JP2001174959A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in scene depicting power, particularly a silver halide color photographic sensitive material which increases the volume of information on the greens of trees, etc., enhances color reproducibility, is excellent in distant view depicting power and attains stable hue reproduction of neutral colors (black and gray). SOLUTION: The silver halide color photographic sensitive material has at least one yellow coupler-containing blue-sensitive layer, at least one magenta coupler-containing green-sensitive layer and at least one cyan coupler-containing red-sensitive layer each containing a surface latent image type silver halide emulsion and at least one infrared sensitive layer containing an infrared sensitized internal latent image type silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material having improved color reproduction, and more particularly, to a halogenated light-sensitive material which is excellent in reproducibility and reproducibility of green color of plants and neutral color (gray). It relates to a silver photosensitive material.

[0002]

2. Description of the Related Art Various technical improvements have been made to silver halide color photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials, color light-sensitive materials or color films) since the launch of Kodachrome by Eastman Kodak Company in 1935. The result is a dramatic improvement in quality. The quality improvement of the color light-sensitive material includes miniaturization of the image structure, more specifically, improvement of granularity and sharpness, improvement of color reproducibility, and the like. Among them, various innovative technologies have been proposed, particularly in the technology for improving color reproducibility, and the image quality has been drastically improved each time.

One example is the proposal of a colored coupler having an automask function (described in US Pat. No. 2,455,170). At present, colored couplers are widely used mainly for improving color reproducibility of color negative films. The colored coupler has an effect of compensating for illegal absorption (secondary absorption) of the coloring dyes of the yellow, magenta, and cyan couplers used in the color film. By employing this colored coupler, it was possible to compensate for the illegal absorption of the coloring dye of the color negative film in an image-wise manner, and as a result, it was possible to greatly improve the color reproducibility.

[0004] In particular, in the case of a color negative film, from the viewpoint of realizing more vivid color reproducibility, a means for enhancing a development effect, that is, a multilayer effect, has been proposed in Belgian Patent No. 710,344 and German Patent No. 2,043. 9
No. 34 etc.

Further, as one of the techniques for improving the layering effect, there is a so-called DIR coupler, which is an inhibitor releasing coupler disclosed in US Pat. No. 3,277,554. The development of this DIR coupler has realized a significant improvement in color purity reproducibility.

In color films, as described above, while aiming for vivid color reproduction with higher saturation,
Several technical means have been proposed for achieving faithful color reproduction as seen by humans. One example is disclosed in
This is a method for optimally controlling the spectral sensitivity distribution of a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer of a color film disclosed in -150411 and the like. Some techniques for improving color reproducibility that focus on the fact that the spectral sensitivity distribution of the cone of the human eye and the spectral sensitivity distribution of a color film are different have also been proposed. In general, the spectral sensitivity distribution of a color film is such that the blue photosensitive layer has a sensitivity maximum at a long wavelength, the green photosensitive layer has a sensitivity maximum at a slightly longer wavelength, and the red photosensitive layer has a considerable sensitivity compared to the spectral sensitivity distribution of the human eye. Has maximum sensitivity to long waves. Further, the red cone of the human eye has a region having a negative sensitivity near 500 nm. Means for adjusting the spectral sensitivity distribution of a color film to the spectral sensitivity distribution of the human eye is disclosed in
It is disclosed in, for example, US Pat. Specifically, by skillfully controlling the spectral sensitivity distribution of the sensitizing dye and the layering effect using a so-called donor layer, intermediate colors, which had been difficult to reproduce up to now, can be reproduced to some extent. With the development of the above technology, the color reproducibility of the color film has made it possible to reproduce the hue of the subject more faithfully, but on the other hand, in the reproduction of specific colors,
Conversely, color distortion results.

As described above, the color reproducibility of a color film has been steadily developed by various innovative technical proposals, but from the viewpoint of ideal color reproduction, it still satisfies the user's requirements sufficiently. It is not possible, and there is a continuing demand for further improvement in color reproducibility.

[0008] One example of the reason is that when a general user photographs a subject with a color film and obtains the color print, there is often an opportunity to feel disappointed with the quality. In particular, many cases in which the general user feels disappointed include, for example, photographing fresh green trees, red flowers, distant mountains, and the like. When I shot these scenes and got the finished print, I found the gaps I expected or remembered, specifically the dullness of fresh green trees, the loss of subtle gradations of red flower petals, Many users feel disappointed because they become so-called red blinds, and the distant mountains look hazy and lose their three-dimensional effect as if they were actually seen.

Thus, for a color film,
Simply achieving faithful and vivid color reproduction is not enough to respond to user demands, and the scene when shot is sharper and the image rendering power beyond expectations is strongly required. Is coming.

In view of such circumstances, Japanese Patent Application No. 9-17 / 1997.
No. 9656 discloses that a new infrared-sensitive layer is provided, and the image information of this infrared-sensitive layer is added to an existing visible image to increase the amount of information and improve specific color reproduction. I have. As a result, the amount of information was dramatically increased, and although reproducibility of green leaves and the like was surely improved, it was found that there was a problem in color stability. For example, when a red flower is photographed, the infrared-sensitive layer is exposed to both green leaves and red petals. As a result, when a magenta coupler is incorporated in the infrared-sensitive layer, the color reproduction of a red flower is deteriorated, and when a cyan coupler is incorporated, the color reproduction of a green leaf is deteriorated. . In addition, when both magenta and cyan couplers are used, both of them are deteriorated, and there is an urgent need for technical development that satisfies both.

In addition, when an infrared-sensitive layer containing a coupler is provided, a part of an object which looks gray to human eyes, the color of the object having reflection in the infrared wavelength region is changed to the infrared-sensitive layer. It was found that the hue was changed to a complementary color of the color coupler contained in the layer. For example, some clothes that look black to the human eye have strong reflections in the infrared wavelength range, and when taken with a color film that has an infrared-sensitive layer, the black clothes become greenish. It has a drawback.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in depiction of scenes, more specifically, information such as green of trees. An object of the present invention is to provide a silver halide color photographic light-sensitive material which is improved in quantity and color reproducibility, is excellent in distant view descriptive power, and has stable hue reproduction of neutral colors (black and gray).

[0013]

The above objects of the present invention have been attained by the following constitutions.

1. An infrared-sensitized internal latent image comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler each containing a surface latent image type silver halide emulsion; A silver halide color photographic material having at least one infrared-sensitive layer containing a silver halide emulsion.

2. 2. The silver halide color photographic material according to claim 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having a spectral sensitivity in a blue light sensitive region.

3. 2. The silver halide color photographic light-sensitive material according to item 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having spectral sensitivity in a green light-sensitive region.

4. 2. The silver halide color photographic material according to claim 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having a spectral sensitivity in a red-sensitive region.

5. 5. The silver halide color photographic material as described in any one of items 1 to 4, wherein the infrared-sensitive layer contains a magenta coupler.

6. The infrared-sensitive layer is a yellow coupler,
5. The silver halide color photographic light-sensitive material as described in any one of the above items 1 to 4, which contains a magenta coupler and a cyan coupler.

[7] FIG. The relationship between the maximum yellow density (D _Y ), the maximum magenta density (D _M ), and the maximum cyan density (D _C ) of the infrared-sensitive layer after the color development processing is 0.1 ≦ D _M −D _Y ≦
The silver halide color photographic light-sensitive material according to the item 6, characterized in that 0.5 and is _{0.1 ≦ D M -D C ≦ 0.5} .

8. A silver halide color photographic light-sensitive material comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler each containing a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material, wherein at least one of the blue-sensitive layers contains an infrared-sensitized internal latent image type silver halide emulsion.

9. A silver halide color photographic light-sensitive material comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler each containing a surface latent image type silver halide emulsion. A silver halide color photographic material, wherein at least one of the green photosensitive layers contains an internal latent image type silver halide emulsion sensitized by infrared rays.

10. A silver halide color photographic light-sensitive material comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler each containing a surface latent image type silver halide emulsion. Wherein at least one of the red-sensitive layers is
A silver halide color photographic material containing an internal latent image type silver halide emulsion sensitized by infrared rays.

11. A surface latent image type silver halide emulsion having a spectral sensitivity in a visible light region contained in at least one of a blue light-sensitive layer, a green light-sensitive layer, a red light-sensitive layer, and an infrared light-sensitive layer is a silver haloiodide Wherein said emulsion is an emulsion.
Item 10. The silver halide color photographic light-sensitive material according to any one of items 0 to 10.

12. Silver halide having at least one photographic constituent layer comprising a yellow photosensitive layer containing a yellow coupler, a green photosensitive layer containing a magenta coupler and a red photosensitive layer containing a cyan coupler, each containing a surface latent image type silver halide emulsion. In a color photographic light-sensitive material, the infrared-sensitive layer has two infrared-sensitive layers having a center-of-gravity wavelength of a spectral sensitivity distribution having a longer wavelength of 30 nm or more than the center-of-gravity wavelength of the spectral sensitivity distribution of the red-sensitive layer. A silver halide color photographic light-sensitive material characterized in that one contains an infrared-sensitized internal latent image type silver halide emulsion and the other contains a yellow coupler, a magenta coupler and a cyan coupler.

Hereinafter, the present invention will be described in detail. In the present invention, the infrared-sensitive layer means a layer containing a silver halide emulsion having a maximum photosensitive wavelength in a wavelength region longer than the photosensitive wavelength of 400 to 680 nm, which is a visible region.
The photosensitive wavelength range of the infrared-sensitive layer is 690 nm or more and 850 n.
m or less, more preferably 730 nm or more and 780 nm or less.

The photographic material of the present invention is characterized by using an internal latent image type silver halide emulsion sensitized by infrared rays.

The non-pre-fogged internal latent image type silver halide grains which can be used in the light-sensitive material of the present invention include:
An emulsion containing silver halide grains which mainly forms a latent image inside the silver halide grains and has most of the photosensitive nuclei inside the grains is preferred.

The internal latent image type silver halide emulsion and the surface latent image type silver halide emulsion in the present invention are defined and classified by the following methods.

The silver halide emulsion has a coating silver amount of about 1-3.
Apply to a transparent support to a range of 5 g / m ² , expose a portion of the sample over a defined period of time from about 0.1 seconds to about 1 second on a light intensity scale, substantially The same sample as described above was exposed similarly to the maximum density obtained when developing at 20 ° C. for 4 minutes using the following surface developer A that does not contain a silver halide solvent and develops only the surface image of the grains. Develop the image inside the particles with the following internal developer B
It can be determined by comparing with the maximum density obtained when developing at 0 ° C. for 4 minutes. That is, an emulsion in which the ratio represented by the maximum density in the surface developer A / the maximum density in the internal developer B is less than 1/5 is referred to as an internal latent image type silver halide emulsion. Is defined as a surface latent image type silver halide emulsion.

(Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water is added to 1000 ml (Internal developer B) Methol 2 0.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Water added 1000ml Internal latent image type halogen according to the present invention The maximum concentration of the silver halide emulsion obtained using the surface developer A is less than 1/5, preferably less than 1/10, the maximum concentration obtained with the internal developer B.

The surface latent image type silver halide emulsion according to the present invention has a maximum density obtained by using the surface developer A which is 1/5 or more of a maximum density obtained by the internal developer B. , And preferably ２ or more.

The internal latent image type silver halide emulsion preferably used in the present invention includes those prepared by various methods. For example, conversion type silver halide emulsions described in U.S. Pat. No. 2,592,250 and U.S. Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. Silver halide emulsion having internally chemically sensitized silver halide grains, US Pat. Nos. 3,271,157 and 3,447,927
Having silver halide grains containing polyvalent metal ions described in U.S. Pat. No. 3,761,
No. 276, No. 276, No. 50-38525, No. 53-2408 and the like. A silver halide emulsion comprising grains having a laminated structure described in JP-A-52-15
And silver halide emulsions described in JP-A-59-133542 and JP-A-6-133549.
And a core / shell type internal latent image type silver halide emulsion described in JP-A-3-264740.

The internal latent image type silver halide grains preferably used in the present invention are silver halide having an arbitrary halogen composition, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide. And silver chloroiodobromide. Particles containing silver chloride are preferred because they have excellent development processing properties and are suitable for rapid processing.

The shapes of the internal latent image type silver halide grains used in the present invention are cubic, octahedral, (100) plane and (1).
It may be any of a tetrahedron composed of a mixture of 11) planes, a shape having a (110) plane, a sphere, a flat plate, and the like. Those having an average particle size of 0.05 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having a uniform grain size and crystal habit or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having a uniform grain size and crystal habit Is preferred.

The monodisperse silver halide emulsion in the present invention means that the weight of silver halide contained in a grain size range of ± 20% around the average grain size rm is 60% or more of the total weight of silver halide grains. And preferably 70% or more, more preferably 80% or more. here,
The average particle size rm is defined as the frequency ni and r of the particles having the particle size ri.
The particle size ri when the product ni × ri3 with i3 is the maximum is defined (three significant figures and the smallest figure are rounded off to the nearest 4).
The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical. 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 on the print or the area at the time of projection (the number of measured particles is 1000 or more indiscriminately). Particularly preferred highly monodisperse emulsions have a particle size distribution defined by the following formula of 20% or less.

Particle size distribution = (particle size standard deviation / average particle size) × 100 (%) The average particle size and the particle size standard deviation in the above equation are determined from the particle size ri defined above.

The internal latent image type silver halide emulsion according to the present invention is characterized by infrared sensitization. In the present invention, a compound represented by the following general formula [1-a] or [1-b] is preferable as the infrared sensitizing dye used in the infrared-sensitive layer.

[0039]

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In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a group of nonmetal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring. Thiazole ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring,
Examples include a quinoline ring, a 3,3-dialkylindolenin ring, a benzimidazole ring, and a pyridine ring.

These heterocycles may be substituted with a lower alkyl group, an alkoxy group, a hydroxyl group, an aryl group, an alkoxycarbonyl group or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, -N <W
Representing a ₁ W _2. Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are mutually linked. It can also form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ ^- and X ₂₁ ^- is an anion. n11, n12, n21 and n22 represent 0 or 1.

Specific examples of the compounds represented by the general formulas [1-a] and [1-b] include Compound Examples A-1 to A-14, B1 to B25 and JP-A-7-13289. No. The compound described as 13 can be mentioned. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a silver halide emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (hereinafter, also simply referred to as RD) 176, 17643 (Dec. 1978).
Monthly) Page 23, IV, J, or JP-B-49-255
No. 00, No. 43-4933, JP-A-59-19032
Nos. 59-192242, 62-123454 and JP-A-3-15049. The content of the sensitizing dye is 1 × 1 per mol of silver halide.
0 ^-7 to 1 × 10 ^-2 mol, particularly 1 × 10 ^{-6 to} 5 × 10 ^-3
Used in the molar range.

The following formulas [1-a] and [1-
b), but the present invention is not limited to these compounds.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The above sensitizing dyes are described, for example, by FM Hammer, The Chemistry of Het.
Erocyclic Compounds Volume 18, Th
eCyanine Dyes and Related
Compounds (A. Weissherger
ed. New Science, published by Interscience
k 1964).

The use of the infrared-sensitized internal latent image type silver halide emulsion according to the present invention makes it possible, for example, for human eyes to be compared with a surface latent image type infrared sensitized silver halide emulsion. Some clothes that look black have a strong reflection in the infrared wavelength range, and when photographed with a color film that has an infrared-sensitive layer, the black clothes become greenish. I was able to.

According to a twelfth aspect of the present invention, two infrared photosensitive layers having a center of gravity wavelength of the spectral sensitivity distribution which is 30 nm or more longer than the center of gravity of the spectral sensitivity distribution of the red photosensitive layer are provided. It is.

The spectral sensitivity distribution referred to in the present invention means that a silver halide color photographic light-sensitive material has a thickness of 400 to 850 nm.
Exposure with spectral light at intervals of several nm up to a characteristic curve consisting of density D-exposure amount LogE after development processing,
The reciprocal of the amount of exposure that gives a constant density at each wavelength is the sensitivity at each wavelength, and the sensitivity is a function of the wavelength.

The center-of-gravity wavelength of the spectral sensitivity distribution in the present invention can be determined by the method described in JP-A-11-72870.

The center of gravity wavelength of the spectral sensitivity distribution of the infrared-sensitive layer in the present invention is preferably longer than the wavelength of the center of gravity of the spectral sensitivity of the red photosensitive layer by 30 nm or more, more preferably from 40 nm to 150 nm. preferable.

In the case where two infrared-sensitive layers according to the present invention are provided, the center of gravity wavelength of the spectral sensitivity distribution of the infrared-sensitive layer containing the infrared-sensitized internal latent image type silver halide emulsion is as follows. The wavelength is preferably shorter than the center of gravity wavelength of the spectral sensitivity distribution of the infrared-sensitive layer containing no silver halide emulsion.

The position of the infrared-sensitive layer of the present invention can be set at any position in the photographic constituent layer, but is preferably on the support side of the green-sensitive layer, particularly preferably the red-sensitive layer and the green-sensitive layer. It is to be disposed between the photosensitive layers or between the red-sensitive layer and the support side and between the red-sensitive layer and the antihalation layer.

Next, the surface latent image type silver halide emulsion having visible light sensitivity will be described. The surface latent image type silver halide emulsion according to the present invention may be a normal crystal such as a cubic, octahedral, or tetradecahedral, a flat or columnar twin, or a twin having an irregular polysurface. . The halogen composition of the grains is not particularly limited, and may be, for example, any of silver iodide, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. In the invention according to claim 11,
It is characterized in that the surface latent image type silver halide emulsion is silver haloiodide, and in the present invention, silver iodobromide is particularly preferred.

In the present invention, it is preferable to use tabular twin grains (hereinafter referred to as tabular grains). The tabular grains used in the present invention usually have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope, and a specific method is as follows. First,
A silver halide photographic emulsion is coated on a support so that the contained tabular grains are oriented substantially parallel to the main plane, to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed. The distance between the twin planes in the tabular grains is arbitrarily selected at least 1,000 tabular grains exhibiting a cross section cut almost perpendicularly to the main plane in observation of the slice using the transmission electron microscope described above, The distance between the two twin planes having the shortest distance among the even twin planes parallel to the principal plane is obtained for each particle, and is obtained by averaging. The distance between twin planes is a factor that affects the supersaturation state at the time of nucleation, for example, a combination of various factors such as gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, pH, ion supply speed, and stirring speed. Can be controlled by appropriate selection. In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be. For details on the supersaturation factor, see, for example, JP-A-63-92924 or JP-A-1-21-1.
No. 3637 or the like can be referred to. The average of the distance between twin planes is preferably 0.01 to 0.05 μm, and more preferably 0.013 to 0.025 μm.

The thickness of the tabular grains according to the present invention can be obtained by observing a section using a transmission electron microscope as described above, similarly calculating the thickness of each grain, and averaging. Tabular grain thickness is 0.05-1.5μ
m is preferable, and more preferably 0.07 to 0.50 μm
It is.

The tabular grains according to the present invention have a total projected area of 5%.
0% or more refers to those having an aspect ratio (particle diameter / grain thickness) of 5 or more, preferably 60% or more of the total projected area has an aspect ratio of 7 or more, and more preferably 70% or more of the total projected area. Has an aspect ratio of 9 or more.

The grain size of the tabular grains according to the present invention is represented by the equivalent circle diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains).
0.1 to 5.0 μm is preferable, and more preferably 0.5 to 5.0 μm.
〜3.0 μm. The particle diameter can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles). Is 100 indiscriminately
0 or more).

The average particle size rm mentioned here has the same meaning as the average particle size rm in the internal latent image type silver halide emulsion.
The average thickness dl is the frequency m of the particles having the thickness di.
It is defined as the thickness di when i and di ³ become maximum (three significant figures and the minimum figure are rounded off to the nearest 4).

The tabular grains according to the present invention preferably comprise a monodispersed silver halide emulsion. The monodispersed silver halide emulsion as used herein means an average particle diameter rm and an average thickness dl.
The weight of silver halide contained within a grain size range of ± 20% with respect to each other is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more of the total silver halide grain weight. It is.

The monodisperse emulsion is specifically defined by a particle size distribution and a thickness distribution, and the particle size distribution is the same as that in the internal latent image type silver halide emulsion. When the width of the distribution is defined by the distribution (coefficient of variation of thickness) (%) = (standard deviation / average thickness) × 100,
25% or less, preferably 20% or less,
More preferably, it is 16% or less. Here, the average particle size, the average thickness, and each standard deviation are determined from the particle sizes ri and di defined above.

The tabular grains according to the present invention are emulsions mainly containing silver iodobromide as described above, but silver halides having other compositions such as silver halide, for example, as long as the effects of the present invention are not impaired.
Silver chloride can be included. The distribution state of silver iodide in silver halide grains can be detected by various physical measurement methods.
It can be measured by low-temperature luminescence measurement, EPMA method, or X-ray diffraction method as described in the abstract of the 1st Annual Meeting.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (Electron Probe Micro Ana).
(lyzer method).

The tabular grains according to the present invention preferably have a more uniform silver iodide content. When the distribution of silver iodide content among grains is measured by the EPMA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.

The silver iodide content on the surface of the tabular grains according to the present invention is at least 1 mol%, preferably from 2 to 20 mol%, and more preferably from 3 to 15 mol%.

The surface of the tabular grain is the outermost layer of the grain including the outermost surface of the silver halide grain, and means the depth from the outermost surface of the grain to 50 angstroms. The halogen composition on the surface of the tabular grains is determined by an XPS method (X-ray Photo).
(electron spectroscopy method: X-ray photoelectron spectroscopy).

The silver halide grains according to the present invention preferably have a dislocation line.
F. Hamilton; Photo. Sci. En
g. , 11 (1967) 57 and T.S. Shiozawa;
J. Soc. Photo. Sci. , Japan35 (1
972) can be observed by a direct method using a transmission electron microscope at low temperature described in 213.

The tabular grains according to the present invention have a number ratio of 30.
% Or more have dislocation lines in both the central region and the outer peripheral region of the main plane, and the number of dislocation lines in the outer peripheral region is 20 or more per particle. ) Has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1
It is preferable that the number of tabular grains is 30 or more per grain, and 70% or more (number ratio) of tabular grains has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1 More preferably, it has 40 or more particles per particle.

The method of introducing dislocation lines into silver halide grains is as follows.
For example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jet, a method of adding a fine grain emulsion containing silver iodide, a method of adding only a solution containing iodide ions JP-A-6-117
A known method such as a method using an iodide ion releasing agent as described in No. 81 can be used to form a dislocation as a source of a dislocation line at a desired position. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable. When an iodide ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate, 2-iodoethanol,
-Iodoacetamide and the like can be preferably used.

The tabular grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder), and preferably a colloidal protective substance. It is an aqueous solution containing gelatin.

When gelatin is used as the protective colloid in the present invention, the gelatin may be either lime-treated or acid-treated. For details on the gelatin production method, see Arthur Guice,
It is described in The Macromolecular Chemistry of Gelatin (Academic Press, 1964). Examples of hydrophilic colloids other than gelatin that can be used as a protective colloid include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, and the like. Sugar derivatives such as cellulose derivatives, sodium alginate, starch derivatives, etc .; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. For gelatin,
It is preferable to use one having a jelly strength of 200 or more in the puggy method.

In the present invention, the tabular grains are formed during the formation and / or growth of the grains by cadmium salts, zinc salts, lead salts, thallium salts, iron salts, rhodium salts, iridium salts, indium salts (including complex salts). )), Metal ions are added using at least one selected from
Alternatively, these metal elements can be contained on the particle surface.

As a means for forming tabular grains according to the present invention, various methods well known in the art can be used. That is, single jet method, controlled double jet method, controlled triple jet method, etc. can be used in any combination,
In order to obtain highly monodispersed grains, it is important to control the pAg in the liquid phase in which the silver halide grains are formed in accordance with the growth rate of the silver halide grains. pA
As the g value, an area of 7.0 to 12 is used, and preferably, an area of 7.5 to 11 can be used. In determining the addition rate, JP-A-54-48521,
The technique described in JP-A-8-49938 can be referred to.

In the production of the tabular grains according to the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

The tabular grains according to the present invention may be those obtained by removing unnecessary soluble salts after the growth of the silver halide grains, or may be those containing them. Also, desalting can be performed at any point during silver halide growth, as in the method described in JP-A-60-138538. When removing the salts, research and
Disclosure (Research Disclo
Sure) 17643 No. II. More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, it is possible to use a Noudel washing method performed by gelling gelatin, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (eg, polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. As a specific example, a method described in JP-A-5-72658 can be preferably used.

The silver halide emulsion according to the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

An antifoggant, a stabilizer and the like can be added to the tabular grains according to the present invention. It is advantageous to use gelatin as the binder. Emulsion layers and other hydrophilic colloid layers can be hardened and can contain plasticizers, dispersions (latexes) of water-insoluble or soluble synthetic polymers.

The surface latent image type silver halide emulsions having visible light sensitivity according to the present invention other than those described above include R.I.
D308119 can be used. The pages described below are listed.

[Item] [RD308119] Iodine composition 993 IA section Manufacturing method 993 IA and 994 E crystal habit normal crystal 993 IA crystal habit twin crystal 993 IA epitaxial 999 I- Item A Halogen composition uniform 993 IB Item Halogen composition is not uniform 993 IB Item Halogen conversion 994 IC Halogen substitution 994 IC Item Metal-containing 994 ID Monodispersion 999 IF Solvent Addition 995 I-F Latent image formation position Surface 995 I-G Applicable photosensitive material negative 995 I-H Emulsion is mixed 995 I-J Desalination 995 II-A In the invention according to claim 6, And the infrared-sensitive layer contains yellow, magenta and cyan couplers. With the configuration according to the present invention, the infrared-sensitive layer is sensitive to infrared light emitted from the subject, and the drawing power of a yellow, magenta, and cyan image formed by visible light can be further improved. . In particular,
Sensitive to infrared light emitted from a distant mountainous subject, which improves the descriptive power of a distant view.

The yellow, magenta and cyan couplers that can be used in the infrared-sensitive layer are not particularly limited.
The coupler may be the same as or different from the coupler used in the photosensitive layer having a spectral sensitivity distribution in the visible light region.

The coupler used in the light-sensitive material according to the present invention includes a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm by a coupling reaction with an oxidized form of a color developing agent, and a spectral coupler in a wavelength range of 500 to 600 nm. Magenta coupler having absorption maximum wavelength, wavelength range 350
Yellow couplers having a spectral absorption maximum wavelength of about 500 nm. Further, colored cyan and colored magenta couplers for correcting secondary absorption of cyan and magenta dyes formed by cyan couplers and magenta couplers, and DIR compounds for improving sharpness, granularity, etc., can also be preferably used.

As the cyan coupler, magenta coupler and yellow coupler, known couplers can be used. For example, phenolic and naphthol compounds are used as cyan couplers, 5-pyrazolone, indazolone, pyrazolotriazole and pyrazoloazole compounds are used as magenta couplers, and ketomethylene compounds are used as yellow couplers. No.

In the present invention, the DIR compound is preferably a diffusible inhibitor releasing DIR compound in which the released inhibitor exhibits diffusivity.
No. 53, D-1 to D-34, U.S. Pat.
4,678, 3,227,554, 3,64
7,291, 3,958,993, 4,41
Nos. 9,886 and 3,933,500,
No. 56837, No. 51-13239, No. 58-140
740, U.S. Pat. Nos. 2,072,363 and 2,072
No. 0,266, RD Dec. 21,228 No. 21228, and the like.

Various couplers other than those described above can be used, and specific examples are described in the following RD. The following shows the pages where relevant items are described.

[Items] [RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VIIG DIR compound 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E The couplers and the like used in the present invention are RD308119XI.
It can be added by the dispersion method described in V or the like.

In the invention according to claim 7, the yellow, magenta and cyan couplers contained in the infrared-sensitive layer are
It is characterized in that the maximum yellow density (D _Y ), the maximum magenta density (D _M ), and the maximum cyan density (D _C ) after the development process are in the following formula.

0.05 ≦ D _M −D _Y ≦ 0.4 and 0.0
5 ≦ D _M −D _C ≦ 0.4 By setting the color density balance of each coupler in the infrared-sensitive layer within the range of the above formula, the color reproduction of green leaves is improved, and more preferably, 0.1 ≦ D _M −D _Y ≦ 0.3 and 0.1 ≦ D _M −D _C ≦ 0.3.

In the present invention, each silver halide emulsion used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD17
643, RD18716 and RD308119. The pages where related items are described are listed below.

[Items] [RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23-24 648-649 H , I, J Section Supersensitizer 996 IV-AE, J Section 23-24 648-649 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographs usable in the present invention. Additives for use are also described in the above-mentioned Research Disclosure. The following shows pages where relevant items are described.

[Items] [RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII-I Section XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1001 XXB The photosensitive material of the present invention includes the aforementioned RD308119VII-K
An auxiliary layer such as a filter layer or an intermediate layer described in the section can be provided.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

In the present invention, various kinds of transparent supports can be used. Examples of the support that can be used include polyester films such as polyethylene terephthalate and polyethylene naphthalate, cellulose triacetate films, cellulose diacetate films, polycarbonate films, polystyrene films, and polyolefin films.

The polyester support is not particularly restricted but includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4-butanediol and the like. Condensation polymers with alkylene glycols such as, for example, polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate and the like, and copolymers thereof.

In particular, JP-A-1-244446, JP-A-291248, JP-A-1-298350, JP-A-2-89045, JP-A-2-93641, and JP-A-1-244446, JP-A-1-291248, JP-A-2-93645, JP-A-2-181749, JP-A-2-214852 and JP-A-2-291135
It is preferable to use a polyester having a high water content as described in Japanese Patent Application Laid-Open No. H10-260, etc. These polyesters may have a polar group and other substituents. In the present invention, the support is preferably polyethylene terephthalate or polyethylene naphthalate.

The polyester is preferably stretched in an area ratio of 4 to 16 times in order to satisfy the mechanical strength and dimensional stability of the film support. After the film is formed, it is preferable to perform a heat treatment (annealing treatment) as described in JP-A-51-16358.

On the support, a matting agent, an antistatic agent, a lubricant,
Surfactants, stabilizers, dispersants, plasticizers, UV absorbers,
Conductive substances, tackifiers, softeners, flowability improvers, thickeners, antioxidants and the like can be added.

The support is used for the purpose of neutralizing the tint of the minimum density portion, preventing the light piping phenomenon (edge fogging) that occurs when light enters the film coated with the photographic constituent layer from the edge, and preventing halation. Dyes can be included.

The type of the dye is not particularly limited, but when a polyester film is used as the support, it is preferable to use a dye having excellent heat resistance in the film-forming step, for example, an anthraquinone-based chemical dye. As for the color tone, when the purpose is to prevent light piping, it is preferable to carry out gray dyeing as seen in general photosensitive materials. The dyes may be used alone or in combination of two or more.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (T
he Theory of The Photograph
ic Process Forth Edition)
Pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical So
city), vol. 73, p. 3, 100 (1951), a developer known per se can be used, and the aforementioned RD17643, pages 28 to 29,
Development can be carried out by a usual method described in RD18716, page 615 and RD308119XIX.

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EXAMPLES Hereinafter, the effects of the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto.

Example 1 Samples 101 to 109, which are multilayer color photographic materials, were prepared according to the following method.

<Preparation of Sample 101> The following constituent layers were sequentially coated on a 120 μm-thick cellulose triacetate film support provided with an undercoat layer to prepare Sample 101 as a multilayer color photosensitive material.

In all the examples described below, the amount added in each constituent layer is 1 unless otherwise specified.
Shown in grams per m ² . Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.80 Sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitization Dye (SD-2) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 2.0 × 10 ^-4 sensitizing dye (SD-5) ) 2.8 × 10 ^-4 cyan coupler (C-1) 0.42 colored cyan coupler (CC-1) 0.02 high boiling point organic solvent (Oil-1) 0.35 gelatin 1.02 fourth layer: medium sensitivity red-sensitive layer silver iodobromide emulsion E 0.40 sensitizing dye (SD-3) 1.8 × 10 -5 sensitizing dye (SD-4 2.4 × 10 ^-4 Sensitizing dye (SD-5) 4.5 × 10 -4 Cyan coupler (C-1) 0.26 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.01 High boiling organic solvent (Oil-1) 0.31 Gelatin 0.78 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion G 1.51 Sensitizing dye (SD-3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 3.1 × 10 ^-4 sensitizing dye (SD-5) 2.7 × 10 ^-4 cyan coupler (C-2) 0.11 colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.04 High boiling organic solvent (Oil-1) 0.17 Gelatin 1.15 6th layer: Intermediate layer Yellow coupler (Y-1) 0.02 Yellow coupler (Y- 2) 0.06 High boiling organic solvent (Oil-2) 0.02 High boiling organic solvent (Oil-2) -1) 0.17 gelatin 0.69 seventh layer: intermediate layer gelatin 0.80 eighth layer: low-speed green-sensitive layer silver iodobromide emulsion B 0.21 sensitizing dye (SD-1) 5.9 × ^10-5 sensitizing dye (SD-6) 3.1 x ^10-4 sensitizing dye (SD-9) 1.8 x ^10-4 sensitizing dye (SD-11) 5.6 x ^10-5 magenta coupler (M-1) 0.20 Colored magenta coupler (CM-1) 0.05 DIR compound (D-1) 0.02 High boiling organic solvent (Oil-2) 0.27 Gelatin 1.34 Ninth layer: Medium Sensitive green-sensitive layer Silver iodobromide emulsion E 0.82 sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitizing dye (SD-6) 2.7 × 10 ^-4 sensitizing dye (SD-9) ) 1.7 × 10 ^-4 sensitizing dye (SD-11) 4.8 × 10 ^-5 magenta coupler (M-1) 0.21 Colored magenta coupler (CM-) 1) 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil-2) 0.33 Gelatin 0.89 10th layer: Highly sensitive green-sensitive layer Silver iodobromide emulsion D 0.99 increase Sensitizing dye (SD-6) 3.6 × 10 ^-4 sensitizing dye (SD-7) 7.0 × 10 ^-5 sensitizing dye (SD-8) 4.8 × 10 ^-5 sensitizing dye (SD- 11) 6.2 × 10 ^-5 Magenta coupler (M-1) 0.05 Magenta coupler (M-2) 0.06 Colored magenta coupler (CM-2) 0.03 High boiling organic solvent (Oil-2) 0 .25 Gelatin 0.88 11th layer: Intermediate layer High boiling organic solvent (Oil-1) 0.25 Gelatin 0.50 12th layer: Yellow filter layer Yellow colloidal silver 0.11 Color stain inhibitor (SC-1) 0.12 High boiling organic solvent (Oil-2) 0.16 Gelatin 1.0 0 13th layer: intermediate layer Gelatin 0.36 14th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion B 0.37 sensitizing dye (SD-10) 5.6 × 10 ^-4 sensitizing dye (SD- 11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 9.8 × 10 ^-5 yellow coupler (Y-1) 0.39 yellow coupler (Y-2) 0.14 DIR compound (D-5) 0.03 High-boiling organic solvent (Oil-2) 0.11 Gelatin 1.02 15th layer: Medium-sensitivity blue-sensitive layer Silver iodobromide emulsion D 0.46 Silver iodobromide emulsion F 0.10 Sensitizing dye (SD-10) 5.3 × 10 ^-4 sensitizing dye (SD-11) 1.9 × 10 ^-4 sensitizing dye (SD-13) 1.1 × 10 ^-5 yellow coupler (Y-1) 0 .28 Yellow coupler (Y-2) 0.10 DIR compound (D-5) 0.05 High boiling organic solvent (Oil-2) 0.0 Gelatin 1.12 16th layer: high sensitivity blue-sensitive layer Silver iodobromide emulsion D 0.04 Silver iodobromide emulsion G 0.28 Sensitizing dye (SD-11) 8.4 × 10 -5 Sensitizing dye ( SD-12) 2.3 × 10 ^-4 Yellow coupler (Y-1) 0.04 Yellow coupler (Y-2) 0.12 High boiling organic solvent (Oil-2) 0.03 Gelatin 0.85 17th layer : First protective layer Silver iodobromide emulsion (average particle size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.03 UV absorber (UV-3) ) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling organic solvent (Oil-1) 0.44 High Boiling point organic solvent (Oil-3) 0.07 Gelatin 1.35 18th layer: 2nd protective layer Potassium soluble matting agent (PM-1, average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 Other than the above composition Compounds SU-1, SU-2, S
U-3, SU-4, viscosity modifier V-1, hardener H-1,
H-2, stabilizer ST-1, antifoggant AF-1, AF
-2, two kinds of AF-3 having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, dye AI-
1, AI-2, AI-3, compounds FS-1, FS-2,
The preservative DI-1 was appropriately added to each layer.

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Table 1 shows the emulsions used for preparing the above samples. In addition, the average particle size was shown by the particle size converted into a cube. Further, to each emulsion, after adding the sensitizing dye, sodium thiosulfate, chloroauric acid, potassium thiocyanate, selenium sensitization and the like are added, and chemical sensitization is performed so that the relationship of fog sensitivity is optimized. And spectral sensitization.

[0128]

[Table 1]

The silver iodobromide emulsions A, B and F contain 1 × 10 ⁻⁷ mol / 1 mol Ag of iridium.

<Preparation of Sample 102> In the same manner as in Sample 101, except that a nineteenth layer which is an infrared-sensitive layer shown below was provided between the second and third layers in Sample 101. Sample 102 was manufactured.

Nineteenth layer: First infrared-sensitive layer Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye (1-10) 2.0 × 10 ^-4 magenta coupler ( M-1) 0.20 High boiling organic solvent (Oil-1) 0.34 Gelatin 0.90 <Preparation of Sample 103> Sample 102 was prepared except that the composition of the 19th layer in Sample 102 was changed to the content shown below. A sample 103 was prepared in the same manner as described above.

Nineteenth layer: First infrared-sensitive layer Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye (3-3) 2.0 × 10 ^-4 yellow coupler ( Y-1) 0.28 Magenta coupler (M-1) 0.15 Cyan coupler (C-1) 0.30 High boiling organic solvent (Oil-1) 0.60 Gelatin 1.80 <Preparation of sample 104> Sample A sample 104 was prepared in the same manner as the sample 102, except that a twentieth layer serving as a second infrared-sensitive layer shown below was further provided between the 19th layer and the third layer in 102.

Twentieth layer: Second infrared-sensitive layer Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye (2-1) 2.0 × 10 ^-4 DIR compound ( D-1) 0.20 High-boiling point organic solvent (Oil-1) 0.07 Gelatin 0.90 <Preparation of sample 105> For silver iodobromide emulsion E and silver iodobromide emulsion G in the 19th layer of sample 102, A sample 105 was prepared in the same manner as the sample 102 except that the internal latent image type silver bromide emulsion H was replaced with an equal silver amount. The internal latent image type silver bromide emulsion H was prepared as follows.

<< Preparation of Internal Latent Image Type Silver Bromide Emulsion H >> 13 g
Aqueous solution containing 0.05 g of potassium bromide and 0.05 g of 1,8-dihydroxy-3,6-dithiaoctane
While maintaining the temperature at 75 ° C., a 0.4 mol / L aqueous solution of silver nitrate and a 0.4 mol / L aqueous solution of potassium bromide are brominated so that pBr becomes 1.30 by a controlled double jet method. While controlling the addition rate of the aqueous potassium solution, 300 ml of an aqueous silver nitrate solution was added over 40 minutes. Octahedral silver bromide crystals (core) having a uniform particle size with an average particle size (equivalent sphere size) of about 0.8 μm were produced. Next, 0.7 mg of sodium thiosulfate was added to the silver bromide particles,
And 0.4 mg of potassium chloroaurate were added in an aqueous solution, and heated at 75 ° C. for 80 minutes to perform a chemical sensitization treatment. In the same manner as in the preparation of the core particles, a 0.8 mol / L silver nitrate aqueous solution and a 0.8 mol / L potassium bromide aqueous solution were added to the chemically sensitized core particles while maintaining the temperature at 75 ° C. While controlling the addition rate of the aqueous potassium bromide solution so that the pBr becomes 1.30 by the controlled double jet method, 740 ml of the aqueous silver nitrate solution is added to 6
Added over 0 minutes. This emulsion was washed with water by a conventional flocculation method, and gelatin was added to the emulsion to form an octahedral silver bromide crystal having an average particle size (equivalent sphere size) of about 1.4 μm (internal latent image type emulsion). ) Got. Next, 0.4 mg / mol of silver was added to the internal latent image type core / shell emulsion.
Of sodium thiosulfate and 20 mg of poly (N-vinylpyrrolidone), and heated at 60 ° C. for 60 minutes to chemically sensitize the grain surface, thereby preparing an octahedral internal latent image type silver bromide emulsion H.

<Preparation of Sample 106> The nineteenth sample 102
Layer, silver bromoiodide emulsion D, sodium thiosulfate, chloroauric acid, potassium thiocyanate, selenium sensitization and sensitizing dye (S
D-1), sensitizing dye (SD-6), sensitizing dye (SD-9)
The same as Sample 102 except that a green light-sensitive silver halide emulsion chemically sensitized and spectrally sensitized so as to optimize the fog-sensitivity relationship was newly added by 0.3 g / m ^{2 in} terms of silver. To prepare a sample 106.

<Preparation of Sample 107> In the nineteenth layer of Sample 105, 0.3 g of a silver-sensitive silver halide emulsion using the same silver iodobromide emulsion D as used in Sample 106 was converted to silver.
Sample 107 was prepared in the same manner as Sample 105 except that / m ^{2 was} newly added.

<Preparation of Sample 108> 19th sample 103
Silver iodobromide emulsion D in the same manner as that prepared in Sample 106, except that silver iodobromide emulsion E and silver iodobromide emulsion G in the layer were replaced with the above-mentioned internal latent image type silver bromide emulsion H with the same silver amount. Sample 108 was prepared in the same manner as Sample 103 except that 0.3 g / m ² of a green photosensitive silver halide emulsion was added in terms of silver.

<Preparation of Sample 109> The amount of the yellow coupler, magenta coupler and cyan coupler of the 19th layer in Sample 108 was set to 0.20, 0.20, 0.
Sample 109 was prepared in the same manner as Sample 108, except that the amount of the high boiling point organic solvent (Oil-1) was changed to 0.60 and the amount of the gelatin used was changed to 1.80.

The samples 101 to 1 produced as described above
09, the following measurements and evaluations were performed.

(Measurement of Centroid Wavelength of Spectral Sensitivity Distribution) Each sample was subjected to spectral exposure with spectral light at intervals of several nm in a wavelength region of 400 to 850 nm through a wedge, and then subjected to the following color development processing. For each of the obtained color images, a densitometer X-rite310 type (X-rit
(manufactured by eCo., Ltd.), and a characteristic curve composed of the vertical axis density D and the horizontal axis exposure amount LogE was prepared. The reciprocal of the amount of exposure required to obtain a constant density in the characteristic curve was defined as the sensitivity at that wavelength, and the sensitivity distribution for each wavelength was calculated to create a spectral sensitivity distribution curve. Next, using the obtained spectral sensitivity distribution curve, Japanese Patent Application No. 10-21967.
According to the method described in No. 3, the center of gravity wavelength of the spectral sensitivity distribution of the red-sensitive layer and the infrared-sensitive layer was calculated, and the results are shown in Table 2. In Table 2, in Samples 106 to 109, both the infrared-sensitive emulsion and the visible-sensitive emulsion were used for the infrared-sensitive layer. It was calculated from:

[0141]

[Table 2]

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment Amount * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

<Color developing solution> Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4- Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

<Color developing replenisher> Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline sulfate 6.3 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g water was added to make 1 liter, and potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

<Bleaching Solution> Water 700 ml 1,3-diaminopropanetetraacetic acid ammonium iron (III) salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was added. Adjust to pH 4.4 with.

<Bleaching Replenisher> Water 700 ml 1,3-diaminopropanetetraacetate ammonium iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjusted to pH 4.4 using aqueous ammonia or glacial acetic acid After adjustment, add water to make 1 liter.

<Fixing Solution> Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

<Fixing replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

<Stabilizing Solution and Stabilizing Replenisher> Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

(Measurement of D _Y , D _M , and D _C of Infrared Sensitive Layer)
Each sample was subjected to white exposure through a wedge, and then subjected to the color development treatment to prepare a developed sample. The obtained developed sample was measured for D _Y , D _M and D _C in infrared sensitivity by the following method.

The developed sample was adhered to the emulsion surface with the reference light-sensitive material for density correction using Bond Aron Alpha manufactured by Konishi Co., Ltd., the cut surface was adjusted with an ultramicrotome equipped with a glass knife, and the ultra-microtome equipped with a diamond knife was used. A section having a thickness of about 2 μm was prepared using a microtome.

The cut section was sandwiched between a glass plate and a flat metal plate and pressed with a vice to expand wrinkles generated during cutting of the ultramicrotome, and then collected on a slide glass. Drop and cover glass with a Zeiss high-resolution optical microscope Axio Ph
Transmission observation was performed with oto. Observation image is C of optical microscope
Mounted CCD camera HMC-1 from Hoeisha
Photographs were taken at 010 and input to a computer for image analysis. Conditions for photographing and image input are as follows.
Objective lens: Zeiss Plan Apo × 100
oil, condenser aperture: constant (scale: 0.4),
Bright field stop: open, lamp color temperature: 3200 ° K, filter: ND No. 2. Magnification: 0.05 μm / pixel.

The input image is corrected for the thickness of the section, the unevenness of the brightness of the optical microscope, and the unevenness at the time of capturing the image by using a photo-retouch photoshop manufactured by Adobe Systems, Inc. The boundaries were determined. Then, MEDIA CYBERNETI
Image analysis software Image-Pro manufactured by CS (USA)
Input an image to PLUS, and use Line Profile
The thickness of each layer × the density of one pixel (0.05 μm) was measured by a command, and stored as a text file. The text file is Microsoft Excel
1, the average density of each layer × 2 μm is measured every 1 μm, and each maximum color density D in the infrared-sensitive layer is measured.
_Y , D _M and D _C concentrations were calculated and the results obtained are shown in Table 3.

[0155]

[Table 3]

(Evaluation of Color Reproducibility) Samples 101 to 109 were cut to the standard of 35 mm size 24EX, stored in an existing patrone, and mounted on a Konica Hexa camera manufactured by Konica Corporation to obtain a black color under daylight. A person scene wearing a jacket, a scene shot of a Macbeth color checker against a green background of trees, and a scene shot of the color checker in a composition including a distant mountain range and a building were shot. Each of the photographed samples was subjected to the same color development processing as described above to produce each developed sample.

Next, the developed sample was printed on a Konica color paper type QAA7 manufactured by Konica Corporation using a stretching machine Super Chroma F Dichroic II manufactured by Chroma Corporation to produce an L-size color print sample.

Each of the color print samples prepared as described above was subjected to "reproducibility of leaf green", "reproducibility of flesh color", and "reproducibility of black clothing" by ten panelists according to the following criteria. And sensory evaluation for "distant view descriptiveness",
Table 4 shows the obtained results.

<< Green leaf reproducibility >> ：: Bright and vivid reproduction ：: Vivid reproduction △: Slightly dull reproduction ×: Very dull reproduction unlike the original << Skin color reproducibility »○: Natural skin color reproduction ×: Unnatural reproduction with insufficient redness (magenta) << Reproducibility of black clothes >> ○: Reproduction faithful to original △: Brightness too high, original ×: The color reproduction is clearly different from the original << Distant view depiction >> ◎: The contrast of the distant view is clear and the contour is clear ○: The contour of the distant view is clear C: The distant view is slightly hazy and the outline is unclear. X: The distant view looks fairly hazy. Of the above-mentioned judgment ranks, ◎ and ○ were judged to be practically preferable.

[0160]

[Table 4]

As is clear from Table 4, the color print sample produced by the sample according to the present invention realizes a bright, vivid and preferable color reproduction of the leaf green without impairing the reproducibility of the black clothes (neutral color). In addition, excellent results were obtained in the distant view description power.

Example 2 In sample 109 of Example 1, sensitizing dyes SD-1, SD-6 and SD-9 used in green photosensitive emulsion D were replaced with sensitizing dyes SD-10, SD-11 and SD-9. A sample 201 was made in the same manner as the sample 109 except that the value was changed to -13.

Further, the sensitizing dye of the green photosensitive emulsion D in the sample 109 was changed to sensitizing dyes SD-3 and SD-4.
Sample 202 was prepared in the same manner as Sample 109 except that the sample was changed to SD-5.

The samples 201 and 2 produced as described above
The sample 101 prepared in Example 1 was added to Sample No. 02, and the color reproducibility was evaluated in the same manner as in Example 1. In addition,
As a shooting scene, a red flower scene and an eggplant purple scene were newly added to the scene performed in Example 1.

As a result of evaluating each color print sample produced in the same manner as in the evaluation of color reproducibility in Example 1, the samples 201 and 202 according to the present invention were compared with the comparative sample 101 in Example 1. As with the results of Example 1, the sample 201 has excellent black reproducibility and excellent distant view descriptive power. Furthermore, the sample 201 has a fine rendition of red flowers, and the sample 202 has a more natural color reproducibility of purple such as eggplant. Was confirmed, and the effect of using the configuration of the present invention was recognized.

Example 3 The infrared-sensitized internal latent image type silver bromide emulsion H used in Sample 105 of Example 1 was mixed with the fifth layer and the tenth layer of Sample 101.
Samples 301 and 302 were prepared in the same manner as Sample 101 except that 0.3 g / m ^{2 in} terms of silver was added to each of the layer and the sixteenth layer.
And 303 were produced.

For the samples 301 to 303 produced as described above, the color reproducibility of the color print samples obtained in the same manner as in Example 2 was evaluated. As a result, the black reproducibility was maintained and the distant view description was improved. Was confirmed, and the characteristic color reproducibility of the red, green, and purple subjects was improved for each sample.

[0168]

According to the present invention, a silver halide color photographic light-sensitive material excellent in the descriptive power of scenes, in particular, the information content and color reproducibility of trees such as green are improved, the distant descriptive power is excellent, and neutral colors are obtained. A silver halide color photographic light-sensitive material having stable (black, gray) hue reproduction was provided.

Claims (12)

[Claims] 1. Infrared sensitization of at least one yellow coupler-containing blue light-sensitive layer, magenta coupler-containing green light-sensitive layer and cyan coupler-containing red light-sensitive layer, each containing a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material comprising at least one infrared-sensitive layer containing an internal latent image type silver halide emulsion. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having a spectral sensitivity in a blue light-sensitive region. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having a spectral sensitivity in a green light sensitive region. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein the infrared-sensitive layer contains a surface latent image type silver halide emulsion having a spectral sensitivity in a red-sensitive region. 5. The silver halide color photographic material according to claim 1, wherein the infrared-sensitive layer contains a magenta coupler. 6. The silver halide color photographic material according to claim 1, wherein the infrared-sensitive layer contains a yellow coupler, a magenta coupler and a cyan coupler. 7. The relationship among the maximum yellow density (D _Y ), maximum magenta density (D _M ) and maximum cyan density (D _C ) of the infrared-sensitive layer after the color development processing is 0.1 ≦ D _M − D _Y ≦ 0.5 and 0.1 ≦ D _M −D _C ≦
7. The silver halide color photographic light-sensitive material according to claim 6, wherein the value is 0.5. 8. A silver halide comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler, each containing a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material, wherein at least one of the blue light-sensitive layers contains an infrared-sensitized internal latent image type silver halide emulsion. 9. A silver halide comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler and a red light-sensitive layer containing a cyan coupler, each containing a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material, wherein at least one of the green light-sensitive layers contains an infrared-sensitized internal latent image type silver halide emulsion. 10. A silver halide comprising at least one blue light-sensitive layer containing a yellow coupler, a green light-sensitive layer containing a magenta coupler, and a red light-sensitive layer containing a cyan coupler, each containing a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material, wherein at least one of the red light-sensitive layers contains an infrared-sensitized internal latent image type silver halide emulsion. 11. A surface latent image type silver halide emulsion having a spectral sensitivity in a visible light region contained in at least one of a blue light-sensitive layer, a green light-sensitive layer, a red light-sensitive layer and an infrared light-sensitive layer. , A silver halo iodide emulsion.
11. The silver halide color photographic light-sensitive material according to any one of items 10 to 10. 12. A photographic constituent layer comprising at least one yellow-sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler and a red-sensitive layer containing a cyan coupler, each containing at least a surface latent image type silver halide emulsion. A silver halide color photographic light-sensitive material having two infrared-sensitive layers having a center-of-gravity wavelength of a spectral sensitivity distribution of 30 nm or more longer than the center-of-gravity wavelength of the spectral sensitivity distribution of the red-sensitive layer,
One of the infrared-sensitive layers contains an infrared-sensitized internal latent image type silver halide emulsion, and the other one has a yellow coupler,
A silver halide color photographic material comprising a magenta coupler and a cyan coupler.