JPS62178249A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stress an inter-layer effect and to improve color reproducibility by incorporating a twin silver halide particles into >=1 layers of silver halide emulsion layers and incorporating a diffusive DIR compd. into >=2 photosensitive silver halide emulsion layers having different color sensitivities. CONSTITUTION:The emulsion layer in which the development restrainer or development restrainer precursor released from the DIR compd. is diffusive satisfies the following conditions: The DIR compd. is added and incorporated therein in such a manner that the magnitude relation of the development restraining powder of the development restrainer released from the DIR compd. incorporated into one color sensitive silver halide emulsion layer and the development restrainer released from the DIR compd. incorporated into the other color sensitive silver halide emulsion layer is reversed in the magnitude when the DIR compd. is exchanged and is incorporated into the photosensitive silver halide emulsion layer and that the development restraining power to the other photosensitive silver halide emulsion layer is larger than the development restraining power to the photosensitive silver halide emulsion layer incorporated with said restrainer. The inter-layer effect of both layers is thereby made larger between the different color sensitive layers by which the color reproducibility is improved and the photosensitive material having the excellent stability with age, and particularly the excellent stability at a high temp. and under a high humidity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically to an interimage effect (interlayer effect, hereinafter referred to as IIE).
This invention relates to a silver halide color photographic light-sensitive material that has enhanced color reproducibility, improved stability over time, particularly stability under high temperature and high humidity conditions.

[Prior art and its problems]

In recent years, with the increasing sensitivity of silver halide photographic materials and the miniaturization of cameras, there has been a strong demand for higher image quality. Among these, demands are particularly high regarding color reproduction. Furthermore, with the spread of compact labs and automatic printers, the demand for quality stabilization has become increasingly high.

Automatic masking technology using colored couplers is known as a technique for improving color reproducibility, and is commonly used in negative silver halide color photographic materials, but color reproducibility is Not at a satisfactory level. In order to further improve color purity, an isolation layer (IL), also called an intermediate layer, is installed between different color-sensitive layers, and a scavenger for the oxidized product of a color developing agent and a colorless coupler are added to the isolation layer (IL). It is known to add diffusion inhibitors such as sensitizing dyes, such as fine silver halide particles, cationic hydrophilic synthetic polymers, polymer latex, etc. to the isolation layer (IL). However, even these methods have not yet achieved the ability to exhibit sufficiently satisfactory color reproducibility.

A method is also disclosed that uses a DIR coupler and emphasizes il, E. Various types of these DIR compounds are used. For example, during development,
A so-called DIR coupler that reacts with an oxidized form of a color developing agent to form a coloring dye and releases a development inhibitor; during development, it reacts with an oxidized form of a color developing agent to release a development inhibitor but forms a coloring dye. So-called DIR substances that do not release a development inhibitor directly by reacting with an oxidized form of a color developing agent, and those that release a development inhibitor indirectly.
For example, JP-A-54-145135, JP-A No. 57-1542
No. 34, No. 5B-162949, No. 58-20515
No. 0, No. 59-195643, No. 59-206834
No. 59-206836, No. 59-210440, No. 60-7429 (hereinafter referred to as timing DIR compounds). Collectively called DIR compounds.

When these DIR compounds are used in a silver halide color light-sensitive material, a development inhibitor is released from the DIR compound during development, and the effect of suppressing the development of other silver halide emulsion layers, ie, 1.1. In particular, DIR compounds that can release so-called diffusible inhibitory groups or diffusible development inhibitor precursors are effective, and are used in recent silver halide color films, and their effects are limited. I am raising it, but 1.1. Because the directionality of E is strong (for example, it is strong from the blue-sensitive silver halide emulsion layer to the green-sensitive silver halide emulsion layer, but weak in the opposite direction), it is expected that the saturation (chroma) of specific colors will improve. Although it is possible, it has the undesirable effect of "hue shift".

In addition, even though it is diffusive, the suppressing effect is strongest in the additive layer, which causes problems such as lower gamma (7), lower sensitivity, and lower color density of the additive layer, and the amount of the additive layer is large enough to have a sufficient effect on other layers. is difficult to use.

So-called diffusible DIR compounds are used for different color-sensitive layers consisting of 1.1. Japanese Patent Publication No. 55-47379, Japanese Patent Publication No. 57-93344, Japanese Patent Publication No. 57-56837, and Japanese Patent Publication No. 57-56837 disclose techniques for emphasizing E.
No. 9-1.31937, etc., but even with these techniques, as mentioned above, only an insufficient improvement in color reproducibility can be expected.

Furthermore, Japanese Patent Application No. 60-93411 describes a technology containing an IR compound so that the development suppressing power for the other photosensitive layer is greater than that for the photosensitive layer to which the diffusive DIR is added. Although it is insufficient, the color reproducibility is improved compared to the conventional technology. However, when these DIR compounds are used, the maximum color density and sensitivity decrease over time at high temperatures, and in color photosensitive materials in particular, color layer shifts occur, which is a serious drawback in practice. have.

[Purpose of the invention]

An object of the present invention is to improve color reproducibility by increasing 112 in both directions between different color-sensitive layers, and to provide a silver halide photographic light-sensitive material with excellent stability over time, particularly under high temperature and high humidity conditions. It is to provide.

[Structure of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having two or more light-sensitive silver halide emulsion layers having different color sensitivities on a support, in which at least one silver halide emulsion layer contains twinned halogen. The light-sensitive silver halide emulsion layer having different color sensitivities and containing embedded grains has at least two compounds containing a compound that reacts with an oxidized form of a developing agent to release a development inhibitor or a development inhibitor precursor (in this specification). A silver halide photographic light-sensitive material containing a DIR compound (hereinafter referred to as a DIR compound) and in which a development inhibitor or a development inhibitor precursor released from the DIR compound is diffusive; This is achieved by a silver halide photographic light-sensitive material characterized in that the silver halide emulsion layer satisfies the following condition A.

[Condition A]

D contained in one color-sensitive silver halide emulsion layer
The magnitude relationship between the development inhibitory power released from the IR compound and the development inhibitor released from the DIR compound contained in the other color-sensitive silver halide emulsion layer determines whether the DIR compound is replaced or not. When it is contained in a photosensitive silver halide emulsion layer, the size is reversed, and the development suppressing power for the other photosensitive silver halide emulsion layer is greater than the development suppressing force for the photosensitive silver halide emulsion layer containing it. A DIR compound is added so that the suppressing power is greater.

The present invention will be explained in more detail below.

The twinned silver halide grains of the present invention preferably have an aspect ratio of 8:1 or less and 2:1 or more, more preferably 6=1 or less and 2:1 or more. Aspect ratio refers to the diameter:thickness ratio of a particle.

The diameter of a silver halide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the twinned silver halide grains is 0.2 to 5.0 μm, preferably 0.2 to 4.0 μm.

Generally, when twinned silver halide grains are twins having two parallel planes, the thickness is the distance between the two parallel major planes.

The silver halide composition of the twin grains according to the present invention is preferably composed of silver bromide and silver iodobromide, and preferably silver iodobromide having a silver iodide content of 0 to 20 mol %. More preferably, it is 2 to 18 mol%, particularly preferably 2 to 15 mol%.

Further, the twinned particles according to the present invention may be polydisperse or monodisperse, but monodisperse is more preferable. Preferable monodispersity means that the weight of silver halide grains contained within a grain size range of ±20% around an average grain size of 7 is 60% or more of the weight of all silver halide grains. .

Here, the average particle size 7 is the frequency nl of particles having particle size ri
It is defined as the particle diameter r+ (3 significant figures, minimum digit is 5 people to the nearest 4) when the product n1Xri' of 3 and r is the maximum.

The grain size rl here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than spherical.
This is the diameter when the projected image is converted into a circular image with the same area.

This particle size is, for example, 10.00 by electron microscopy.
Take a photo magnified from 0 times to so, ooo times, and calculate the particle diameter or the area of the projected image on the print to 3 significant figures (4
It can be obtained by actually measuring the 4th decimal place (5th person). (The number of particles to be measured is assumed to be 1,000 or more at random.)

The monodisperse silver halide grains used in the present invention can be used by mixing silver halide emulsions with different grain sizes within a range that does not impede the effect of monodispersity. It means that those having the following are also included in the present invention. Including such cases, the grain size distribution of silver halide grains consisting of substantially monodisperse silver halide grains falls within a grain size range of ±20% around r defined above. The weight of the silver halide grains contained is 60% or more, more preferably 70% or more.

Hereinafter, in this specification, ±20% around the average particle size 7
The weight of silver halide grains included in the grain size range relative to the weight of all silver halide grains is called the U value.

In order to produce an emulsion consisting of monodisperse twinned grains, Japanese Patent Application Laid-open Nos. 51-39027, 52-153428, and 5
The manufacturing method described in No. 4-118823 etc. can be referred to.

In addition, as a preferred method for obtaining an emulsion consisting of monodisperse tabular grains, a seed population consisting of monodisperse spherical grains is obtained by physically ripening core grains consisting of multiple twins in the presence of a silver halide solvent. A method that can be used is to create one and then grow it. As a more preferred method, a tetrazaindene compound is present during the growth of tabular grains to increase the proportion of tabular grains and to improve monodispersity.

The twin grains used in the present invention may have a uniform distribution of silver halide (for example, silver iodide) throughout the grain, or may have a so-called core grain structure in which the silver halide composition differs between the interior and surface layer of the grain. /It may be shell type.

In the layer containing twinned grains used in the present invention, it is preferable that twinned grains exist in an amount of 40% by weight or more, more preferably 60% by weight or more of all silver halide grains present in this layer. preferable.

The layer containing twin grains used in the present invention may be contained in any layer when there are multiple layers with the same color sensitivity, but it is preferable to contain it in a layer with higher sensitivity because it is more effective. be.

The twin grains can be produced by appropriately combining various methods.

For example, forming seed crystals in which twin grains exist in an amount of 40% or more by weight in an atmosphere with a relatively high pAg value of pBrl, 3 or less,
It is obtained by growing seed crystals while simultaneously adding silver and halogen solutions while keeping the pBr value at the same level.

During this grain growth process, it is preferable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the twin grains can be adjusted by controlling temperature, selection of the type and amount of solvent, silver salt used during grain growth, rate of addition of halide, etc.

When producing the twinned grains used in the present invention, grain size, grain shape (aspect ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary.

Wear. The amount of solvent used is 101 to 1.0% by weight of the reaction solution.
, particularly preferably 10-t to 10-wt%.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas. For thioethers, U.S. Patent No. 3,271.1
No. 57, No. 3.790,387, No. 3.574°628, etc. can be referred to.

In the present invention, during the production of twin grains, the addition rate, amount, and concentration of silver salt solvent (e.g., A g N O! aqueous solution) and halide solution (e.g., KBr aqueous solution) that are added to accelerate grain growth are determined. Preferably, a method of increasing the

The twin grains having an average aspect ratio of 8:1 or less according to the present invention may be doped with various metal salts or metal complex salts during silver halide precipitate formation, during grain growth, or after grain growth is completed. For example, gold, platinum, palladium,
Metal salts or complex salts such as iridium, bismuth, cadmium, copper, etc., and combinations thereof can be applied. In the method for producing an emulsion containing the above-mentioned particles, the Tardel water washing method, the dialysis method, or the pseudoprecipitation method, which are commonly used in general emulsions, can be appropriately used as a means for desalting.

Next, the above-mentioned [condition A] will be explained in more detail.

Usually, when a DIR compound is used in the color-sensitive layer,
Even if the released development inhibitory precursor (hereinafter referred to as the development inhibitor) is diffusible, the additive layer itself, which is the release layer, is most inhibited, and the DIR compound is It is difficult to use large amounts of.

When a DIR compound is used in another layer, that layer experiences a development inhibitory force of the magnitude described above due to the development inhibitor of the DIR compound in its own layer. Therefore, a phenomenon occurs in which the development inhibitory effect supplied from other layers is not sufficiently exerted. That is, between the two color-sensitive layers, 1. I.

If you want to cause E, both 1. Both t and E will be at a low level, or only one direction will be strong and the other direction will be extremely weak.

However, it has been found that the released development inhibitor exhibits different development inhibitory powers in different color-sensitive layers, and that the development inhibitory powers differ depending on the type of development inhibitor.
411.

For example, when development inhibitor A and development inhibitor B are used in approximately equal moles in a green-sensitive silver halide emulsion layer and a red-sensitive silver halide A emulsion layer, the If the development inhibitory power is A>B, but the development inhibitory power in the red-sensitive silver halide emulsion layer is A>B, then a DIR compound having a development inhibitor B in the green-sensitive silver halide emulsion layer is added to the red-sensitive halogen emulsion layer. By adding a DIR compound having a development inhibitor A to the silveride emulsion layer, the white layer suppressing ability of each added layer is weakened, and the other color-sensitive layers are significantly affected.
Big 1.1. E) in both directions, 1.1. It became possible to dramatically increase E.

The method of using the IR compound, that is, the method or criteria for determining the color-sensitive layer to which the DIR compound should be added, is based on the above example,
That is, it is effective not only between a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, but also between other types of different color-sensitive layers.

In the present invention, the usage of the DIR compound, that is, the selection of the inhibitory group of the DIR compound, can be carried out by the following method.

Three types of photosensitive materials having layers having the following compositions are prepared on a (transparent) support.

Sample (■): A sample having a red-sensitive silver halide emulsion layer Spectrally sensitized to red-sensitivity silver iodobromide (silver iodide 6 mol%, average grain size 0.48 μm) and exemplary coupler (C-7). silver 1
A gelatin coating solution containing 0.08 moles per mole was coated so that the coated silver amount was 1.4 g/rd.

Sample (■): A sample having a green-sensitive silver halide emulsion layer Spectrally sensitized to green-sensitivity silver iodobromide (16 mol% iodide, average grain size 0.48 μm) and the exemplary coupler (M-2) were mixed with silver A gelatin coating solution containing 0.07 mol/mol of gelatin was applied so that the amount of coated silver was 1.1 g/rd.

Sample (■): A sample having a blue-sensitive silver halide emulsion layer Spectrally sensitized to blue-sensitivity silver iodobromide (silver iodide 6 mol%, average grain size 0.48 μm) and exemplary coupler (Y-4). silver 1
A gelatin coating solution containing 0.34 moles per mole was coated so that the coated silver amount was 0.5 g/nf.

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

After exposing the obtained samples (1) to (I[[) to white light using a wedge, the development time was 1 minute 45 seconds for (I),
Processing was performed according to the processing method of Example 1 described later, except that I) was set to 2 minutes and 40 seconds, and (II[) was set to 3 minutes and 15 seconds.

The developer used was one in which various development inhibitors were added in varying amounts and one in which no development inhibitor was added so that the development inhibitory power of sample (I[) was approximately the same. The sensitivity of each sample N) ~ (I [[) processed with a developer without a development inhibitor added and the sensitivity of each sample obtained by development with a developer with a development inhibitor added ( The difference (ΔS) from S) is taken as a measure of the development inhibitory power of each color-sensitive layer by each development inhibitor.

*1) Exposure i1 at the density point of fog density +0.3. (Eo
), that is, −1ogEo, is the sensitivity S.

shall be.

*2) Similarly to *1) above, the sensitivity S is the logarithm of the reciprocal of the exposure amount (E) at the density point of fog density +0.3, that is, -1ogE.

Table 1 below shows the differences in the development inhibitory power of several types of development inhibitors for each color-sensitive layer based on the above standard experiment.

When using the DIR couplers having the development inhibitors A-1 to A-6 above, they may be used in a combination in which the additive layer itself has a small development inhibition and the other layer has a large development inhibition.

In order to create a preferable combination between a red-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer due to the difference in the development suppressing power of each development inhibitor exemplified in Table 1, for example, red-sensitive silver halide The value of the emulsion layer (sample (■)) is normalized to the value of one compound, and the value of the blue-sensitive silver halide emulsion layer (sample (■)) is divided by the ratio at that time. (See Table 2).

Table 2 That is, Table 1 lists the following combination examples.

[Development inhibitor of DIR compound added to red-sensitive silver halide emulsion layer/DI added to green-sensitive silver halide emulsion layer
Examples of combinations of development inhibitors for R compounds] ■A-1/A-2,
■A-1/A-3, ■A-1/A-4, ■A-1/A-
5, ■A-1/A-6, ■A-2/A-3, ■A-2/
A-4, ■A-2/A-5, ■A-2/A-6, ◎A-
4/A-3.0A-5/A-3, @A-5/A-4, ■
A-6/A-3, @A-6/A-4, etc.

Similarly, between the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer, and between the red-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer, preferred combinations in which the added layer suppression is small and the other layer suppression is large are found. You can choose.

Further, in order to emphasize IIE, it is preferable that the action distance of the inhibitory group is large. That is, it is preferable that the so-called synergistic effect is large.

In the present invention, the diffusibility of the inhibiting group can be evaluated by the following method.

Photosensitive material samples (rV) and (V) consisting of layers having the following compositions on a (transparent) support were prepared.

Sample (■): A sample having a green-sensitive silver halide emulsion layer Spectrally sensitized to green-sensitivity silver iodobromide (silver iodide 6 mol%, average grain size 0.48 μm) and exemplary coupler (M-2). silver 1
Coating gelatin coating solution containing 0.07 mol per mole, coating silver amount 1.1 g / rd, gelatin coating amount 3.0 g
/rrr, and on top of that a protective layer: gelatin coating containing silver iodobromide (silver iodide 2 mol%, average grain size 0.08 μm) that has not been chemically sensitized or spectrally sensitized. The amount of silver applied is 0. Ig/rrr, amount of gelatin added is 0.8
It was applied so that it was g/rd.

Sample (■) 2 The protective layer of the above sample (r/) except that silver iodobromide was removed.

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

After exposing the samples (rV) and (V) to white light using a wedge,
The processing was carried out in accordance with the processing method of Example 1 described later, except that the development time was 2 minutes and 40 seconds. 519 of sample (V) is used in the developer.
One was used in which various development inhibitors were added in an amount that inhibited the growth rate to 60% (-ΔlOgE=0.22 in logarithmic representation), and one in which no development inhibitor was added was used.

The sensitivity of sample 'IV) when no development inhibitor is added is SO, the sensitivity of sample (V) is SO', the sensitivity of sample (rV) when a development inhibitor is added is 31 y, and the sensitivity of sample (V) is 31 y. ), the sensitivity of sample (IV) is ΔSowSo '-3V % The sensitivity of sample (V) is Δ5=So-3. v.

Diffusivity - expressed as ΔS/ΔSO.

However, all sensitivities were expressed as the logarithm (-log E) of the reciprocal of the n light amount at the density point of fog density +0.3.

The value obtained by this method was used as a measure of diffusivity.

Table 3 illustrates the diffusibility of several types of development inhibitors.

Those with relatively low diffusivity (A-5: 0.34 or less) are 1.1. Since E is also small, it is preferable that the diffusivity exceeds 0.34. In the present invention, it is more preferable that the diffusivity is 0.4 or more.

In the silver halide color light-sensitive material of the present invention, each (or at least one layer) has three emulsion layers of the same light sensitivity.
Although it can be divided into more than two layers, it is preferable not to exceed three layers due to the diffusibility of the inhibitor or inhibitor precursor produced from the DIR compound of the present invention in the layers.

In recent years, there has been a demand for silver halide color photographic materials with high sensitivity, high image quality, and good color reproducibility. It is also effective when applied to materials; in fact, it is even more effective.

The following are known as layer configurations for achieving higher sensitivity. For example, in the sequential layer structure of each of the light-sensitive silver halide emulsion layers, ie, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, which are coated sequentially on a support, one For some or all of the light-sensitive silver halide emulsion layers, a highly sensitive silver halide emulsion layer containing a diffusion-resistant coupler that develops substantially the same hue as each other is used. There is a layer structure in which the silver halide emulsion layer is divided into a silver halide emulsion layer (hereinafter referred to as a high sensitivity emulsion layer) and a silver halide emulsion layer with a low absolution (hereinafter referred to as a low sensitivity emulsion layer), and these layers are stacked adjacent to each other. Note that this layer configuration will hereinafter be referred to as a high-sensitivity layer configuration.

On the other hand, the following technology is known as an inverted layer structure that achieves high sensitivity.

(A) First, JP-A No. 51-49027 describes (a) each low-sensitivity emulsion layer (RG low-anger layer unify layer) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in order from the support side. 1-), and (on the bHic low-sensitivity layer unit,
Coating each high-sensitivity emulsion layer (RG high-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in order from the support side, (c) on the RG high-anger layer unit. , the blue-sensitive silver halide emulsion layer and the low-speed emulsion layer (B
CB) Also, in JP-A No. 53-97424, the above-mentioned (A) is described.
) in the silver halide color photographic light-sensitive material having the structure R
A configuration is described in which each of the red-sensitive halide limited emulsion layer and the green-sensitive silver halide emulsion layer of the G low 1ε degree layer unit is coated separately into medium sensitivity and low sensitivity, and (C) further, Japanese Patent Application No. 58-52115 describes a structure in which an RGB low-sensitivity layer unit and an RGB high-sensitivity layer unit are sequentially coated on a support.

Silver halide color photographic materials having these (A), (B), and (C) structures (hereinafter referred to as high-sensitivity reverse layer structure) are:
In either case, at least a highly sensitive red-sensitive silver halide emulsion layer is provided between a green-sensitive silver halide emulsion layer having high sensitivity and a green-sensitive silver halide emulsion layer having lower sensitivity than the high-sensitivity emulsion layer. It is an effective means to achieve the objectives of high sensitivity and high image quality.

The present invention is effective when applied to either the above-described high-sensitivity layer structure or high-sensitivity reverse layer structure, and is even more effective.

In order to apply the present invention to the case where there are a plurality of layers with the same color sensitivity as described above, it is sufficient that the DIR compound that is the object of the combination of the present invention is added to one of the layers. The effect will be even greater if it is used in multiple layers. When the same color-sensitive layer is added to only one layer, it is advantageous to use it in the layer containing the largest amount of silver.

Next, the diffusible DIR compound preferably used in the present invention will be explained.

The diffusible DIR compound preferably used in the present invention is represented by the following general formula (1).

Diffusible DIR compound general formula (1) A+Y).

In the formula, A represents a coupler component, m represents 1 or 2, and Y is a group that binds to the coupling position of the coupler component and leaves by reaction with the oxidized product of the color developing agent, and is a highly diffusive development inhibitor. represents a group capable of releasing an agent or a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling.

In the present invention, the group Y in the above general formula (1) is D represented by the following formulas (2A) to (2E), (3) to (5).
IR compounds can be preferably used. More preferably, the leaving group Y has the formula (2A) (2B) (2E) (4
), particularly preferably a compound represented by the formula (2B
)(2E)(4).

General formula of Y (2 people) General formula of Y (2B) General formula of Y (2C) General formula of Y (2D) General formula of Y (2E) X is O, S or Se General formula of Y (3) General formula (4) of Y General formula (5) of Y In the above general formulas (2A) to (2D) and (3), R
1 is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, an N.
N-dialkylcarbamoyl group, nitro group, amino group,
N-7 arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group,
It represents an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R, may be the same or different, and n R. The total number of carbon atoms contained in is preferably 0 to 10.

R2 in the above general formula (2E) is R in (2A) to (2D),
X represents an oxygen atom or a sulfur atom, and in general formula (4), R2 represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (5), R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, or an aryloxycarbonyl group. It represents an amino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, an alkylthio group, or an amino group.

When R+, Rt, Rx or R4 represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl. Substituents include halogen atom, nitro group, cyano group, aryol group,
Examples include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, and an arylthio group.

When R+, Rz, Rs or R4 represents an aryl group, the aryl group may be substituted.

Substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, cyano group or ureido group.

R1R2, R's or R4 represents a heterocyclic group and represents a fused ring, such as a pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imido group , oxazine group, etc., and these may be further substituted with the substituents listed for the aryl group.

In general formulas (2E) and (4), the number of carbon atoms contained in Rz is preferably 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R3 and R4 is preferably 1 to 15.

In the above general formula (1), Y can take the structure of the following general formula (6).

General formula (6) of Y % formula % In the formula, the TIME group is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and is a group that can release an INHIBIT group in an appropriately controlled manner after being cleaved from a coupler.

The INHIBIT group is a group that provides a development inhibitor or a compound capable of releasing a development inhibitor.

In general formula (6), the -TIME-INHIBIT group can be represented by the following general formulas (7) to (13).

General formula of Y (7) General formula of Y (8) C) It INHIBIT General formula of Y (9) General formula of Y (10) h CHZ INHIBIT General formula of Y (11) General formula of Y (12) Y General formula (13) n In general formulas (7) to (13), R5 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group , cyano group, nitro group,
Represents a sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (11) and (13)
, l represents 1 or 2, k represents an integer from 0 to 2 in general formulas (7), (11), (12) and (13), and general formulas (7), (10) and ( In 11), R.

represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an atomyl group, and in the general formulas (12) and (13), B represents an oxygen atom. ), and the INHIBIT group has the general formula (2A), (2B), (3)
, has the same meaning as the general formula defined in (4) and (5). However, the number of carbon atoms is different.

However, in general formulas (2A), (2B) and (3),
-The total number of carbon atoms contained in each R1 in the molecule is 1 to 32
In the general formula (4), the number of carbon atoms contained in Rz is 1 to 32, and in the general formula (5), R1 and R
The total number of carbon atoms contained in 4 is 0 to 32.

When R5 and R4 represent an alkyl group, they may be substituted or unsubstituted, chain or cyclic. Examples of the substituent include the substituents listed when RI'=Ra is an alkyl group.

When Rs and Rh represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R1 to R4 are aryl groups.

Among the above diffusible DIR compounds, general formula (2A), (
Those having a leaving group represented by 2B), (2E) or 4) are particularly preferred.

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Coupler residues of benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, heterozygous compounds included in U.S. Pat. No. 3,841,880 Coupler residues derived from ring-substituted acetamides or heterocycle-substituted acetates or U.S. Pat. No. 3,770,44
No. 6, British Patent No. 1,459.171, West German Patent (O
LS) No. 2.503,099, Japanese Unexamined Patent Publication No. 50-1397
No. 38 or Research Disclosure 15737
Examples thereof include coupler residues derived from acylacetamides described in No. 1, No. 1, and heteroprototypical coupler residues described in US Pat. No. 4,046,574.

The magenta image-forming coupler residue represented by A includes a 5-oxo-2-pyrazoline nucleus, pyrazolo-(1,5
-a) Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, or an indacylon or pyrazolotriazole coupler residue.

Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. Coupler residues of this type represented by A include U.S. Pat.
No. 2,213, No. 4,088,491, No. 3,6
32.345, 3.958,993 or 3
, 961,959, and the like.

Next, the preferred specification of the DIR compound that can be used in the present invention is 7'4'+2' (no change in content)'i'l+鈇-J
""+1・, no change to self 1j) I7 D 9 CzHzsOCOCHCOOC+z
llzs ■ Akira+:'If rlノ;'l', ='('l',
I-f: Change "EsuL) Not Request for details 3: (No change in content) O2 N = N Which part of the specification I north゛ (No change in content D ~ 17 m/ in the specification) Φ (No change in content) I D-25 i'' of Mei 41: I word (No change in content) D-30p'
I'rl valley of disorder (no change in content) Czl amount.

D-32 Engraving of specification (no change in content) I ll D-34 iY+ of specification (no change in content) D-35
0 L;zH5L+stl:++ D-36 bar? No. 171 (No change in content) Section 1- of the specification: (No change in content)), j.

Purification of Mei II (no changes in content) @'dJ Miyako no 14+, 1. , no change to CF'zu°shi)
D-460H N (h NO -578□ Nobohi ♂'s Teiichikichi (no change in content) OH 8・〆jJJ4 Kikkichi's C ¥1 death (no change in content) lh, death in the specification tr: No change in content. These compounds are described in U.S. Pat. Nos. 4,234,678 and 3,227.55
No. 4, No. 3,617,291, No. 3,958.993
No. 4゜149.886, No. 3,933,500, JP-A No. 57-56837, No. 51-13239, U.S. Patent No. 2,072.363, U.S. Patent No. 2,070,266, Research Disclosure -21st December 1981
It can be easily synthesized by the method described in No. 228.

The amount of the diffusible DIR compound of the present invention added is generally preferably from 2.times.10-' to 5.times.10-' moles, more preferably from 5.times.10-' to 1.times.10-' moles per mole of silver in the emulsion layer.

To explain the photosensitive material of the present invention in more detail,
The green-sensitive emulsion layer of the present invention has conventional color a
゛・7: (No change in content) Domagenta coupler can be used together. Colored magenta couplers include U.S. Pat. Nos. 2,801.171 and 3,519,4
Those described in No. 29 and Japanese Patent Publication No. 48-27930 can be used.

Particularly preferably used colored magenta couplers are as follows.

(CM-4) l (CM-2) I Engraving of the detailed description (no changes to the contents) (CM-3) (CM-4)　　　　　　　　.

II3 In the specification; Colored cyan couplers include Japanese Patent Publication No. 55-32461 and British Patent No. 1,084,480.
Items listed in the number can be used.

A particularly preferred colored cyan coupler is:

The following may be mentioned.

(CC-3) H Each of the light-sensitive emulsion layers constituting the light-sensitive material of the present invention can contain a corresponding coloring coupler.

It is generally preferred that the blue-sensitive layer of the present invention contains a coupler that forms a yellow dye, and as the yellow color-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pinoylacetanilide compounds can be advantageously used.

A specific example of a yellow coupler is disclosed in Japanese Patent Application Laid-Open No. 47-26133.
No. 4B-29432, No. 5Q-87650, No. 51-17438, No. 51-102636, Japanese Patent Publication No. 45-19956, U.S. Patent No. 2,875.057,
No. 3,408.194, No. 3,519,429, No. 7 (end-, j; (: Hakushin (no change)) No. 51-33410, No. 51-10783, Same 46-
There is one with a number such as No. 19031.

Particularly preferred couplers are as follows.

(Y-1)　　　　　　　　,.

(Y-2) Purification of the statement (no changes to the contents) (Y-3) (Y-4) (Y-5)　　　　　　　.

Clear statement of specification (no change in content) (Y-6) C)!3 (Y-8) Clearance of specification (no change in content) (Y-6) -9) (Y-10) COO)I Meikyou 1 Chu's 1.1 [↓: (No change to i'q'r;) (
Y-11) (Y-12) (Y-13) rρ C,H.

(No change in content) (Y-14) rρ Magenta color-forming couplers used in the light-sensitive material of the present invention include pyrazolone compounds, indashilon compounds,
Cyanoacetyl compounds, pyrazolotriazole compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

A specific example of a magenta color forming coupler that can be used is disclosed in Japanese Patent Application Laid-open No. 49
-111631, Japanese Patent Publication No. 48-27930, JP-A-56-Moe'4e i-miniaturization (*no changes to content) 2923
6, U.S. Patent No. 2,600.788, U.S. Patent No. 3,062,
No. 653, No. 3.408.194, No. 3,519.4
No. 29, JP-A No. 57-94752, Research Disclosure No. 12443, and the like.

Particularly preferred couplers are the following →4.

shiL (M-2) (M-3) Il+ Details) of Jyo 2° (no change in content) shiE CM-5) CM-6) Ming, gospel ・'dko (no change in content) ( M-15) As the cyan coloring coupler used in the light-sensitive material of the present invention, phenolic compounds, naphthol compounds, etc. can be used.

Specific examples include U.S. Patent No. 2.423.730, U.S. Pat.
No. 474゜293, No. 2.895.826, Japanese Unexamined Patent Publication No. 1973
There are those described in No. 0-117422 and the like.

Particularly preferred couplers are as follows.

C! II % (C-5) Item S, 1゛I Otsu' (white, 3, 2 unchanged) (C-6
) OCIIzCONIIICIIzCHzOC1hC411
q Engraving of the specification (no changes to the contents) C2) l.

C41j.

No. 'I#: "1 Basa no Otsu・ni: :"'! CJL Western style of specification (no change in content) C6H,3 The silver halide emulsion layer of the present invention and other photographic constituent layers contain non-diffusible DIR compounds and oxidized developing agents. Couplers other than the diffusible DIR compound of the present invention, such as non-diffusible couplers and polymer couplers, which react to form a diffusible dye that bleeds appropriately may also be used. Non-diffusible couplers that react with non-diffusible DIR compounds and oxidized developing agents to form diffusible dyes that bleed moderately are described in the applicant's patent application spec. Nonenwa 59-19
For polymer couplers, reference may be made to the description in Japanese Patent Application No. 172151/1983 filed by the present applicant. The total amount of coupler used in each layer is
The maximum density varies depending on the coloring property of each coupler, so it may be selected appropriately, but it is 0.0 per mole of silver halide.
It is preferable to use about 1 to 0.30 mol.

In order to incorporate these diffusible DIR compounds and couplers into coating solutions for silver halide emulsions and other photographic constituent layers according to the present invention, when the diffusible DIR compounds and couplers are alkali-soluble, they can be added as an alkaline solution. If it is oil-soluble, it may be added, for example, U.S. Pat. No. 2,322.027, U.S. Pat.
Diffusible DIR compounds and couplers are added to high-boiling solvents according to the methods described in Patent No. 2.801.171, Patent No. 2.272.191 and Patent No. 2.304,940, as necessary. It is preferable to dissolve it in combination with a low-boiling point solvent, disperse it in the form of fine particles, and add it to a silver halide emulsion or the like. At this time, other hydroquinone derivatives, if necessary,
Ultraviolet Absorption Specification 4 Can (no change in content) It is okay to use it together with anti-browning agents, anti-browning agents, etc.

It is also possible to use a mixture of two or more types of diffusible DIR compounds and couplers. Furthermore, in detail, the method of adding the diffusible DIR compound and coupler which is preferable in the present invention is as follows.
Compounds and couplers may be combined with other couplers, hydroquinone derivatives, anti-browning agents, ultraviolet absorbers, etc. as necessary, as well as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc. G
n-butyl phthalate, triresyl phosphate,
Triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether , di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2.5-di-5ec-amylphenyl butyl ether, monophenyl-di-chlorophenyl ether? 41
1 side: '7+ store (inner opening 1'', no change to ')' High boiling point solvent such as phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclo hexanol,
diethylene glycol monoacetate, nitromethane,
Dissolved in low-boiling solvents such as carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquiolein. The mixture is mixed with an aqueous solution containing an acid ester and a nonionic surfactant such as sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and then mixed with a high-speed rotating mixer,
It is emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and then added to a silver halide emulsion.

In addition, the diffusible DIR compound and coupler may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A No. 71-745 (no change in content) No. 38, No. 51-59943, No. 54-32552, Research Disclosure August 1976, IIh14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Seven-dimensional pomopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

The silver halide emulsion according to the present invention includes activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiol dioxide, etc. Urea, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specification - 6'!゛6 (No change in content) Specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Sensitizers, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadate (these types act as sensitizers or fog suppressants depending on the amount), etc. Chemical sensitization may be carried out either alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is selected from appropriate M-book engravings (
(No change in content) 5X10-” to 1 mole of silver halide with aggravating dye
Optical sensitization can be achieved by adding 3×10 −3 mol.

Various sensitizing dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as aggravating dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929,080, US Patent No. 2.23L658, US Pat.
No. 503゜776, No. 2,519,001, No. 2.9
No. 12.329, No. 3,656゜959, No. 3,67
No. 2,897, No. 3,694,217, No. 4, 02
5.

No. 349, No. 4,046,572, British Patent L242
, No. 588, Special Publication No. 44-14030, No. 52-24
Examples include those described in No. 844 and the like. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
No. 72,908, No. 2,739.149, No. 2,94
Typical cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 5,763, British Patent No. 505,979, etc.6. [Shoa jyosen (inside')
(without any change in δ). moreover,
Sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
, No. 378, No. 2.442,710, No. 2,454.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 629, No. 2,776.280, and the like.

Furthermore, U.S. Patent Nos. 2,213,995 and 2,493
, No. 748, No. 2,519,001, West German Patent No. 929
．． Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

Particularly preferred spectral sensitization methods include, for example, Japanese Patent Publication Nos. 43-4936 and 43-22884 concerning the combination of benzimidazolocarbocyanine and lupocyanine (no changes to the content). No. 45-
No. 18433, No. 47-37443, No. 48-282
No. 93, No. 49-6209, No. 53-12375,
JP 52-23931, JP 52-51932, JP 54-80118, JP 58-153926, JP 59
Examples include the methods described in No. 116646 and No. 59-116647.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 5820, No. 51-135528, No. 52-104
No. 916, No. 52-104917, and the like.

Further, regarding combinations of benzoxaprocarbocyanine (oxacarbocyanine) and other carbocyanins, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, Purification of JP-A-56-2 Ming'$8 (no change in content) No. 5728, No. 58-10753, No. 58-9144
No. 5, No. 59-116645, No. 50-33828, and the like.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

It may be added at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of W1 formation, and in some cases, it may be added at a step immediately before emulsion coating.

Engraving of Specification O (no change in content) The silver halide color photographic light-sensitive material of the present invention contains a water-soluble dye in the hydrophilic colloid layer for the purpose of preventing irradiation and other various purposes. Good too. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584, 609 and 1,27.
7.429, JP-A-48-85130, JP-A No. 49-9
No. 9620, No. 49-114420, No. 49-129
No. 537, No. 52-108115, No. 59-2584
No. 5, U.S. Patent No. 2,274,782, U.S. Patent No. 2,533,
No. 472, No. 2956.879, No. 3,125,4
No. 48, No. 3.148.187, No. 3.177.07
No. 8, No. 3,247,127, No. 3,540,887
No. 3,575.704, No. 3,653,905, No. 3,718.472, No. 4,071,312,
It is described in No. 4.070,352.

It is more effective to fix these water-soluble dyes in the form of a mordant. Regarding the technology related to mordant formation, see U.S. Patent No. 2,326,057, U.S. Pat. Store 2 (No changes have been made to the contents, but you can refer to the description in No. 899, etc.)

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, color stain preventive agents described in JP-A No. 46-2128 and US Pat. inhibitor, color image browning inhibitor,
Antistatic agents, hardeners, surfactants, plasticizers, wetting agents, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, M1 gelatin, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

An engraving of the specification of the silver halide color photographic light-sensitive material of the present invention (for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, with a reflective layer or with a reflector) transparent supports such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are used for the purpose of use of the photosensitive material. be selected accordingly.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761.791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

There are no particular limitations on the method of processing the photographic material according to the present invention, and any processing method can be applied. for example,
Typical methods include bleach-fixing after color development, followed by washing and/or stabilization if necessary; Separately, followed by further water washing and/or stabilization treatment as necessary; alternatively, pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post-hardening, and water washing in this order. Method: color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, stabilization method: The developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to produce the dye. Any method may be used for processing, such as a developing method that increases the amount.

The color developing solution used for processing the silver halide color photographic light-sensitive material of the present invention is, but not limited to, an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or higher, more preferably a pH of 9 to 12. be. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenethia, or those of the amine type mentioned in the specification (no change in content), and the following are mentioned as preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β, -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methoxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-
Acetamido-4-amino-N.

N-dimethylaniline, N-ethyl-N-β~[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochloride, sulfite,
p-) Luen Mingki11-Ki°'s 1-piece +1+ (Mukami T
(This is an unmodified sulfonate, etc.)

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amine compounds to be used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used. The amount used ranges from 0.0002 mol/l to 0.7 mol/β. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example 3-
Methyl-4-amino-N,.N-diethylaniline and 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-niethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino- N-ethyl-N-β
-Hydroxyethylaniline, etc. can be freely used in combination depending on the purpose.

Various ingredients commonly added to water, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, and water softeners. , a thickening agent, a development accelerator, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in the bleaching solution or bleach-fixing solution in the bleaching process include aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid.
(+Mukojuku: without any change) Those in which metal ions are coordinated are generally used. Representative examples of the above-mentioned aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetraprobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may also contain additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the cleaning solution (no change in content) in bleach specification S above, various other additives, such as pH
Buffers, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below. However, as a matter of course, the embodiment of the present invention is not limited to this.

Example 1 The silver iodobromide emulsion shown in Table 4 was prepared using JP-A-54-11882.
No. 3, JP-A-58-113928, JP-A-58-21
It was produced by the method described in No. 1143, etc., and the usual function addition method.

A multilayer color negative photographic material (sample 11hl comparison) was prepared by coating the layers shown below on a cellulose triacetate film.

1st layer: antihalation layer 2nd layer: middle layer gelatin・−・−・−・・−・−・・−−−1−−−−
---・-・--1--・-・1.2 g/% 3rd layer: Low-sensitivity red-sensitive emulsion layer 4th layer: High-sensitivity red-sensitive emulsion 5th layer: Intermediate layer gelatin --- −−−・−・−・−・−−−−−
---・--m----------・0.80 g /
m 6th layer: Low sensitivity green sensitive layer 7th layer: High sensitivity green sensitive layer 8th N: Yellow filter 1 layer 9th layer: Low sensitivity blue sensitive layer 10th layer: High sensitivity blue sensitive layer 11th layer: 1st protection Layer 12: Second protective layer In addition to the above composition, each emulsion layer contains 4-hydroxy-6-methyl-1+ 3+ 3a,
7-chitrazaindene, 1-phenyl-5-mercaptotetrazole, etc. In addition to the above composition, each layer also contains gelatin hardeners H-1 and H-2.
and surfactants were added. And 3.4.6,7,
Samples 2 to 11 were prepared by adding the emulsions shown in Table 4 and diffusible DIR exemplified compounds to Sample No. 9.1011 as shown in Table 5. The amount of diffusible DIR compound added to each color-sensitive layer is the desensitization of the white layer.

The concentration was controlled so that the decrease in concentration was approximately equal.

V-1 H c, u, Bnom2 CJs 2H5 B5-2 Sensitizing dye-■rρ Shi! N-N H I CHz=CHCH□CHzSOzC
Il=ClbQ-1 0H 011
Blue light and green light are applied to each sample through a wedge respectively.

A dye image was obtained by applying red light and white light and processing with the following processing steps.

Development process (38℃) Processing time Color development...
・・・・・・・・・・・・ 3 minutes 15 seconds bleach ・・・・・・・・・・・・ 6 minutes 30 seconds water
Washing ・・・・・・・・・・・・ 3 minutes 15 seconds Fixing ・・・・・・・・・・・・ 6 minutes 30 seconds Washing ・・・・・・・・・・・・・・・・・・ 3 minutes 15
Second stabilization bath: Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer composition: (Add 1.0 g of potassium hydroxide water to make the solution 11, and adjust the pH to 10.0.

Bleach solution composition: Add water to bring the volume to 11 and adjust the pH to 6.0.

Fixer composition: Add water to make 1N and adjust pH to 6.5.

Stabilizing liquid composition: Add water to make 11.

The obtained characteristic values are shown in Table 5.

rlE is expressed as γA/TN of each silver halide emulsion layer, where γ1 is 18 when exposed to white light and TA is γ1 when exposed to blue light, green light, and red light.
I represents the magnitude of E and receives I.

1. It shows that the larger E is, the larger TA/TH is.

γ0; If D is the density at an exposure point (Δlog E = 1.0) that is 10 times the exposure amount at the density point with fog +0.3, then T = (D-(fog +0.3)) /1.0 becomes.

In addition, the display of aging characteristics is for frozen products at 40℃8.
It is shown by the afterimage rate of the Dmax area compared to that processed at 0% RH for 15 days. The closer it gets to 100%, the more stable it becomes.

As is clear from Table 5, Samples Nos. 4 to 9 of the present invention have a much larger IIE in each color-sensitive layer than the comparative sample, indicating that high chroma colors can be reproduced. Furthermore, it is clear that the stability over time, which has been a drawback in the past, has been surprisingly improved in such systems as well.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material having good color reproducibility and excellent stability over time, especially stability under high temperature and high humidity.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki Shite Tsuki Shuho Seishi (Method) % formula % 1. Indication of the case 1988 Patent Application No. 19526 2. Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the amended person case Patent application Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment Specification

Claims (1)

[Scope of Claims] A silver halide photographic material having two or more light-sensitive silver halide emulsion layers having different color sensitivities on a support,
The at least one silver halide emulsion layer contains twin silver halide grains, and the light-sensitive silver halide emulsion layers having different color sensitivities are developed by reacting with an oxidized form of a developing agent in at least two of the light-sensitive silver halide emulsion layers. A silver halide emulsion layer containing a compound that releases an inhibitor or a development inhibitor precursor, that is, a DIR compound, and in which the development inhibitor or development inhibitor precursor released from the DIR compound is diffusible, satisfies the following condition A. A silver halide photographic material characterized by: [Condition A] D contained in one color-sensitive silver halide emulsion layer
The magnitude relationship between the development inhibitory power released from the IR compound and the development inhibitor released from the DIR compound contained in the other color-sensitive silver halide emulsion layer determines whether the DIR compound is replaced or not. When it is contained in a photosensitive silver halide emulsion layer, the size is reversed, and the development suppressing power for the other photosensitive silver halide emulsion layer is greater than the development suppressing force for the photosensitive silver halide emulsion layer containing it. A DIR compound is added so that the suppressing power is greater.