JP2613371B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic material. The present invention relates to a silver halide color photographic light-sensitive material having improved stability over time, and particularly excellent stability under high temperature and high humidity.

[Conventional technology and its problems]

In recent years, with the increase in sensitivity of silver halide photographic materials and the miniaturization of cameras, demands for higher image quality have been increasing.
Among them, the demand for color reproduction is particularly high. In addition, the demand for quality stabilization has been increasing due to the spread of compact labs and automatic printers.

As a technique for improving color reproducibility, an automatic masking technique using a colored coupler is known as a method for improving color mixing, and is commonly used in negative silver halide color photographic light-sensitive materials. Not at a satisfactory level. As a technology to further enhance color purity, an isolation layer (IL), also called an intermediate layer, is installed between different color-sensitive layers, and a scavenger of an oxidized color developing agent and a colorless coupler are added to the isolation layer (IL). It is known that a diffusion inhibitor such as a sensitizing dye, for example, fine silver halide particles, a cationic hydrophilic synthetic polymer, or a polymer latex is added to the separating layer (IL). However, these methods have not yet attained a satisfactory color reproducibility.

Also disclosed is a method using a DIR coupler to enhance IIE. Various DIR compounds are used. For example, at the time of 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 developing printing agent, and reacts with an oxidized form of a color developing agent during development to release a development inhibitor. A so-called DIR substance that does not form a coloring dye, one that directly releases a development inhibitor by reacting with an oxidized form of a color developing agent and one that indirectly releases a development inhibitor, for example, JP-A-54-145135, No. 57-154234, No. 58-162949, No. 58-
205150, 59-195643, 59-206834, 59-20683
No. 6, No. 59-210440, No. 60-7429 (hereinafter referred to as timing DIR compound) and the like. In the present specification, those exhibiting the DIR effect are collectively referred to as 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 to suppress the development of other silver halide emulsion layers,
That is, IIE can be obtained, and in particular, a DIR compound capable of releasing a so-called diffusible suppressing group or a diffusible development inhibitor precursor is effective, and is used for a recent silver halide color film. The effect is increasing,
Since the IIE has a strong directivity (for example, strong from the blue-sensitive silver halide emulsion layer to the green-sensitive silver halide emulsion layer, but weak in the reverse direction), an improvement in the color saturation (chroma) of the characteristic is expected. Yes, but with the undesirable effect of "hue shift". In addition, even if it is diffusible, the addition layer exerts the strongest inhibitory action, so that the addition layer has a problem such as a decrease in gamma (γ), a decrease in sensitivity and a decrease in color density, and an amount sufficient to give a sufficient effect to other layers. Is difficult to use.

JP-B-55-47379 and JP-A-57-93344 disclose techniques for using a so-called diffusible DIR compound to emphasize IIE from one color-sensitive layer to a different color-sensitive layer.
Nos. 57-56837 and 59-131937, but even with these techniques, only insufficient improvement in color reproducibility can be expected as described above.

Further, Japanese Patent Application No. 60-93411 describes a technology containing a DIR compound that has a larger development inhibiting power on the other photosensitive layer than a photosensitive layer to which diffusive DIR is added. However, the color reproducibility is improved, though insufficient, as compared with the prior art. However, when these DIR compounds are used, a decrease in the maximum color density and a decrease in sensitivity occur over time under high temperature and high humidity. have.

[Object of the invention]

An object of the present invention is to improve the color reproducibility by increasing IIE in both directions between different color-sensitive layers, and to improve the aging stability, especially the stability under high temperature and high humidity. It is to provide.

[Configuration of the invention]

An object of the present invention is to provide a silver halide photographic material having two or more photosensitive silver halide emulsion layers having different color sensitivity on a support, wherein at least one of the silver halide emulsion layers has the following structure. Wherein the at least two photosensitive silver halide emulsion layers having different color sensitivity have a U value of 60 or more, and the at least two photosensitive silver halide emulsion layers react with an oxidized form of a developing agent to suppress the phenomenon. Or a compound that releases a development inhibitor precursor, that is, at least one DIR compound, wherein the development inhibitor or development inhibitor precursor released from the DIR compound is diffusible and further satisfies the following condition A: This is achieved by a silver halide photographic light-sensitive material characterized by the following.

[Condition A]

The development inhibitor or the development inhibitor precursor released from each of the at least one DIR compound is different from each other, and the magnitude relation of the development inhibition power of the development inhibitor or the development inhibitor precursor with respect to the photosensitive silver halide agent layer is different. The relationship can be changed by the photosensitive silver halide emulsion layer containing those DIR compounds,
In addition, the DIR compound having a smaller development resistance of at least two of the DIR compounds among those DIR compounds has a development inhibiting power for the contained photosensitive silver halide emulsion layer.

Definition of U value: The weight of silver halide grains contained within a grain size range of ± 20% around the average grain size is 10% of the weight of all silver halide grains.
00 The value shown for the case of the following. Hereinafter, the present invention will be described in more detail.

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:
It is 1: 1 or less and 2: 1 or more. Aspect ratio is the particle diameter:
It refers to the thickness ratio.

Here, the diameter of a silver halide grain 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 from 0.2 to 50 μm, preferably
0.2 to 4.0 μm.

Generally, when a twinned silver halide grain is a twin having two parallel faces, the distance between the two parallel major faces is the thickness.

As the silver halide composition of the twin grains according to the present invention,
Those composed of silver bromide and silver iodobromide are preferred, and silver iodobromide having a silver iodide content of 0 to 20 mol% is preferred. It is more preferably 2 to 18 mol%, particularly preferably 2 to 15 mol%.

Further, the twin grains according to the present invention are monodisperse, in particular, those having the U value of 60 or more, that is, silver halide contained within a grain size range of ± 20% around the average grain size. The grains have a weight of 60% or more of the weight of all silver halide grains.

Here the average particle diameter, the frequency n _i of grains having a radius r _i
The value n _i × r _i ³ with r _i ³ is the particle size r _i (three significant figures, the least significant digit is 4 discard 5 pcs) when the maximum and is defined as.

Here, the particle diameter r _i is the diameter of a spherical silver halide grain, or the diameter of a spherical silver halide grain.
This is the diameter when the projected image is converted into a circular image having the same area.
The particle diameter can be determined, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times, and calculating the particle diameter or the area of the projected image on the print by three significant figures (fourth digit rounded off).
) Can be obtained by actually measuring (The number of particles to be measured should be 1,000 or more indiscriminately.)

The monodisperse silver halide grains used in the present invention can be used by mixing silver halide emulsions having different grain sizes within a range that does not impair the effect of monodispersity. Is meant to be included in the present invention. Including such a case, the grain size distribution of the silver halide grains substantially composed of monodispersed silver halide grains is within a grain size range of ± 20% around r defined as above. The weight of the silver halide grains used is at least 60%, more preferably at least 70%.

In order to produce an emulsion comprising monodisperse twin grains, the production methods described in JP-A-51-39027, JP-A-52-153428, JP-A-54-118823 and the like can be referred to.

As a preferable method for obtaining an emulsion composed of monodisperse tabular grains, a seed population composed of monodisperse spherical grains is prepared by physical ripening in the presence of a silver halide solvent containing multiple twins. Thereafter, a method of growing this can be used. As a more preferable method, a tetrazaindene compound can be present during the growth of tabular grains to increase the ratio of tabular grains and improve monodispersity.

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

In the layer containing the twin grains used in the present invention, the twin grains are preferably present in an amount of at least 40% by weight, more preferably at least 60% by weight of the total silver halide grains present in the layer. .

The layer containing the twin particles used in the present invention, when the same color-sensitive layer is plural, may be contained in any layer, but preferably contained in a more sensitive layer is more effective. .

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

For example, in an atmosphere having a relatively high pAg value of pBr1.3 or less, twin particles form a seed crystal having a weight of 40% or more, and
It is obtained by growing a seed crystal while simultaneously adding silver and a halogen solution while maintaining the pBr value.

In this grain growth process, it is preferable to add a silver and halogen solution so as not to generate new crystal nuclei.

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

By using a silver halide solvent as needed during the production of the twin grains used in the present invention, the grain size, grain shape (aspect ratio, etc.), grain size distribution, and grain growth rate can be controlled. The amount of the solvent used is preferably 10 ^{-3 to} 1.0% by weight, particularly preferably 10 ^-2 to 10 ^-1 % by weight of the reaction solution.

For example, as the amount of the solvent used increases, the particle size distribution becomes monodispersed, and the growth rate can be increased. On the other hand, there is also a tendency that the thickness of the particles increases with the amount of the solvent used.

Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Patent No. 3,271,157
Nos. 3,790,387 and 3,574,628 can be referred to.

In the present invention, during the production of twin grains, the addition rate, amount and concentration of a silver salt solvent (for example, an aqueous AgNO ₃ solution) and a halide solution (for example, an aqueous KBr solution) to increase the grain growth are increased. The method is preferably used.

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 at the time of silver halide precipitation, at the time of grain growth or after the completion of the growth. For example, metal salts or complex salts of gold, platinum, palladium, iridium, bismuth, cadmium, copper and the like, and combinations thereof can be applied. In the method for producing an emulsion containing the above-mentioned grains, as a means for desalting, a Nudel washing method, a dialysis method or a precipitation precipitation method commonly used in a general emulsion can be appropriately used.

 Next, the [condition A] will be described in more detail.

Usually, when a DIR compound is used for a certain color-sensitive layer,
Even if the released development inhibitor and its precursor (hereinafter referred to as a development inhibitor including this precursor) are diffusible, the release layer itself is most suppressed, and the DIR is reduced due to a decrease in density and sensitivity. It is difficult to use a large amount of the compound.

When a DIR compound is used in a certain layer, the layer suffers a certain level of development inhibitory power as described above by the development inhibitor of the DIR compound in its own layer. Therefore, development occurs in which the development inhibitory effect supplied by the development inhibitor supplied from another layer is not sufficiently exhibited. In other words, when attempting to generate IIE in both directions between two color-sensitive layers, the amount IIE is low, or only one direction is strong, and the other direction is extremely weak.

However, it has been found that the released development inhibitors show different development inhibition powers in different color-sensitive layers, and that the types of the development inhibitors have different development inhibition powers.
It is stated in.

For example, when the development inhibitor A and the development inhibitor B are used in approximately equimolar amounts in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, the development of the green-sensitive silver halide emulsion layer is performed. When the inhibitory power is A> B but the development inhibitory power in the red-sensitive silver halide emulsion layer is A <B, the DIR compound having the development inhibitor B in the green-sensitive silver halide emulsion layer is replaced with a red-sensitive halide. By adding the DIR compound having the development inhibitor A to the silver emulsion layer, the self-layer suppression in each of the added layers is kept weak, and a large influence [large IIE] is exerted on the other color-sensitive layers. It is possible to give a two-way IIE
Can be greatly increased.

The usage of such a DIR compound, that is, the method or standard for determining the color-sensitive layer to which the DIR compound is to be added, is described in the above example, that is, between the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. It is not only effective, but also effective for other types of different color-sensitive layers.

In the sense as described above, in the present invention, the magnitude relationship of the development inhibiting power is a relationship that can be changed by the photosensitive halide emulsion layer containing the DIR compound, and this is premised. In the present invention, at least one DIR compound is contained in at least two photosensitive silver halide emulsion layers having different color sensitivities, and the development inhibiting power for the contained photosensitive silver halide emulsion layer is reduced. Of two of those DIR compounds contained in the photosensitive silver halide emulsion layer (at least two of them when two or more are contained in one layer and thus three or more are contained). The condition of the composition of the photosensitive material is that the DIR compound, which is smaller than the DIR compound, is added and contained. That is, it is sufficient to add and contain such that the development suppression for the added layer itself is small and the development suppression for the other layers is large.

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

On a (transparent) support, three types of photosensitive materials having layers having the following compositions are prepared.

Sample (I): Sample having a red-sensitive silver halide emulsion layer Silver iodobromide (6 mol% of silver iodide, average particle size of 0.48 μm) spectrally sensitized to red-sensitivity and the exemplified coupler (C-7) were converted to silver. 0.08 mol of gelatin coating solution per mol of coated silver
It was applied so as to be 1.4 g / m ² .

Sample (II): Sample having green-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to green sensitivity (silver iodide: 6 mol%, parallel particle diameter: 0.48 μm) and exemplified coupler (M-2) were converted to silver A gelatin coating solution containing 0.07 mole per mole is coated with silver.
It was applied to be 1.1 g / m ² .

Sample (III): Sample having a blue-sensitive silver halide emulsion layer Silver iodobromide (silver iodide, 6 mol%, average grain size: 0.48 μm) spectrally sensitized to blue sensitivity and exemplified coupler (Y-4) were converted to silver. The gelatin coating solution containing 0.34 mol per mol is coated silver amount.
It was applied so as to be 0.5 g / m ² .

Each layer contains a gelatin hardener and a surfactant in addition to the above.

After white exposure of the obtained samples (I) to (III) using a wedge, the development time (I) was 1 minute and 45 seconds, and (II)
The processing is performed according to the processing method of Example 1 described later except that the time is 2 minutes and 40 seconds, and that (III) is 3 minutes and 15 seconds. The sample (I
In order to make the development suppressing powers of I) almost the same, those added with varying amounts of various development inhibitors and those not added were used. Sensitivity ^{* 1} (So) of each sample (I) to (III) treated with the developing solution to which the development inhibitor was not added, and sensitivity ^{* 1 of} each sample obtained by developing the developing solution to which the development inhibitor was added. The difference (ΔS) from (S) is used as a measure of the development inhibiting power of each color-sensitive layer with each development inhibitor.

* 1) The sensitivity So is the logarithm of the reciprocal of the exposure (Eo) at the density point of fog density +0.3, that is, -logEo.

* 2) In the same manner as in * 1), the sensitivity S is the logarithm of the reciprocal of the exposure (E) at the density point of fog density +0.3, that is, -logE.

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

When a DIR coupler having the above-mentioned development inhibitors A-1 to A-6 is used, as described above, a combination may be used in which the addition layer itself has a small development suppression and the other layers have a large development suppression.

To make a preferred combination between a red-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer based on the difference in the development inhibiting power of each development inhibitor exemplified in Table 1, for example, a red-sensitive halide The value can be obtained by normalizing the value of the silver emulsion layer (sample (I)) to the value of one compound and dividing the value of the blue-sensitive silver halide emulsion layer (sample (III)) by the ratio at that time. (See Table 2).

That is, the following combination examples are listed in Table 1.

[Development inhibitor of DIR compound added to red-sensitive silver halide emulsion layer / DIR added to green-sensitive silver halide emulsion layer]
Examples of Combinations of Compound Development Inhibitors] 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, A-5 / A-3, A-5 / A-4, A-6 / A-3,
A-6 / A-4 and the like.

Similarly, the preferred combination has a small addition layer suppression and a large suppression of other layers 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. You can choose.

In order to emphasize IIE, it is preferable that the working distance of the inhibitor is large. That is, it is preferable that the so-called long-acting property is large.

In the present invention, the diffusivity of the inhibitor can be evaluated by the following method.

Light-sensitive material samples (IV) and (V) each having a layer having the following composition were prepared on a (transparent) support.

Sample (IV): Sample having a green-sensitive silver halide emulsion layer Silver iodobromide (6 mol% of silver iodide, average particle size of 0.48 μm) spectrally sensitized to green sensitivity and the exemplified coupler (M-2) were converted to silver. A gelatin coating solution containing 0.07 mole per mole is coated with silver.
1.1 g / m ² Gelatin was coated so as to have a coating weight of 3.0 g / m ² , and a protective layer thereon: silver iodobromide (2 mol% of silver iodide, not subjected to chemical sensitization and spectral sensitization) A gelatin coating solution containing an average particle size of 0.08 μm) was applied so that the coated silver amount was 0.1 g / m ² and the gelatin amount was 0.8 g / m ² .

Sample (V): Sample obtained by removing silver iodobromide from the protective layer of Sample (IV).

Each layer contains a gelatin hardener and a surfactant in addition to the above.

Samples (IV) and (V) were exposed to white light using a wedge and then processed according to the processing method of Example 1 described below, except that the development time was changed to 2 minutes and 40 seconds. 60% sensitivity of sample (V) in developer
(In logarithmic expression, -ΔlogE = 0.22) were used in which various development inhibitors were added in an amount to be suppressed and those in which no development inhibitor was added.

The sensitivity of the sample (IV) when no development inhibitor was added was defined as So,
The sensitivity of the sample (V) and So. ', the sensitivity of the sample (IV) when the development inhibitor added with S _{1 v,} when the sensitivity of Sample (V) and S _v, reduced sensitivity of the sample (IV) DerutaSo = So′−S _v , desensitization of sample (V) ΔS = So−S _1v , diffusivity = ΔS / ΔSo.

However, all the sensitivities were logarithms (-logE) of the reciprocal of the exposure 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 diffusivity of several development inhibitors.

Diffusivity is relatively small (A-5: 0.34 or less)
Since IIE has a small IIE, it is preferred that the diffusivity exceeds 0.34. In the present invention, the diffusivity is more preferably 0.4 or more.

In the silver halide color light-sensitive material of the present invention, the emulsion layer having the same sensitivity can be divided into three or more layers for each (or at least one layer). From the viewpoint of diffusibility in the layer of the agent precursor, it is preferable that the number does not exceed three layers.

In recent years, silver halide color photographic materials having high sensitivity, high image quality and good color reproducibility have been desired. It is effective when applied to materials,
More effective.

The following is known as a layer configuration for achieving high sensitivity or the like. For example, in the above-described layer structure of the photosensitive silver halide emulsion layers of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer sequentially coated on a support, In some or all of the photosensitive silver halide emulsion layers, substantially the same color-sensitive layer is used as a high-sensitivity silver halide emulsion layer containing a diffusion-resistant coupler that develops substantially the same hue on the body (hereinafter referred to as a high-sensitivity silver halide emulsion layer). There is a layer structure in which a light-sensitive emulsion layer is separated into a light-sensitive emulsion layer and a light-sensitive silver halide emulsion layer (hereinafter, referred to as a low-speed emulsion layer), and these layers are adjacently layered. Hereinafter, this layer configuration is referred to as a high-sensitivity normal layer configuration.

On the other hand, the following technique is known as a reverse layer configuration that achieves high sensitivity.

[A] First, JP-A-51-49027 discloses that: (a) low-sensitive emulsion layers (RG low-sensitive layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in order from the support side; (B) On the RG low-sensitivity layer unit, a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer (RG high-sensitivity layer unit) in order from the support side. (C) On the RG high-sensitivity layer unit, a high-sensitivity and low-sensitivity emulsion layer of a blue-sensitive silver halide emulsion layer (B
(B) Further, JP-A-53-97424 discloses that the silver halide color photographic light-sensitive material having the above-mentioned constitution (A) has a low RG sensitivity. The composition describes that each of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer of the layer unit is separately and medium- and low-sensitively coated. No. -52115 describes a configuration in which an RGB low-sensitivity layer unit and an RGB high-sensitivity layer unit are sequentially coated on a support.

Each of the silver halide color photographic light-sensitive materials having the constitutions [A], [B] and [C] (hereinafter, referred to as a high-sensitivity inverted layer constitution) comprises a high-sensitivity green-sensitive silver halide emulsion layer and the high-sensitivity green layer. An at least high-sensitivity red-sensitive silver halide emulsion layer is provided between the green-sensitive silver halide emulsion layer having a lower sensitivity than the light-sensitive silver halide emulsion layer, and an effective method for achieving the object of high sensitivity and high image quality is achieved. Means.

The present invention is effective when applied to any silver halide color photographic light-sensitive material having the above-mentioned high-sensitivity normal layer structure and high-sensitivity reverse layer structure, and is more effective.

In order to apply the present invention to a case where there are a plurality of the same color-sensitive layers as described above, the DIR compound which is the object of the combination of the present invention may be added to one of the layers. If used for a plurality of layers, the curing is even greater. When a plurality of layers having the same color sensitivity are added to only one layer, it is advantageous to use the layer having the largest amount of silver.

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

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

Diffusion DIR compound General formula (1) AY) _{m In the} formula, A represents a coupler component, m represents 1 or 2, Y binds to the coupling position of the coupler component A, and reacts with an oxidized color developing agent. And a group capable of releasing a highly diffusible development inhibitor or a development inhibitor.

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

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

General formula of Y (2A) General formula of Y (2B) General formula of Y (2C) General formula of Y (2D) General formula of Y (2E) General formula of Y (3) General formula of Y (4) General formula of Y (5) 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,
Carbamoyl group, N-alkylcarbamoyl group, N, N-
Dialkylcarbamoyl group, nitro group, amino group, N-
Arylcarbamoyloxy group, sulfamoyl group, N
-Represents an alkylcarbamoyloxy group, a hydroxy group, 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 ₁
May be the same or different, and the total number of carbon atoms contained in n R ₁ is preferably 0 to 10.

R _{2 in the} general formula (2E) has the same meaning as R _{1 in} (2A) to (2D), X represents an oxygen atom or a sulfur atom, and in the general formula (4), R ₂ represents an alkyl group or an aryl group. Alternatively, it represents a heterocyclic group.

In the general formula (5), R ₃ represents a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R ₄ is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, Represents an alkylthio group or an amino group.

When R ₁ , R ₂ , R ₃ or R ₄ represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl. The substituent is a halogen atom, a nitro group, a cyano group, an aryl group, 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 or an arylthio group.

When R ₁ , R ₂ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, a cyano group Or a ureido group.

When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5- or 6-membered monocyclic or condensed ring containing a nitrogen atom, oxygen atom or sulfur atom as a hetero atom;
Pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group,
It is selected from a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group and the like, and these may be further substituted by the substituents listed for the aryl group.

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

In the general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is preferably 1 to 15.

In the general formula (1), Y can have a structure of the following general formula (6).

Formula (6) of Y—TIME-INHIBIT In the formula, the TIME group is a group capable of binding to the coupling position of the coupler and being cleavable by reaction with a color developing agent. After cleavage from the coupler, the INHIBIT group is appropriately controlled. Is a group that can be released. An INHIBIT group is a group that provides a development inhibitor or a compound that can release a development inhibitor.

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

General formula (7) of Y General formula of Y (8) General formula of Y (9) General formula of Y (10) General formula of Y (11) General formula of Y (12) General formula of Y (13) In the general formulas (7) to (13), R ₅ represents 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, a cyano group, or a nitro group. , A sulfonamide group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, and an alkane sulfonyl group, represented by the general formulas (7), (8), (9), (11) and (13) In the formula, l represents 1 or 2, and in the general formulas (7), (11), (12) and (13),
k represents an integer of 0 to 2, and in the general formulas (7), (10) and (11), R ₆ represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; ) And (13), B is an oxygen atom or (R ₆ has the same meaning as defined above), and the INHIBIT group is represented by the general formula (2A), (2B), (3), (4)
And the same meaning as in the general formula defined in (5). However, the number of carbon atoms is different.

However, in the general formulas (2A), (2B) and (3), the total number of carbon atoms contained in R ₁ in one molecule is ₁ to 32, and in the general formula (4), the carbon atom contained in R ₂ is Number is 1
And the total number of carbon atoms contained in R ₂ and R ₄ in Formula (5) is 0 to 32.

When R ₅ and R ₆ represent an alkyl group, they may be substituted or unsubstituted, linear or cyclic. Examples of the substituent include those enumerated when R _{1 to} R ₄ are an alkyl group.

When R ₅ and R ₆ represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R _{1 to} R ₄ are an aryl group.

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

In the general formula (1), the yellow image forming coupler residue represented by A is a pivaloyl acetanilide type, a benzoylacetanilide type, a malon diester type, a malon diamide type, a dibenzoyl methane type, or a benzothiazolylacetamide type. , Malon ester monoamide type, benzothiazolyl acetate type, benzoxazolylacetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolyl acetate type coupler residue, U.S. Patent No. 3,841,880 Or a coupler residue derived from a heterocyclic-substituted acetamide or a heterocyclic-substituted acetate contained in US Pat. No. 3,770,446, US Pat. No. 1,459,171, West German Patent (OLS) 2,503,099
And coupler residues derived from acylacetamides described in JP-A-50-139738 or Research Disclosure 15737, or heterocyclic coupler residues described in US Pat. No. 4,046,574.

The magenta image forming coupler represented by A includes 5-oxo-2-pyrazolin nucleus and pyrazolo- [1,5
-A] A coupler residue having a benzimidazole nucleus or a cyanoacetophenone-type coupler residue is preferable.

As the cyan image forming coupler residue represented by A, a coupler residue having a phenol nucleus or an α-naphthol nucleus, an indazolone-based or pyrazolone-triazole-based coupler residue is preferable.

Further, after the coupler couples with the oxidized form of the developing agent and releases the development inhibitor, the effect as a DIR coupler is the same even when substantially no dye is formed. Coupler residues of this type represented by A include U.S. Pat. No. 4,052,213.
No. 4,088,491, No. 3,632,345, No. 3,958,99
And coupler residues described in No. 3 or 3,961,959.

Next, preferred specific examples of the DIR compound that can be used in the present invention will be described. However, it goes without saying that the DIR compound that can be used in the present invention is not limited to the following examples.

These compounds are disclosed in U.S. Pat.Nos. 4,234,678 and 3,227,554.
Nos. 3,617,291, 3,958,993, 4,149,886,
No. 3,933,500, JP-A Nos. 57-56837 and 51-13239, and U.S. Pat. Nos. 2,072,363 and 2,070,266, and Research Disclosure, December 21, 1981, No. 21228, can be easily synthesized.

The addition amount of the diffusible DIR compound of the present invention is generally preferably 2 × 10 ^{-4 to} 5 × 10 ^-1 mol, more preferably 5 × 10 ^-4 to 1 × 10 ^-1 mol, per mol of silver in the emulsion layer. It is.

If the light-sensitive material of the present invention is described in more detail, an ordinary colored magenta coupler can be used in the green-sensitive emulsion layer of the present invention. As the colored magenta coupler, those described in U.S. Pat. Nos. 2,801,171 and 3,519,429 and JP-B-48-27930 can be used.

Particularly preferably used colored magenta couplers are as follows.

In the red-sensitive emulsion layer of the present invention, an ordinary colored cyan coupler can be used. As a colored cyan coupler, Japanese Patent Publication No. 55-32461, British Patent 1,084,480
No. can be used.

Particularly preferred colored magenta couplers include the following.

The light-sensitive emulsion layers constituting the light-sensitive material of the present invention may contain a corresponding color coupler.

It is generally preferable that the blue-sensitive layer of the present invention contains a coupler that forms a yellow dye. As the yellow color-forming coupler, a known open-chain ketomethylene coupler can be used. Among them, benzoylacetoanilide compounds and pivaloylacetoanilide compounds can be advantageously used.

Specific examples of yellow color couplers are described in JP-A-47-26133,
48-29432, 50-87650, 51-17438, 51-10263
No. 6, JP-B-45-19956, U.S. Patent Nos. 2,875,057, 3,40
8,194, 3,519,429, JP-B-51-33410, 51-107
No. 83 and No. 46-19031.

 Particularly preferred couplers are:

As the magenta color-forming coupler used in the light-sensitive material of the present invention, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, pyrazolotriazole compounds and the like can be used, and pyrazolone compounds are particularly advantageous.

Specific examples of magenta coloring couplers that can be used are described in
No. -111631, JP-B-48-27930, JP-A-56-29236, U.S. Patents 2,600,788, 3,062,653, 3,408,194,
No. 3,519,429, JP-A-57-94752, and Research Disclosure 12443.

 Particularly preferred couplers are:

As the cyan coloring coupler used in the light-sensitive material of the present invention, a phenol compound, a naphthol compound, or the like can be used.

Specific examples thereof are described in U.S. Pat.Nos. 2,423,730 and 2,474,293.
No. 2,895,826, JP-A-50-117422 and the like.

 Particularly preferred couplers are:

In the silver halide emulsion layer of the present invention, non-diffusible DIR compounds in the other photographic constituent layers, non-diffusable couplers which react with oxidized forms of developing agents to form diffusible dyes that appropriately bleed, such as polymer couplers Couplers other than the diffusible DIR compound of the present invention may be used in combination. A non-diffusible DIR compound and a non-diffusible coupler which reacts with an oxidized form of a developing agent to form a diffusible dye which excessively bleeds are described in Japanese Patent Application No.
Reference can be made to the description of JP-A-193611 and to the description of Japanese Patent Application No. 59-172151 by the present applicant for polymer couplers. The total amount of couplers used in each layer may be appropriately selected since the maximum density varies depending on the color developing properties of each coupler, but it is preferable to use about 0.01 to 0.30 mol per mol of silver halide.

In order to incorporate these diffusible DIR compounds and couplers in the silver halide emulsion and other photographic constituent layer coating solutions according to the present invention, when the diffusible DIR compounds and couplers are alkali-soluble, they are used as alkaline solutions. It may be added, and when it is oil-soluble, for example, U.S. Pat.
No. 2,322,027, No. 2,801,170, No. 2,801,171, No. 2,272,191 and No. 2,304,940 The diffusible DIR compound and the coupler according to the method described in each specification to a high boiling solvent, if necessary a low boiling solvent. It is preferable to dissolve them together, disperse them into fine particles, and add them to a silver halide emulsion or the like. At this time, if necessary, all the haloid quinone derivatives, ultraviolet absorbers, anti-browning agents and the like may be used in combination. Further, two or more kinds of diffusible DIR compounds and couplers may be used as a mixture. Further, the method of adding the diffusible DIR compound and the coupler preferred in the present invention will be described in detail.
R compounds and couplers as required with other couplers, hydroquinone derivatives, organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc. In particular, di-n-butyl phthalate, tricresyl 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-nonyl phenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether,
A high boiling solvent such as monophenyl-di-o-chlorophenyl phosphate or fluorine paraffin, and / or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, Dissolved in a solvent having a low boiling point such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone and the like, and anionic surfactants such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or sorbitan sesquioleate and sorbitan An aqueous solution containing a nonionic surfactant such as monolaurate and / or a hydrophilic binder such as gelatin; Combined, high-speed mixer, and emulsified by a colloid mill or an ultrasonic dispersing device or the like, is added to the silver halide emulsion.

In addition, the diffusible DIR compound and the coupler may be dispersed using a latex dispersion method. Latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943,
No. 54-32552 Publications and Research Disclosure 19
August, 76, No. 14850, pp. 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-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like.

The silver halide emulsion according to the present invention is an active gelatin;
Sulfur sensitizers such as allyl thiocarbamide, thiourea and cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines and the like; base metal sensitizers such as gold sensitizer Sensitizers, specifically potassium aurithion cyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride or the like or, for example, ruthenium, palladium, platinum, rhodium,
Sensitizers of water-soluble salts such as iridium, such as ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or fog inhibitors depending on the amount of these substances) May be used alone or in combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, or a combination of a gold sensitizer and a selenium sensitizer) to chemically sensitize. .

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain an appropriate sensitizing dye in an amount of from 5 × 10 ^{−8 to} 3 × 10 ⁻³ per mole of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. Optical sensitization can be performed by adding a mole. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion layer, for example, West German Patent 929,080, U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
Nos. 3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, JP-B-44-14030, and JP-A-52-24844 can be mentioned. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, British Patent No. 505,979, and the like, there can be mentioned cyanine dyes, merocyanine dyes or complex cyanine dyes as typical examples. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,3
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,280 and the like can be cited as typical examples of cyanine dyes, merocyanine dyes and composite cyanine dyes. Furthermore, U.S. Pat.No.2,213,995,
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in 2,493,748, 2,519,001, West German Patent 929,080 and the like can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publication No. 43-4936 (JP-B-43-4936) relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
Nos. 43-22884, 45-18433, 47-37443, 48
-29293, 49-6209, 53-12375, JP-A-52-2393
No. 1, No. 52-51932, No. 54-80118, No. 58-153926, No.
59-116646, 59-116647 and the like.

Examples of a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine include, for example, JP-B-45-25831, JP-B-47-11114, and JP-B-47-11114.
-25379, 48-38406, 48-38407, 54-34535
No., 55-1569, JP-A-50-33220, 50-38526,
No. 51-107127, No. 51-15820, No. 51-135528, No. 52-1
Nos. 04916 and 52-104917.

Further, as for the combination of benzoxazolocarbocyanine (oxa-carboxyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
Nos., JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, JP-B-48-41204, and JP-B-50-406.
No. 62, JP-A-56-25728, JP-A-58-10753, JP-A-58-91445
Nos. 59-116645 and 50-33828.

As for the combination of thiacarbocyanine with other carbocyanines, see, for example, JP-B-43-4932 and JP-B-43-4932.
3-4933, 45-26470, 46-18107, 47-8741
And JP-A-59-114533, and the method described in JP-B-49-6207 using zero-methine or dimethine merocyanine, monomethine or trimethine cyanine and a styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion of the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 is used in advance. Is used by dissolving in a hydrophilic organic solvent.

The timing of addition may be at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening. In some cases, it may be added to the step immediately before the emulsion coating.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. 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 are British Patent Nos. 584,609, 1,277,429, JP-A-48-85130, JP-A-49-9962, JP-A-49-114420, and JP-A-49-1.
No. 29537, No. 52-108115, No. 59-25845, U.S. Pat.
4,782, 2,533,472, 2,956,879, 3,125,448
No. 3,148,187, 3,177,078, 3,247,127,
3,540,887, 3,575,704, 3,653,905, 3,7
Nos. 18,472, 4,071,312 and 4,070,352.

It is better to fix these water-soluble dyes in a
It is effective. For technology related to mordanting,
U.S. Pat.Nos. 3,326,057, 2,882,156, 3,740,228
No., JP-B-49-15820, and JP-B-59-33899 can be referred to.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives. For example, JP 46-2128, color stain inhibitors described in U.S. Pat.No. 2,728,659, antifoggants described in Research Disclosure 17643, stabilizers, ultraviolet absorbers,
Color stain inhibitors, color image browning inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloid used for adjusting the emulsion includes gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, albumin, proteins such as casein, Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
An arbitrary one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a combined use of a reflector, or a glass plate, cellulose acetate, There are a polyester filter such as cellulose nitrate or polyethylene terephthalate, a transparent support such as a polyamide film, a polycarbonate film, and a polystyrene film, and the like. These supports are appropriately selected according to the intended use of the photosensitive material.

In the coating of the emulsion layer and other constituent layers used in the present invention, dipping coating, air doctor coating,
Various coating methods such as curtain coating and hopper coating can be used. U.S. Pat.Nos. 2,761,791, 2,941,898
The simultaneous coating method of two or more layers according to the method described in (1) can also be used.

There is no particular limitation on the processing method of the photographic light-sensitive material according to the present invention, and any processing method can be applied. For example, typical examples thereof include a method of performing bleach-fixing after color development and further performing washing and / or stabilization if necessary. After color development, performing bleaching and fixing separately,
A method of performing further washing and / or stabilizing treatment as needed; or a method of performing pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, and washing with water in this order;
Color development, washing with water, supplemental color development, stop, bleach, fix, wash, stabilize, method of stabilization, developed silver developed by color development, after halogenation bleach, then color development again to increase the amount of dye produced Processing may be performed using any method such as a developing method.

The color developing solution used for processing the silver halide color photographic light-sensitive material of the present invention is not limited, but the pH containing the color developing agent is preferably 8 or more, more preferably 9 or more.
~ 12 alkaline aqueous solutions. The aromatic primary amine developing agent as the color developing agent has a primary amine on the aromatic ring.
It is a compound having a secondary amino group and capable of developing exposed silver halide, and if necessary, a precursor forming such a compound may be added.

Typical examples of the color developing agent include p-phenylenediamines, and the following are 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 sulfate, sulfite, and p-toluenesulfonate.

Further, for example, JP-A-48-64932, JP-A-50-131526,
No. 51-95849 and the Journal of the
American Chemical Society, 73, 3100-31
Those described on page 25 (1951) are also representative.

The amount of the aromatic primary amino compound used can be determined where the activity of the developer is set, but it is preferable to increase the amount of use in order to increase the activity. The amount used is in the range of 0.0002 mol / l to 0.7 mol / l. In addition, 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-ethyl-N
Any combination such as -β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline can be used.

In the color developer used in the present invention, various components which are usually added, for example, sodium hydroxide,
Optionally containing an alkali agent such as sodium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, and a development accelerator. Can also.

Other additives to be added to the color developing solution include, for example, bromides such as potassium bromide and ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl Examples of compounds for rapid processing liquids such as -5-mercaptotetrazole, as well as stain inhibitors, sludge inhibitors, preservatives, layering effect promoters, chelating agents and the like.

As the bleaching agent used in the bleaching solution or bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt, and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid are generally used. I have. The following are typical examples of the above aminopolycarboxylic acids.

Ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid nitrilotriacetic acid iminodiacetic acid ethyletherdiaminetetraacetic acid ethylenediaminetetrapropionic acid ethylenediaminetetraacetic acid disodium salt diethylenetriaminepentaacetic acid pentasodium salt nitrilotriacetic acid sodium salt The bleaching solution contains various additives together with the above bleaching agent. You may. When a bleach-fix solution is used in the bleaching step,
A solution having a composition containing a silver halide fixing agent in addition to the bleaching is used. The bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the above-mentioned bleaching solution, other various additives such as a pH buffer, an antifoaming agent, a surfactant, a preservative, a chelating agent, a stabilizer, and an organic solvent are added and contained. Is also good.

As the silver halide fixing agent, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, water-soluble as a reaction of silver halide as used in a normal fixing process such as thioether. Compounds that form silver salts can be mentioned. The processing temperatures of various processing steps such as color development, bleach-fixing (or bleaching and fixing) of the silver halide color photographic light-sensitive material of the present invention, and optionally, washing, stabilization, and drying are performed from the viewpoint of rapid processing. It is preferably performed at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in
-14834, 58-105145, 58-134634 and 58-186
No. 31, Japanese Patent Application Nos. 58-2709 and 59-89288, etc., may be subjected to a washing alternative stabilization treatment.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, it goes without saying that the embodiment of the present invention is not limited to this.

Example 1 A silver iodobromide emulsion shown in Table 4 was prepared by the method described in JP-A-54-118823,
JP-A-58-113928, the method described in JP-A-58-211143,
And by the usual function addition method.

The following layers were applied on a cellulose triacetate film to prepare a multilayer color negative photographic material (compared to Sample No. 1).

First layer: Anti-halation layer Second layer: intermediate layer Gelatin ..................... 1.2g / m ² Layer 3: Low Sensitivity Red-sensitive emulsion layer Fourth layer: high-sensitivity red-sensitive emulsion Layer 5: Intermediate Layer Gelatin ..................... 0.80g / m ² Layer 6: Low Sensitivity Green-Sensitive Layer 7th layer: High-sensitivity green-sensitive layer Eighth layer: yellow filter layer Ninth layer: low-sensitivity blue-sensitive layer 10th layer: High-sensitivity blue-sensitive layer 11th layer: 1st protective layer 12th layer: 2nd protective layer In each emulsion layer, in addition to the above composition, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole, etc. Gelatin hardeners H-1 and H-2
And a surfactant were added. Samples 2 to 11 were prepared by adding the emulsions shown in Table 4 and the diffusable DIR exemplified compounds to the third, fourth, sixth, seventh, ninth and tenth layers as shown in Table 5. The amount of the diffusible DIR compound added to each color-sensitive layer was controlled so that the desensitization and temperature drop of the layer were almost equal.

H-1 CH ₂ = CHCH ₂ CH ₂ SO ₂ CH = CH ₂ Each sample was provided with blue light, green light, red light and white light through a wedge, respectively, and processed in the following processing steps to obtain a dye image.

Developing process (38 ° C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixed 6 6 Rinse for 30 minutes Minutes: 3 minutes 15 seconds Fixing bath: 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is as follows.

Color developer composition: Adjust the pH to 10.0 by adding water.

Bleach composition: Adjust the pH to 6.0 with water.

Fixer composition: Adjust to pH 6.5 with water.

Stabilizer composition: Add water to make 1.

Table 5 shows the obtained characteristic values.

Viewing IIE is a gamma ^* gamma _N when the white exposure, respectively blue light, green light, when the gamma ^* when exposed with red light and γ _A, γ _A / γ _N is the silver halide emulsion layer Represents the magnitude of the IIE received, and indicates that γ _A / γ _N increases as the IIE received increases.

gamma ^*; 10 times the exposure point of the exposure amount of density point of fog +0.3 (ΔlogE = 1.0) to a concentration of When D γ = {D- (head +0.3)} / 1.0 made.

In addition, the display of the aging characteristics is as follows.
% RH is shown in the residual image ratio of the Dmax part after the treatment for 15 days. The stability increases as it approaches 100%.

As is clear from Table 5, the samples Nos. 4 to 9 of the present invention have IIEs which are very large in each color-sensitive layer and can reproduce a high chroma color as compared with the comparative samples. It is also clear that the stability with time, which has been a drawback in the past, has been surprisingly improved even in such a system.

〔The invention's effect〕

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

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-144826 (JP, A) JP-A-58-217932 (JP, A) JP-A-59-131934 (JP, A) JP-A-62 178249 (JP, A)

Claims (1)

(57) [Claims] In a silver halide photographic material having two or more light-sensitive silver halide emulsion layers having different color sensitivity on a support, at least one of the silver halide emulsion layers is defined as follows. At least two photosensitive silver halide emulsion layers having different color sensitivity have a U value of 60 or more, and the at least two photosensitive silver halide emulsion layers react with an oxidant of a developing agent to be a development inhibitor or a developing agent. The development inhibitor or the development inhibitor precursor released from the DIR compound is diffusible, and further satisfies the following condition A: Silver halide photographic material. [Condition A] The development inhibitor or the development inhibitor precursor released from each of the at least one DIR compound is different from each other, and the development inhibition power of the development inhibitor or the development inhibitor precursor to the photosensitive silver halide emulsion layer is different. Is a relationship that can be changed by the photosensitive silver halide emulsion layer containing those DIR compounds,
In addition, the DIR compound having a smaller development resistance of at least two of the DIR compounds among those DIR compounds has a development inhibiting power for the contained photosensitive silver halide emulsion layer. Definition of U value: The weight of silver halide grains included in a grain size range of ± 20% around the average grain size is 100 times the weight of all silver halide grains.
And the value indicated for it