JPH0439655A - Silver halide color photographic sensitive material improved in sharpness and processing fluctuation characteristic - Google Patents

Abstract

PURPOSE:To improve sharpness and to improve the processing stability with a change in the compsn. of a developer by setting the iodine content of a high- sensitivity emulsion layers lower by >=0.5mol% than the iodine content of a low-sensitivity emulsion layer. CONSTITUTION:This photosensitive material has the three silver halide emulsion layers which are red sensitive, green sensitive and blue sensitive. At least one thereof consist of two layers of the emulsion layer groups varying in sensitivity. The silver deposition of the high-sensitivity emulsion layer of the emulsion layer group is larger by >=0.1g/m<2> than the silver deposition of the low- sensitivity emulsion layer and the total silver deposition is <=4.6g/cm<2>. The iodine content in the emulsion of the high-sensitivity emulsion layer is lower by >=0.5gmol% than the iodine content of the low-sensitivity emulsion layer. The good sharpness is obtd. in this way and the processing stability to the change in the compsn. of the developer is improved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material having improved sharpness and processing variability. It's about materials.

[Conventional technology]

In recent years, there has been an increasing demand for higher image quality for silver halide color photographic materials.

Generally, the sharpness of a photographic light-sensitive material decreases as the thickness of the emulsion layer increases due to light scattering by silver halide emulsion grains. In particular, in multilayer silver halide color light-sensitive materials having red-sensitive, green-sensitive and blue-sensitive emulsion layers, light scattering accumulates due to the multilayer structure, and the sharpness of the underlying emulsion layer is significantly reduced. growing.

Conventionally, various techniques for improving sharpness are known. One is light scattering prevention technology, and the other is edge effect improvement technology.

Examples of the latter technique include a method using a so-called DIR coupler and a method using an unsharp mask. Among these, the method using an unsharp mask has a practical limit because it may cause a decrease in sensitivity and deterioration of graininess. D.I.
Many methods using R couplers are known, and useful IR couplers include Japanese Patent Publication No. 55-34933;
JP 57-93344, U.S. Patent No. 3,227.55
No. 4, No. 3,615,506, No. 3,317.291
There are compounds described in No. 3,701,783, etc. However, when using a DIR coupler to emphasize the edge effect, MTF (s+
oduration transfer function
on = modulation transfer function), but it cannot be expected to improve MTF in the high frequency/region required for high magnification, and it also has undesirable side effects such as decreased sensitivity and concentration.
By using DIR couplers such as diffusive DIR and timing DIR, which have long-distance effects, it is possible to reduce the decrease in sensitivity and density, but the area of MTF improvement shifts further to the lower frequency side, and it is difficult to use at high magnifications. We cannot expect much improvement in sharpness.

On the other hand, known techniques for preventing light scattering include adding a coloring substance, reducing the amount of silver halide, and making the film thinner. A significant reduction in the amount of coated silver reduces the number of coloring points, leading to deterioration of graininess. There is also a reduction in the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but all of these methods lead to deterioration in coating properties and a decrease in coloring density, so they have their limits.

In the former case, attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness. For example, methods to prevent irradiation by dyeing with water-soluble dyes are known, but However, it has not been possible to sufficiently improve the MTF in the high frequency region due to undesirable side effects such as a decrease in the MTF.

Furthermore, in the case of color reversal bright light materials, the above-mentioned enhancement of IfE (interimage effect) has been studied in each of the first development (monochrome development) and second development (color development).

Regarding the second development, a technique is known in which a compound that releases a development inhibitor during development, such as a DIR coupler, is contained in the light-sensitive material, but this has not been sufficient.

Regarding the first development, a technique is known in which a photosensitive material contains a compound that releases the developing side during development. For example, JP-A-49-129536, US Pat.
No. 529, No. 3,620,746, No. 4,332,8
DIR described in No. 78, No. 4, No. 377, No. 634, etc.
-Hydroquinones; DIR-aminophenols described in JP-A-52-57828, etc., EP-4512
Examples include the P-nitrobenzyl derivative described in No. 9. Further, JP-A No. 61-213847 discloses a type of compound as a redox compound that releases a photographically useful group while causing an oxidation-reduction reaction within the molecule.

However, these compounds also did not have sufficient improvement effects.

Regarding the first development, it is known that IIE using iodide ions released during development is effective.
No. 946 discloses a technology that utilizes fogging emulsions and internal fogging. However, this technique has the disadvantage of requiring a significantly higher amount of silver. Similarly, IIE using iodide ions can also be obtained by controlling the silver halide composition and silver halide grain structure of the silver halide emulsion in each color-sensitive layer. However, even with these techniques, the improvement effect is not sufficient, and further improvements are desired.

It is known that silver halide color light-sensitive materials (hereinafter abbreviated as color light-sensitive materials), particularly multilayer color light-sensitive materials, contain non-photosensitive fine grain silver halide for various purposes.

For example, a technique is known in the art in which fine grain silver halide containing silver iodide is contained in a protective layer in order to suppress fluctuations in photographic performance due to fluctuations in the composition of a developing solution.

However, even when this technique was actually applied to color photosensitive materials, the improvement effect was insufficient.

On the other hand, the composition of the developing solution varies depending on the developing machine used or the days of use due to management methods and the like. Along with this, the photographic performance of color photosensitive materials fluctuates due to compositional changes during development processing. In order to suppress these fluctuations, fine-grained silver halide containing silver iodide is contained in the protective layer, but depending on the composition, fluctuations in photographic performance may not be sufficiently suppressed even if fine-grained silver halide is contained in the protective layer. In particular, there was a problem in that photographic performance fluctuated greatly due to fluctuations in iodide ions in the processing solution.

In addition, in the compact labs that have been emerging in recent years, fluctuations in finish quality due to fluctuations in photographic performance due to changes in the composition of the developer have become a major problem, and there are strong demands for improvements in these.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material which has good sharpness and good processing stability against changes in the composition of a developer.

[Structure of the invention]

As a result of extensive studies, the present inventors have found that the object of the present invention can be achieved with the configuration described below.

That is, the present invention has three silver halide emulsion layers, one blue-sensitive, one green-sensitive, and one blue-sensitive, and at least one of which is composed of at least two emulsion layer groups having different sensitivities. The amount of silver deposited in the high-sensitivity emulsion layer group is 0.1 g/rrr or more greater than the amount of silver deposited in the low-sensitivity emulsion layer, and the amount of gold and silver deposited is 4
．． A silver halide color light-sensitive material having a density of 6 g/m2 or less, characterized in that the iodine content in the emulsion of the high-sensitivity emulsion layer group is 0.5 mol% or more smaller than the iodine content of the low-sensitivity emulsion layer. This is a silver halide color photographic light-sensitive material which achieves the above object.

The present invention will be explained in detail below.

The color photographic light-sensitive material of the present invention consists of at least two emulsion layers in which at least one of the blue-sensitive, green-sensitive, and red-sensitive emulsion layers has different sensitivity. The emulsion layer group is
Preferably, the two or more photosensitive layers consist of two or more layers, more preferably two or three emulsion layers, in which the two or more photosensitive layers have different sensitivities. At least two layers refers to at least two layers with the same spectral sensitivity distribution (distribution that gives photosensitivity that is visually perceived as the same color) and different sensitivities. When consisting of a group of emulsion layers, the emulsion layer with the lowest sensitivity is referred to as the low-speed layer, and the emulsion layer with higher sensitivity is referred to as the high-sensitivity layer.The high-sensitivity layers in the light-sensitive material of the present invention have the same spectral sensitivity characteristics. It may form a high-sensitivity layer group consisting of two layers: a highest-sensitivity layer and a medium-sensitivity layer that is lower in sensitivity than that but more sensitive than the low-sensitivity layer, or it may be simply a single high-sensitivity layer. good.

In the present invention, the amount of silver in the high-sensitivity layer (including when it is a group of high-sensitivity layers, the same applies hereinafter) and the low-sensitivity layer is 0.1 g/n in the high-sensitivity layer relative to the low-sensitivity layer. The amount is more than 0.11 to 0.60 g/m2, preferably 0.11 to 0.60 g/m2.

The amount of gold and silver deposited in the photosensitive material of the present invention (total silver deposit of colloidal silver, non-photosensitive fine grain silver halide, and photosensitive silver halide) is 4.60 g/m2 or less, and more preferably 4.60 g/m2 or less. It is 50 g/po to 2.50 g/bo.

In the present invention, the iodine content in the emulsion of the high-sensitivity emulsion layer is 0.5 mol% or more lower than the iodine content of the low-sensitivity layer.
In this case, the difference in silver iodide content is preferably 0.6 mol% to 3 mol%.

The iodine content of the low-speed emulsion layer is 0.5 mol% to 8 mol%.
is preferable, and 1.5 mol% to 6 mol% is more preferable.

The iodine content of the high-sensitivity emulsion layer, which has a lower iodine content than the low-sensitivity emulsion layer, is preferably 0.6 mol% to 5.8 mol%, and 1
．． 2 mol % to 5 mol % is more preferable, and both the high-speed emulsion layer and the low-sensitivity emulsion layer may be composed of one layer or two or more layers (preferably one or two layers), but 2 When it consists of one or more layers,
The two emulsion layers may have the same iodine content, or
The emulsion layer constituting the light-sensitive material of the present invention may be a mixture of two silver halide emulsions having different iodine contents, which may be different. The halide composition other than silver halide is arbitrary, but
A silver iodobromide emulsion is preferred; in that case, it may contain silver chloride to the extent that the effects of the present invention are not impaired.

In the present invention, the layer in which the iodine content distribution is different between the high-sensitivity layer and the low-sensitivity layer is preferably a green-sensitive layer or a red-sensitive layer, more preferably a blue-sensitive layer,
The immersion content of each color sensitive layer, green sensitive layer and red sensitive layer, is set to 0.
It is advantageous in terms of effectiveness to consist of a high-sensitivity layer and a low-sensitivity layer with a difference of 5 mol% or more.

It is preferable to use a monodisperse silver halide emulsion as the emulsion constituting the silver halide color photographic light-sensitive material of the present invention.A monodisperse silver halide emulsion means a grain size of ±20% centered on the average grain size a. The weight of silver halide contained within the grain size range is 70% or more of the total silver halide weight, preferably 80% or more, and more preferably 90% or more.

Here, the average particle diameter is the particle diameter d when the product of the frequency n of particles having particle diameter d1 and d2, ni Xd, is maximum.
, (3 significant figures, minimum digits are rounded to 5 digits).

The particle size referred to here is the diameter when a projected image of the particle is converted into a circular image with the same area.

The particle size can be determined by, for example, dispersing the particles on a flat sample stand so that they do not overlap, photographing them with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the particle diameter or projected area on the print. (The number of particles to be measured is assumed to be 1000 or more at random).

Particularly preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is the arithmetic mean.

The average grain size of the silver halide emulsion used in the present invention is 0.1
It is preferably ~10.0 μm, more preferably 0.2-5.0 am, particularly preferably 0.3-3.0 μm.
It is m.

The silver halide grains constituting the silver halide emulsion used in the present invention preferably have a high silver iodide content phase inside the grains.

In that case, the silver iodide content of the high silver iodide content phase is 15 to
It is preferably 45 mol%, more preferably 20 to 42 mol%, particularly preferably 25 to 40 mol%.

When using silver halide grains having a high silver iodide content phase inside the grains, the grains are coated with a low silver iodide content phase having a lower silver iodide content than the high silver iodide content phase. Preferably.

In the above case, the average silver iodide content of the silver iodide content phase lower than the high silver iodide content phase forming the outermost phase is preferably 6 mol% or less, particularly preferably 0 to 4 mol%. %. Further, a silver iodide-containing phase (intermediate phase) between the outermost phase and the high silver iodide content phase may be present.

If a mesophase is present, its silver iodide content is between 10 and 22
The mole % is preferred, particularly preferably 12 to 20 mole %.

The difference in silver iodide content between the outermost phase and the middle phase, and between the middle phase and the inner high silver iodide content phase is preferably 6 mol% or more, and particularly preferably 10 mol% or more each. There is a difference between

In the above embodiment, the center of the internal high silver iodide content phase,
Further silver halide phases may be present between the inner high silver iodide content phase and the intermediate phase, and between the intermediate phase and the outermost phase.

Further, the volume of the outermost phase is preferably 4 to 70 mol%, more preferably 10 to 50 mol% of the entire particle. The volume of the high silver iodide content phase is preferably 10 to 80% of the total grain, preferably 20 to 50%, and more preferably 20 to 45%.The volume of the intermediate shell is 5 to 60% of the total grain. %, even 20-55
% is good.

These phases may be a single phase with a uniform composition, a phase group consisting of multiple phases with a uniform composition whose composition changes in a stave-like manner, or a continuous phase within any phase. It may be a continuous phase whose composition changes, or
A combination of these may also be used.

Another aspect of the silver halide grains constituting the silver halide emulsion used in the present invention is that silver iodide localized within the grains does not form a substantially uniform phase, but the silver iodide content is low in the grains. An example of this is a U-shape that changes continuously from the center toward the outside. In this case, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content within the grain is maximum toward the outer side of the grain.

The silver iodide content at the point where the silver iodide content is maximum is
15 to 45 mol% is preferable, more preferably 25 to 4
It is 0 mol%.

Further, the silver iodide content of the grain surface phase is preferably 6 mol% or less, particularly preferably 0 to 4 mol% silver iodobromide.

The silver halide emulsion used in the present invention preferably satisfies at least one of the following conditions.

■ Average silver iodide content determined by X-ray fluorescence analysis (
J,) and the silver iodide content (Jt) on the grain surface determined by X-ray photoelectron spectroscopy, J,>J! The relationship must be satisfied.

The particle size referred to here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

X-ray photoelectron spectroscopy is as follows.

The emulsion to be measured is pretreated as follows prior to measurement by X-ray photoelectron spectroscopy. First, a pronase solution was added to the emulsion and the gelatin was decomposed by stirring at 40° C. for 1 hour. Next, centrifugation is performed to sediment the emulsion particles, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the same conditions as above. This sample is centrifuged again, and after removing the supernatant, Distilled water is added to redisperse the emulsion particles in the distilled water, centrifuged and the supernatant liquid removed.

After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to serve as a measurement sample.

For measurements by X-ray photoelectron spectroscopy, for example, P
Using H1 ESCA/SAM560 type, excitation X
It can be carried out using alpha rays for Mg- rays under the conditions of an X-ray source voltage of 15 KV, an X-ray source current of 40 mA, and a pass energy of 50 eV.

In order to obtain the surface halide composition, Ag5d
, Br5d, r3d Calculation of the 0 composition ratio for detecting 3/2 electrons is performed by the relative sensitivity coefficient method using the integrated intensity of each peak, Ag5d, Br5d.

5.1 each as I 3 d 3/2 relative sensitivity coefficient
By using 0°0.81.4.592, the composition ratio is given in atomic percent.

■ Average silver iodide content determined by X-ray fluorescence analysis (
Jl) and the average value of the silver iodide content measured on silver halide crystals that are 80% or more away from the center in the grain diameter direction of the silver halide grains using the X-ray microanalysis method ( When comparing J,), the relationship J,>Js must be satisfied.

Here, the center is the center of a circle circumscribing the particle.

The X-ray microanalysis method is as follows.

Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer in an electron microscope, the magnification was set so that one particle entered the field of view of the CRT with liquid nitrogen cooling, and AgLα, AgLα, Integrate the intensity of ILα rays. The silver iodide content can be calculated using a calibration curve in which the intensity ratio of ILα/AgLα is calculated in advance.

(4) Using CuKα radiation as a radiation source, at the highest peak height x o, is of the X-ray diffraction signal, the signal must exist continuously over a diffraction angle of 1.5 degrees or more.

More preferably, the highest peak height of the signal x 0.15
In this case, it is preferable that the signal exists continuously over a diffraction angle of 1.5 degrees or more, and more preferably that the signal exists over a diffraction angle of 1.8 degrees or more, particularly 2.0 degrees. It is preferable that the amount of carbon dioxide is present over a period of more than 30 minutes.

The presence of a continuous signal means that the highest peak height Xo
, 13 or Xo, 15, a signal spanning 1.5 degrees or more exists continuously, that is, without being divided into two or more waveforms.

The above (420) X-ray diffraction signal using CuKα radiation as a vA source is more preferably one having two or three peaks, particularly preferably one having three peaks.

Here, the XvA diffraction signal is obtained by X-ray diffraction, which is known as a method for investigating the crystal structure of halogen (11).

In this case, various characteristic X-rays can be used as the X-ray source. Among them, the above-mentioned CuK targeting Cu
Alpha rays are the most widely used.

For example, silver iodobromide has a rock salt structure and is
20) Diffraction spectra are generally observed at 2θ=71 to 74 degrees. Since the signal intensity is relatively strong and the angle is high, the resolution is good and it is ideal for investigating crystal structures.

When measuring the X-ray diffraction of the emulsion, gelatin is removed and
It is necessary to mix a standard sample such as silicon and measure using the powder method.

Regarding the measurement method, reference can be made to Basic Analytical Chemistry Course 24 [X-ray Analysis] (Kyoritsu Publishing).

(2) When the average silver iodide content of each silver halide grain is measured by the aforementioned X-ray microanalysis method, the relative standard deviation of the measured value is 20% or less.

The content is preferably 15% or less, particularly preferably 12% or less.

The relative standard deviation here is, for example, the value obtained by dividing the standard deviation of the silver iodide content when measuring the silver iodide content of at least 100 emulsions by the average silver iodide content at that time x 100
It is.

The silver halide emulsion used in the present invention may be a normal crystal such as a cube, a tetradecahedron, or an octahedron, or may be a twin crystal such as a tabular crystal.

Alternatively, a mixture of these may be used.

In the case of tabular twins, the ratio of the equivalent circular diameter to the grain thickness is 1 to 20, which accounts for 60% of the projected area.
It is preferably 1.2 or more and less than 8.0, particularly preferably 1.5 or more and less than 5.0.

Monodisperse normal crystal emulsions are disclosed, for example, in JP-A-59-1775.
No. 35, No. 60-138538, No. 59-52238
No. 60-143331, No. 60-35726,
It can be manufactured by referring to the methods disclosed in Japanese Patent No. 60-258536 and Japanese Patent No. 61-14636.

Monodisperse twin emulsions are disclosed, for example, in JP-A-61-14636.
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in the above publication.

During growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by a double jet method, and silver iodide can also be supplied into the system. The addition rate should be such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening.
That is, it is preferable to add at a rate of 30 to 100% of the rate at which new nuclei are generated.

Another condition for enlarging the grains is a method of enlarging the grains by adding silver halide fine grains, dissolving and recrystallizing them, as shown in the 1988 Annual Conference Abstracts of the Japan Photographic Society, page 88.

The growth conditions for the silver halide emulsion include PAg5-11.
, a temperature of 40 to 85°C, and a pH of 1.5 to 12 are preferable.

The color photosensitive material of the present invention can form a dye image by an appropriate color development process. The color developing solution used in the development process is generally preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples include amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include

In addition, if necessary, preservatives such as hydroxylamine or sulfites, organic abrasives such as triethanolamine and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers,
Examples include nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Various chelating agents, antioxidants, etc. may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-
Known black and white developers such as 3-pyrazolidones such as 3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The present invention can be preferably applied to color negative films, color reversal films, color reversal papers, and the like.

Color negative films, color reversal films, and color reversal papers generally consist of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers and non-photosensitive hydrophilic colloid layers, and the present invention does not require any modification to the arrangement of these layers. It is not subject to any restrictions.

Furthermore, each of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer has at least one low-sensitivity layer and one high-sensitivity layer. A layer structure in which at least one of the sensitive layer and the blue-sensitive layer is divided into three partial layers, a layer structure in which a high-speed emulsion layer unit and a low-speed emulsion layer unit are separated as seen in JP-A-51-49027; West German Publication No. 2.622922, No. 2,622.9
No. 23, No. 2,622,924, No. 2.704826
It is possible to use the layer structure shown in No. 2,704,797.

Further, in the present invention, it is also possible to apply the layer configurations described in JP-A-59-177551, JP-A-59-177552, and JP-A-59-180555.

The silver halide emulsion according to the present invention is preferably used in at least one layer for each color sensitivity, and more preferably in two or more layers in a color photosensitive material consisting of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. It is used for.

The dry total film thickness of the color photosensitive material of the present invention is 0.8 to 30μ
m is preferable, 10 to 24 μm is more preferable, and 12 to 24 μm is more preferable.
More preferably, the thickness is 22 μm.

The silver halide emulsion used in the light-sensitive material of the present invention 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.

Color-forming couplers are generally used in the emulsion layer of light-sensitive materials for color photography.

Furthermore, by coupling a colored coupler with a competitive coupler and an oxidized form of a developing agent, which has a correcting effect, a development accelerator, a bleach accelerator, a silver halide solvent, a toning agent, a hardening agent, a fogging agent can be obtained. , antifoggants, chemical aggravators,
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 of the light-sensitive material or bleached during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color cast inhibitor, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

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

A dye image can be obtained using the light-sensitive material of the present invention by performing a commonly known color photographic process after exposure.

〔Example〕

The present invention will be described in more detail below with reference to Examples. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Comparative sample 101 of a multilayer color light-sensitive material was prepared by sequentially coating each layer having the following composition on a subbed cellulose triacetate film support from the support side. The coating amount of each component is shown in g/%; however, silver halide is shown in the coating amount converted to silver.

1st layer (antihalation layer) Black colloidal silver 0.24 Ultraviolet absorber U-10,14 Ultraviolet absorber U, -20,072 Ultraviolet absorber U -30,072 Ultraviolet absorber U -40,072 High boiling point solvent 0-1 0.31 High boiling point solvent 0-2 0.098 PolyN vinylpyrrolidone 0.15 Gelatin
2.02 2nd layer (intermediate layer) Dye D -10,011 High boiling point solvent 0-3 0.011 Gelatin 1.17 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye S-1,S- A silver iodobromide emulsion spectrally sensitized with No. 2 (silver iodide content: 3.0 mol%).

Average particle size: 0.3 μm) 0.60 Coupler C-10,37 High boiling point solvent 0-2 0.093 PolyN
Vinylpyrrolidone 0.074 gelatin
1.35 Fourth layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (silver iodide content 3.0 mol%).

Average particle size: 0.80 am) 0.
60 coupler C-1 High boiling point solvent 0-2 PolyN vinylpyrrolidone gelatin 5th layer (intermediate layer) Color mixing inhibitor High boiling point solvent Matting agent Gelatin 6th layer (low sensitivity green sensitive layer) Green sensitizing dye S-3 A silver iodobromide emulsion (E
m-A) (silver iodide content 3.0 mol%.

Average particle size 0.30μm) 0.70
Coupler M-10,31 Coupler M-20,076 High boiling point solvent 0-3 0.059 PolyN
Vinylpyrrolidone 0.074 gelatin
1.29 7th layer (high sensitivity green sensitive layer) Iodobromide s spectrally sensitized with green sensitizing dye S-3 0.85 0.21 0.093 1.56 0.20 0.25 0. 0091 1.35 MA Silver emulsion (silver iodide content 3.0 mol%, average grain size 0.80
μm) 0.70 Coupler M-10,80 Coupler M-20,19 Color mixture prevention A S-10,055 High boiling point solvent
0-3 0.16 polyN vinylpyrrolidone 0.12 gelatin
1.91 8th layer (middle N) Gelatin 0.90 9th layer (
Yellow filter N) Yellow colloidal silver 0,11 Color mixture prevention analysis A S-10,068 High boiling point solvent 0-3
0.085 Matting agent MA-10,
012 Gelatin 0.68 10th layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (silver iodide content 3.0 mol%, average grain size 0. 30 μm) 0.
70 Coupler Y-10,86 Image stabilizer G-10,012 High boiling point solvent 0-3 0.22 PolyN vinylpyrrolidone 0.0?8 compound
F-10,020 Compound F-20,040 Gelatin 1.09 11th layer (high sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (silver iodide content 3) .0 mol%, average particle size 0.85 μm)
0.70 coupler Y-
11,24 Image stabilizer C, -10,017 High boiling point solvent 0-3 0.31 PolyN vinylpyrrolidone 0.10 Compound
F -10,039 Compound F -20,077 Gelatin 1.73 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide content 1.0 mol%,
Average particle size: 0.08 μm) Ultraviolet absorber U-1 Ultraviolet absorber [1-2 Ultraviolet absorber U-3 Ultraviolet absorber U-4 High boiling point solvent 0-1 High boiling point solvent 0-2 Compound F-1 Compound F -2 Gelatin 13th layer (protective layer -2) Slip agent WA X -10,041 Matte agent
MA-20,0090 Mat agent MA-30,
051 Surfactant S U -10,0036 Gelatin
0.55 (Note: The average molecular weight of polyN vinyl pyrrolidone used in each layer is 350.0
It is 00. ) In addition to the above composition, the above sample also contained gelatin hardeners H-1, H-2, H-3, and antifungal agent D.
0.075 0.048 0.024 0.024 0.024 0.13 0.13 0.0?5 0.15 1.2 Requires I-1, stabilizer 5T-1, and anti-capri agent AF-1 It was added as appropriate. The dry film thickness was 19.5 μm.

The silver halide emulsion used in each photosensitive layer was JP-A-59-1
It was prepared with reference to the method of Example 1 of No. 78447.

All were monodisperse emulsions with a distribution width of 20% or less.

After each emulsion was desalted and washed with water, it was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate. , 7-chitrazaindene, and -phenyl-5-mercaptotetrazole were added.

The structure of each compound shown above is shown.

C-1 0M A-1 Colloidal silica particles (average particle size 3.5 μm) A Polymethyl methacrylate particles (average particle size 3.0 μm) A-3 (jl!: m: n=30:30:40) U- 1
~U (b) H CaHe(t) H CaHq(t) CaHw(t) C4H9(t) H3 Ce -C,H,(t) -CaHq(t) Ce Ethylhexyl phthalate diptylphthalate- tricresyl Phosphate S WAX-1 AI-3 T (Average molecular weight: 30,000) f (CHz = CHSOzCHz) 5ccHtsO
z (CHz) z]□N(CHz) zsOJI-1 AI Next, the legal content and silvering amount of the emulsion in the 3.4th, 6th, 7th, 10th and 11th layers were changed as shown in Table 1. Table 1
Samples Nos. 102 to 123 were prepared as shown in FIG.

All of the emulsions used were core/shell emulsions with high internal immersion, monodispersed emulsions with a distribution width of 20% or less, and grain sizes that matched the sample! 11[It was the same as Llol's.

Samples Nα101 to Nα123 were exposed to white light through a step wedge for sensitometric measurement, and the following development treatments were performed.

Processing process Processing time First development 6 minutes Wash with water 2 minutes Reversal 2 minutes Color development 6 minutes Adjustment 2 minutes Bleached white 6 minutes Fixed arrival time: 4 minutes Wash with water 4 minutes Stability 1 minute drying drying Processing temperature 38°C 38℃ 38°C 38°C 38°C 38°C 38°C 38℃ At normal temperature The composition of the treatment liquid used in the above treatment step is as follows.

<First developer> Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g Sodium carbonate (monohydrate) 30
g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution > 2d Add water (pH 9.60)
) 1000d〈Reversal solution〉 Nitrilotrimethylenephosphonic acid, hexasodium salt 3g Stannous chloride (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide
8g glacial acetic acid
Add 15% water <pH 5,75)
1000ad color developing solution> Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium tertiary phosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution> 90d Sodium hydroxide 3g Citrazic acid
1.5gN~ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 11g2.2-ethylenedithiogetanol Add 1g water (pH 1
1,70) 1000d <Adjustment solution> Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4-glacial acetic acid
3- Add water (pH 6,1
5) 1000d〈Bleach solution〉 Sodium ethylenediaminetetraacetate (dihydrate) 2g Iron ethylenediaminetetraacetate (I) Ammonium (dihydrate) 120g Ammonium bromide Add 100g water (
pH 5,65) 1000111 <Fixer> Ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water (pH 6,6
0) 1000d (stabilizing liquid) Formalin (37% by weight) Sd.

Konidanx (manufactured by Konica Corporation) 5 d Add water for 1000 d Sensitivity and sharpness (MTF) for each sample whose image was obtained by the above processing
The stability against changes in developer composition was measured.

Regarding sensitivity, the green sensitivity of sample Nα101 was set to 10.
It is expressed as relative sensitivity when it is set to 0.

Regarding sharpness, the density of the sample exposed to the square wave chart was measured using a microdensitometer model PDM-5 type AR (manufactured by Konica Corporation) using a slit with a width of 300 μm in length and 2 μm in width, and the resolution relative to the input was expressed as a percentage. Find, M T F (ModulationTransf
er Function) value was determined. Specifically, the MTF is determined using red light, and the MT at a spatial frequency of 30 lines/■
This is the relative value of F (100 was obtained for the sample with 101).

Stability against changes in developer composition was determined by exposing each sample to white light for sensitometry, and using the same composition and treatment except for increasing the amount of potassium iodide in the first developer composition by three times. We investigated the sensitivity difference.

The larger the difference in sensitivity is, the greater the variation in photographic performance due to changes in the composition of the first developer is undesirable.

As is clear from the results in Table 2, sample floors 109 to 116 and 120 to 123 according to the present invention do not impair sensitivity;
Moreover, it has excellent sharpness (MTF) and is the first
It can be seen that there is little dependence on the amount of potassium iodide in the developer, sensitivity fluctuations are improved, and the effect on processing condition fluctuations is remarkable.

〔Effect of the invention〕

As described above, the silver halide color photographic light-sensitive material of the present invention has the effects of good sharpness and good processing stability against changes in developer composition.

Claims (1)

[Claims] 1. It has three silver halide emulsion layers: blue-sensitive, green-sensitive, and blue-sensitive, and consists of at least two emulsion layer groups, at least one of which has different sensitivities, and a high-sensitivity emulsion layer of this emulsion layer group. The amount of silver coating is 0.1 higher than that of the low-speed emulsion layer.
g/m^2 or more, and the total silver coating amount is 4.60 g/m^
2 or less, in which the iodine content in the emulsion of the high-sensitivity emulsion layer is 0.5 mol% or more lower than the iodine content of the low-sensitivity emulsion layer. Silver color photographic material.