic solvent of the present invention is used, sample No. .

Comparison of 103 and No, 109, No, 104 and No,
llO comparison, no.

Comparison of 105 and No, 111 and No, 106 and No,
As is clear from the comparison of No. 112, it is a significant improvement. In addition, the samples of the present invention exhibited good color development.

Further, the effects of the present invention were observed not only in the high boiling point organic solvents used in the examples but also in all the compounds shown as exemplified compounds.

Further, this effect was observed to be greatest when all three of the blue-sensitive, green-sensitive, and red-sensitive layers were formed into a single layer structure.

In addition, sample No. 109 B-2 DIR compound D-42
Each sample using D-2, D-4, D-29 instead of
Each sample using D-2, D-6, D-10 instead of DIR compound D-26 of G-2 of sample No. 110, R of sample No. 112, DIR compound D-23 of -1 The effects of the present invention were also observed in samples using D-17, D-19, and D-21 instead.

Also, KsRhCL (7) substituted RuC123,0s
The emulsion prepared by using a seed emulsion prepared by adding C(23,Pb(NOx)* instead of EM-2 was used as sample No.
The effects of the present invention were also observed for each sample used in place of EM-3 of Nos. 107 to 112.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] A silver halide color photographic material comprising at least blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers on a support, which contains a DIR compound and has a dielectric constant. 4.00 (25° C., 00 KHz) or higher, and at least two of the blue, green, and red color-sensitive layers have a single-layer structure. Silver halide color photographic material.