JPH02219052A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance shelf life and that of a latent image by incorporating a DIR compound to be allowed to release a development inhibitor or its precursor by reaction with the oxidation product of a color developing agent in a color developing solution and forming at least two of blue-, green-, and red- sensitive layers having single layer structures. CONSTITUTION:The DIR compound to be incorporated is allowed by reaction, such as coupling or redox reaction, with the oxidation product with a color developing agent to release a development inhibitor convertible into a compound weak in development inhibitory action (deactivation type DIR) in a color develop ing solution or to release its precursor, and at least one of green-, and red- sensitive silver halide emulsion layers has single layer structures, and as the reaction of conversion of the DIR compound into the compound weak in the development inhibitory action, the following reactions are recommended: The cleavage reaction due to a nucleophilic reagent added to the color developing solution, and the like reactions resulting in producing the desired compound, thus permitting displacement of gradation to be reduced and storage stability of gradation to be improved in the storage stability of the photosensitive mate rial and in that of the latent image.

Description

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

[Prior art]

Currently, color photographs are taken with color negative film and then enlarged and printed on color paper.
The positive method is widely used.

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

"Having a wide exposure latitude" means a wide exposure range from shadow areas with low exposure to highlight areas with high exposure in the so-called characteristic curve where the horizontal axis is the exposure and the vertical axis is the color density. This means that the gradation is good compared to the other. If this gradation is poor, the color reproducibility and tone reproducibility of the dye image will deteriorate.

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

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

On the other hand, there are known compounds that can release a development inhibitor or its precursor that changes into a compound with a small development inhibitory effect in a color developer upon reaction with an oxidized product of a color developing agent.

However, as a result of studies conducted by the present inventors, the photosensitive materials using the above-mentioned compounds have the effect of improving the optical stability, but as mentioned above, the photosensitive materials have multiple emulsion layers containing silver halide grains with different grain sizes. Furthermore, since the gradation is strictly controlled using the above-mentioned compounds, the gradation may change if the photosensitive material is stored for a long period of time after being manufactured, or if the time between exposure (photography) and development is long. This had the disadvantage that color reproducibility and tone reproducibility deteriorated.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material that has excellent storage stability and latent image storage stability.

[Structure of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. Contains a development inhibitor that changes into a compound with a small development inhibitory effect in the color developer upon reaction with an oxidant, or a compound that can release a precursor thereof (hereinafter referred to as a deactivated DIR compound), and This invention was achieved by a silver halide color photographic material characterized in that at least one of the green and red color-sensitive layers has a single-layer structure.

The present invention will be explained in more detail below.

First, the deactivated DIR compound will be explained.

Examples of the reaction between the deactivated DIR compound and the oxidized color developing agent include a coupling reaction and a redox reaction.

When a development inhibitor is produced from a precursor of a development inhibitor, it may be produced in a non-imagewise manner such as hydrolysis or an intramolecular nucleophilic substitution reaction, or it may be produced by a coupling reaction with an oxidized form of a developing agent, etc. The development inhibitor may also be produced imagewise, such as by a redox reaction.

A compound with a small development inhibitory effect only needs to have a smaller development inhibitory effect than the development inhibitor before being changed, and also includes compounds that do not substantially exhibit a development inhibitory effect.

Reactions in which a development inhibitor changes into a compound with a small development inhibitory effect include a cleavage reaction with a nucleophile (e.g., hydroxyl ion, hydroxylamine, etc.) in a color developing solution, or a nucleophile such as sulfite ion or hydroxylamine. As a result of the addition reaction, etc., a compound having the desired properties is obtained.

The deactivated DIR compound in the present invention can preferably be represented by the following general formula CDIR-1).

General formula CDIR-I) A (L+)a Zx (Lx Y*)b In the above formula, A represents a coupler component or a hydroquinone component, which releases the following by reaction with the oxidized form of the developing agent, and preferably represents a coupler component, Z represents a basic part of a compound that exhibits a development inhibiting effect, and connects directly to the coupling position of the coupler (in the case of a-0) or via the linking group Ll (in the case of a-1). be combined.

Y represents a substituent that is bonded to Z via a linking group and exhibits a development inhibiting effect on Z. The linking group represented by L2 contains a chemical bond that is cleaved in the developer.

a represents O or l, and b represents l or 2. When b represents 2, -ri and -Y may each be the same or different.

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

When the compound of the present invention is contained in an emulsion layer, it is 0.01 to 50 mol %, preferably 0.1 to 5 mol %, per mol of silver halide.

When the compound of the present invention is contained in a non-photosensitive hydrophilic colloid layer, the coating amount is 10-' to 10-'
The amount is preferably 10-6 to 10-'mol/tsuru.

The yellow image-forming coupler residue represented by A is preferably pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide, malon ester monoamide, etc. Type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malone diester type, benzimidazolylacetamide type or benzimidaglylacetate type coupler residue, US Patent 3
, 841.880 or U.S. Pat. No. 3,770,446, British Patent No. 1
, No. 459,171, West German Patent (OLS) 2,503,
Coupler residues derived from acylacetamides described in No. 099, JP-A No. 50-139738 or Research Disclosure No. 15737, or heterocyclic coupler residues described in U.S. Pat. No. 4.046.574, etc. Can be mentioned.

The magenta image-forming coupler residues represented by A in Table 9 include a 5-pyrazolone nucleus, a pyrazolobenzimidazole nucleus,
Coupler residues having a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus, 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.

Further, 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, the effect as a deactivated former R compound remains the same. This type of coupler residue represented by A is described in U.S. Pat.
, No. 213, No. 4,088.491, No. 3,632.
No. 345, No. 3,958.993, No. 3,961,9
Examples include coupler residues described in No. 50 and the like.

The basic moiety of the development inhibitor represented by 2 is preferably a divalent heterocyclic group or a heterocyclic thio group, such as the following examples.

The substitution positions of the A-(L,)a- group and the -(L!Yz)b group are shown below.

L, -Y.

However, in the above formula, X represents a hydrogen atom or a substituent, and the substituent (-included in the z8 part in formula CDIR-I) is a halogen atom, an alkyl group, an alkenyl group, an alkane Represents an amide group, an alkenamide group, an alkoxy group, a sulfonamide group, or an aryl group.

- Examples of the group represented by Y in formula (DIR-1) include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a heterocyclic group.

- In formula [DIR-1], the linking group represented by is incorporated into the precursor of the development inhibitor released when the deactivated DIR compound of the present invention reacts with the oxidized form of the color developing agent. When the precursor produces a development inhibitor,
At the site where the chemical bond with the development inhibitor moiety is cleaved non-imagewise, such as hydrolysis and intramolecular nucleophilic substitution reactions, or imagewise, such as campling reactions with oxidized developing agents, redox reactions, etc. It is preferable that there be some, and examples include the following.

It is shown below together with A and Zz (L! Yl)b.

A 0CHz lx (Lx Yz)b (US Patent 4,
146.396) A 5CH22!
(L2 Yl)b OtoriA QC22(Lx Yx)b (linking group described in West German Published Patent No. 2,626.315) (U.S. Patent No. 4,
The linking group C described in No. 248.962 represents an integer of θ to 2. ) (Linking group described in JP-A No. 56-114946) (Linking group described in JP-A-56-114946) (Linking group described in JP-A-56-114946)
-154234) These deactivated bases DI
In the R compound (-Formula 1: DIlil -I) a
= 1), the leaving group released after reacting with the oxidized form of the developing agent releases the development inhibitor (H-Z, -(-L, -Yl)b) with a delay or immediately. Therefore, the compound (
- case of a-1 in formula (DIR-I)) and the effects of the present invention are the same.

In general formula (DIR-1), the linking group represented by includes a chemical bond that is cleaved in a developer.

Such chemical bonds include the examples listed in the table below. Since these are cleaved by nucleophilic reagents such as hydroxyl ions or hydroxylamine, which are components in the color developer, the effects of the present invention can be obtained.

In the chemical bonding mode shown in the preceding table, Z is linked directly or via an alkylene group or (and) a phenylene group, and the other is directly linked to Y2. When linked to Z through an alkylene group or phenylene group, the intervening divalent group may contain an ether bond, amide bond, carbonyl group, thioether bond, sulfone group, sulfonamide bond, or urea bond. good.

Among the couplers represented by the general formula (DIR-r), useful ones are those represented by the following formulas (DIR-n), [old R-■] and (DIR-IV). These couplers are preferred because they have a strong development inhibitory effect after the leaving group leaves.

One formula CDIR-m) L, -Y.

L, -11 DIR-1 A, L! represented by the general formula [:DIR-I[)! and Y.

represents the same meaning as already explained in the formula CDIR-I).

At represented by the general formula (DIR-111) is the general formula (D
It represents a coupler residue other than the cyan coupler residue among those explained in IR-1).

-A represented by the formula (DIR-■) is -the formula (DIR
- represents a cyan coupler residue in A explained in I).

X2, L2, and Y represented by the formulas CDIR-I [1) and (:DIR-IV) are - DIR-2 DIR-3 DIR DIR-6 lR IR explained by the formula [DIR-I], ■ R-13 IR-14 IR-20 IR DIR-24 Old 1-28 H DIR DIR DIR-26 DIR-27 DIR-34 DIR-35 DIR-40 DIR-36 Old 1-37 DIR-38 A known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the deactivated DIR compound and the coupler that can be used in combination into the silver halide emulsion layer. Also, Special Publication No. 51-39853,
The dispersion method using a polymer described in JP-A-51-59943 can also be used.

In addition, a development inhibitor or its precursor is released by reaction with an oxidized product of a color developing agent, but the released product is a compound (hereinafter referred to as a non-deactivated compound) that does not particularly change its development inhibitory effect in a color developer. (referred to as the old type R compound), the inactivated type D
It may be used in combination with an IR compound. In that case, non-inactivated DI
Preferably, the amount of R compound used is less than 50 mole percent of all DIR compounds.

A single color-sensitive layer means that the color-sensitive layer is a single layer, which means that the emulsion layer contains multiple photosensitive layers having the same type of coupler, grain size of silver halide grains, halogen composition and crystal habit, and the same ratio of coupler and silver halide. It also includes a case where emulsion layers having the same color property are arranged as a continuous layer.

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

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

When the color-sensitive layer has a single-layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional multi-layer structure, making it possible to form a thin film. Therefore, production efficiency, sharpness, and graininess are improved. The film thickness is 2 after drying.
The thickness is preferably 0 to 3 μm, particularly preferably 15 to 5 μm.

Exposure latitude is the width of the amount of received light that produces significantly different exposure effects, and is the exposure range from highlights to deep shadows in the characteristic curve, as described in Photo Chemistry, page 393 (
Shashin Kogyo Shuppansha, 1982).

That is, it is the difference in (log H) between two points where the slope of the tangent line at the foot and shoulder of the characteristic curve, where the horizontal axis is QogH' and the vertical axis is the transmission density, is 0.2.

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

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

Silver halide grains with different grain sizes used in combination to obtain a wide exposure latitude have an average grain size of 0.2.
A combination of silver halide grains having a maximum average grain size of ~2.0 μm and a silver halide grain having a minimum average grain size of 0.05 μm to 1.0 μm is preferable, and a combination of silver halide grains having a minimum average grain size of 0.05 μm to 1.0 μm is preferable, and intermediate average grain size One or more types of silver halide grains having different diameters may be combined.

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

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

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

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

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

In the present invention, a metal ion doping method is preferred. Metal ions used for doping include Group Ib, Group ■b, and Group ■a in the periodic table of elements.

Examples include metal ions of the mb group, the ``b'' group, the Va group, and the ``group''. Preferred metal ions include Au, Zn, and Cd.

TQ, Sc, Y, Bi, Fa, Ru, Os, Rh,
Examples include metal ions of Ir, Pd, Pr, Ss, and Yb. Particularly preferred are Rh, Ru, and Os.

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

The amount of metal ion doping varies depending on the type of metal ion, the particle size of silver halide grains, the doping position of metal ions, the desired sensitivity, etc.
Preferably IQ-17 to 1O-2 mol per 1 mol,
Furthermore, 10-"-10-3 mol is preferred, especially IO-
1 to 1 O-4 mol is preferred.

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

If the doping amount is less than 10-'' mol/AgX mol, there is little effect on grain growth, so silver halide grains with a narrow grain size distribution are prepared under the same grain growth conditions and even under the same batch growth. be able to.

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

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

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

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

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

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

Further, the coefficient of variation defined by the ratio S/r of the standard deviation (S) of the grain size to the average grain size (〒) of the grain size as a whole including the silver halide grains contained in each silver halide emulsion layer is 0. 4
The following is preferable, 0.33 or less is more preferable, 0
．． It is more preferably 25 or less, particularly preferably 0.20 or less.

The average grain size (7) means, in the case of grain size (cubic) 10-genide silver grains, the length of its side, or, in the case of grains with a shape other than a cube, converted to a cube having the same volume. When the number of particles of ri (length of one side) is ni, it is defined by the following formula.

The relationship between particle size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photography," The Photographic Journal, Vol. LXXIX (1949) 330.
This can be determined by the method described in the article by Tribel and Smith on pages ~338.

The silver halide emulsion used in the light-sensitive material of the present invention is as follows:
Any conventional silver halide emulsion can be used, but silver halides containing substantially iodine in the halide composition (for example, silver iodobromide, silver iodochlorobromide) are preferred;
Silver iodobromide is particularly preferred in terms of sensitivity. The amount of iodine is 1
mol% to 20 mol% is preferred, particularly 3.5 mol% to 1
2 mol% is preferred.

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

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

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

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

Furthermore, the effect of color correction is achieved through the coupling of colored couplers with competing couplers and oxidized forms of developing agents, such as developing agents, silver halide solvents, toning agents, hardeners, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

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

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

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

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

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

〔Example〕

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

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

Preparation of Seed Emulsion Pour the aqueous gelatin solution into a reaction vessel,
While controlling Ag and r) H, silver nitrate aqueous solution, potassium iodide aqueous solution and potassium bromide aqueous solution were added simultaneously while controlling the cooling time, and then precipitated and desalted using isogenic gelatin (pH 19) and gelatin was added. A seed emulsion was prepared.

The obtained emulsion is called NE-1. Also, in the reaction pot, K, R
hCI2. Seed emulsion N
E-2 was prepared.

The emulsions and their contents are shown in Table 1.

Table 1 It was added in proportion to the surface area at the time, and at an appropriate particle size, it was changed to an aqueous potassium bromide solution and then added.

Similar to the seed emulsion, precipitation and desalting were performed, gelatin was added, and the mixture was redispersed to a pA g7.8. An emulsion with a pH of 6.0 was obtained.

In this way, the inside of the grain is a silver iodobromide emulsion E with a moderately high content.
M-1-EM-4 was prepared.

Table 2 shows the emulsions and their contents.

Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling the pAg and pH in the reaction vessel, an ammoniacal silver nitrate aqueous solution, a potassium iodide aqueous solution and a potassium bromide aqueous solution were added to the particle growth book NE-1 and NE-2.
were used in equimolar amounts.

Example 1 Preparation of sample 101 (comparison) A multilayer color photosensitive material 101 having a multilayer structure having the following composition was deposited on a subbed cellulose acetate support.
I did FFR.

The coating amount is the amount expressed in g/m2 for silver halide and colloidal silver, and the amount expressed in g/m'' for additives and gelatin. The dyes, couplers and old R compounds are expressed in moles per mole of silver halide in the same layer.

The emulsion contained in each color-sensitive emulsion layer was optimally sensitized with sodium thiosulfate and chloroauric acid, and each layer was coated with a surfactant in addition to the above components. type DIR compound) (Non-deactivated type DIR compound) Sensitizing dye■ M-1 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ υ H-1 S-1 Below, each layer of the above composition is described above. HC, IL-1.

R-1, R-2, IL-2, G-1, G-2, YC.

B-1, 8-2, Pro-1, Pro-2 shall be used as abbreviations.

Sample 102 Except for B-2 of sample 101, the emulsion contained in B-1 was
Sample 102 was prepared in the same manner, except that the amounts of the emulsion, gelatin, and TCP contained in B1 were increased by 15% instead of the equimolar mixture of M-1 and EM-2. (The amounts of the sensitizing dye, coupler, and DIR compound in B-1 per mole of silver halide are the same as in Sample 101.) Samples 103 to 104 Except for G-2 in Sample 101, the emulsion contained in G-1 was
Instead of using an equimolar mixture of M-1 and EM-2, the amounts of emulsion, gelatin, and TCP contained in G-1 were increased by 30%, and the DIR compounds contained in G-1 are shown in Table 3. Samples 103 and 104 were prepared in the same manner except for the following changes.

(Amounts of sensitizing dye, coupler, and DIR compound per mole of silver halide in G-1 are the same as in sample 1 old) Sample 105
~109 Except for B-2 and G-2 of sample 101, the emulsions contained in B-1 and G-1 were replaced with equimolar mixtures of EM-1 and EM-2, respectively, and B-1 and G- Emulsion, gelatin and TCP contained in 1 are each 15%.

Samples 105 to 109 were prepared in the same manner except that the amount was increased by 30% and the old R compounds contained in B-1 and G-1 were replaced as shown in Table 3.

(The amount of B-1, 0-1 sensitizing dye and coupler DIR compound per mole of silver halide is the same as Sample January) Samples 110 to 112 B-2, G-2, R-2 of Sample 101 B-1, except for
The emulsion contained in G-1 was changed as shown in Table 3 (R-
1 is the same as G-1) The emulsion, gelatin, and TCP (R-1 is DOP) contained in B-1, 0-1, and R-1 are increased by 15%, 30%, and 25%, respectively, and -1,
Samples 110-112 were prepared in the same manner except that the old R compounds contained in G-1 and R-1 were replaced as shown in Table 3 (R-1 is the same as G-1).

The sample thus prepared and its contents are shown on the front and back.After dividing the sample into two parts and exposing them to wedge light according to the usual method, one part was stored in the refrigerator (5°0), and the other part was stored at 25°0, relative humidity. It was left for 15 days under 80% conditions and developed using the following processing steps, and the gradation storage stability in latent image storage was evaluated. The results for the green sensitive layer are shown in Table 4.

Evaluation of gradation preservation <Tone preservation> A method for evaluating gradation preservation will be explained using figures.

FIG. 1 shows a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line). Also, △12og H is 3 from the exposure point that gives the minimum density +0.1 in Figure 1.
．． 0 Each exposure point between increasing exposure points (Δa between each exposure point
ogH=0.15) is shown in FIG.

From Figure 2, the absolute value of the difference in point gamma at each exposure point between the characteristic curve to be evaluated and the characteristic curve to be compared is △
Find γ.

The average value of Δγ multiplied by 1000 (8r) and the standard deviation σ of Δγ were determined, and the gradation preservation property was expressed as the value 1000 times σ (Σ).

That is, the larger the value of △r, the larger the difference in point gamma between the reference characteristic curve and the characteristic curve to be evaluated.
The larger the value of Σ, the less uniform the change in gradation is, and the worse the gradation preservation is.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
3 minutes 15 seconds stabilization 1 minute 30
Second drying The composition of the processing solution used in each processing step is shown below.

Color developer 4-ami7-3-methyl-N-ethyl-N-(β-hydroxyethyl) Aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine l/2 sulfate 2.0 g Anhydrous carbonate Potassium 37.5 g Potassium bromide 1.3 g Nitrilotriacetic acid.
Trisodium salt (l hydrate) 2.5 g Potassium hydroxide 1.0 g Bleach solution with water to make IQ Iron(III) ethylenediaminetetraacetate Ammonium salt 100.0 g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Odor Ammonium chloride 150.0g glacial acetic acid
Add 10.0g water and
Q and adjusted to pa 16.0 using ammonia water.

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1 (2), and adjust to pH 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.5m
ff Konidax (manufactured by Konica Corporation) 7.5m
(! Add water to make 1 (2).

After dividing the sample into two parts, one part was stored refrigerated (5°C), the other part was left at 40'O and 80% relative humidity for 7 days, and developed using the above processing steps to form a photosensitive material. The gradation preservability during storage was evaluated in the same manner as the above-mentioned evaluation method. The results for the green sensitive layer are shown in Table 4.

Table 4 As is clear from Table 4, the sample of the present invention has a small gradation shift from 71 illite to shadow in the characteristic curve and has good gradation preservation in storage of sensitive materials and latent image storage. I understand that.

Sample 102.1 in which the blue-sensitive layer or the green-sensitive layer had a single layer structure and further contained the DIR compound according to the present invention.
Although 03 has an improvement effect, it is small, and the green color-sensitive layer or the blue color-sensitive layer and the green color-sensitive layer are made into a single layer structure,
and sample 104.1 containing a non-deactivated DIR compound
Although the improvement effect of 05 is recognized, it is still not at a satisfactory level. However, samples 106 to 112, in which the blue-sensitive layer and the green-sensitive layer had a single structure and used the DIR compound according to the present invention, showed a remarkable improvement effect.

This result was also unexpected to the inventors.

When compared in the present invention, Samples 110 to 112 in which all the photosensitive layers were made into a single layer are preferable because of their large improvement effect.

In addition, it can be seen that sample Ill, 112, which contains an emulsion in which Rh ions are doped inside the grains, has a narrow grain size distribution of silver 10 genide grains in each color-sensitive layer and is preferable because the improvement effect is even greater.

Sample 112 is preferable in terms of production efficiency compared to other samples because physical ripening and chemical ripening can each be performed once in the preparation of the emulsion.

It should be noted that Samples 111 and 112 have improved stability against pH and temperature fluctuations during development by about 30% compared to Sample 110, and are found to be preferred embodiments of the present invention in terms of processing stability. Ta.

Further, the effect of the present invention was also obtained in a sample in which 40 mol% of the DIR compound contained in B-1 and G-1 of Sample 106 was replaced with D-2.

Also, instead of DIR-4 of B-1 of sample 106, old R-
22, each sample using DIR-25, DIR-40, each sample using old R-34° DIR-35 instead of old R-41 of G-1 and R-1 of sample 111, each sample using DIR-35 of sample 112 DIR-38, DIR- instead of DIR-4 of B-1
The effects of the present invention were also observed for each sample using No. 39.

Also, RuCQs+0sCQ instead of K, RhC12,
The seed emulsion prepared by adding s+ Pb(NOs)z was
The effects of the present invention were also observed for each sample in which an emulsion prepared using E-2 instead of EM-3 was used instead of EM-3 of sample 111 and EM-4 of sample 112.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support, by reaction with an oxidized form of a color developing agent, , containing a development inhibitor that changes into a compound with a small development inhibitory effect in a color developer or a compound capable of releasing a precursor thereof, and at least two of the blue, green and red color-sensitive layers are a single layer. A silver halide color photographic light-sensitive material characterized by the following composition.