JPH03217840A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the sensitivity of a sensitive material and the yield of prints and to prevent the lowering of the yield with the lapse of time by specifying the min. densities of yellow, magenta and cyan in the sensitive material having prescribed ISO sensitivity or above. CONSTITUTION:This sensitive material is a color negative film having >=300 ISO sensitivity and has min. densities Dmin (Y), Dmin (M), Dmin (C) of yellow, magenta and cyan satisfying relations represented by inequalities I-III. In this film, a silver halide emulsion contg. singly dispersible silver halide particles each made of silver iodobromide having a prescribed average silver iodide content and contg. an internal silver iodide-rich phase may be used and a cyanine dye may be used as a sensitizing dye.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, in a color negative photographic material for printing, it is possible to reduce loss during printing in a developing laboratory. This invention relates to a silver halide color photographic luminescent material.

[Background of the invention]

In recent years, in the market, demand for photographic consumer goods has been growing at a very high level, at an annual rate of about 10%. This is due to a number of factors, including the fact that product development is progressing smoothly to accommodate the increasing number of photo opportunities, and the fact that we are able to provide photos with print quality that satisfies photographers. It is thought that there are points. In particular, with the active introduction of compact cameras into the market and the subsequent penetration of zoom lenses, photographers have come to expect the best quality results at any time and in any location when they want to preserve their photographs. Opportunities to press the shutter are increasing.

In order to meet the expectations of photographers, photo labs make various efforts to ship the best possible prints. However, as cameras have become more compact and zoom lenses have become more popular, the F-number of lenses used in cameras has become large, meaning that it has become necessary to use dark lenses, resulting in problems such as underexposed photographs and insufficient peripheral light. Furthermore, in the case of exposure with so-called single-use cameras, which have become rapidly popular in recent years, there is no choice but to print ungained color film taken under various shooting conditions, from underexposure to overexposure. ing.

Various measures are being taken to finish the best prints at photofinishing labs, but when we look at statistics on the finished print yields of the best prints, we find that the print yields are not that great for photosensitive materials with a 150 sensitivity and a sensitivity of less than 200. It was found that the print yield was not low, but was specific to sensitive materials with an ISO sensitivity of 300 or higher.

Upon further investigation, it was found that lofts that have passed since the production date of silver halide color photographic light-sensitive materials tend to lower print yields.

With the recent spread of automatic printers, printers in photo labs have adopted a method of presetting printing conditions, and models equipped with an automatic negative image judgment device are becoming mainstream. However, rather than negative density, it is necessary to pay attention to the experience and intuition of the operator who operates the printer, such as the printing conditions required during printing, such as density correction, color correction by shooting with different light sources, and color correction for color phaeria scenes. It is true that the best print cannot be obtained unless detailed printing conditions are set.

[Problems to be solved]

Against the background of such current conditions in the market and photofinishing labs, the present inventors have conducted intensive research to improve the print yield of high-sensitivity photosensitive materials.

The problem mentioned above is that after thorough investigation into the experience and intuition of print workers, it was found that no matter how strictly the various printing conditions are controlled, individual differences among print workers are It was found that this problem could not be completely filled, and unless improvements were made to the negative color film used for printing, this problem essentially remained unsolved.

In particular, we focused on changes over time after manufacturing, and conducted intensive research on ways to improve print yield.

[Purpose of the invention]

That is, the object of the present invention is (1) to obtain a color negative film with high sensitivity and high print yield. (2) To obtain a color negative film in which the print yield does not decrease over time.

[Structure and effects of the invention]

The object of the present invention is to provide a silver halide color photographic material having at least one red-sensitive layer, green-sensitive layer, and blue-sensitive layer on a support, with a minimum density of yellow, magenta, and cyan color development. (Dmin(Y
), D+win(M), Dmin(C)) simultaneously satisfy the following relationships from ■ to ■.
A silver halide color photographic light-sensitive material having a sensitivity of 300 or more Dmin(C)≦0. 3 0
...(1) Dmin(M) − Dm
in(C)≦0.40 −・・■−0.20≦
D+win(Y)−Dmin(M)≦0. 3 0
...Achieved by ■.

The ISO sensitivity of the photosensitive material referred to in the present invention shall be determined according to the test method shown below. JIS K7614-1
981) (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 condition 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 Relative spectral energy <<1>> 2 8 l4 23 45 57 63 62 Wavelength nll 360 370 380 390 400 410 420 430 Wavelength nm 440 450 460 470 480 490 500 510 520 53・0 54 0 550 560 570 580 590 600 610 Table■ (continued) Relative spectral energy (1) 3l 93 97 98 101 97 100 101 100 104 102 103 100 97 98 90 93 94 Table 1 (continued) Wavelength n+m Relative spectral energy (1) 620
92 630 88 640 89 650 86 660 86 670 89 680 85 690 75 700 77 ■ Illuminance changes on the exposed surface are performed using an optical wedge, and the optical wedge used has a wavelength range of 360 to 700 nm where the spectral transmission density changes at any part. The area where the 400 nm groove is not grooved is within 10%, and the area where the groove is 400 nm or more is within 5%.

■ 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℃2. Bleaching・－＝－・・・１・１・・・－・・・
6 minutes 30 seconds 38.0±3.0°C3. Washing with water...
・・−・−・−−−−−・・ 3 minutes 15 seconds 24-41
゜C4. Fixation 11--1--・1・--・- 6 minutes 3
0 seconds 38.0±3.0°C5. Washing with water------
---------- 3 minutes 15 seconds 24-41°C6.
Stable - - - - - - - - - - - - - - - - - - - - - - - - 1 minute
5 seconds 38.0±3.0°C7. Drying---1---
--11・--------- Below 50°C The composition of the treatment liquid used in each step is shown below.

(Color developer) 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxyamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) (bleaching) Liquid) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and use aqueous ammonia. Adjust pH to 6.0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 liter
and adjust the pH to 6.0 using acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5mf
f Konidax (manufactured by Konica Corporation) 7.5a+
f Add water to make 12.

(4) Concentration measurement The concentration is log. It is expressed as (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. Further, during measurement, the emulsion film surface shall face the light receiving device side. Concentration measurements are performed using Status M concentrations of blue, green, and red, and their spectral characteristics are determined by the light source used for the concentration needle, optical system, optical filter,
The overall characteristics of the photodetector are shown in Table 2. Status M concentration spectral characteristics (logarithmic display, normalized to 5.00) 0.106/nm, blue slope 0.250/nm, red slope 0.040/nm, green slope 0-1
20/nm, blue slope 0.220/nm5) Iso
Determination of sensitivity Using the results of processing and density measurement under the conditions shown in 1) to 4), the ISO sensitivity is determined by the following procedure.

■ 0.15 for each minimum density of blue, green, and red.
The exposure amount corresponding to high density is expressed in units of le nox seconds as HB18G and }IR, respectively.

■ HB, } Set the larger value (lower sensitivity) of IR as HS.

The minimum density values of yellow, magenta, and cyan in the present invention are the minimum density Dm+ used in determining the ISO sensitivity mentioned above.
in(Y). I)+in(M), means Dmin(C). Dmin (C) in the present invention is an optical density of 0.
The present invention cannot be achieved unless it is 30 or less, and preferably 0.
．． It is 25 or less, more preferably 0.20 or less.

Further, in the present invention, the value of Datn (M) - Dmin (C) must be 0.40 or less in optical density difference to achieve the present invention, preferably 0.35 or less, and more preferably 0. It is 30 or less. Furthermore, in the present invention, Dmin(Y)-Dmin(M)
The present invention cannot be achieved unless the optical density difference is in the range of -0.20 to 0.30, and preferably -0. 1
It is in the range of 0 to 0.20, more preferably in the range of -0.05 to 0.10.

The silver halide color photographic light-sensitive material of the present invention has the above-mentioned Dmin(Y), Dmin(M), and Dmin(C).
The yellow, magenta, and cyan densities obtained in the next processing, that is, D mas (Y), D was (M),
The value F (Y), F (M), which is the value obtained by subtracting D was (C),
It is preferable that F (C) satisfies the following relationship.

F (Y) = Dmin(Y) Da+as(Y)
≦0.15F (M) - DIlin (M) - D
i+as(M)≦0.15F(C)=Dmin(
C) - Dmas(C)≦0, l5F (Y), F
(M). F (C) is each more preferably 0.10
It is as follows.

D Iaas (Y), D mas (M), D wa
The processing process for determining s(C) is the same as the processing process for determining ISO sensitivity, changing the color developing solution used in the color development step to the following processing solution A during the processing process for determining ISO sensitivity. The optical density of the sample was determined using a Status M filter.

Treatment liquid A Anhydrous sodium sulfite 4.25 g Hydroxyamine l/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (l hydrate) 2. Add 5 g of water to bring the pH to 112, and use potassium hydroxide to adjust the pH to -
1 0. l l: Adjust.

The silver halide photographic light-sensitive material of the present invention contains cesium 137 (
Using a gamma ray generator using Cs) as a gamma ray source,
After 40 minutes of irradiation at 2.5 mR/IIin intensity, is
o DIIlin obtained by the same operation as the sensitivity determination method
(Y), Dmin (M), and Dmin (C) have a variation range of 0. It is preferably 15 or less, more preferably 0.10 or less, still more preferably 0.05 or less.

It is preferable to use a monodisperse silver halide emulsion in the silver halide color photographic light-sensitive material of the present invention. Monodisperse silver halide emulsion refers to 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, and is preferably 80%
It is more preferably 90% or more.

Here, the average particle diameter d is defined as the particle diameter di when the product ni The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with 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 assumed to be 1000 or more indiscriminately.

Particularly preferred monodispersed emulsions of the present invention have a distribution width defined by deletion of one character of 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 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.

The silver halide emulsion of the present invention 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 45 mol%, more preferably 20 to 42 mol%, particularly preferably 25 to 40 mol%.

The silver halide grains having a high silver iodide content phase inside the grains of the present invention 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. It is.

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 center of the internal high iodide content phase, between the internal high iodide content phase and the intermediate phase, and between the intermediate phase and the outermost phase. You may.

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 intermediate shell is 5 to 60%, and even 20 to 55%, of the entire 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 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 the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship J,>Jx 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. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase 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. This is applied thinly onto a mirror-polished silicon wafer to use as a measurement sample.

For measurements by X-ray photoelectron spectroscopy, for example, P
Using ESCA/SAM5 60 model manufactured by HI Corporation, the experiment 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
, 13d3/2 electrons are detected. The composition ratio is calculated by the relative turbidity coefficient method using the integrated intensity of each peak.

Ag3d, Br3d, 13d3/2 relative sensitivity coefficients are 5.1 0, 0.8 1, 4.59, respectively.
2, the composition ratio is given in units of atomic percent.

■ Silver halide grains that are 80% or more away from the center in the grain diameter direction of silver halide grains using the average silver iodide content (J1) determined by the aforementioned X-ray fluorescence analysis method and the X-ray microanalysis method. When the average value (J,) of the silver iodide content measured on the crystal is compared, the relationship J,>J3 is satisfied.

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/^gLα in advance and using a calibration curve.

■ At the highest peak height X0.13 of the (420) X-ray diffraction signal using CuKα radiation as the radiation source, 1 of the diffraction angle
．． It is characterized by the presence of a signal continuously over 5 degrees or more. More preferably, the signal exists continuously over a diffraction angle of 1.5 degrees or more at the highest peak height of the signal, 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 signal intensity is greater than or equal to the maximum peak height x 0, l3 or x0.15.

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 are the most widely used.

Silver iodobromide has a rock salt structure and has a (420)
Diffraction lines are observed at 2θ7l 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 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.

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 10
It is 0.

The silver halide emulsion of 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 preferable that the value is 1.2 or more and 8. It is preferably less than 0, particularly preferably 1.5 or more and less than 5.0.

A normal monodisperse emulsion is disclosed in, for example, JP-A-59-1775.
No. 35, No. 60-138538, No. 59-522
No. 38, No. 60-143331, No. 60-357
No. 26, No. 60-258536 and No. 61-14
It can be manufactured by referring to the method disclosed in No. 636 and the like.

A monodisperse twin emulsion can be obtained, for example, by referring to the method of growing a spherical seed emulsion disclosed in JP-A-61-14636.

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

As another condition for enlarging the particles, the Photographic Society of Japan
As shown in Makoto on the 8th of the 8th Annual Conference Abstracts, there is a method of enlarging silver halide by adding fine particles of silver halide, dissolving it, and recrystallizing it.

The growth conditions for the silver halide emulsion include pAg 5-1
1. Temperature 40-85°C. ．． pll1.5-12 is preferred.

The photosensitive silver halide emulsion can be chemically sensitized by a conventional method. That is, a sulfur amplification 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.

Photosensitive silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic art as sensitizing dyes. 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 superchromatic sensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

As the mesmerizing pigment, cyanine pigment, merocyanine pigment,
Complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Also known as antifoggants or stabilizers, used during, at the end of, and/or during a stagnation period before application, for the purpose of preventing fog during photographic processing or to maintain stable photographic performance. You can add compounds that are present. Binder (or protective colloid) for silver halide emulsion
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or 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 capable of hardening the photosensitive material to such an extent that it is not necessary 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 (dimethylol urea, 'methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1, 3, etc.). 5-triacryloyl-hexahydro-s-triazine,
1,3-vinylsulfonyl-2-propanol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

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 plasticizers 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 poorly soluble synthetic polymer for the purpose of improving dimensional stability.

When using the emulsion according to the present invention in a color photosensitive material,
In the color development process for the emulsion layer, a color coupler is used which forms a dye by performing a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, a ρ-phenylenediamine derivative or an aminophenol derivative). 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 for the red-sensitive emulsion layer, and a cyan coupler is used for 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.

A color coupler has a color correction effect and is combined with an oxidized form of a developing agent to produce 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 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 bivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat.
No. 83, JP-A No. 58-95346, etc.

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

Specific examples of magenta couplers that can be used include, for example, U.S. Pat. No. 3,891,445, West German Patent No. 1,810,464, West German Patent Application No. No. 408, 665,
Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 53-55122,
Examples include those described in .

As the cyan coupler, phenol or naphthol couplers are generally used. Preferred examples of cyan couplers that can be used include those described in U.S. Pat.

Hydrophobic compounds such as color-forming couplers, colored couplers, DIR compounds, image stabilizers, color fog preventive agents, ultraviolet absorbers, and optical brighteners that are 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 inhibitor can be used to prevent oxidized developing agents or electron transfer agents from moving between emulsion layers of a light-sensitive material, causing color turbidity, deterioration of sharpness, and conspicuous graininess. .

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 the protective layer and intermediate layer of the photosensitive material contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent deterioration of the image due to ultraviolet rays. Good too.

To prevent deterioration of magenta couplers and the like due to formalin during storage of photosensitive materials, formalin scavengers can be used in photosensitive materials. Compounds that change 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. Preferably as a development accelerator, the compounds that can be used are the compounds described in Sections B-D of Section XXI of R017643, and the development retardant is
This is a compound described in No. 3, Section XXI, Section 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 luminescent material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing brightness, increasing contrast, or promoting development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, etc.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

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.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
It can be added to matting agents for the purpose of preventing luminescent materials from sticking to each other.

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 opalescent layer is not laminated, and may be used as a protective colloid in the emulsion layer and/or the emulsion layer other than the emulsion layer in the case where the emulsion layer is laminated on the support. May be used for layers. Preferably used antistatic agents are the compounds described in RD 17643 X■.

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.

Supports used in the luminescent material of the present invention include paper laminated with α-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), flexible reflective supports such as synthetic paper, and acetic acid. Films made of semi-synthetic or synthetic polymers such as cellulose, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports made of these films with reflective layers, glass, metals, and ceramics. etc. are included.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet 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 does not impose any restrictions on the arrangement of these layers on the support. isn't it.

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 water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleaching solution and the process using a fixing solution. In addition, a bleach-fixing process can be carried out using a one-bath bleach-fix solution, or color development, bleaching, and fixing can be carried out in one bath.
A monobath processing step using a bath development bleach-fix processing solution can also be carried out.

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

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per unit unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Example 1 Multilayer color photographic material Sample-101 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side. Sample 101 1st layer: Antihalation layer (HC-1) Black colloidal silver 0.2 UV absorber (UV-1)
0.23 High boiling point solvent (Oil 1)
0.18 gelatin
1.4 2nd layer: First intermediate layer (IL-1) Gelatin 1.3 3rd layer: Low-temperature red-lighting emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.4 μm) 1. 0 Exacerbating Dye (SD-1) 1. 8 x 10-' moles/silver 1
Molar sensitizing dye (SD-2) 2. 8 x 10-
'mol/silver 1 mol Sensitizing dye (SD-3) 3. O
X 10-' mole/silver 1 mole cyan coupler (C-1
) 0.70 colored cyan coupler (C
C-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. 4th layer: Medium red-sensitive emulsion layer (RM) Silver iodobromide emulsion (average grain size 0.7 μm) 0.8 Sensitizing dye (SD-1) 2. I x LO-' mol/silver 1
Molar sensitizing dye (SD-2) 1. 9 x 10-'
Mol/1 mole of silver Confusing dye (SD-3) 1. 9 X
IO-' 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 (Oil-1)
0.26 gelatin
0.6 5th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.8 μm) 1.70 Sensitizing dye (So-1) 1. 9 x 10-' mol/silver 1 mol sensitizing dye (SD-2) 1. 7 x 10-
'mol/silver 1 mol Sensitizing dye (SD-3) 1. 7
XIO-' mole/silver 1 mole cyan coupler (C-1)
0.05 cyan coupler (C-2)
0.10 colored cyan coupler (CG-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) Gelatin 0.8 7th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 1.1 Sensitizing dye (S Rho 4) 6.8xlO-' mol/silver 1 mol Sensitizing dye (S Rho 5) 6.2 x 10-' mol/silver 1 mol Mazenk coupler (M-1) Magenta coupler CM-2) Colored magenta coupler -(CM-1)DIR compound (
D-2) DIR compound (D-3) High boiling point solvent (Oil-2) Gelatin 8th layer: medium-sensitivity green-sensitive emulsion layer CGM) Silver iodobromide emulsion (average grain size 0.7 μm) 0.7 sensitization Dye (SD-6) 1. 9 XIO-'mol/silver 1
Molar sensitizing dye (SD-7) 1.2XlO-'mol/
Silver 1 mole sensitizing dye (SD-8) 1. 5 XIO-
'mol/silver 1 mole magenta coupler (M-1)
0.07 magenta coupler (M-2) 0
．． 03 Colored Magenta Cobbler (CM-1) 0
．． 0 4DIR compound (D-2) 0.
018 High boiling point solvent (Oil-2) 0.3
0 Gelatin 0.8 9th layer:
High sensitivity green sensitive emulsion layer (OH) Silver iodobromide emulsion (average grain size 1.Ollm) 1.70.
54 0. l9 0.06 0.017 0. OI O. 81 1.8 Sensitizing dye (SD-6) 1. 2 X 10-4 mol/silver mol sensitizing dye (SD-7) l. O x 1
0-4 mol/silver mol sensitizing dye (SD-8) 3.
4 X 10-6 moles/l mole of silver 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)
0.3 1 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 (O
il-2) 0.1 3 gelatin
0.7 Formalin scavenger (HS-1) 0.0 9 Formalin scavenger (HS-2) 0.0 7 11th layer: Low sensitivity emulsion layer (BL) Sensitizing dye (SD-9 ) 5.2
X 10-4 mol/silver 1 mol sensitizing dye (SD-10)
L. 9 x 10-5% l/silver 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 (l{S-1
) 0. 0 8 12th layer: Highly sensitive blue-sensitive emulsion layer (
BH) Silver iodobromide emulsion (average grain size 1.0 μm) 1.0
Sensitizing dye (SD-9) 1. 8 x 10-' moles/silver 1 mole enhancing dye (Sn-10) 7. 9xlO
-' mol/silver 1 mol Yellow coupler (Y-1)
0.15 Yellow Cabler (Y-2)
0.05 high boiling point solvent (Oil-2)
0.0 7 4 Gelatin 1
．． 30 Formalin Scavenger (HS-1) 0
．． 05 Formalin Scavenger (FIS-2)
0. 1 2 13th layer: 1st protective layer (Pro −
1) Fine grain silver iodobromide emulsion 0. 4
(Average particle size 0.08 μm, Agl mol%)
Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) High boiling point solvent (Oi!-1) High boiling point solvent (Oil3) Formalin scavenger (Its-1) Formalin scavenger (HS- 2) Gelatin 14th layer: 2nd protective layer (Pro-2) 0.10 0.07 0.07 0.13 0.37 1.3 Slip agent (WAX-1) 0.04 Gelatin 0.6 Improvement In addition to the composition, coating aid Su-1, dispersion aid Su-2, viscosity regulator,
Hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, Mw: 10.000 and ■Ma: 1
, 100. Two types of AF-2 of 000 were added.

The emulsion used in the above sample is as follows.

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

Each emulsion was optimally gold-sulfur sensitized.

C-1 C-2 0I M-1 LIJt M-2 Y 2 CC ■ n' HaaU35 SLI3Na CM 1 D-1 0H D-2 D 3 Oil -1 0H 01J υn Oil =2 SC-1 UV- 1 0 ■ Shi41'Iq (tno UV-2 WAX 1 Weight average molecular weight Mw=3.000 Su-1 NaOzS CHCOOCsH+t CH1COOCsH+? Su-2 HS-1 HS-2 SD-1 SD-2 SD-3 SD-4 SD -5 SD-6 SD-7 SD-8 SD 9 SD 10 H-1 H-2 (CHz = CHSOzCHz) z0ST-1 AF-1 AF-2 Next, the 5th layer, 9th layer, and 9th layer of sample-101 Samples 102 and 103 were created in which the 12 layers were changed as follows.

Sample 102 5th layer: High intensity red emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) 1.70 sensitizing dye (SD-1) 1. 9 XIO-'mol/silver 1
Molar sensitizing dye (SD-2) 1. 7 X 10-' mol/ml mol sensitizing dye (SD-3) 1. 7 XI
O-' mole/silver 1 mole cyan coupler (C-1)
0.04 cyan coupler (C-2)
0.09 colored cyan coupler (CC-1)
0. 0 20IR compound (D-1)
0.025 high boiling point solvent (Oi!-1)
0.17 Gelatin 1.2 Sample 102 9th N: High-sensitivity glaucoma emulsion layer (G}I) Silver iodobromide emulsion (
Average grain size 0. 9 μm) 1.7 sensitizing dye (SD-6
) 1.2 XIO-' mol/silver 1 mol sensitizing dye (S
D-7) 1. OX10-' mol/silver 1 mol sensitizing dye (SO-8) 3. 4 XIO-' mole/silver 1 mole magenta coupler CM-1) 0.08 magenta coupler (M-3) 0.03 colored magenta coupler (CM-1) 0. 0 4 High boiling point solvent (Oil-2) 0.31 Gelatin
1.2 Sample 102 12th layer: Highly sensitive blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (
Average particle size 0. 9 μm) 1.0 sensitizing dye (SD-9
) 1. 8 X 10-' moles/silver 1 mole sensitizing dye (SD-10) 7. 9 XIO-5 mole/silver 1 mole Yellow coupler (Y-1) 0.13 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-2) 0.0 7 4 Gelatin 1.30 Formalin scavenger (HS-1) 0. 0 5 formalin scavenger (l{S-2) 0. 1 2 Sample 103 5th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) 1, 3 sensitizing dye (SD-1) 1. 9 x 10-' mol/silver 1
Molar enhancing dye (SD-2) 1.7X10-'mol/
Silver 1 mole enhancing dye (SD-3) 1. 7 x 10
- 'mol/silver 1 mole cyan coupler CC-1)
0.05 cyan coupler (C-2)
0.10 colored cyan coupler (CC-1)
0. 0 2DIR compound CD-1)
0.025 high boiling point solvent (Oil-1)
0.17 Gelatin 1.2 Sample 103 9th layer: High brightness green-sensitive emulsion layer (GH) Silver iodobromide emulsion, (average grain size 0.9 μm) 1.3 Multiplying dye (SD-6) I. 2 XIO-'mol/l
! 1 mole sensitizing dye (SD-7) 1. O x 10
-' mol/silver 1 mol Sensitizing dye (SO-8) 3. 4
xlO-”mol/!]!1mol Magenta coupler (M
-1) 0.09 Magenta Cobra (M-3)
0.04 Colored Magenta Coupler (CM-
1) 0. 0 4 High boiling point solvent (Oil-2)
0.31 gelatin
1.2 Sample 103 12th layer: High-sensitivity blue-bewitching emulsion layer (BH) Silver iodobromide emulsion (
Average particle size: 0.9 μm) 0.8 sensitizing dye (so-9)
! ．． 8 xlO-' mol/silver 1 mol aggravating dye (S
D-10) 7. 9 XIO-' mol/silver 1 mol Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-2) 0.0 7 4 Gelatin 1.30 Formalin scavenger (HS -1) 0. 05 Formalin Scavenger (HS-2>0.1 Second) Sample 104 was prepared with the following configuration.

1st layer; antihalation layer black colloidal silver gelatin 2nd layer; intermediate layer 2,5-di-t-pentadecylhydroquinone EX-1 EX-3 U-1 U-2 HBS-1 HBS-' 2 Gelatin third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.70μ) Sensitizing dye 1 6.9X 10-' mol/Silver sensitizing dye II l. 8X 10-'mol/silver sensitizing dye DI 3. IX 10-' mol/silver 0.18 0.40 0.18 0.07 0.02 0.08 0.08 0.10 0.02 l. 04 0.50 1 mol 1 mol 1 mol Sensitizing dye IV 4. OX 10-'mol/silver 1
Mol 0.350 0.005 0.012 Gelatin 1.08 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.7 Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX- 1 0 HBS-2 5th gelatin layer (3rd red-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.00μ) 1.44 Sensitizing dye II 5. 4 x l O-5 mol/silver 1 mol EX- 2 l.08 1 mol 1 mol 1 mol 1 mol 0.300 0.050 0.004 0.050 1.17 5 μ) 5. lX 10-' moles/silver 1.4X 10-' moles/silver 2.3X 10-' moles/silver 3. OX 10-' mol/silver HBS-1 Sensitizing dye It l. 4X 1 Sensitizing Dye I[1 2.4X 1 Sensitizing Dye IV 3. lX I EX- 5 EX- 3 EX-4 EX-11 HBS-1 Gelatin 6th layer (intermediate layer) HBS-20.01 Gelatin EX- 1 2 7th layer (first glaucoma emulsion layer) Silver iodobromide Emulsion (average grain size 0.65μ) Sensitizing dye X l. 5X1 sensitizing dye V 3. OX1 Sensitizing dye Vl l. OXl Sensitizing dye ■ 3.8Xl 0-5 mol/silver 1 mol 0-4 mol/silver 1 mol 0-5 mol/silver mol 0.150 0.055 0. B60 0.005 0.32 1.47 1.06 0.02 0.36 0''' mole/silver 1 mole o-' mole/silver 1 mole 01 mole/silver 1 mole 0-4 mole/silver 1 mole R-4 EX-6 EX- 1 EX-7 EX-8 HBS-1 HBS-4 Gelatin 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.70μ) Sensitizing dye X l.OXl Sensitizing dye V 2.1Xl Sensitizing dye VI 7.OXl Sensitizing dye ■ 2.6X I R-4 EX-6 EX-8 EX- 1 EX-7 0.017 0.260 0.021 0 .030 0.025 0.100 0.060 0.68 0.72 0-5 mol/silver 1 mol 0-5 mol/silver 1 mol 0-5 mol/silver 1 mol O-4 mol/silver 1 mol 0 .019 0.150 0.010 0.008 0.012 HBS-1
0.60HBS-
4 0
．． 050 gelatin 0.99
9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.0μ) 1.08 sensitizing dye X l. 2x l O-' mol/silver 1 mol sensitizing dye v 3.5x l O-' mol/silver 1 mol sensitizing dye Vl 8. OX l O-' mol/silver 1 mol sensitizing dye■ 3. OX l O-' mol/silver 1 mol EX-a O. 06
5EX-1 0.0
25HBS-2 0.5'5
Gelatin 1.57th lθ layer (yellow filter layer) Yellow colloidal silver 0.05E
- 1 2 0.04H
BS-1 0.02
Gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 0.6μ) Sensitizing dye ■ 3.5X 1 0 EX-9 EX-8 EX-11 HBS-1 Gelatin 12th layer (211r emulsion layer) Silver iodobromide emulsion (average grain size 0.80μ) Sensitizing dye■ 2. lX 10 EX-9 EX-10 HBS-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (average grain size 1.2μ) Sensitizing dye ■ 2.2X 10 0.22 4 mol/silver 1 mol 0.85 0.12 b. 030 0.28 1.15 0.41 1 mole/1 mole of silver 0.20 0.015 0.03 0.41 0.69 4 mole/1 mole of silver EX-9 HBS-1 Gelatin 14th layer (first Protective layer) Silver iodobromide emulsion (average grain size 0.07 μm) U-1 U-2 HBS-1 Gelatin 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) S-1 S -2 In addition to the above-mentioned components, gelatin-1 and H-2, an antifoggant AF, and a surfactant were added to each layer of gelatin.

0.20 0.07 0.62 0.07 0.11 0.17 b. 90 l. B0 0.54 0.05 0.05 0.72 Tin hardening agent H 1, AF-2 Structure of compound used in Examples EX 1 EX-2 0H EX-3 0H SO. Na SO. Na EX-4 0H EX 5 0■ EX 6 EX-7 EX-8 EX-9 EX-10 EX- 1 1 OH SCIhCHtCOOCH3 0H HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate HBS-3 Bis(2- ethylhexyl) phthalate HBS-4 H-1 OF[ H-2 CIb=CH-SOx-C}IzCONH CHzl Cll! =CH-Sow-CH2-CONH-CHzS
-1 S 2 Exacerbating dye ■ ■ (CHi)nsO3N&R 4 0H AF- 1 AF 2 Furthermore, sample 105 was prepared with the following configuration.

1st layer; antihalation layer (HC-1) black colloidal silver 0.18 UV absorber (UV-
1) 0.29 high boiling point solvent (Oil-1)
0.23 High boiling point solvent (Oil-2)
0.0 1 1 Colored magenta coupler (CM-3) 0.011 Gelatin 1.57 Second layer;
First intermediate layer (IL-1) Third gelatin layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.4 μm) 1.27 0.80 Silver iodobromide emulsion (average grain Diameter 0.7μm) 1.21 Sensitizing dye (SD-1) 1.3X10-S (mol/silver 1 mol) Sensitizing dye (SD-2) 2.2X10 (mol/silver 1 mol) Sensitizing dye ( SD-3) 2.2xlO-'(
1.21 (C(,-1)0.032 0.05 1.04 2.00 Cyan coupler (C-1) Colored cyan coupler DIR compound (D-1) High boiling point solvent (Oil -1) Gelatin 4th layer; 2nd intermediate layer (IL-2) Gelatin 0.80 5th layer;
High-temperature red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.3 μm) 0.30 silver iodobromide emulsion (average grain size 0.7 μm) 0.54 silver iodobromide emulsion (average grain size Diameter: 1.2 μm) 1.61 Sensitizing dye (SD-1) 7.1X10-' (mol/silver 1 mole) Enhancing dye (SD-2) 1.2X1 0-
'(mol/1 mole of silver) Sensitizing dye (SD-3) 1.2X10-'(
mol/1 mol of silver) Cyan coupler (C-1) 0.05 Cyan coupler (C-2) 0.19DIR compound (D-3) 0.0066DI
R compound (D-1) 0.007
6 High boiling point solvent (Oil-1) 0.28 Gelatin 1.37 6th layer; 2nd intermediate layer (IL-2) Gelatin 0.80 High boiling point solvent (Oil 2) 0.08SC-2
0.071 7th layer; low sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 0.46 Silver iodobromide emulsion (average grain size 0.7 μm) 0.69 Sensitization Dye (SD-4) 2.7X1 0-' (mol/
1 mol of silver) Sensitizing dye (SD-5) 2.5xl O-'
(mol/silver mol) Sensitizing dye (SD-7) 8. Oxl O-'
(mol/silver mol) Enhanced dye (SD-8) 1.9X1 0-'
(Mole/1 mole of silver) Sensitizing dye (SD-1 1) 1.4X1 0
-' (mole/l mole of silver) Magenta coupler (M-3) 0.34 Colored magenta coupler (CM-3) 0. 0 4 8 DIR compound (D-3) 0.00
25DIR compound (D-4) 0.013
DIR compound (D-2) 0.02 High boiling point solvent (Oi1-4) Gelatin 8th layer; 3rd intermediate layer (IL-3) High boiling point solvent (Oil-1) Gelatin 9th layer; High sensitivity green sensitivity Emulsion layer (G}{) Silver iodobromide emulsion (
Average particle size 0. 7μm) 0.38 0. 1 7 1.13 0.83 0.56 Silver iodobromide emulsion (average grain size 1.2 μm) 2.26 Sensitizing dye (SD-11) 4,5X10-5 (mol/silver 1 mol) Enhanced color I ' (SD-6) 9.6X1 0
-' (mol/silver 1 mol) Exacerbating dye (SD-7) 8.8X1 0-'
(mol/silver 1 mol) Aggravating dye (SD-8) 1.4X10-'(
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 (Oil-2) 0.57
Gelatin 1.97 10th layer; Yellow filter layer (yc) Yellow colloid lli!
0. 0 5 color stain prevention agent (S
C-2) O. 054 High boiling point solvent (Oil
-2) 0.0 6 3 gelatin
0.49 formalin scavenger
(MS-1) 0.08 Formalin scavenger (MS-2) 0. l0 11th layer; low sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (
Average particle size 0. 4 μm) 0.226 silver iodobromide emulsion (
Average particle size 0. 7 μm) 0.239 sensitizing dye (SD
-12) 5.5xlO-' (mol/silver 1 mol) Sensitizing dye (SD-1 0) 5. OX1 0-
'(Mole/1 mole of silver) Yellow coupler (Y-1) 0.99 Yellow coupler (Y-2) 0.085DIR
Compound (D-1) 0.012 High boiling point solvent (Oil-2) 0.25 Gelatin
1.60 Formalin scavenger (I{S-1) 0.12 Formalin scavenger (HS-2) 0.29 12th layer; High sensitivity blue angry emulsion layer (BH) Silver iodobromide emulsion (
0.20 silver iodobromide emulsion (average grain size 0.7 μm) 0.20 silver iodobromide emulsion (average grain size 1.2 μm) 0.80 sensitizing dye (SD-12)
2. oX1o-' (mol/silver ■mol) Exacerbating dye (SD-1 0) 4.8XI O-
'(Mole/1 mole of silver) Yellow coupler (Y-2) 0.27 High boiling point solvent (Oil-2) 0.17 Gelatin 1.22 Formalin scavenger (HS-2) 0. 0 8 3 13th layer; 1st protective layer (Pro Fine grain silver iodobromide emulsion (average grain size 0.08μtn Agl Isodene absorber (UV-1) Isoeite absorber (UV-2) High boiling point solvent (Oil -1) 1) 0.4 1 mol%) 0. 0 5 8 0. 0 B 3 0.06 High boiling point solvent (Oil 3) 0.06 Formalin scavenger (HS-1) 0. 0 4 7 Formalin scavenger (HS-2) 0.22 Gelatin 1.49 14th layer; 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μs) O. I 2 Polymethyl methacrylate (average particle size 3 μn+) 0.018 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, viscosity regulator, hardening agent H-1 , H-2, stabilizer ST-1, antifoggant AF-1, and AF-2 of t, too, ooo were added.

The emulsion used in the above sample is as follows.

The average grain size is expressed as the long side grain diameter converted to a cube with the same volume. Each emulsion was optimally gold-sulfur sensitized.

M-4 CM 2 CM- 3 D-4 D 5 0I+ 0I Off-4 nI+ SC-2 0H SD-11 SD-12 The detailed explanations for samples 101 to 105 obtained in this way are as follows. According to the ISO sensitivity determination method, each sample 1
I decided on 30 sensitivity. At this time, Dmin(Y)Dmin(M), Dii mentioned in the detailed explanation of each sample.
n(C) was determined. Next, F(Y), F(M), and F(C) were determined using the method described in the detailed explanation. Next, Dmtn (Y, M, C
), as described in the detailed explanation, using 137Cs as a radiation source (100 mR irradiation), and Dm according to the rso sensitivity determination method.
in(Y). Dmin(M). Dmin(C)
was determined and obtained. Furthermore, each sample was divided into two parts, one of which was used as it was, and the other part was irradiated with 100 mR of r L'A, and 500 scenes of each were actually photographed using a compact camera Z-up80Rc manufactured by Konica. This sample
A negative film was obtained by carrying out the same development process as in the No. 30 determination method.

Ten print workers were asked to observe the negative films and rank them in order of relative ease of printing. (Negatives with fewer seats are easier to print).

Furthermore, using this negative, Konica NPS CLP-200
Print exposure was performed using an OL printer, and prints were obtained using Konica's paper processing process CPK-18.

Five panelists discussed and determined the ratio of prints that produced the best results.

The above results are summarized in a table.

As shown in the table, the print yield of the samples of the present invention is higher than that of the comparative samples, and the difference is particularly noticeable in evaluations using samples after γ-ray irradiation.These are negatives that are easy to judge as negatives when using a printer. It was shown that Dmin(C)≦0.40 and Dmin(M) Da+in(C)≦0.40 and −0.20≦D min (Y) − D IIIi
It was a material of ISO 300 or higher with n(M)≦0.30. Also, F(Y), F(M),
F(C)≦0.20, and ΔDIIlin(Y)
, ΔD+nin(M). It was found that it is additionally characterized by the feature that ΔDmin(C)≦0.15.

Example 2 The evaluation conducted in Example 1 was carried out under the following conditions.

Note that the processing is performed at a rate of 3 times the capacity of the stabilizing tank. The tank was replenished, and the overflow flowed into the tank in front of it.

In addition, part of the overflow of the stabilization tank following the fixer tank (
2 7 5 IIIl/n? ) was poured into a stabilizing tank.
The composition of the color developing solution used is as follows.

Potassium carbonate 30 g Sodium bicarbonate 2.7 g Potassium sulfite 2.8 g Sodium bromide 1.3 g Hydroxylamine sulfur FIR salt 3.2 g Sodium chloride
0.6g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfur salt 4.6
g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.3g Add water to 1 liter, and add potassium hydroxide or 20% sulfuric acid.
tno. Adjust to ot.

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

Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite 7 g Sodium bromide
0.5g hydroxylamine sulfate 3.2g 4-amino-3-methyl-N-
Ethyl-N-(β-hydroxylethyl)aniline 6M
M salt 5. Q gdiethylenetriaminepentaacetic acid
3.0g potassium hydroxide
Add 2g water to make 12, and use potassium hydroxide or 20% sulfuric acid to make pFI10. Adjust to 12.

The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3 diaminopropane tetraacetate 0.35 mole Disodium ethylenediamontetraacetate 2g ammonium bromide 150g glacial acetic acid
40II11 Ammonium nitrate
Add 40g water and 1! 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.

1.3 Diaminopropanetetraacetic acid ferric ammonium 0.40 mole Disodium ethylenediamontetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid
61 If water is added to make if, the pH is adjusted to 3.5 using ammonia water or glacial acetic acid, and adjustment is made as appropriate to maintain the pi+ of the bleach tank liquid.

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

Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Water was added to make 700 Ill1, and the pFI was adjusted to 6.5 using glacial acetic acid and aqueous ammonia. do.

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

1.2penzisothiazolin-3one 0.1g2
．． 0mf Hexamethylenetetramine 0.2g Hexahydride-1.3.5-tris(2-hydroxyethyl)-5-triazine 0.3g Water was added to make 12, and using potassium hydroxide and 50% sulfuric acid pH
Adjusted to 7.0.

The results were similar to those in Example-1.

Out wish Man Konica Co., Ltd.

Claims (1)

[Scope of Claims] In a silver halide color photographic material having at least one red-sensitive layer, green-sensitive layer, and blue-sensitive layer on a support, the minimum density of yellow, magenta, and cyan color development ( Dmin(Y), Dmin(M), respectively
A silver halide color photographic light-sensitive material having an ISO sensitivity of 300 or more, characterized in that Dmin(C)) satisfies the following relationships (1) to (3) at the same time. Dmin(C)≦0.30...(1) Dmin(M)-Dmin(C)≦0.40...(2
) −0.20≦Dmin(Y)−Dmin(M)≦0.3
0...(3)