JP2005134815A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material whose sensitivity and sharpness are synthetically more excellent than those of a conventional one. <P>SOLUTION: The silver halide color photographic sensitive material has, on a support, photographic constituent layers including one or more each of red-, green- and blue-sensitive silver halide emulsion layers in order from the support side, wherein silver halide grains contained in the highest sensitivity layer in at least one of the red- and green-sensitive silver halide emulsion layers have a total projected area, (a) ≥50% of which is occupied by tabular silver halide grains having an aspect ratio of ≥4 and (b) 0.5-5% of which is occupied by normal crystal grains having an equivalent spherical diameter of ≤0.5 μm, and wherein a cyan dye is fixed in a photographic constituent layer remoter from the support than the red-sensitive silver halide emulsion layers or a magenta dye is fixed in a photographic constituent layer remoter from the support than the green-sensitive silver halide emulsion layers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also referred to as “photosensitive material”), which includes tabular silver halide grains and silver halide normal crystal grains in one layer of a photosensitive layer, and is supported from the photosensitive layer. The present invention relates to a silver halide color photographic light-sensitive material which contains a dye fixed in a photographic constituent layer far from the body and which is excellent in sensitivity and sharpness.

  In silver halide color photographic light-sensitive materials, particularly color light-sensitive materials for photographing, a light-sensitive material having high sensitivity and good sharpness is desired. As a means for improving the sharpness, a method is known in which a fixed dye is placed on the photosensitive emulsion layer (see, for example, Patent Documents 1 to 6). Certainly, sharpness was improved to some extent by these methods. Among these, as described in Patent Document 4 and Patent Document 6, sharpness has been considerably improved by using it together with tabular silver halide grains. However, the photographic sensitivity is lowered with the improvement of sharpness, which is a problem as a high-sensitivity photographic material.

As a means for improving photographic sensitivity, there is a method of scattering light in a film. This is a method of increasing the effective optical path length in the film, and silver halide grains are effective as scatterers because they have a higher refractive index than gelatin films. Since normal crystal grains have a greater degree of light scattering than tabular grains, mixing tabular grains and normal crystal grains meets the above objective. There are Patent Documents 7 to 9 relating to silver halide color photographic light-sensitive materials in which tabular grains and normal crystal grains are mixed. Patent Document 7 discloses a silver halide photographic light-sensitive material comprising a photographic constituent layer containing a tabular grain emulsion having an aspect ratio of 5 or more and a normal crystal grain emulsion, and Patent Document 8 discloses an aspect ratio of 1.2. A silver halide photographic light-sensitive material containing an emulsion layer composed of the above tabular grain emulsion and core / shell type normal crystal grains is disclosed. In Patent Document 9, the aspect ratio is 5 or more and the thickness is 0.01 to 0. A silver halide photographic light-sensitive material comprising an emulsion layer composed of tabular grain having a diameter of 0.08 μm and core / shell type normal crystal grains is disclosed. However, although these can improve the photographic sensitivity, the sharpness is lowered as described later, and side effects which are undesirable for the image quality occur.
Japanese Patent Laid-Open No. 62-10650 JP 62-47640 A JP-A 62-103641 JP-A-62-166330 U.S. Pat. No. 4,855,220 European Patent Application No. 566082 JP 11-119361 A Japanese Patent No. 2881315 Japanese Patent No. 2683625

  An object of the present invention is to provide a light-sensitive material that is comprehensively superior in sensitivity and sharpness than conventional ones.

  The above problems have been solved by the following silver halide color photographic light-sensitive material.

(1) On the support, at least one red light-sensitive silver halide emulsion layer, green light-sensitive silver halide emulsion layer, and blue light-sensitive silver halide emulsion layer, respectively, in order from the side close to the support. Silver halide grains contained in at least one of the most sensitive layers of the red light-sensitive silver halide emulsion layer and the green light-sensitive silver halide emulsion layer,
(A) The tabular silver halide grains having an aspect ratio of 4 or more have a projected area of 50% or more with respect to the total projected area of the silver halide grains.

(B) Normal crystal grains having a sphere equivalent diameter of 0.5 μm or less have a projected area of 0.5% to 5% with respect to the total projected area of the silver halide grains.

Satisfying the condition (a) and the condition (b)
In addition, a cyan dye is fixed to a photographic component layer farther from the support than the red light-sensitive silver halide emulsion layer and / or from the support than the green light-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material, wherein a magenta dye is fixed to a photographic composition layer far away from the viewer.

  (2) The highest sensitivity layer of the red light sensitive silver halide emulsion layer contains silver halide grains satisfying the above conditions (a) and (b), and is supported by the red light sensitive silver halide emulsion layer. The silver halide color photographic light-sensitive material as described in (1) above, wherein a cyan dye is fixed to a photographic constituent layer far from the body.

  (3) The highest sensitivity layer of the green light sensitive silver halide emulsion layer contains silver halide grains satisfying the above conditions (a) and (b) and is supported by the green light sensitive silver halide emulsion layer. The silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein a magenta dye is fixed to a photographic constituent layer far from the body.

  (4) Two or more red light-sensitive silver halide emulsion layers having different sensitivities and two or more green light-sensitive silver halide emulsions having different sensitivities from the side closer to the support in that order. The silver halide color photographic light-sensitive material as described in any one of (1) to (3) above, comprising a photographic constituent layer comprising a layer and at least one blue light-sensitive silver halide emulsion layer .

  Hereinafter, the present invention will be described in detail.

  The silver halide photographic light-sensitive material of the present invention comprises at least one red light-sensitive silver halide emulsion layer, green light-sensitive silver halide emulsion layer, and blue light-sensitive silver halide emulsion layer, respectively, in the order from the support. The red light-sensitive silver halide emulsion layer or the green light-sensitive silver halide emulsion layer has two or more layers having different sensitivities, more preferably This is when the red light-sensitive silver halide emulsion layer and the green light-sensitive silver halide emulsion layer have two or more layers having different sensitivities.

  The silver halide photographic light-sensitive material of the present invention relates to a silver halide photographic light-sensitive material having the above layer structure, wherein silver halide grains satisfying the following conditions (a) and (b) are It may be contained in at least one of the highest sensitivity layers of the silver halide emulsion layer and the green light-sensitive silver halide emulsion layer. Preferably, it is contained in both highest sensitivity layers.

(A) Tabular silver halide grains having an aspect ratio of 4 or more have a projected area of 50% or more with respect to the total projected area of the silver halide grains in the emulsion layer.

(B) Normal crystal grains having a sphere equivalent diameter of 0.5 μm or less have a projected area of 0.5% or more and 5% or less with respect to the total projected area of silver halide grains in the emulsion layer.

  In the present invention, the sensitivity is the exposure amount giving a magenta density or cyan density of (fog + 0.2) when the color photographic material is subjected to the exposure and color development processing described in (Evaluation) of Example 1 of the present application. Are the sensitivity to green light and the sensitivity to red light, respectively.

  The emulsion contained in at least one of the red-light and green-light-sensitive silver halide emulsion layers of the silver halide color photographic material of the present invention is a tabular silver halide having an aspect ratio of 4 or more. The projected area meter of tabular grains containing one or more grains (hereinafter also referred to as “tabular grains”), preferably having an aspect ratio of 4 or more, has a total projected area of the silver halide grains contained in the emulsion. It accounts for 50% or more, preferably 80% or more. Here, tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane. These tabular grains are triangular, hexagonal or rounded when viewed from above, with triangular being triangular, hexagonal being hexagonal, circular Have circular outer surfaces which are parallel to each other.

  In the present invention, the aspect ratio of a tabular grain is a value obtained by dividing the diameter of a circle (equivalent circle diameter) equal to the projected area of each grain by the thickness. To measure the projected area and thickness of the particles, deposit the metal from the oblique direction of the particles together with the reference latex (replica method), measure the shadow length on an electron micrograph, and refer to the latex shadow length. This can be done easily by calculating. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of the particle.

  The equivalent sphere diameter of the tabular grains is preferably 0.3 to 10.0 μm, more preferably 0.5 to 2.0 μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm.

  The tabular grains used in the present invention preferably have an aspect ratio of 4 or more, more preferably 4 or more and less than 50. Further, more preferable results may be obtained when monodispersed tabular grains are used. The structure and production method of monodispersed tabular grains follow the description of, for example, JP-A No. 63-151618. However, when the shape is briefly described, 50% or more of the total projected area of silver halide grains is the minimum. The ratio of the side having the maximum length to the length of the side having the length of is a hexagon that is 2 or less, and is occupied by the tabular silver halide having two parallel surfaces as the outer surface Furthermore, the variation coefficient of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area by the average grain size] is 20. % Monodispersity or less.

  U.S. Pat. No. 4,797,354 and JP-A-2-838 describe a process for producing monodispersed hexagonal tabular grains having a high tabularization rate. In addition, European Patent No. 514,742 describes a method for producing tabular grains having a variation coefficient of grain size distribution of less than 10% using a polyalkylene oxide block copolymer. These tabular grains are preferably used in the present invention. Further, particles having a high uniformity of thickness with a coefficient of variation of particle thickness of 30% or less are also preferred.

The tabular grains used in the present invention preferably have dislocation lines.
The dislocations of tabular grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eeg. 11, 57 (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213 (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocations to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. In this case, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, the observation using the high-voltage type electron microscope (acceleration voltage 200 kV or more for a particle having a thickness of 0.25 μm) is more clearly observed. be able to. From the photograph of the particles obtained by such a method, the position of dislocation for each particle when viewed from the direction perpendicular to the main plane can be obtained.

  The position of dislocations in the tabular grains is generated from the distance of x% of the length from the center to the side to the side in the major axis direction of the tabular grain. The value of x is preferably 10 ≦ x <100. Yes, more preferably 30 ≦ x <98. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but it may be distorted rather than a perfect shape. The direction of the dislocation line is approximately from the center to the side, but is often meandering.

  Regarding the number of dislocations in the tabular grains, it is preferable that 50% (number) or more of grains containing 10 or more dislocations exist. More preferably, particles containing 10 or more dislocations are 80% (number) or more, particularly preferably particles containing 20 or more dislocations are 80% (number) or more.

  The manufacturing method of the tabular grain used by this invention is described. Tabular grains used in the present invention are described in “Theory and Practice of Photography” by Cleeve (Cleve, Photographic Theory and Practice (1930)), p. 13; Gatoff, Photographic Science and Engineering (Gutuff, Photographic Science and Engineering). 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439, It can be prepared by improving the method described in the specification of No. 520 and British Patent No. 2,112,157.

  In the tabular silver halide emulsion used in the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

  The silver halide emulsion used in the present invention may have a double or multiple structure with respect to the halogen composition in the grains. The dislocations of the tabular grains used in the present invention are introduced by providing a high iodine phase inside the grains. The high iodine phase is a silver halide solid solution containing iodine. In this case, the silver halide is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but silver iodide or iodobromide. Silver is preferable, and silver iodide is particularly preferable. The amount of silver halide forming the high iodine phase is 1 mol% or more and 30 mol% or less, and more preferably 3 mol% or more and 10 mol% or less of the total silver amount of the grains. The phase grown on the outside of the high iodine phase needs to be lower than the iodine content of the high iodine phase, and the preferred iodine content is 0 to 12 mol%, more preferably 0 to 6 mol%, most preferably 0 to 0 mol%. 3 mol%.

  In order to improve the sharpness, it is important to select the particle thickness in consideration of the light incident on the photosensitive material or the wavelength of the light to be sensitized. It is preferable to arrange particles having a thickness of 0.08 to 0.10 μm in a layer that scatters blue light of 400 to 500 nm or a layer that is sensitive to blue light. Next, a thickness of 0.19 to 0.21 μm is preferable. It is preferable to arrange particles having a thickness of 0.11 to 0.13 μm in a layer that scatters green light of 500 to 600 nm or a layer that is sensitive to green light. Next, a thickness of 0.23 to 0.25 μm is preferable. It is preferable to arrange particles having a thickness of 0.14 to 0.17 μm in a layer that scatters red light of 600 to 700 nm or a layer that is sensitive to red light. Next, a thickness of 0.28 to 0.30 μm is preferable. It is preferable to arrange particles having a thickness of 0.17 to 0.19 μm in the layer that scatters infrared light or the layer that is sensitive to infrared light. When one photosensitive layer is composed of a plurality of photosensitive layers having different sensitivities, it is best to arrange particles having a preferable thickness in all the layers. Next, it is preferable to dispose the photosensitive layer at a position farther from the support. It is particularly preferable to use a combination of particles having a preferable thickness for each photosensitive layer, for example, to arrange particles having a preferable thickness in both the blue light-sensitive layer and the green light-sensitive layer. Any combination of blue, green and red light sensitive layers can be selected.

  The silver halide normal crystal grains (hereinafter also referred to as normal crystal grains) used in the present invention are any of cubic, octahedral, dodecahedron, tetrahedral, tetrahedral and spherical. Normal crystal particles in which other surfaces appear on the surface due to surface dissolution or the like may be used. Of these, normal crystal particles other than spherical ones can have any ratio of (100) plane to (111) plane. The sphere equivalent diameter of the normal crystal particles used in the present invention is 0.5 μm or less, more preferably 0.2 μm to 0.5 μm. The ratio of the projected area occupied by normal crystal grains having a sphere equivalent diameter of 0.5 μm or less is 0.5% or more and 5% or less, and the upper limit of the ratio of projected area occupied by normal crystal grains is preferably 3% or less. .

  The sphere equivalent diameter of the normal crystal particles used in the present invention is preferably excellent in monodispersity, and has a core / shell structure, a dislocation line, and an epitaxially grown portion as seen in the following publication. JP-A-59-177535, JP-A-60-138538, JP-A-59-52238, JP-A-60-143331, JP-A-60-35726, and JP-A-60-258536. It can be produced by referring to the methods disclosed in Japanese Patent Laid-Open Nos. 61-14636 and 5-323485. Spherical silver halide grains, as disclosed in JP-A-57-182730, JP-A-59-179344, JP-A-59-178447, etc., completed the formation of silver halide grains. Thereafter, it can be obtained by ripening in the presence of a silver halide solvent. The monodispersity of the sphere equivalent diameter of the normal crystal particles is preferably 25% or less, more preferably 20% or less in terms of variation coefficient.

  In the present invention, when at least one of the red light-sensitive silver halide emulsion layer and the green light-sensitive silver halide emulsion layer contains normal crystal grains, the equivalent sphere diameter is larger than 0.5 μm. The projected area of normal crystals is preferably 20% or less with respect to the projected area of all normal crystals in the layer, and most preferably contains no normal crystals having a sphere equivalent diameter of more than 0.5 μm.

  The normal crystal grains used in the present invention may contain silver chloride as long as the effects of the present invention are not impaired. The normal crystal grains used in the present invention may have a high silver iodide content phase inside the grains, or may have a uniform composition. The silver halide grains having a high silver iodide content phase inside the grains used in the present invention are a high silver iodide content phase or a low silver iodide content phase or a salty odor having a lower silver iodide content. It is coated with a silver halide phase. The average silver iodide content of the silver iodide content phase, which is lower than the high silver iodide content phase forming the outermost phase, is preferably 6 mol% or less, particularly preferably 0 to 4 mol%. There may also be a silver iodide-containing phase (intermediate phase) between the outermost phase and the high silver iodide content phase. The silver iodide content in the intermediate phase is preferably 10 to 22 mol%, particularly preferably 12 to 20 mol%. The silver iodide content between the outermost phase and the intermediate phase, and between the intermediate phase and the internal high silver iodide content phase is preferably 6 mol% or more, particularly preferably 10 mol% or more. There is a difference. In the above embodiment, there is another silver halide phase in the center of the internal high silver iodide content phase, between the internal high silver iodide content phase and the intermediate phase, and between the intermediate phase and the outermost phase. May be. The volume of the outermost phase is preferably 4 to 70 mol%, more preferably 10 to 50 mol% of the entire particle. The volume of the high silver iodide content phase is preferably 10 to 80% of the whole grain, and is preferably 20 to 50%, and more preferably 20 to 45%. The volume of the intermediate shell is preferably 5 to 60%, more preferably 20 to 55% of the whole particle.

  These phases may be a single phase having a uniform composition, or may be a phase group composed of a plurality of phases having a uniform composition, the composition of which is changed stepwise, or continuous in an arbitrary phase. It may be a continuous phase in which the composition changes, or a combination thereof. In another embodiment of the normal crystal grains used in the present invention, the silver iodide localized in the grains does not form a substantially uniform phase, but the silver iodide content increases from the grain center toward the outer side. The aspect which changes continuously is mentioned. In this case, the silver iodide content is preferably monotonically decreasing from the point where the silver iodide content in the grain is maximum toward the outside of the grain. The silver iodide content at the maximum silver iodide content is preferably 15 to 45 mol%, more preferably 25 to 40%. The silver iodide content of the grain surface phase is preferably 6 mol% or less, and particularly preferably 0 to 4 mol% of silver iodobromide.

  In addition, when the normal crystal grains used in the present invention are introduced into the highest sensitivity layer of red light and / or green light together with the tabular grains, the normal crystal grains may be post-ripened in advance and are the same as the introduction layer. It may be sensitized to have spectral sensitivity.

  Spectral sensitization and chemical sensitization of normal crystal grains can be performed with reference to those described in the explanation of tabular silver halide grains below. There is no particular limitation on the method of mixing the normal crystal grains and the tabular grains, but in order to minimize the change over time after mixing, the necessary compounds are added to each layer immediately after mixing the emulsion and coating is performed. Is preferred.

  Below, the difference of this patent and the patent documents 7-9 mentioned above about the case where a normal crystal grain is mixed and used for a tabular grain is described. In Patent Documents 7 to 9, there is no general description regarding the definition of the size of normal crystal grains, and the size of normal crystal grains used in a mixture with tabular grains in the examples is 0.7 μm or more. Such normal crystal particles are unfavorable in that sharpness is reduced because the size is too large, which is different from the present invention. In Patent Document 8, the ratio of the projected area occupied by the normal crystal grains to the tabular grains is defined as 40% or less, and a particularly preferable region is described as occupying a projected area of 5 to 15%. ing. This patent is also different from the region preferred in Patent Document 8. As a cause of such a difference, while only a tabular grain having an aspect ratio of about 2 to 4 is actually used in Patent Document 8, a tab having an aspect ratio of 4 or more is used in the present invention. This is because the light scattering characteristics of the particles are different. In a system including tabular grains having a high aspect ratio as in the present invention, use of an amount which is preferable in Patent Document 8 is not preferable because sharpness deterioration is conspicuous.

  Next, the magenta dye and the cyan dye used in the present invention will be described. The magenta dye in the present invention is not limited as long as it has a spectral absorption maximum wavelength of substantially 500 to 600 nm in the dry film of the photosensitive material to which the dye is added. The dye may be used alone or in combination of two or more. good.

  The cyan dye in the present invention may be any dye having a spectral absorption maximum wavelength of 600 to 700 nm substantially in the dry film of the photosensitive material to which the dye is added. The dye may be used alone or in combination of two or more. good.

  In the present invention, the fact that the dye is immobilized means that the dye added during the preparation of the photosensitive layer during the production of the photosensitive material does not diffuse to the layer other than the target layer even after the production. To be present in the target layer. Here, “substantially in the target layer” means that the added dye is present in 80% or more in the target layer. Any means may be used for fixing the target layer, for example, the following method.

  The method of adding the dye to the target layer is a method of directly dyeing gelatin, an oil-in-water dispersion method as described later, that is, using a high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure. Depending on the method, a method of adding an organic solvent having a boiling point of 50 ° C. or more and 160 ° C. or less and emulsifying and dispersing in an aqueous gelatin solution containing a surfactant, International Publication No. 88/4974, Special Table There are a method of adding a so-called solid dispersion described in Japanese Patent Application Laid-Open No. 1-502912 and European Patent Publication No. 456,148, or a method of preventing dye diffusion through a polymer mordant. Typical polymer mordants are those described in [Chemical Formula 9] of JP-A No. 5-188548, for example. Any of these methods can be used in the present invention, but the addition by the oil-in-water dispersion method is particularly preferred because it does not desensitize the emulsion layer. Therefore, oil-soluble dyes are preferred as the dye used in the present invention.

  In the present invention, the added amount of the dye is 0.005 in the average optical density in the range of 500 to 600 nm for the magenta dye in the dry film of the target layer and in the range of 600 to 700 nm for the cyan dye. It is -0.50, Preferably it is 0.02-0.30. This concentration is determined as follows. The actual measurement method is to apply a dye on a transparent support together with geratan and dry the sample, measure the concentration of 500 to 600 nm, or 600 to 700 nm with a spectrophotometer, and calculate the integrated value from 500 to 600 nm or 600 to 700 nm. The average optical density at is determined.

  In the fixed magenta dye used in the present invention, the silver halide grains satisfying the conditions (a) and (b) defined in the present invention are contained in the highest sensitivity layer of the green light-sensitive emulsion layer. Is preferably contained in the photographic component layer farther from the support than the green light-sensitive layer, but is preferably added to the light-sensitive emulsion layer, and is preferably added to the blue light-sensitive emulsion layer. Is particularly preferred.

  The fixed cyan dye used in the present invention contains silver halide grains satisfying the conditions (a) and (b) defined in the present invention in the highest sensitivity layer of the red light-sensitive emulsion layer. In this case, it is preferable to add it to a photographic constituent layer farther from the support than the red light-sensitive layer, but it is preferable to add it to the photosensitive emulsion layer, and to add to the blue or green light-sensitive layer. It is particularly preferable to do this.

  In a preferred embodiment of the present invention, both the red and green light-sensitive emulsion layers contain silver halide grains satisfying the conditions (a) and (b) defined in the present invention, and the magenta dye is added to the blue light-sensitive layer. In addition, a cyan dye is added to the blue and green photosensitive layers.

  In the present invention, a mixture of the above tabular grains and normal crystal grains, and a cyan or magenta dye fixed to a photographic constituent layer farther from the support than the green and red photosensitive layers are contained. Occasionally, a surprising effect was obtained in that the sensitivity and sharpness were excellent in terms of superadditivity compared to when each technology was used alone.

Specific examples of the magenta dye and cyan dye used in the present invention are shown below, but the present invention is not limited thereto.

  The above exemplified compounds are disclosed in JP-A-61-48854, 61-7838, 60-243654, 60-32851, 62-276539, 52-92716, It is described in International Publication No. 88/04794, JP-A-3-7931, JP-A-4-45436, and JP-A-5-43809, or can be synthesized according to the method described therein.

  The light-sensitive material of the present invention comprises at least one red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, and a blue light-sensitive halogenated halide on the support in order from the side close to the support. It is only necessary to have a silver emulsion layer. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is composed of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in German Patent 1,121,470 or British Patent 923,045. Are preferably arranged such that the photosensitivity decreases sequentially toward the support. Further, as described in JP-A-57-112751, JP-A-62-2200350, JP-A-62-206541, and JP-A-62-206543, a low-sensitivity emulsion layer is provided on the side away from the support. A high-sensitivity emulsion layer may be provided on the side close to the body. As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of.

  Further, as described in JP-B-55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. . In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer from the side away from the support in the same color-sensitive layer. They may be arranged in the order of / high sensitivity emulsion layer / low sensitivity emulsion layer. In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.

  Further, the arrangement may be changed as described above even when there are four or more layers. In order to improve the color reproducibility, BL, GL, RL described in the specifications of U.S. Pat.Nos. 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850 It is preferable to dispose a donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as adjacent to or close to the main photosensitive layer.

  In the silver halide photographic color light-sensitive material of the present invention, at least one of the photographic constituent layers reacts with an oxidized form of a color developing agent as disclosed in JP-A No. 62-103641 to perform diffusive development. It may contain a DIR compound that releases the inhibitor or its precursor.

The preferred tabular grains used in the present invention are silver iodobromide, silver iodochloride or silver iodochlorobromide grains containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 2 mol% to about 10 mol% of silver iodide. The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22 to 23, “I. Emulsion preparation and types”. No. 18716 (November 1979), 648, No. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monter Glafkides, Chimie et Phisique Photographique, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966) , Focal Press, Inc. (VLZelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like.

  Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, pages 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048. No. 4,439,520 and British Patent No. 2,112,157, and can be easily prepared. The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. Also, a mixture of various tabular grains may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

  As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such processes are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. Silver halide grains with fogged grain surfaces as described in US Pat. No. 4,082,553, silver halide grains with fogged grains as described in US Pat. No. 4,626,498 and JP-A-59-214852 Preferably, colloidal silver is applied to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodispersed (at least 95% of the silver halide grain weight or number of grains have an equivalent sphere diameter within an average of ± 40%) It is preferable that

  In the present invention, it is preferable to use non-photosensitive fine grain silver halide in the non-photosensitive photographic constituent layer. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868, supersensitizer, page 649, right column 4. Whitening agent page 24, page 647, right column, page 868, 5 Light Absorber, Filter Dye, page 25-26, page 649, right column, page 873 UV absorber-page 650, left column 6. Binder page 26, page 651, left column, pages 873-874 7. Plasticizer, lubricant page 27, page 650 Right column, page 876 8. Coating aid, surfactant 26-27 pages 650, right column 875-876 pages 9. Antistatic agents, page 27 650, right column, pages 876-877
10. Matting agent 878-879 pages

Various dye forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferred.
Yellow coupler: coupler represented by formulas (I) and (II) described in EP 502,424A; formulas (1) and (2) described in EP 513,496A (Especially Y-28 on page 18); coupler represented by the formula (I) of claim 1 described in EP 568,037A; column 1 of US Pat. No. 5,066,576 A coupler represented by the general formula (I) described in lines 45 to 55; a coupler represented by the general formula (I) described in paragraph 0008 of JP-A-4-74425; European Patent Application Publication No. 498,381A1 Couplers described in claim 1 on page 40 (especially D-35 on page 18); couplers represented by formula (Y) described on page 4 of EP-A-447,969A1 (especially Y-1 (Page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) described in columns 7 to 36-58 of US Pat. No. 4,476,219 (particularly II-17, 19 ( Lamb 17), II-24 (column 19)).

  Magenta couplers; L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13) described in JP-A-3-9737; European Patent No. 456,257 (A-4) -63 (page 134), (A-4) -73, -75 (page 139); M-4, -6 (page 26) described in EP 486,965 M-7 (page 27); M-45 (page 19) described in European Patent Application No. 571,959A; (M-1) (page 6) described in JP-A-5-204106; M-22 described in paragraph 0237 of JP-A-4-362631.

Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) described in JP-A-4-204843; C-7 described in JP-A-4-43345 , 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385, general formula (1) A coupler represented by Ia) or (Ib).
Polymer coupler: P-1, P-5 (page 11) described in JP-A-2-44345.

As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, and German Patent No. 3,234,533 are preferable.
A coupler for correcting unwanted absorption of a coloring dye is a yellow colored compound represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP-A-456,257A1. Cyan couplers (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the European Patent Application Publication, Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US Pat.No. 4,833,069, (2) (column 8) described in US Pat. A colorless masking coupler represented by the formula (A) of claim 1 described in the pamphlet of WO92 / 11575 (especially exemplified compounds on pages 36 to 45) is preferred.

  Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of EP-A-378,236A1 (especially T-101 (page 30)) ), T-104 (31 pages), T-113 (36 pages), T-131 (45 pages), T-144 (51 pages), T-158 (58 pages)), European Patent Application Publication No. 436, 938A2 Compounds represented by formula (I) described on page 7 of the specification (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly ( 23) (page 11)), and compounds represented by formulas (I), (II), (III) described on pages 5 to 6 of European Patent Application Publication No. 440,195A2 (especially I- ( 1)); bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP-A 310,125A2 (especially (60) and (61) on page 1) And a compound represented by the formula (I) in claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: LIG- described in claim 1 of US Pat. No. 4,555,478 X Compounds (especially compounds in columns 12 to 41 of column 12); leuco dye releasing compounds: compounds 1 to 6 in columns 3 to 8 of US Pat. No. 4,749,641; fluorescent dye releasing compounds: US Pat. No. 4,774,181 Compound represented by COUP-DYE in claim 1 of the specification (especially compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: formula (1 in column 3 of US Pat. No. 4,656,123) ), (2), (3) (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36-38 of EP 450,637A2; The compound which releases the group which becomes a pigment for the first time: a compound represented by the formula (I) of claim 1 of US Pat. No. 4,857,447 (especially Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 described in JP-A-62-215272 (Pages 140-144); Latex for impregnation with oil-soluble organic compounds: Latex described in US Pat. No. 4,199,363; Oxidizing agent scavenger: Columns 54-62 of US Pat. No. 4,978,606 Compounds of formula (I) as described (especially I- (1), (2), (6), (12) (columns 4-5), 5-10 of column 2 of US Pat. No. 4,923,787 The formulas described in the rows (especially compound 1 (column 3); stain inhibitors: formulas (I) to (III) described in European Patent Application Publication No. 298321A, page 4, lines 30 to 33, especially I-47 , 72, III-1,27 (pages 24-48); antifading agent: A-6,7,20,21,23,24,25,26,30 described in European Patent Application Publication No. 298321A , 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118), U.S. Pat.No. 5,122,444, columns 25 to 38, II-1 to III-23, especially III-10 , Europe I-1 to III-4 described on pages 8 to 12 of the permitted application 471347A, in particular II-2, A-1 to 48 described in columns 32 to 40 of U.S. Pat.No. 5,139,931. In particular, A-39, 42; a material that reduces the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15 described on pages 5 to 24 of EP-A-411324A, particularly I- 46; formalin scavenger: SCV-1 to 28 described on pages 24 to 29 of European Patent Application Publication No. 477932A, particularly SCV-8; hardener: described on page 17 of JP-A 1-214845 Compounds (H-1 to 54) represented by formulas (VII) to (XII) described in columns 13 to 23 of H-1,4,6,8,14, U.S. Pat. No. -214852, compound (H-1 to 76) represented by formula (6) described at the lower right of page 8, particularly H-14, compound described in claim 1 of US Pat. No. 3,325,287; development inhibition Agent precursor: P-24,37,39 (pages 6-7) described in JP-A-62-168139; U.S. Pat.No. 5,019,492 Compounds of claim 1 in particular, 28, 29 of column 7; preservatives, fungicides: I-1 to III-43, in particular II-, of columns 3 to 15 of US Pat. No. 4,923,790 1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) described in columns 6 to 16 of U.S. Pat.No. 4,923,793, in particular I-1,60, ( 2), (13), compounds 1 to 65 described in columns 25 to 32 of U.S. Pat.No. 4,952,483, especially 36: chemical sensitizer: triphenylphosphine selenide, described in JP-A-5-40324 Compound 50; Dye: a-1 to b-20, particularly a-1,12,18,27,35,36, b-5,27 to 29 described on pages 15 to 18 of JP-A-3-156450 Pages V-1 to 23, especially V-1, FI-1 to F-II-43, particularly FI-11, F-II-8 described on pages 33 to 55 of EP-A-445627A. Dye-1 described on pages 17-28 of EP-A-457153A, particularly III-1,3, especially on pages 8-26 of WO88 / 04794. ~ 124 crystallite dispersion , Compounds 1 to 22 described on pages 6 to 11 of EP 319999A, particularly compound 1, compounds D represented by formulas (1) to (3) of EP 519306A -1 to 87 (pages 3 to 28), compounds 1 to 22 (columns 3 to 10) represented by formula (I) described in U.S. Application No. 4,268,622, formulas described in U.S. Application No. 4,923,788 Compounds (1) to (31) represented by (I) (Columns 2 to 9); UV absorbers: Compounds (18b) to (18r) represented by the formula (1) described in JP-A-46-3335 ), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) and formula (III) represented by the formula (I) described in EP-A-520938A Compounds HBT-1 to 10 (page 14), and compounds (1) to (31) represented by formula (1) described in European Patent Application No. 521823A (columns 2 to 9).

  In this invention, it is preferable to use together with the technique which improves a light absorptivity with a spectral sensitizing dye. For example, by utilizing intermolecular force, the sensitizing dye is adsorbed to the surface of the silver halide grain more than the saturated coating amount, or two or more separately unconjugated dye chromophores are covalently linked. For example, a dye, a so-called linked dye, is adsorbed on silver halide grains, and is described in, for example, the following patents.

  JP 10-239789, JP 11-133531, JP 2000-267216, JP 2000-275772, JP 2001-75222, JP 2001-75247, JP 2001-75221, Special JP 2001-75226, JP 2001-75223, JP 2001-255615, JP 2002-23294, JP 10-171058, JP 10-186559, JP 10-197980, JP JP 2000-81678, JP 2001-5132, JP 2001-166413, JP 2002-49113, JP 64-91134, JP 10-110107, JP 10-171058, JP JP 10-226758, JP 10-307358, JP 10-307359, JP 10-310715, JP 2000-231174, JP 2000-231172, JP 2000-231173, JP 2001 -356442, European Patent Application Publication No. 985965A, European Patent Application Publication No. 985964A, European Patent Application Publication No. 985966A, European Patent Application Publication No. 985967A, European Patent Application Publication No. 1085372A, European Patent Application Publication No. 1085373A European Patent Application Publication No. 1172688A, European Patent Application Publication No. 1199595A, Europe Patent Application Publication No. 887700A1.

  Further, it is preferable to use in combination with the techniques described in the patents shown in JP-A-10-239789, JP-A-2001-75222, and JP-A-10-171058.

  In the light-sensitive material of the present invention, it is preferable that a one-electron oxidant produced by one-electron oxidation contains a compound capable of emitting one electron or more. The one-electron oxidant produced by one-electron oxidation can emit one or more electrons is a compound selected from the following types 1 and 2.

(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.

(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific Examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1 (Specific Examples: Compounds INV1-35), “One-photon two-electron sensitizer” or “deprotonated electron-donating sensitizer” described in patents such as European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. No. 5,994,051 Compounds referred to. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

Further, as a compound of type 1 that can be emitted by one-electron oxidant formed by one-electron oxidation and further undergoing bond cleavage reaction, one or more electrons can be emitted from the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in Japanese Patent Application Laid-Open No. 2003-75950), and general formula (7) (Japanese Patent Application Laid-Open No. 2003-75950). And general formula (8) (Japanese Patent Application No. 2). The reaction represented by the general formula (1) described in 003-25886 or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in Japanese Patent Application No. 2003-33446) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formulas (1) and (2), RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form or hexahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle) together with carbon atom (C) and RED ₁ Represent. R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Lv ₁ and Lv ₂ represent a leaving group. ED represents an electron donating group.

In the general formulas (3), (4) and (5), Z ₁ represents an atomic group capable of forming a 6-membered ring together with the nitrogen atom and the two carbon atoms of the benzene ring. _{R 5, R 6, R 7} , R 9, R 10, R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19 represents a hydrogen atom or a substituent. R ₂₀ represents a hydrogen atom or a substituent. When R ₂₀ represents a group other than an aryl group, R ₁₆ and R ₁₇ are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ₈ and R ₁₂ represent a substituent that can be substituted on the benzene ring, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 4. Lv ₃ , Lv ₄ and Lv ₅ represent a leaving group.

In the general formulas (6) and (7), RED ₃ and RED ₄ represent a reducing group. R _{21 to} R ₃₀ represent a hydrogen atom or a substituent. Z ₂ represents —CR ₁₁₁ R ₁₁₂ —, —NR ₁₁₃ —, or —O—. R ₁₁₁ and R ₁₁₂ each independently represents a hydrogen atom or a substituent. _R113 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In general formula (8), RED ₅ is a reducing group and represents an arylamino group or a heterocyclic amino group. R ₃₁ represents a hydrogen atom or a substituent. X represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Lv ₆ is a leaving group and represents a carboxy group or a salt thereof, or a hydrogen atom.

The compound represented by the general formula (9) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by further oxidizing after two-electron oxidation accompanied by decarboxylation. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation. In the general formula (9), R ₃₂ , R ₃₃ and Z ₃ have the same meanings as those in the chemical reaction formula (1). Z ₅ and Z ₆ each represent a group that forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with CC.

Next, the type 2 compound will be described.
As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing a reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446). And a compound represented by the general formula (11) (synonymous with the general formula (2) described in Japanese Patent Application No. 2003-33446). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formula (10), RED ₆ represents a reducing group that is one-electron oxidized. Y reacts with one-electron oxidant produced by one-electron oxidation of RED ₆ to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or Reactive group containing a non-aromatic heterocyclic moiety of a benzo-fused ring. Q represents a linking group that links RED ₆ and Y.

The compound represented by the general formula (11) is a compound that causes a bond formation reaction represented by the chemical reaction formula (1) by being oxidized. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. Z ₅ and Z ₆ each represent a group that forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with CC. M represents a radical, a radical cation, or a cation. In the general formula (11), R ₃₂ , R ₃₃ , Z ₃ and Z ₄ have the same meanings as in the chemical reaction formula (1).

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferable examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing terocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkylphosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Can be mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of quaternary salt counter anions include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

In general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (═O ) —, —SO ₂ —, —SO—, —P (═O) — each independently or a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and are selected from a range in which i + j is 2 to 6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number in the range of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

  The type 1 and type 2 compounds of the present invention may be used at any time during the preparation of the emulsion or during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compounds of type 1 and type 2 of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

The compounds of type 1 and type 2 of the present invention are preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per 1 mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper. Moreover, it is suitable for the film unit with a lens described in Japanese Patent Publication No. 2-332615 and Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention include, for example, the RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and page No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C for 3 minutes and 15 seconds with a color developer is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling ratio is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.

  The light-sensitive material of the present invention is prepared by the usual methods described in the above-mentioned RD. No. 17643, pages 28 to 29, RD. No. 18716, 651, left column to right column, and RD. No. 307105, pages 880 to 881. It can be developed. The color developer used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof include European Patent Application Publication No. 556700A, page 28, pages 43 to 43. The compound described in the 52nd line is mentioned. These compounds may be used in combination of two or more depending on the purpose. Color developers are pH buffers such as alkali metal carbonates, borates or phosphates, developers such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In general, an inhibitor or an antifoggant is included. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Various chelating agents such as ethylenepolytetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanedia Tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, Add ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When reversing is performed, color development is usually performed after black and white development. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Or they can be used in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions is generally 3 liters per square meter of photosensitive material (hereinafter also referred to as “L”) or less depending on the color photographic light-sensitive material to be processed. By reducing the bromide ion concentration, it can be reduced to 500 milliliters (hereinafter, milliliter is also expressed as “mL”). When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with air. The processing effect due to contact of photographic processing solution and air in the processing tank is
Opening ratio (= [contact area between treatment liquid and air cm ² ] ÷ [volume of treatment liquid cm ³ ])
Can be evaluated. The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a floating lid or other shielding object on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, JP-A-63-3 A slit developing method described in Japanese Patent No. 216050 can be exemplified. The aperture ratio is preferably reduced not only in both color development and black-and-white development, but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developer. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to high and using the color developing agent at a high concentration.

  The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, depending on the purpose, it is possible to carry out processing in two continuous baths for bleach-fixing, fixing processing before bleach-fixing processing, or bleaching processing after bleach-fixing processing. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other amino acids. Polycarboxylic acids or complex salts such as citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acids such as iron (III) complex salts of ethylenediaminetetraacetic acid and 1,3-diaminopropanetetraacetic acid are preferred from the viewpoint of rapid processing and prevention of environmental pollution. . Furthermore, aminopolycarboxylic acid iron (III) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8. However, it can be processed at a lower pH in order to speed up the processing.

  A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: US Patent 3,893,858, German Patents 1,290,812, 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53. -37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424, 53-141623, 53- Compound having mercapto group or disulfide group described in Japanese Patent No. 28426, RD No. 17129 (July 1978); Thiazolidine derivative described in Japanese Patent Laid-Open No. 50-140129; No. 52-20832, No. 53-32735, US Pat. No. 3,706,561, a thiourea derivative described in German Patent 1,127,715, an iodide salt described in JP-A-58-16,235, German Patent No. 966,410, Polyoxyethylene compounds described in JP 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49-40,943, 49-59, Compounds described in 644, 53-94,927, 54-35,727, 55-26,506, 58-163,940; bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, compounds described in U.S. Pat.No. 3,893,858, German Patent 1,290,812 and JP-A-53-95,630 are described. preferable. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed. In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferred. Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. However, the use of thiosulfates is common. In particular, ammonium thiosulfate is most widely used. A combination of thiosulfate and thiocyanate, a thioether compound, or thiourea is also preferable. As a preservative for the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in European Patent Application No. 294769A is preferable. Further, aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

  The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved and the occurrence of stain after the treatment is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or a rotating means of JP-A-62-183461 is used. To improve the stirring effect, and further improve the stirring effect by moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface to make the emulsion surface turbulent. The method of increasing the circulation flow rate of the is mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is thought to speed up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increase the desilvering rate. The stirring improving means is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator. The automatic processor used for the photosensitive material of the present invention preferably has the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. . As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance deterioration of the treatment liquid. This is particularly effective for shortening the processing time in the process and reducing the replenishment amount of the processing liquid.

  In general, the light-sensitive material of the present invention undergoes a washing and / or stabilization process after desilvering. The amount of water to be washed in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as coupler), the usage, the washing water temperature, the number of washing tanks (the number of washing tanks), the replenishment method such as countercurrent and forward flow, and various other conditions Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system should be determined by the method described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, pages 248-253 (May 1955). Can do. According to the multi-stage countercurrent system described in this document, the amount of water to be washed can be significantly reduced. However, bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 is extremely effective. In addition, isothiazolone compounds described in JP-A-57-8542, siabendazoles, chlorinated fungicides such as chlorinated isocyanurate sodium, other benzotriazoles, written by Hiroshi Horiguchi, (1986) Sankyo Publishing, Hygiene Technology Association edited by “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association, Japanese Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986) It is also possible to use the disinfectant described in 1. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set depending on the characteristics and application of the photosensitive material. In general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. . Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, known methods described in JP-A-57-8543, 58-14834 and 60-220345 can be applied. In addition, there may be a further stabilization treatment following the water washing treatment, and examples thereof include a stabilization bath containing a dye stabilizer and a surfactant used as a final bath of a color photographic material for photographing. Can do. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to the stabilizing bath.

  The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process. In the processing using an automatic developing machine or the like, when each processing solution is concentrated by evaporation, it is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate it, it is preferable to use a precursor of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base compounds described in Research Disclosure No. 14,850 and No. 15,159, aldol compounds described in 13,924, U.S. Pat.No. 3,719,492 Examples thereof include metal salt complexes described in the specification and urethane compounds described in JP-A-53-135628. The light-sensitive material of the present invention may incorporate various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but the temperature can be increased to accelerate processing and shorten the processing time, or conversely, the temperature can be lowered to improve image quality and improve the stability of the processing solution. be able to.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
Support The support used in this example was prepared by the following method.
1) First layer and undercoat layer A polyethylene naphthalate support having a thickness of 90 μm has a treatment atmosphere pressure of 2.66 × 10 Pa, an H ₂ O partial pressure of 75% in an atmospheric gas, a discharge frequency of 30 kHz on each of both surfaces. Glow discharge treatment was performed at an output of 2500 W and a treatment strength of 0.5 kV · A · min / m ² . On this support, a coating solution having the following composition was applied as a first layer at a coating amount of 5 mL / m ² using the bar coating method described in JP-B-58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass
10% aqueous dispersion. (Secondary agglomerates with a primary particle size of 0.005μm and average particle size of 0.05μm)
Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene sorbitan monolaurate 0.1 parts by weight

Further, after coating the first layer, it is wound around a stainless steel core having a diameter of 20 cm, and subjected to a heat treatment at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours to carry out an annealing treatment and then support. A coating solution having the following composition was applied as an undercoat layer for emulsion on the side opposite to the first layer side with a bar coating method at a coating amount of 10 mL / m ² .
Gelatin 1.01 parts by mass Salicylic acid 0.30 parts by mass Resorcin 0.40 parts by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-propanol 10 .08 parts by mass

  Further, the second and third layers described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having the composition described later is coated on the opposite side to form a transparent magnetic recording with a silver halide emulsion layer. A medium was made.

2) Second layer (transparent magnetic recording layer)
(i) Dispersion of magnetic substance Co-coated γ-Fe ₂ O ₃ magnetic substance (average major axis length: 0.25 μm, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A / m, σ s: 77.1 Am ² / kg, σr: 37.4 Am ² / kg) 1100 parts by mass, 220 parts by mass of water, and silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165 parts by mass Part was added and kneaded well with an open kneader for 3 hours. This coarsely dispersed viscous liquid was dried at 70 ° C. for one day to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Furthermore, it knead | mixed again with the following prescription for 4 hours with the open kneader.
Surface-treated magnetic particles 855 g
Diacetylcellulose 25.3 g
Methyl ethyl ketone 136.3 g
Cyclohexanone 136.3 g

Furthermore, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours. As media, 1 mmφ glass beads were used.
45 g of the above kneaded liquid
Diacetylcellulose 23.7 g
Methyl ethyl ketone 127.7 g
Cyclohexanone 127.7 g

Furthermore, the magnetic substance containing intermediate liquid was produced with the following prescription.
(ii) Production of magnetic substance-containing intermediate liquid 674 g of the above magnetic substance fine dispersion
Diacetylcellulose solution 24280 g
(Solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Cyclohexanone 46 g
After mixing these, it stirred with the disperser and the "magnetic substance containing intermediate liquid" was produced.

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.
(A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g)
Preparation of particle dispersion Sumicorundum AA-1.5 152 g
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicon Co., Ltd.) 0.48 g
Diacetylcellulose solution 227.52 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Using the above formulation, fine dispersion was performed at 800 rpm for 4 hours using a ceramic-coated sand mill (1/4 G sand mill). As media, 1 mmφ zirconia beads were used.

(B) Colloidal silica particle dispersion (fine particles)
“MEK-ST” manufactured by Nissan Chemical Co., Ltd. was used.
This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and the solid content is 30%.

(iii) Preparation of second layer coating liquid 19053 g of the above magnetic substance-containing intermediate liquid
Diacetylcellulose solution 264 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Colloidal silica dispersion “MEK-ST” [dispersion b] 128 g
(Solid content 30%)
AA-1.5 dispersion [dispersion a] 12 g
Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g
(Solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Methyl ethyl ketone 170 g
Cyclohexanone 170 g
The coating solution obtained by mixing and stirring the above was coated with a wire bar so that the coating amount was 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the magnetic layer after drying was 1.0 μm.

3) Third layer (layer containing higher fatty acid ester slip agent)
(i) Preparation of Dispersion Stock Solution for Sliding Agent The following solution A was heated and dissolved at 100 ° C., added to the solution A, and then dispersed with a high-pressure homogenizer to prepare a dispersion stock solution for slip agent.
Liquid A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H ₁₀₁
The following compound 171 parts by mass nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
Cyclohexanone 830 parts by mass Liquid I Cyclohexanone 8600 parts by mass

(ii) Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicon)
Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2)
5.53 parts by mass W-5 2.93 parts by mass Seahosta KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.)

  After stirring for 10 minutes according to the above formulation, the following is added.

252.93 parts by mass of diacetone alcohol The above liquid was dispersed for 3 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON Co., Ltd.)” with ice cooling and stirring to complete a spherical inorganic particle dispersion c1.

(iii) Preparation of spherical organic polymer particle dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.
XC99-A8808 (Toshiba Silicone Co., Ltd., spherical cross-linked polysiloxane particles, average particle size 0.9μm)
60 parts by mass Methyl ethyl ketone 120 parts by mass Cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
While cooling with ice and stirring, the mixture was dispersed for 2 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON)” to complete a spherical organic polymer particle dispersion c2.

(iv) Preparation of third layer coating solution The above was added to 542 g of the slip agent dispersion stock solution to prepare a third layer coating solution.
Diacetone alcohol 5950 g
Cyclohexanone 176 g
Ethyl acetate 1700 g
Seahosta KEP50 dispersion [c1] 53.1 g
300 g of the above spherical organic polymer particle dispersion [c2]
FC431 (manufactured by 3M, solid content 50%, solvent: ethyl acetate) 2.65 g
BYK310 (manufactured by BYK Chemi Japan, solid content 25%) 5.3 g
The third layer coating solution was applied onto the second layer at a coating amount of 10.35 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film.
(Composition of photosensitive layer)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

(Sample 101)
First layer (first antihalation layer)
Black colloidal silver Silver 0.074
Silver iodobromide emulsion Silver 0.010
(Average grain size: sphere equivalent diameter 0.07 μm, silver iodide content: 2 mol%)
Gelatin 0.740
ExM-1 0.068
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
F-8 0.001
HBS-1 0.099
HBS-2 0.013

Second layer (second antihalation layer)
Black colloidal silver Silver 0.094
Gelatin 0.667
ExF-1 0.002
F-8 0.001
Solid disperse dye ExF-7 0.100
HBS-1 0.066

Third layer (intermediate layer)
ExC-2 0.050
Cpd-1 0.089
Polyethyl acrylate latex 0.200
HBS-1 0.054
Gelatin 0.458

4th layer (low sensitivity red sensitive emulsion layer)
Em-C Silver 0.320
Em-D Silver 0.414
ExC-1 0.354
ExC-2 0.014
ExC-3 0.093
ExC-4 0.193
ExC-5 0.034
ExC-6 0.015
ExC-8 0.053
ExC-9 0.020
Cpd-2 0.025
Cpd-4 0.025
Cpd-7 0.015
UV-2 0.022
UV-3 0.042
UV-4 0.009
UV-5 0.075
HBS-1 0.274
HBS-5 0.038
Gelatin 2.757

5th layer (medium sensitivity red emulsion layer)
Em-B Silver 1.152
ExM-5 0.011
ExC-1 0.304
ExC-2 0.057
ExC-3 0.020
ExC-4 0.135
ExC-5 0.012
ExC-6 0.039
ExC-8 0.016
ExC-9 0.077
Cpd-2 0.056
Cpd-4 0.035
Cpd-7 0.020
HBS-1 0.190
Gelatin 1.346

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-A Silver 0.932
ExM-5 0.156
ExC-1 0.066
ExC-3 0.015
ExC-6 0.027
ExC-8 0.114
ExC-9 0.089
ExC-10 0.107
ExY-3 0.010
Cpd-2 0.070
Cpd-4 0.079
Cpd-7 0.030
HBS-1 0.314
HBS-2 0.120
Gelatin 1.206

7th layer (intermediate layer)
Cpd-1 0.078
Cpd-6 0.369
Solid disperse dye ExF-4 0.030
HBS-1 0.048
Polyethyl acrylate latex 0.088
Gelatin 0.739

Eighth layer (a layer that gives a layered effect to the red sensitive layer)
Em-E Silver 0.408
Cpd-4 0.034
ExM-2 0.121
ExM-3 0.002
ExM-4 0.035
ExY-1 0.018
ExY-4 0.038
ExC-7 0.036
HBS-1 0.343
HBS-3 0.006
HBS-5 0.030
Gelatin 0.884

9th layer (low sensitivity green emulsion layer)
Em-H Silver 0.276
Em-I Silver 0.238
Em-J Silver 0.325
ExM-2 0.344
ExM-3 0.055
ExY-1 0.018
ExY-3 0.014
ExC-7 0.004
HBS-1 0.505
HBS-3 0.012
HBS-4 0.095
HBS-5 0.055
Cpd-5 0.010
Cpd-7 0.020
Gelatin 1.382

10th layer (medium sensitive green sensitive emulsion layer)
Em-G Silver 0.439
ExM-2 0.046
ExM-3 0.033
ExM-5 0.019
ExY-3 0.006
ExC-6 0.010
ExC-8 0.010
ExC-9 0.009
HBS-1 0.046
HBS-3 0.002
HBS-4 0.035
HBS-5 0.020
Cpd-5 0.004
Cpd-7 0.010
Gelatin 0.446

11th layer (high sensitivity green emulsion layer)
Em-F Silver 0.497
Em-H Silver 0.286
ExC-6 0.007
ExC-8 0.012
ExC-9 0.014
ExM-1 0.019
ExM-2 0.056
ExM-3 0.013
ExM-4 0.034
ExM-5 0.039
ExM-6 0.021
ExY-3 0.005
Cpd-3 0.005
Cpd-4 0.007
Cpd-5 0.010
Cpd-7 0.020
HBS-1 0.248
HBS-3 0.003
HBS-4 0.094
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.950

12th layer (yellow filter layer)
Cpd-1 0.090
Solid disperse dye ExF-2 0.070
Solid disperse dye ExF-3 0.010
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-6 0.010
HBS-1 0.055
Gelatin 0.589

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-M Silver 0.327
Em-N Silver 0.174
Em-O Silver 0.097
ExC-1 0.006
ExC-3 0.033
ExC-7 0.014
ExY-1 0.088
ExY-2 0.404
ExY-4 0.056
ExY-5 0.404
Cpd-2 0.102
Cpd-3 0.004
HBS-1 0.337
HBS-5 0.070
Gelatin 1.876

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.421
Em-K Silver 0.421
ExM-5 0.012
ExC-1 0.010
ExC-7 0.010
ExY-1 0.041
ExY-2 0.119
ExY-3 0.008
ExY-4 0.070
ExY-5 0.120
Cpd-2 0.074
Cpd-3 0.001
Cpd-7 0.030
HBS-1 0.122
Gelatin 0.905

15th layer (first protective layer)
Silver iodobromide emulsion Silver 0.278
(Average grain size: sphere equivalent diameter 0.07 μm, silver iodide content: 2 mol%)
UV-1 0.167
UV-2 0.066
UV-3 0.099
UV-4 0.013
UV-5 0.160
F-20 0.008
F-11 0.008
S-1 0.077
HBS-1 0.175
HBS-4 0.017
Gelatin 1.297

16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.029
S-1 0.200
Gelatin 0.748

  Furthermore, in order to improve the preservability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-11, B-4 to B-6, F-1 thru | or F-19 and lead salt, platinum salt, iridium salt, and rhodium salt are contained.

Preparation of Dispersion of Organic Solid Disperse Dye The solid disperse dye ExF-2 of the twelfth layer was dispersed by the following method.
ExF-2 wet cake (containing 17.6 wt% water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate (31 wt% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH)

After the slurry having the above composition is stirred and roughly dispersed by a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.29 to obtain a solid disperse dye ExF-2. The average particle size of the dye fine particles was 0.29 μm.
In the same manner, solid disperse dyes ExF-4 and ExF-7 were obtained. The average particle diameters of the fine dye particles were 0.28 μm and 0.49 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

In Table 1, emulsions Em-A to C are added with an optimal amount of spectral sensitizing dyes 1 to 3, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsions Em-E to G are added with an optimal amount of spectral sensitizing dyes 4 to 6, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsion Em-J is added with an optimal amount of spectral sensitizing dyes 7 and 8, and is optimally gold sensitized, sulfur sensitized and selenium sensitized. Emulsion Em-L is added with an optimal amount of spectral sensitizing dyes 9 to 11, and is optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsion Em-O is added with an optimal amount of spectral sensitizing dyes 10 to 12, and is optimally gold sensitized and sulfur sensitized. Emulsions Em-D, H, I, K, M, and N are added with an optimum amount of spectral sensitizing dyes described in Table 5, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized.

The sensitizing dyes listed in Table 5 are shown below.

For preparation of tabular grains, low molecular weight gelatin is used according to the examples described in JP-A-1-158426.
Emulsions Em-A to J contain optimum amounts of Ir and Fe.
Emulsions Em-L to O are reduction sensitized during grain preparation.
Emulsions Em-A to C and Em-J were dislocation-introduced using an iodide ion releasing agent according to the examples described in JP-A-6-11787.
Emulsion Em-E was introduced with dislocations using silver iodide fine grains prepared immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570.

The compounds used for each layer are shown below.

The above silver halide color photographic light-sensitive material is designated as sample 100.
Development was performed by the following method using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, a modification was made so that the overflow solution of the bleaching bath was not discharged to the rear bath but was discharged to the waste solution tank. This FP-360B is equipped with an evaporation correction means described in public technique 94-4992 (published by the Association of Inventions and Innovations).

The treatment process and the treatment liquid composition are shown below.
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Wash with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to one shot per 24)

The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL, respectively, per photosensitive material 35 mm width 1.1 m, 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)

(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

Preparation of Emulsions ai In the preparation of tabular grains, low molecular weight gelatin is used according to the examples described in JP-A-1-158426. The preparation of the normal crystal grains was made by referring to the production method of Emulsion B described in Examples of JP-A-3-237450. Each emulsion was adjusted to obtain the target size and aspect ratio of the silver halide grains by adjusting the ripening process time, the amount of added silver, the addition speed, and the like. Table 6 shows the shape characteristics of the obtained emulsion.

(Production of Sample 101 to Sample 116)
In Sample 100, as shown in Table 7, a magenta dye was added, and the emulsion of the 11th layer was replaced with Emulsion 1 and Emulsion 2 to prepare Samples 101 to 116. Except for Sample 113, the emulsion to be replaced was optimally spectrally sensitized so as to have a sensitivity to green. In Sample 113, only emulsion a was subjected to optimum spectral sensitization, and emulsion b was not given spectral sensitivity.

8 mg / m ² of dye D-8 is added to the added layer of magenta dye. The method for adding magenta dye D-8 is as follows. 17.5 g of magenta dye (D-8) and 15 mL of high boiling organic solvent (HBS-1) were added to 100 mL of ethyl acetate and heated to 40 ° C. to completely dissolve. This ethyl acetate solution was mixed with 400 g of a 13% gelatin aqueous solution containing 7.0 g of a surfactant (W-4), and emulsified and dispersed with a homoblender. The emulsified dispersion thus obtained was added to the target layer.

(Evaluation)
Using the above sample, the color development processing described above was performed after 1/100 exposure with a continuous wedge through a gelatin filter SC-39 manufactured by FUJIFILM Corporation, and the sensit curve was obtained to obtain a magenta density (fog + 0.2) and a cyan density. Sensitivity (S0.2) at (fog + 0.2) was evaluated. Further, the MTF value measurement pattern was exposed to red light, developed, and the MTF value of the magenta image at 25 cycles / mm was measured.

The results are shown in Table 8. Both sensitivity and sharpness are normalized by setting the result of the sample 101 as a type (each is 100). The sensitivity and sharpness values obtained for each sample are expressed as relative values. For sensitivity, the value obtained by dividing the sensitivity value obtained for each sample by the sensitivity value obtained for the type sample was multiplied by 100, and for sharpness, the MTF value of the type was It is expressed as an amount obtained by multiplying the value obtained by dividing by the MTF value obtained for the sample by 100. When the photographic sensitivity is relatively increased or the sharpness is increased, a value greater than 100 is obtained. “Gain” (= relative sensitivity × relative sharpness ÷ 10000) is defined by multiplying each relative value, and when the gain is 1.10 or more, it is judged that sensitivity and sharpness are comprehensively excellent. .

  From the above results, the effect of comprehensively excellent sensitivity and sharpness is obtained because the silver halide grains contained in the green photosensitive layer are tabular silver halide grains having an aspect ratio of 4 or more. The normal crystal grains having a projected area of 50% or more with respect to the total projected area of the silver halide grains and having a sphere equivalent diameter of 0.5 μm or less have a diameter of 0. It can be seen that it has a projected area of 5% or more and 5% or less, and the magenta dye is fixed to a photographic composition layer farther from the support than the green light-sensitive silver halide emulsion layer.

[Example 2]
(Production of Sample 201 to Sample 204)
In Sample 100, as shown in Table 9, a magenta dye was added, and the emulsion of the 11th layer was replaced with Emulsion 1 and Emulsion 2 to prepare Samples 201 to 204. All replacement emulsions were optimally spectrally sensitized to have a green sensitivity.

Table 10 shows the results of performing the same processing and evaluation on Sample 201 to Sample 204 as in Example 1.

  From the above results, when tabular silver halide grains having an aspect ratio of 4 or less have a projected area of 50% or more with respect to the total projected area of the silver halide grains, other conditions are set according to the present invention. However, it can be seen that the effect of excellent overall sensitivity and sharpness cannot be obtained.

[Example 3]
In the sample 101 in Example 1, the emulsion in the sixth layer was replaced with Emulsion 1 and Emulsion 2 in the same manner as in Table 7, and in the 13th to 15th layers as in Samples 102 to 116 in Example 1, the cyan dye D- A sample was prepared by adding 8 mg / m ^{2 of} No. 32 in the same manner as the method for adding the magenta dye in Example 1. This sample was subjected to color development processing in the same manner as in Example 1 to obtain a sensitometric curve, to evaluate the sensitivity for giving a cyan density of (fog + 0.2), and to measure the MTF value with red light. The MTF value of the cyan image at 25 cycles / mm was measured after the exposure. For this result, the gain was evaluated in the same manner as in Example 1. As a result, the effect of comprehensively excellent sensitivity and sharpness is obtained because the silver halide grains contained in the highest sensitivity layer of the red light-sensitive silver halide emulsion layer have an aspect ratio of 4 or more. The tabular silver halide grains have a projected area of 50% or more based on the total projected area of the silver halide grains, and normal crystal grains having a sphere equivalent diameter of 0.5 μm or less are silver halide grains. The cyan dye has a projected area of 0.5% or more and 5% or less with respect to the total projected area, and the cyan dye is fixed to the photographic composition layer farther from the support than the red light-sensitive silver halide emulsion layer. It was when.

[Example 4]
In Sample 101 in Example 1, the emulsions in the 10th and 6th layers were replaced with Emulsion 1 and Emulsion 2 as in Table 7, and in the 12th to 14th layers as in Samples 102 to 116 in Example 1. Magenta dye D-8 and cyan dye D-32 were added by the same addition method as in Example 1 and Example 3 to prepare a sample. This sample was subjected to color development processing, and a sensitometric curve was obtained in the same manner as in Example 1 to evaluate each sensitivity giving a magenta density and a cyan density of (fog + 0.2), and green light or red The MTF value measurement pattern was exposed to light and developed, and the MTF value of each magenta image or cyan image at 25 cycles / mm was measured. For this result, each gain was evaluated in the same manner as in Example 1. As a result, the effects of excellent sensitivity and sharpness can be obtained because the silver halide contained in the highest sensitivity layers of the red light-sensitive silver halide emulsion layer and the green light-sensitive silver halide emulsion layer. The tabular silver halide grains having an aspect ratio of 4 or more have a projected area of 50% or more with respect to the total projected area of the silver halide grains, and the equivalent sphere diameter is 0.5 μm or less. The normal crystal grains have a projected area of 0.5% to 5% with respect to the total projected area of the silver halide grains, and the magenta dye is viewed from the support from the green light-sensitive silver halide emulsion layer. It was when the cyan dye was fixed to the far photographic constituent layer as viewed from the support rather than the red light-sensitive silver halide emulsion layer.

[Example 5]
The color photographic light-sensitive material according to the present invention used was packaged as described below.
For 135 size, cassette packaging described in paragraphs 0057 and 0058 of JP-A-08-122981; stick pack packaging described in paragraphs 0020 to 0027 of JP-A-11-265042; paragraph number of JP-A-2001-151270 Blister packaging described in 0008 to 0019 and collective packaging described in paragraph Nos. 0009 to 0046 of JP-A-2001-125229 were performed. In the cartridges used in these, the cartridges described in JP-A No. 2002-173627, paragraph numbers 0015 to 0055, the cartridges described in JP-A No. 2002-173627, paragraph numbers 0015 to 0018, and JP-A No. 2000-112079. A cartridge copper plate described in paragraph Nos. 0012 to 0018 and a cartridge cap described in paragraph Nos. 0009 to 0023 of JP-A No. 09-90568 were used. (Furthermore, as a light-shielding ribbon for a cartridge, Comparative Example 2 of Japanese Patent Application No. 2002-129478, Paragraph No. 0042 and 0043, Example 1 of Japanese Patent Application No. 2002-113954, Paragraph Nos. 0044 to 0046, Paragraph No. 0034 of Japanese Patent Application No. 2002-258445. Example 1 described in ˜0037 was used.)
About 120 and 220 size, roll film packaging of Unexamined-Japanese-Patent No. 09-288335 paragraph number 0011-0032 was performed. JP-A 09-090568, paragraph numbers 0009 to 0023 was used as a tape for joining light-shielding paper and photosensitive material. (A tape described in paragraph Nos. 0014 to 0077 of JP-A-2003-035946 was used as the end seal tape).

  For color negative films for movies, bagging / canning packaging described in paragraph Nos. 0011 to 0022 of JP-A No. 2000-171944 was performed.

[The invention's effect]
According to the present invention, it is possible to provide a photosensitive material having excellent overall sensitivity and sharpness.

Claims (4)

Photographic composition comprising at least one red light-sensitive silver halide emulsion layer, green light-sensitive silver halide emulsion layer, and blue light-sensitive silver halide emulsion layer on the support in order from the side closest to the support. Silver halide grains contained in at least one of the most sensitive layers of the red light-sensitive silver halide emulsion layer and the green light-sensitive silver halide emulsion layer,
(A) The tabular silver halide grains having an aspect ratio of 4 or more have a projected area of 50% or more with respect to the total projected area of the silver halide grains.
(B) Normal crystal grains having a sphere equivalent diameter of 0.5 μm or less have a projected area of 0.5% to 5% with respect to the total projected area of the silver halide grains.
Satisfying the condition (a) and the condition (b)
In addition, a cyan dye is fixed to a photographic component layer farther from the support than the red light-sensitive silver halide emulsion layer and / or from the support than the green light-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material, wherein a magenta dye is fixed to a photographic composition layer far away from the viewer.   The highest sensitivity layer of the red light-sensitive silver halide emulsion layer contains silver halide grains satisfying the above conditions (a) and (b), and is viewed from the support from the red light-sensitive silver halide emulsion layer. The silver halide color photographic light-sensitive material according to claim 1, wherein a cyan dye is fixed to a far photographic constituent layer.   The highest sensitivity layer of the green light sensitive silver halide emulsion layer contains silver halide grains satisfying the above conditions (a) and (b), and is viewed from the support from the green light sensitive silver halide emulsion layer. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein a magenta dye is fixed to a far photographic constituent layer.   Two or more red light-sensitive silver halide emulsion layers having different sensitivities and two or more green light-sensitive silver halide emulsion layers having different sensitivities from one another on the support in order from the side close to the support, and 4. The silver halide color photographic light-sensitive material according to claim 1, further comprising a photographic constituent layer including at least one blue light-sensitive silver halide emulsion layer.