JPH03215854A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration in image quality when the silver halide color photographic sensitive material is subjected to rapid processing by selecting the material which is deteriorated in the RMS graininess of the min. density part when irradiated with radiations at a specific value or below. CONSTITUTION:The deterioration in the RMS graininess of the silver halide color photographic sensitive material having >=300 ISO sensitivity when irradiated with 100 milli Rontgen is confined to <=30%, by which the deterioration in the image quality at the time of the rapid processing is prevented. The term 'the deterioration in the RMS graininess of the min. density part when the photosensitive material is irradiated with the radiation of 100 milli Rontgen' means bisecting of the photosensitive material to be measured and subjecting of one material to the force deterioration by the radiations, then subjecting the another material to ordinary development processing and comparing the RMS graininess of the min. density part. The above-mentioned term further means that the increase in the measured RMS value of the min. density part of the forcibly deteriorated sample as compared with the sample allowed to stand as it is <=30% at this time.

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 particularly to a high-sensitivity silver halide color photographic light-sensitive material with excellent image quality.

[Background of the invention]

In recent years, in the field of silver halide color photographic materials, there has been an increase in ultra-high sensitivity as typified by ISO-1600 to 3200, as well as small formats as typified by disk film, and higher image quality is required. . Therefore,
Requirements for silver halide color light-sensitive materials are becoming increasingly strict, and even higher standards are being demanded for a wide range of photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog, and a wide exposure range. In response to these demands, as a result of intensive efforts to improve technology, the image quality of high-sensitivity color photographic materials with ISO300 or higher has been significantly improved year by year, and the opportunities for use in photography are steadily increasing. There is.

These high-sensitivity color photographic materials are used not only for photographing subjects outdoors during the day, but also for photographing indoors in many cases. At that time, artificial light sources such as electronic flashes (so-called strobes), incandescent tungsten bulbs, fluorescent lights, and mercury lamps are usually used, but with the spread of flash-equipped compact cameras and flash-equipped disposable cameras, electronic flash using flash,
Opportunities to be photographed are increasing.

On the other hand, from the viewpoint of processing silver halide color photographic materials, rapid processing has been desired in recent years in this industry. Generally, color photosensitive materials are processed on an automatic processing machine installed in each laboratory, but as part of improving service to users, it is required that they be processed and returned to users on the same day they are received. In recent years, it has become necessary to return items within a few hours from the time they are received, and various efforts have been made to shorten the processing time.

The present inventors have discovered that when such rapid processing is applied to high-sensitivity color photosensitive materials photographed with strobe lights, the underexposed areas, especially objects with smooth surfaces (such as walls in the background), are Noticeable deterioration in image quality (unevenness, occurrence of mottles),
I noticed that the development significantly degraded the image quality of the scene. This development was not observed when normal development processing was performed, and analysis revealed that it was caused by poor desilvering.

In view of the above-mentioned problems, the present inventors have conducted various studies, and as a result, in a silver halide color photographic light-sensitive material having an ISO sensitivity of 300 or more, the present inventors have developed a silver halide color photographic light-sensitive material that is exposed to radiation of 100 milli-roentgen. It has been discovered that the above-described deterioration in image quality during rapid processing can be prevented by using a silver halide color photographic material characterized by a deterioration of RMS granularity of 30% or less when exposed to irradiation.

[Object and structure of the invention]

The present invention uses a rapid processing process after (flash) photography.
ISO sensitivity 30 with minimal image quality deterioration even after processing
The purpose of the invention is to provide a silver halide color photographic material with a high sensitivity of 0 or more. , IS with blue-sensitive silver halide emulsion layer
A silver halide color photographic material having an O sensitivity of 300 or more, the silver halide color photographic material having an O sensitivity of 300 or more.
This invention relates to a silver halide color photographic light-sensitive material characterized in that the RMS granularity of the minimum density portion deteriorates by 30% or less when irradiated with milli-roentgen radiation.

[Specific description of the invention]

The present invention will be specifically explained below.

The present invention relates to a highly sensitive silver halide color photographic light-sensitive material having an ISO sensitivity of 300 or more, and the ISO sensitivity of the light-sensitive material as used in the present invention is determined according to the test method shown below. (According to JIS K7614-1981) (1) Test conditions The test is conducted indoors at a temperature of 20±5° C. and a relative humidity of 60±10%, and the photosensitive material to be tested is left in this state for at least one hour before use.

(2) Exposure ■ The relative spectral energy distribution of the reference light on the exposure surface is as shown in Table 1.

Table 1 Wavelength nm Relative spectral energy Note (1) The value is determined by standardizing the value of 560 nm to 100.

■ Illuminance changes on the exposed surface are performed using an optical wedge, and the optical wedge used has a variation in spectral transmission density in the wavelength range of 360 to 700r+n+, within 10% in the region less than 400 nm, and 5% in the region over 400 nm. Use the following.

■ Exposure time is 1/100 seconds.

(3) Development processing ■ From exposure to development processing, the photosensitive material to be tested is maintained at a temperature of 20±5°C and a relative humidity of 60±10%.

■Development processing should be completed within 30 minutes or more and within 6 hours after exposure.

■ Development processing shall be performed as follows.

1. Color development...3 minutes 15 seconds, 38.0±0.1°C2. Bleaching...6 minutes 30 seconds, 38.0±3.0°C3
．． Washing with water...3 minutes 15 seconds, 24-41°C4. Establishment...
・6 minutes 30 seconds, 38.0±3.0°C5. Washing with water...3
Minutes 15 seconds, 24-41°C6. Stable…3 minutes 15 seconds,
38.0±3.0℃7. Drying: Below 50°C The composition of the treatment liquid used in each step is shown below.

(Color developer) Anhydrous sodium sulfite hydroxylamine/1/2 sulfate Anhydrous potassium carbonate Sodium bromide 4.25g 2.0g 3 7. 5 g 1.3 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 1 0.1) (bleach solution) Ethylenediaminetetraacetic acid iron (III) ammonium salt 1 0 0. 0 g ethylenediaminetetraacetic acid 2 ammonium salt 1 0. 0 g ammonium bromide 1 5 0. 0 g glacial acetic acid io. Add o g water to make 1 liter, and adjust to pi{6.0 using ammonia water.

(Fixer) Ammonium thiosulfate 1 7 5. 0g
Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to 1j2
and adjust the pH to -6.0 using acetic acid.

(Stable liquid) Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konica Corporation) 7.5mj! Add water to make 1 liter.

(4) Concentration measurement Concentration is expressed as log+o (φ./φ). φ. is the illumination light flux for density measurement, and φ is the transmitted light flux of the part to be measured. The geometric conditions for concentration measurement are that the illumination light flux is parallel light flux in the normal direction, and that the total light flux that is transmitted as a transmitted light flux and diffused in a half space is used.When using other measurement methods, the standard Perform correction using density pieces. Also, during measurement, the emulsion film q surface shall face the light receiving device side. The density measurement is performed using Status M density of blue, green, and red, and the spectral characteristics are set to the values shown in Table 2 as the comprehensive characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.

10 Note * Red slope 0. 2 6 0 /nm, green slope 0. 1 0 6 /nm, blue slope 0. 2 5 0 /nm** Red slope - 0.0
407nm, green slope-〇. 120/nm, blue slope - 0. 2 2 0 /nm (5) Determination of specific photographic sensitivity Using the results of processing and density measurement under the conditions shown in (1) to (4), the specific photographic sensitivity is determined by the following procedure.

(2) For each of the minimum densities of blue, green, and blue, the exposure amounts corresponding to 110.15 higher densities are expressed in lux seconds and are HE, HG, and HR, respectively.

■ The larger value of Ha, H+t (lower sensitivity)
Let be Hs.

■ Calculate the specific photographic sensitivity S according to 2.

In the present invention, when irradiated with 100 milli-Roentgen radiation, the RMS granularity of the minimum density portion deteriorates by 3.
0% or less means that the photosensitive material to be measured is divided into two,
One is subjected to forced deterioration due to radiation, and the other is subjected to normal development processing, and the RMS granularity of the minimum density portion is compared. At that time, the increase in the measured RMS value of the minimum concentration part of the forced-degraded sample relative to the self-released sample was 30
% or less.

The present invention relates to a high-sensitivity silver halide color photographic light-sensitive material, which is characterized by a deterioration of RMS granularity of the minimum density portion of 30% or less when irradiated with 100 milli-Roentgen radiation. It is more preferable that the deterioration of the RMS granularity of the minimum density portion during the radiation irradiation is 20% or less, particularly preferably 15% or less.

In the present invention, it is necessary to evaluate the RMS granularity of the minimum density area by irradiating it with 100 milli-Roentgen radiation. A forced deterioration test was conducted using the wire. +37CS was used as the T-ray source.

When evaluating the RMS granularity of the minimum density portion, the sample is developed using the normal development process described in the above 130 sensitivity measurement method.

RMS granularity is the standard deviation of concentration value fluctuations obtained by scanning the concentration of the measured part of the sample using a microdensitometer with an aperture scanning area of 1800 μmR (slit width 10 μm, slit length 180 μm), and measuring the concentration with a sample number of 1000 or more. was multiplied by 1000 times. In addition, the blue-sensing layer,
To measure the granularity of the green-sensitive layer and the red-sensitive layer, Eastman Kodak Rat 13 Ten Filter W-47, W-99 and W-26 were used, respectively.
was used.

In the color light-sensitive material of the present invention, it is preferable to use a monodisperse, core/shell type silver halide emulsion.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 70% or more of the total weight of silver halide. preferably 80% or more, more preferably 90%
% or more.

Here, the average particle size d is the frequency nl of particles with particle size d,
The particle size d is defined as the product n+Xd,3 of xd,3 is the maximum. (3 significant digits, minimum digit is 4 to 5) The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image of the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of particles to be measured is indiscriminately 100,014 or more.) A particularly preferred highly monodisperse emulsion of the present invention has a distribution width defined by 20% or less, more preferably 15% or less. belongs to.

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

The silver halide emulsion according to the present invention has an average silver iodide content of 4
It preferably consists of ~20 mol% silver iodobromide;
Particularly preferred is 5 to 15 mol%.

The silver halide emulsion of the present invention may contain silver chloride to the extent that the effects of the present invention are not impaired.

When a core/shell type silver halide emulsion is used in the present invention, the silver halide emulsion has a high silver iodide content phase inside the grains.

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

The silver halide grains of the present invention having a high silver iodide content phase inside the grains are those in which the high silver iodide content phase is coated with a low silver iodide content phase having a lower silver iodide content. be.

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, another silver iodide-containing phase (intermediate phase) may exist between the outermost phase and the high silver iodide content phase.

The silver iodide content of the intermediate phase is preferably 10 to 22 mol%,
Particularly preferably 12 to 20 mol%.

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, another silver halide phase is present in the core of the internal high iodide content phase, between the internal high silver iodide content phase and the intermediate phase, and between the intermediate phase and the outermost phase. May exist.

In addition, the volume of the outermost phase is preferably 4 to 70 mol% of the entire particle.
More preferably 10 to 50 mol%. The volume of the high silver iodide content phase is preferably 10 to 80% of the entire grain,
20 to 50%, more preferably 20 to 45%. The volume of the mesophase is 5 to 60%, and even 20 to 55% of the whole particle.
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 stepwise, 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 embodiment of the silver halide emulsion of the present invention is that the silver iodide localized within the grains does not form a substantially uniform phase, but the silver iodide content is continuous from the center of the grains toward the outside. Examples include aspects that change depending on the situation.

In this case, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content 17 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 preferably 15 to 45 mol%, more preferably 2
It is 5 to 40 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 of the present invention preferably satisfies at least one of the following conditions (1) to (4).

■ Average silver iodide content determined by X-ray fluorescence analysis (
When comparing J1) with the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship J,>J2 is 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 will be explained.

Prior to measurement by X-ray photoelectron spectroscopy, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and stirred at 40°C for 1 hour to decompose gelatin. The emulsion particles are then sedimented by centrifugation.
After removing the supernatant, a pronase aqueous solution is added and gelatin decomposition is performed again under the above conditions.

The sample is centrifuged again, the supernatant liquid is removed, and then distilled water is added to redisperse the emulsion particles in the distilled water, centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. A thin layer of this was applied onto a sharply polished silicon wafer to prepare a measurement sample.

For measurements by X-ray photoelectron spectroscopy, for example, P
Using ESCA/SAM 560 model manufactured by H1 Co., Ltd., the test is carried out under the following conditions: Mg-Kα rays are used as excitation X-rays, X-ray source voltage is 15 kV, X-ray source current is 40 mA, and bus energy is 50 eV.

Ag3d, Br3d to determine the surface halide composition
+I3d3/2 electrons are detected. The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak.

8g3d, Br3d. 13d3/2 relative sensitivity coefficient: 5.1 0, 0.8 1, 4.5, respectively
By using 92, the composition ratio is given in atomic percent.

■ Using the average silver iodide content (J,) determined by the above-mentioned X-ray fluorescence analysis method and the X-ray microanalysis method, the halogenated grains are separated by 80% or more from the center in the grain diameter direction of the silver halide grains. When comparing the average value (J3) of the silver iodide content measured on the silver crystal. This satisfies the relationship L > J3.

The X-ray microanalysis method will be explained.

AgLα, Integrate the intensity of ILα rays. The silver iodide content can be calculated by preparing an intensity ratio of ILα/AgLα in advance and using a calibration curve.

■ Maximum peak height of the (420) X-ray diffraction signal using CuKα radiation as the radiation source xo. ia, the signal is continuously present over a diffraction angle of 1.5 degrees or more. More preferably 20 is one in which a signal exists continuously over a diffraction angle of 1.5 degrees or more at the highest signal peak height X0.15. Furthermore, the diffraction angle at which the signal exists is 1
．． It is preferable that it exists over 8 degrees or more, and it is particularly preferable that it exists over 2.0 degrees or more.

The presence of a signal means that the highest peak height x 0813 or X O. 15, it means that the signal intensity is higher than that height.

A more preferred embodiment of the silver halide emulsion of the present invention is Cu
The above (420) X-ray diffraction signal using Kα radiation as a radiation source has two or three peaks. Particularly preferred is one having three peaks.

X-ray diffraction is known as a method for investigating the structure of silver halide crystals.

Various characteristic X-rays can be used as the X-ray source. Among them, CuKα rays targeting Cu (,,j
: Most widely used.

Silver iodobromide has a rock salt structure and has a (420)
Diffraction lines are observed at 2θ71 to 74 degrees. Since the signal intensity is relatively strong and the angle is high, the resolution is good and it is optimal for investigating crystal structures.

When measuring X-ray diffraction of a photographic emulsion, it is necessary to remove gelatin, mix with a standard sample such as silicon, and measure using a 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.

Here, the relative standard deviation 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 10
It is 0.

The silver halide grains used in the color light-sensitive material of the present invention may be 22 normal crystals such as cubic, tetradecahedral or octahedral, may be composed of twin crystals, or may be a mixture thereof.

The growth conditions for the silver halide grains used in the color photosensitive material of the present invention may be any of the acidic method, neutral method, and ammonia method.
-14630, 61-112142, 62-1
No. 57024, No. 62-18556, No. 63-929
No. 42, No. 63151618, No. 63-161345
No. 1, No. 63-220238 and No. 63-31124
Although known methods such as No. 4 can be used, ammonia methods and acid methods are preferred, and acid methods are particularly preferred.

When forming silver halide grains used in the present invention,
Iodine can be supplied by adding an aqueous solution of its soluble salt, or by adding it as fine grain silver halide (for example, silver iodide or silver iodobromide) and growing it by Ostwald ripening. However, a method of supplying it as fine grain silver halide is more preferable.

Known silver halide solvents such as ammonia, thioale, and thiourea may be present during the growth of silver halide grains used in the color photographic light-sensitive material of the present invention. Furthermore, a crystal shape control agent may be used.

The silver halide grains contain at least one salt selected from thallium salts, iridium salts, rhodium salts, and iron salts, including cadmium salts, zinc salts, lead salts, and complex salts, in the process of grain formation and/or grain growth. Metal ions can be added using seeds to contain these metal elements inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, they can be reduced inside the particles and/or on the particle surfaces. Can provide sensitizing nuclei.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may remain contained. When removing the salts,
Research Disclosure
closure (hereinafter abbreviated as RD)) It can be carried out based on the method described in No. 17643, Section 3.

The silver halide grains used in the color photosensitive material of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain 24.

The silver halide emulsion used in the present invention may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion used in the present invention can be prepared by mixing two or more types of silver halide emulsions formed separately. can. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The light-sensitive silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic field. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holoboracyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine 26 merocyanine pigments, and complex merocyanine pigments.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Also known as antifoggants or stabilizers, they are used during, at the end of, and/or during a stagnation period before application to chemical sensitization for the purpose of preventing fog during photographic processing or to keep photographic performance stable. compounds can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

An emulsion layer of a light-sensitive material using the silver halide emulsion of the present invention,
Other hydrophilic colloid layers can be hardened by using one or more hardening agents that crosslink binder (or protective colloid) molecules and increase film strength.

The hardening agent can be added in an amount sufficient to harden the photosensitive material without the need to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (L3,5-triacryloyl- Hexahydro S- }Riazine, 1l
(3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or in combination. Can be used.

A plasticizer can be added to the emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred desensitizing agents are the compounds described in RD 17643, section x■, A.

The emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the silver halide color photographic light-sensitive material according to the present invention, in the color development process, the emulsion layer is subjected to oxidation of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) and camping. A chromogenic coupler is used that reacts to form a dye. The color-forming coupler is usually selected for each emulsion layer so that a dye that absorbs light in the light-sensitive spectrum of the emulsion layer is formed, with a yellow coupler for the blue-sensitive emulsion layer and a yellow coupler for the green-sensitive emulsion layer. A magenta coupler is used in the red-sensitive emulsion layer, and a cyan coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above combinations.

The color forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent. Compounds that release photographically useful fragments such as agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, so-called DIR compounds which release a development inhibitor during development and improve image sharpness and image graininess may be used.

As the yellow coupler, known acylacetanilide couplers can be preferably used. Among these, penzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057 and West German Patent No. 1547.868.
No., British Patent No. 1,425,020, Special Publication No. 1984-10
No. 783, JP-A No. 58-95346, etc.

As the magenta coupler, known 5-pyrazolone couplers, virazolobenzimidazole couplers, virazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers, and the like can be used.

Specific examples of Mazenk couplers that can be used include, for example, U.S. Pat.
Examples include those described in No. 0-6031, JP-A No. 53-55122, and the like.

As the cyan coupler, phenol or naphthol couplers are generally used. Specific examples of cyan couplers that can be used include, for example, U.S. Pat. No. 3,893,044;
A coupler described in Japanese Patent Application Laid-Open No. 58-98731 is preferred.

Hydrophobic compounds such as color forming couplers, colored couplers, DIR compounds, image stabilizers, color fog preventive agents, ultraviolet absorbers, and optical brighteners to be emulsified and dispersed in silver halide emulsions can be prepared using the solid dispersion method, latex dispersion method, or in water. Various methods such as oil droplet emulsion dispersion method can be used, and this method can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler.

A color cast prevention agent is used to prevent oxidized developing agents or electron transfer agents from moving between emulsion layers of light-sensitive materials, causing color turbidity, deterioration of sharpness, and conspicuous graininess. I can do it.

The color fog preventive agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of RD17643.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of photosensitive materials due to friction, etc., and to prevent deterioration of images due to ultraviolet rays. good.

In order to prevent deterioration of magenta couplers and the like due to formalin during storage of the photosensitive material, a formalin scavenger can be used in the photosensitive material.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators are the compounds described in Section XXI (7) B-D of RD 17643, and development retardants are those described in Section XXI (7) B-D of RD 17643.
This is a compound described in item xr and item E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of the photographic light-sensitive material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

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.

It can be added to the mantle agent in the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material for the purpose of reducing the gloss of the photosensitive material, improving writeability, preventing the photosensitive materials from sticking to each other, etc.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for Preferably used antistatic agents are the compounds described in RD 17643X■.

Furthermore, in the photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, additives are added for the purpose of improving coating properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (promoting development, increasing contrast, sensitization, etc.). Various surfactants can be used as the surfactant.

The support used in the photosensitive material of the present invention includes α-olefin polymers (for example, polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, 34 polycarbonate, polyamide, etc. These include films made of molecules, flexible supports provided with reflective layers on these films, glass, metals, ceramics, and the like.

Extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously, are particularly useful as coating methods, but bucket coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The present invention can be particularly preferably applied to color negative films.

Color negative films generally consist of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers and non-light-sensitive hydrophilic colloid layers, and the present invention is not subject to any restrictions on the arrangement of these layers on the support. do not have.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a washing process, and, if necessary, a stabilizing process. Alternatively, the bleach-fix process can be carried out using a one-bath bleach-fix solution, or the monobath process can be carried out using a one-bath bleach-fix solution that allows color development, bleaching, and fixing to be carried out in one bath. It is also possible to perform a process.

The temperature of the treatment liquid is usually selected in the range of 10°C to 65°C, but it may also be a temperature exceeding 65°C. Preferably 25
The temperature is between 45°C and 45°C.

The light-sensitive material of the present invention can be subjected to various treatments as described above, and the effects of the present invention can be effectively exhibited in rapid processing, particularly in a rapid bleaching process.

〔Example〕

Hereinafter, the present invention will be explained in detail by giving examples.

Example 1 (Preparation of spherical seed emulsion A) A monodisperse spherical dual-species emulsion A was prepared by the method disclosed in JP-A No. 61-6643.

36 DI Ammonia water (28%) 705mA
Liquid B1 and liquid CI were added in 30 seconds to liquid A and liquid stirred vigorously at 40°C by a double jet method to generate nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, liquid C was added over 20 seconds and aged for 5 minutes. The K B r concentration during ripening is 0. 0 7 1 mole/7! , the ammonia concentration was 0.63 mol/l.

Thereafter, the pH was adjusted to 6.0, and the solution was immediately desalted and washed with water. When this seed emulsion was observed under an electron microscope, it was found to be a monodisperse 37 globular emulsion with an average grain size of 0.36 μm and a distribution width of 18%.

Example 2 (Preparation of Emulsion Em-1) Emulsion Em-1 having an average silver iodide content of 8.0 mol % was prepared by the method shown below.

38 Add B3 to A3 solution stirred at high speed at 1000 rpm at 75°C.
-1 liquid and C3-1 liquid were added by a double jet method.

The initial flow rate at this time was 24.2 mβ/min, and the final flow rate was 50. 8 ml/min, addition time 5
It was 5 minutes and 9 seconds. The pAg was maintained at 8.0 during the addition. p
H was maintained at 2.0 with nitric acid.

Next, B3-2 liquid and 03=2 liquid were added to this solution by the double jesotho method. The initial addition rate was 7.98 mβ/m
in, the final addition rate is 10. 6 2 mj! /
The addition time was 35 minutes and 3 seconds. pl'lg during addition is 8
．． 0, and the pH was maintained at 2.0.

Subsequently, B3-2 liquid and C3-3 liquid were added to this solution by the double jesotho method. The initial addition rate is 39. 0
9 mA/min, final addition rate 6 9. 1 m
l! /min, and the addition time was 24 minutes and 19 seconds. During addition, pllg was maintained at 8.0 and pH at 2.0. After the addition was completed, the pH was adjusted to 6.0, and desalting and washing with water were performed by a conventional method.

When the particles were observed with an electron microscope after mixing, it was found that 100
It consisted of monodisperse particles with a twin ratio of 82% and a distribution width of 14%, each having two or more parallel twin planes.

The average value of the average grain diameter/grain thickness ratio of twin grains having two or more parallel twin planes in this emulsion was 1.9.

This emulsion is called Em-1.

Example 3 (Preparation of Emulsion Em-2) Emulsion Em-2 of the present invention having an average silver iodide content of 10.1% was prepared in the same manner as in Example 2 using the seed emulsion of Example 1.

This emulsion consisted of 100% twinned grains, monodisperse grains having two or more parallel twin planes, a twin ratio of 78%, and a distribution width of 14%.

Example 4 (Preparation of emulsion Em-3) Next, a method for preparing emulsion Em-3 will be described.

The following aqueous solutions (A4) to (D4) were used.

41 Into an aqueous solution (A4) having the above composition that was vigorously stirred at a temperature of 60°C, a solution containing 2 mol % of silver iodide and an average grain size of 0.
27 μm monodisperse normal crystal silver iodobromide emulsion 0. 4 0
The equivalent of 7 moles was added as seed particles, and the pH and pAg were adjusted using acetic acid and aqueous KBr solution.

After that, while controlling the pH and pAg as shown in Table-2, at the flow rates shown in Table-3 and Table-4,
(B4). (C4) and (D4) aqueous solutions were added by a simultaneous mixing method.

Next, a phenylcarbamyl gelatin solution was added to the solution obtained above, and the particles were sedimented and agglomerated by adjusting the PU of the solution, followed by desalting and washing with water.

Thus, with an average grain size of 0.8 μm and an average silver iodide content of 8.
．． A 0 mol % monodisperse emulsion Em-3 was obtained.

42 Table-3 * At the position where the Ag content is 29%, the pH and pllg environment were suddenly changed.

In all of the following Examples, the amount added in the silver halide photographic light-sensitive material is expressed in Durham's number per unit unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Each layer having the composition shown below was sequentially formed on a triacetyl cellulose film support from the support side to prepare a multilayer color photographic material sample-101.

Emulsions Em-1~ obtained in Examples 2~4 for sample preparation
3 was chemically sensitized using sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and stabilizer S
T-1 and antifoggant AF-1 were added as appropriate.

Sample-101 1st layer: Antihalation layer (HC-1) Black colloidal silver 0.2 UV absorber (UV-1)
0.2346 High boiling point solvent (Oil-1) 0.1 Gelatin 1.4 Second layer: First intermediate layer (rL-1) Gelatin 1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) 8 Increase Sensitive dye (SD-1) 1. 8 X 10-5 mol/silver 1 mol sensitizing dye (SD-2) 2. 8 XIO
-' mol/silver 1 mol sensitizing dye (SD-3) 3. O
x 10-' mol/silver 1 mol cyan coupler ((,-
1) 0.70 colored cyan coupler (
CC-1) 0. 0 6 6DIR compound (D
-1) 0.03DIR compound (D-3)
0.01 high boiling point solvent (oil 1)
0.64 gelatin
1.2 Fourth layer: Medium red-sensitive emulsion layer (RM) Sensitizing dye (SD-1) 2. 1 xlO-5 mol/
Silver 1 mole sensitizing dye (SD-2) 1. 9 x 10
-' mol/silver 1 mol 47 Sensitizing dye (sD-3) 1. 9 x 10-' mole/silver 1 mole cyan coupler (C-1) 0
．． 28 colored cyan coupler (CG-1)
0. 0 2 7DIR compound (D-1)
0.01 high boiling point solvent (Oi1-1)
0.2 6 gelatin 0
．． 6 5th layer: High sensitivity red light emulsion layer (R H) Emulsion Em-
3 (average particle size 0.8, crm) 1.70 sensitizing dye (
sD-1) 1.9xlO-5 mol/silver 1 mol sensitizing dye (sD-2) 1. 7 x 10-' mol/silver 1
Molar sensitizing dye (SD-3) 1.7xlO-'mol/
Silver 1 Morcian coupler (C-1) 0.
05 Cyan coupler (C-2) 0.10
Colored cyan coupler (CC-1) 0. 0
2DIR compound (D-1) 0.025
High boiling point solvent (Oil-1) 0.17 Gelatin 1/2 6th layer: 2nd intermediate layer (IL-2> 48 7th layer: Low sensitivity green-sensitive emulsion layer (GL) Sensitizing dye (So
-4) 6. 8 xlO-5 mol/silver 1 mol sensitizing dye (SD-5) 6. 2 x 10-' mol/silver 1
Mol magenta coupler (M-1) 0.54
Magenta coupler (M-2) 0.19 Colored magenta coupler (CM-1) 0. 0 6
DIR compound (D-2) 0.017DI
R compound (D-3) 0.01 High boiling point solvent (Oi1 2) 0.81 Gelatin
1.8 8th layer: medium-sensitivity green-sensitive emulsion layer (GM) sensitizing dye (sD-6) 1.9xlO-'mol/silver 1
Molar distracting dye (SD-7) 1.2X10-'mol/
1 mole of silver sensitizing dye (SD-8) 1.5 x 10-' mole/1 mole of silver magenta coupler (M-1)
0.07 magenta coupler (M-2) 0.
03 Colored Magenta Coupler (CM-1) 0.
0 449 DIR compound (D-2) 0.018 High boiling point solvent (Oil-2) 0.30 Gelatin 0.8 9th layer: High sensitivity green sensitive emulsion layer (G H) Emulsion Em. -1 (average particle size 1.0μ
m) 1.7 sensitizing dye (SD-6) 1. 2 X
10-' mol/silver 1 mol sensitizing dye (SD-7) 1
．． OX10-' mol/silver 1 mol sensitizing dye (SD-8)
3. 4 XIO-6 mol/silver 1 mol magenta coupler (M-1) 0.09 magenta coupler (
M-3) 0.04 colored magenta coupler (CM-1) 0. 04 High boiling point solvent (Oil
-2) 0.31 gelatin
1.2 10th layer: Yellow filter layer (
YC) Yellow colloidal silver 0.05
Color stain inhibitor (SC-1) 0.1 High boiling point solvent (041-2) 0.13 Gelatin
0. 7 Formalin Scavenger (Is-1) 0. 0 9 Formalin Scavenger (HS-2) 0. 0 750 11th layer: Low sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion
0.5 (average grain size 0.4 μm, silver iodide 8 mol%) silver iodobromide emulsion
0.5 (average particle size 0.7 μm, silver iodide 8 mol %) Sensitizing dye (SD-9) 5.2 x 10-' mol/silver 1 mol Sensitizing dye (SD-10) 1. 9 XIO-5 mol/
Silver 1 mole yellow coupler (Y-1) 0.
65 yellow coupler (Y-2) 0.24
DIR compound (D-1) 0.03 High boiling point solvent (Oil-2) 0.18 Gelatin
1.3 Formalin Scavenger (IIs-1) 0. 0 8 12th layer: High-speed blue-sensitive emulsion layer (BH) Emulsion Em-2 (average grain size 1.0
μm) 1.0 Sensitizing dye (SD-9) 1. 8
X 10-' mol/silver 1 mol sensitizing dye (So-10)
7. 9 xlO-' mol/silver 1 mol Yellow coupler (Y-1) 0.15 Yellow coupler (Y
-2) 0.05 high boiling point solvent (Oi1-2
) 0.0 7 4 Gelatin
1.3051 Formalin scavenger (Is-1) Formalin scavenger (HS-2) 13th layer: First protective layer (Pr
o-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm Ag1 1 mol%) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) High boiling point solvent (Oil-1) High boiling point solvent ( Oil-3) Formalin scavenger (HS-1) Formalin scavenger (HS-2) Gelatin 14th layer: 2nd protective layer (Pro-2) 0.05 0.12 0.4 0.07 0.10 0 .07 0.07 0. Technique 3 0.37 1.3 Sliding agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, coating aid Su. -1, dispersion aid Su-2,
Viscosity modifier, hardener H-1, H52 2, stabilizer ST-1, antifoggant AF-1, V: 1
Two types of AF=2 were added: 0,000 and M W : L 100,000.

The average particle size is expressed as a cubic particle size.

Each emulsion was optimally gold and sulfur sensitized.

Example 6 In Example 5, emulsion Em-1 of the ninth layer of sample 101
Sample 102 was prepared in the same manner as in Example 5, except that Em-3 was replaced with the same amount of Em-3.

Example 7 Multilayer color photographic material sample 103 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-103 (Comparison) 1st layer; antihalation layer (HC-1) black colloidal silver 0.18 UV absorber (UV-1
) 0.29 high boiling point solvent (Oiβ-1
) 0. 2 3 high boiling point solvent (O i 11
-2) 0.0 1 153 Colored magenta coupler (CM-3) 0.011 Gelatin 1.57 2nd layer;
First intermediate layer (IL-1) Gelatin 1.27 Third layer;
Low-speed red-sensitive emulsion layer (RL) Sensitizing dye (SD-1) 1.3 x
1 0-' (mol/1 mol of silver) Sensitizing dye (SD-2) 2.2X 1 0-
4 (mol/silver 1 mol) Sensitizing dye (SD-3) 2.2X1 0-'
(Mole/1 mole of silver) Cyan coupler ((,-1) 1.21 Colored cyan coupler (CC-1) 0.0 3 2
DIR compound (D-1) 0.05 High boiling point solvent (Oi7!-1) 1.04 Gelatin 2.0054 4th layer; 2nd intermediate layer (TL-2> Gelatin 5th layer; high sensitivity red-sensitive emulsion layer) (RH) 0.80 Sensitizing dye (SD 1) Sensitizing dye (SD 2) Sensitizing dye (SD-3) Cyan coupler (C-1) Cyan coupler (C-2) DIR compound (D-3) DIR Compound (D-3) High boiling point solvent (Oij2-1) Gelatin 6th layer; 2nd intermediate layer (IL 7.IX10-6 (mol/1 mole of silver) 1.2X10-' (mol/1 mole of silver) 1 .2XI.O-' (mol/silver 1 mol) 0.05 0.19 0.0066 0.0076 0.28 1.37 2) 55 Gelatin high boiling point solvent (Oi/-2) SC-2 7th layer ;Low-sensitivity green-sensitive emulsion layer (GL) 0.80 0.08 0.071 Sensitizing dye (SD-4) 2.7X10-5
(Mole/1 mole of silver) Sensitizing dye (SD-5) 2.5 X 1
0-' (mol/silver 1 mol) Sensitizing dye (SD-7) 8.0X1 0-
5 (monole/≦1 monole) Sensitizing dye (SD-8) 1.9 x I L
5 (mol/silver 1 mol) Sensitizing dye (SD-1 1) 1.4 X 1
0-' (mol/mol of silver) Magenta coupler (M-3> 0.34 Colored magenta coupler (CM-3) 0.0 4 8 56 DIR compound (I)-3) DIR compound (D-4 > DIR compound (D-2) High boiling point solvent (Oi!-4) Gelatin 8th layer; 3rd intermediate layer (IL-3) High boiling point solvent (Oil-1) Gelatin 9th layer; High sensitivity green-sensitive emulsion layer (GH) 0.0025 0.013 0.02 0.38 1.13 0.17 0.83 Sensitizing Dye Sensitizing Dye Sensitizing Dye Sensitizing Dye (SD (SD (SD (SD 1 1) 6) 7 ) 8) 4.5X].0-5 (monole/t 1 monole) 9.6X10-5 (mol/1 mole of silver) s.sxio-5 (mol/1 mole of silver) 1.4X10-' (mol /silver 1 mole) 57 Magenta coupler (M-1) 0.14 Magenta coupler (M-3) 0.068 Colored magenta coupler (CM-2) 0.11 DIR compound (D-5) 0.00
15 High boiling point solvent (Oiβ-2) 0.57 Gelatin 1.97 10th layer;
Yellow filter layer (VC) yellow colloidal silver
0.05 color stain prevention agent (SC-2)
0.054 High boiling point solvent (○i6-2)
0.063 gelatin 0
．． 49 Formalin scavenger (HS-1) 0.08 Formalin scavenger (HS-2) 0.10 11th layer; low sensitivity blue-sensitive emulsion layer (BL) 58 Sensitizing dye (SD 1 2) Sensitizing dye (SD -10) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-1) High boiling point solvent (Oil-2) Gelatin formalin scavenger Formalin scavenger 5.5XIO-' (mol/silver 1 mol) 5 ．． OX10-5 (mol/silver 1 mol) 0.99 0.085 0.012 0.25 1.60 (HS-1) 0.12 (HS-2) 0.29 12th layer; Highly sensitive blue-sensitive emulsion Layer (B H) Sensitizing dye (SD 12) 2. OX10-4 (mol/silver 1 mol) 59 Sensitizing dye (SD-10) 4.8 x
1 0-' (mol/silver 1 mol) Yellow coupler (Y-2) 0.27 High boiling point solvent (Oiβ-2) 0.17 Gelatin
1.22 Formalin Scavenger (HS-2) 0. 0 8 3 13th layer; 1st protective layer (Pro 1) Isodene absorber (UV-1) Isoeite absorber (UV-2) High boiling point solvent (Oiβ-]) High boiling point solvent (Ofβ-3) Formalin Scavenger Formalin Scavenger Gelatin 14th layer; 2nd protective layer (Pro Alkali-soluble cloak agent 0.0 5 8 0.0 8 3 0.06 0.06 (HS~1) 0.0 4 7 (HS-2 ) 0.22 1.49 2) 60 (average particle size 2 μm) 0.12 Polymethyl methacrylate (average particle size 3 μm) 0.018 Gelatin 0.55 In addition to the above composition, coating aid Su-1, A dispersion aid Su-2, a viscosity modifier, hardeners H-1 and H2, a stabilizer ST-1, an antifoggant AF-1, and an AF-2 having an Mw of 1,100,000 were added.

Example 8 A multilayer color photographic material sample 104 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-104 1st layer; antihalation layer (HC) black colloidal silver 0.15 g UV absorber (UV
-1) 0.20 g colored coupler
(CC-1) 0.02 g high boiling point solvent (
Oi 1! -1) 0.20 g〃(Oi
β-2) 0.20 g61 Gelatin 1.6g 2nd layer; Intermediate layer (IL-1) Gelatin 1.3g 3rd layer; Low sensitivity red-sensitive emulsion layer (R-1) Silver iodobromide emulsion
0.4g (average particle size 0.4μm silver iodide 2
．． 5 mol%)〃 03 g
(Average grain size 0.3 μm, silver iodide 2.5 mol%) Sensitizing dye (SD-3) 3.2 XIO-' (mol/silver 1 mol) // (SD-2) 3.2 XIO-' (
// )〃(SD-1) 0.2 XIO-
' ( ) Cyan coupler (C-1)
0.50 g (C-3)
0.13 g colored cyan coupler (CC-1)
0.07 gDIR compound (D-3)
0.006 gDIR compound (D-1)
0.01 g high boiling point solvent (Of It -1
) 0.55 g gelatin
1.0g 4th layer; Highly sensitive red-sensitive emulsion layer (R
- H) Silver iodobromide emulsion 0.9
g62 (average particle size 0.7 μm silver iodide 8 mol%) sensitizing dye (
sD-3) 1.7xlO-' (mol/1 mol of silver)〃
(SD-2) 1.6 X1.0-' (
)” (SD-1) 0.1 XIO
-' ( ) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g
DIR compound (D-2) 0.02 g
High boiling point solvent (Oiβ-1) 0.25
g additive (SC-1) 0.00
3g gelaten 1.0g 5th
Layer: Intermediate layer (IL-2) Gelatin 0.8g 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion
0.6 g (average particle size 0.46 μm, silver iodide 7.5 mol%) 0.2 g (average particle size 0.3 μm, silver iodide 2.5 mol%) Sensitizing dye (SD-5) 6.7 xlO-' (mol/silver 1 mol) (SD-4) 0.8 XIO-' ( 〃
) Magenta coupler (M-2) 0.17
g63 (M-1) 0.43 g Colored magenta coupler (CM-1) 0.10 gDI
R compound (D-2) 0.02 g High boiling point solvent (Oi E-2) 0.7
g additive (SC-1) 1.0
g Gelatin 1.0g 7th layer; Highly sensitive green-sensitive emulsion layer (GH) Silver iodobromide emulsion
0.9 g (average particle size 0.7 μm silver iodide 8 mol%) sensitizing dye (SD-7) 1.1 xl
O-' (mol/silver 1 mol)〃(SD-6) 2. O
xlO-' ( )〃(SD-8) 0
．． 3 XIO-' ( ) Magenta coupler (M-2) 0.03 g (M-1)
0.13 g Colored magenta coupler (CM-1) 0.04
gDIR compound (D-2) 0.004
g High boiling point solvent (Of 12 -2>
0.35 g gelatin 1. O
g8th layer; Yellow filter layer (Y C) Yellow colloidal silver 0.1 g64 Additive (HS-1) 0.07
g (HS-2) 0.07 g
Additive (SC-1) 0.12
g High boiling point solvent (Oi j2 -2) 0
．． 15 g gelatin 1.0 g
9th layer; low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion 0.25 g (average grain size 0.4
μm silver iodide 7.5 mol%) silver iodobromide emulsion
0.25 g (average particle size 0.3 μm silver iodide 2.5 mol%) sensitizing dye (SD-9) 5.8 xlO
-' (mol/silver 1 mol) yellow coupler (Y-1)
0.6 g〃(Y-2) 0
．． 32 gDIR compound (D-3) 0
．． 003 g〃(D-1) 0.006
g High boiling point solvent (Of l -2) 0
．． 18 g gelatin 1.3 g
10th layer; High sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion 0.5g65 (average grain size 0.85 μm silver iodide 8.5 mol%) Sensitizing dye (SD-12) 3 XIO- ' (Mole/1 mole of silver) (SD40) 1.2 XIO~4 (mol/1 mole of silver) Yellow coupler (Y-1) 0.18
g(Y-2) 0.10 g High boiling point solvent (Oi 12-2) 0.
05 g gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion
0.3g (average particle size 0.08μm silver iodide 2mol%) Ultraviolet absorber (UV-1)
0.07 g (UV-2) 0.
1 g additive (HS-2) 0
．． 2 g (HS-1) 0.1
g High boiling point solvent (Oi It -1)
0.07 g (Oi E-3) 0.0
7 g gelatin 0.8 g
12th layer; 2nd protective layer (PRO-2) Alkali-soluble mantle agent (average particle size 2 μm) 0.13 g66 Polymethyl methacrylate (average particle size 3 μm) 0.02 g gelatin
In addition to the above composition, coating aid SO-2, dispersion aid SU-1, and hardening agents H-1 and I+-2 were appropriately added to each layer.

67 C-2 0H L 68 M-2 C2 M 4 re Y 1 rθ 69 Y 2 CC 1 0H CM 1 CJ! ．． 70 CM 2 Shiki CM 3 C! D 1 0H 7 1 D 2 D-3 D 4 01{ []H 0H 0H 72 D 5 0l o iI! ．． 2 oij2 4 0 ■ 73 SC-1 0H SC 2 0H UV- 1 UV-2 CzHs 74 (CHz) 3SO1 0 (CH.) 3SO3HN (CHz) ssOs O CzH5 (CHz) 3SO3' (CHz) zsO3Na 75 SD 5 SD 6 SD 7 (CHz) 3SO3 0 (CH.) zsOJH (C2Hs) cSD-8 76 SD 9 SD 10 SD-11 SD-12 (CH2) asOc 0 77 (CH.) 3SO3HN (C2H5) sHS-1 HS-2 Su 1 Su-2 ST 1 0 ■ 78 AI-1 AI 2 Example 9 On a subbed cellulose triacetate film support,
Sample 105, which is a multilayer color photosensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component are g/m. For silver halides, the coating amount is shown in terms of silver. However, for sensitizing dyes, the coating amount is shown in moles per mole of silver halide in the same layer.

(Sample-105) 1st layer; antihalation layer black colloidal silver --1-1-1---1 silver 0.18 gelatin 111-11------1-. -0.
4. 0 Second layer; Intermediate layer 2.5-di-t-pentadecylhydroquinone 11----------------------
------ 0. 1 SEX-1 --
−−−−−−−−−−−−−−−−−−−−0.0
7E
----- 0. 0 280 U-1 U-2 HBS-1 HBS-2 Third gelatin layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.70 μ) Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 HBS-1 0.08 0.08 0.10 0.02 1.04 Gelatin 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.75μ ) Sensitizing dye ■ Silver 0.50 6.9X10-' 1.8X10-5 3. IX10-' 4. OX10-' 0. 3 5 0 0. O O 5 0.012 1.08 Ichigin 1.08 5. IX10-' 81 Sensitizing dye [. −−−−−−−−−−−−−−−−−−
1. 4 x 10 sensitizing dye III
−−−−−−−−−−−−−−−−−−−1.3X
10 Sensitizing dye IV-3. 0X
1 0EX-2
-0.30EX-3 --------
−−−−−−−−−−−−−−−−−−−−0.0
SEX-10
0.00HBS-1------------
−−・− 0.05 gelatin−・
1.1 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.00μ) single-lens 1.4 sensitizing dye IX - -5.4X10
Sensitizing Dye II 1.4X10 Sensitizing Dye I 2.4X10 Sensitizing Dye I
I/ −−−−−−−−−−−−・−−−−−−−
-3. IX10EX-5 --------
----- --・0.15EX-3
−−−−−−−−−−−−−−−−11111−−
−−−−−−−−−−−1−0.05EX−4 −
−−−−−− −−− −−−−1・−0.
0 6EX - 1 1 -------
−−−−−−−−−−・− 〇. 0 0H B S
− 1 −−−−−−−−−−−−−−−−−−−−
−−−−−−−−−−−−−−−−−−−− 0. 3
Gelatin-----------1-----
−−−−−−−−−−−−−−−−−−−−−−−−−
1. 482 6th layer (intermediate layer) HBS-2 Gelatin EX-12 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.65μ) Sensitizing dye X Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ R-4 EX-6 EX-1 EX-7 EX-8 HBS-1 HBS-4 Gelatin 8th layer (second green emulsion layer) 0.01 1.06 0.02 ・・− -----One silver 0.36 1.5X10-5 3. OX10-' 1. OX10-'3.8X10-' 0.017 0.260 0.021 0.030 0.025 0. 1 0 0 0. 0 6 0 0.68 83 Silver iodobromide emulsion (average grain size 0.70μ) Sensitizing dye X Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ R-4 EX-6 EX-8 EX-1 EX- 7 HBS-1 HBS-4 Gelatin 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.0 μ) Sensitizing dye X Sensitizing dye ■ Sensitizing dye ■ Silver 0.72 1. Ox10-s 2. IX10-' 7. OX10-5 2. 6 X 1 0 0.019 0. 1 5 0 0.010 0.00B 0.012 0.60 0. 0 5 0 0.99 Silver 1.08 1.2X10-5 3.5X10-5 8. OX10-' 84 Sensitizing dye■ EX-6 EX-1 HBS-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver EX-12 HBS-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Iodobromide Silver emulsion (average particle size 0.6μ) Sensitizing dye ■---1---11---Silver 0.223.5X1
0-' 0.85 0.12 0. 0 3 0 0.28 1.15 EX- 9 EX- 8 EX-11 HBS-1 Gelatin 12th layer (second blue-sensitive emulsion layer) 3. OX10-' 0. O 6 5 0. O 2 5 0.55 1.57 Silver 0.05 0.04 0.02 0.95 85 Silver iodobromide emulsion (average grain size 0.80 μ) Sensitizing dye ■ EX- 9 EX-10 HBS-1 Gelatin Silver 0.41 2. IX10-' 0.20 0.015 0.03 0.41 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.2 μ) Sensitizing dye ■ EX-9 HBS-1 Gelatin Silver 0.69 2.2X10-' 0.20 0.07 0.62 14th layer (first protective layer) Silver iodobromide emulsion (average grain size 0.07μ) U-1 U-2 HBS-1 Silver 0.07 0.11 0.17 0.90 86 Gelatin−−−−−−−−−−−−−=
−−−−−−−−−−−1. 0 0 15th layer (second protective layer) Polymethyl acrylate particles (approximately 1.5 μm in diameter) −−−−−−−−−−−−
--0. 5 43 − 1 −−−−−−−−−−
−−−−−−−−−−−−−−−−−−−−−−−−−
----------- 0. 0 53-2 --------
−−−−−−−−−−−−−−−−−−−−−=−11−−−−−−−−−−−− 0. 0 5 Gelatin----------------
−−−−−−−−−−−−−− 0. 7 2 In addition to the above ingredients, each layer contains a gelatin hardening agent (■)1. H-2 and antifoggant AF-1. , AF-2 and a surfactant were added.

Structure of compound used in Examples 87 EX-1 CI! 88 EX 2 0H EX- 3 0H EX 4 0H 89 EX 5 0H EX 6 90 EX 7 EX- 8 Cl 91 EX 9 EX 10 92 EX-11 0■ SCHzCHzCOOCH3 OH HBS 1 Tricresyl Phosphate HBS 2 dibutyl phthalate i { B S 3 Bis(2 Ethylhexyl) Phthalate 93 HBS 4 H-1 0■ H 2 CHz ? ■One SO■-CH2CON}I CH2 CH2=CI-SOz-CHz-CONH-C■2S-
1 S-2 U 94 Sensitizing dye ■ 95 Cβ CzHs ■ 96 97 R 4 (Compound included in JP-A-57-154234, JP-A-58-162949, etc.) 0H 0H 98 AF 1 AP 1 99 <Negative development processing Conditions> The treatment was carried out after running until the stabilization tank contained three times the capacity of the replenisher.

(The replenishment amount is the value per 1m" of photosensitive material.) However,
The stabilization process was carried out using a three-tank countercurrent system, in which the final stabilizing liquid tank was replenished, and the overflow flowed into the previous tank.

In addition, part of the overflow of the stabilization tank following the fixer tank (
2 7 5 mj2/m2) was poured into a stabilizing tank.

The composition of the color developing solution used is as follows.

Potassium carbonate 30g Sodium bicarbonate 2.7g Potassium sulfite 2.8g 100 Sodium bromide 1.3g Hydroxylamine sulfate 3. 2 g sodium chloride
0.6g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide
Add 1.3g water and 11! ．． The pH was adjusted to 10.01 using potassium hydroxide or 20% sulfuric acid.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate 3.2
g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 2g 1 0 1 Add water to make 12, and adjust the pH to 10.12 using potassium hydroxide or 20% sulfuric acid.

The composition of the bleaching solution used is as follows.

Ammonium bromide 150g Glacial acetic acid 40mI! ．． Ammonium acetate 40g Add water to 1l
and adjust the pH to 4.5 using aqueous ammonia or glacial acetic acid.

The composition of the bleach replenishment solution used is as follows.

Add ammonium bromide, ammonium nitrate, glacial acetic acid water to make 1 liter, adjust to pH 3.5 using 170g 50g 61n4 ammonia water or glacial vinegar 102 acid, and adjust appropriately to maintain PL+ of the bleach tank solution.

The compositions of the fixer and fixer replenisher used are as follows.

Ammonium thiosulfate 100g Ammonium thiocyanate 150g Anhydrous sodium bisulfite 20g Sodium metabisulfite 4.0g Add water to 700mI! ．． Close the mixture and adjust the pH to 6.5 using glacial acetic acid and aqueous ammonia.

The compositions of the stabilizing solution and stabilizing replenisher used are as follows.

1,2benzisothiazolin-3-one 0.1 g Hexamethylenetetramine 0.2 g% The pH was adjusted to 7.0 using sulfuric acid.

Example 10 The multilayer color photographic materials Samples 101 to 105 obtained in Examples 5 to 9 were divided as appropriate and one part was used for measurement of 130 sensitivity. The ISO sensitivity was measured according to the method described above.

In addition, some are self-released, and some are 100 millimeter X-ray T.
After performing forced deterioration by irradiation with radiation and performing a development process, the RMS granularity of the minimum density portion was evaluated. The method of forced deterioration, development processing, and measurement of RMS granularity followed the methods described above.

Additionally, some of the footage was used to film actual scenes.

The actual scene was shot in a dark room using a strobe light. Several different scenes were evaluated, including a person standing away from a flat wall.

The photographed sample film was subjected to negative development under the rapid processing conditions shown below, and then printed on Konica Color PC Paper Type SR, and the image quality (unevenness and mottle) was evaluated. Evaluation was made by visual judgment of the print.

Results in table It's time for 5.

(B: blue-sensitive layer G: green-sensitive layer R: red-sensitive layer) 1 0 5 Visual judgment of the print was conducted by 10 subjects, 2 samples with unevenness and mottle, and 3 samples with no concerns. Samples for which more than 8 out of 10 people judged that they were not concerned were designated as a, samples for which at least 6 and less than 8 out of 10 people judged them not to be concerned were designated as b1, and other samples were designated as C. .

Further, when samples 101 to 105 were evaluated for desilvering properties under the above-mentioned speed processing conditions, it was found that samples 101 and 102 were excellent.

Claims (1)

[Claims] A silver halide color photographic photosensitive material having an ISO sensitivity of 300 or more and having a support and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer coated on the support, respectively. A silver halide color photographic light-sensitive material, characterized in that when the silver halide color photographic light-sensitive material is irradiated with radiation of 100 milli-roentgen, the RMS granularity of the minimum density portion deteriorates by 30% or less. Silver chemical color photographic material.