Silver halide color photographic light-sensitive material having a wide latitude

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic light-sensitive material, more specifically to a silver halide color photographic light-sensitive material having a wide latitude in a high exposure portion and good aptitude for rapid processing, as well as an improved graininess and storage stability of the 3-layered silver halide emulsion layers.
BACKGROUND OF THE INVENTION
In recent years, a silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material) is making marked progress in quality of images, and a multilayer structure has come to be used in each of the red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer for much higher image quality and much wider latitude. Such multilayer structure is particularly useful for the improvement of graininess.
Many techniques are known as a means to improve graininess of a color light-sensitive material. For example, British Patent No. 923,045 disclosed a technique to enhance sensitivity without impairing the graininess by distributing couplers of the same color to a high speed emulsion layer and and a low speed emulsion layer, and adjusting the maximum optical density of the high speed layer to a low level. But this technique is not enough to provide a good graininess.
One technique was proposed in Japanese Patent Examined Publication No. 15495/1974, where at least one of the red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer has a sensitivity which decreases in the order of the top layer, intermediate layer and bottom layer, besides maximum optical densities in the top and intermediate layers are set below 0.6. While this technique can noticeably improve the graininess in medium and high density portions, it is liable to cause a high fog density.
Another technique is described in Japanese Patent Open for Public Inspection No. 91945/1987; that is, in a light-sensitive material having at least one emulsion layer of a 3-layered structure consisting of a low speed silver halide emulsion layer, medium speed silver halide emulsion layer and high speed silver halide emulsion layer, setting the maximum optical density in said medium speed silver halide emulsion layer and low speed silver halide emulsion layer to 0.8 or more is proposed for improving the graininess of an insufficiently exposed portion. But this method cannot provide a good graininess in medium and high exposure portions of the green-sensitive silver halide emulsion layer.
Since the green-sensitive silver halide emulsion layer has the highest spectral luminous efficacy among these color-sensitive layers, quality of this layer is one of the key contributing factors to the property of the light-sensitive material. Particularly, deterioration in the graininess of this layer impairs the overall impression of a color image. Therefore, in forming a green-sensitive three-layered silver halide emulsion layer, distribution of silver halide to each of the high speed layer, medium speed layer and low speed layer is very important, and many of the attempts made till now were to use a larger amount of silver halide in high speed and medium speed layers and a less amount in a low speed layer. As a result, problems have come to arise in the graininess in a middle to highlight portion and the latitude in a high exposure portion, thereby it is difficult to obtain a fairly wide latitude by this method.
Moreover, such attempts were to solve overall problems of the graininess in a color light-sensitive material with three-layer structure of layers sensitive to the same color; therefore, it is difficult to attain a high quality image expressible fine texture of human skin by a color light-sensitive material having simply a red-sensitive three-layer structure. To attain this object, there are required much more techniques for proper distribution of silver amount to each of the high speed, medium speed and low speed emulsion layers; setting of an optimum grain size; addition of a coupler capable of forming a slightly-mobile dye, etc. But improvement in gradation of the medium and low speed emulsion layers inevitably increases the amount of a dye forming coupler used in these layers and thereby results in uneven graininess, losing capability of expressing delicacy of the skin texture.
Further, the distribution of silver to the medium speed layer (the medium layer) and the low speed layer (the lower layer) in a larger amount than that to the high speed emulsion layer (the upper layer) causes troubles such as silver retention in a red-sensitive layer in a rapid process because the red-sensitive layer is the closest to the support.
Taking notice of the above conditions, the present inventor has studied how to improve the graininess in both of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer and found that an excellent graininess, a wide latitude in a high exposure portion of the green-sensitive layer, and an improved storage stability of the red-sensitive layer, as well as a good aptitude for rapid processing of the light-sensitive material can be attained by prescribing the order of arrangement of the high speed, medium speed and low speed emulsion layers in the three-layered structure and the amount of silver used in these emulsion layers.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in graininess.
A second object of the present invention is to provide a silver halide color photographic light-sensitive material improved in graininess of the green-sensitive silver halide emulsion layer of three-layered structure.
A third object of the present invention is to provide a silver halide color photographic light-sensitive material improved in graininess of the red-sensitive layer and aptitude for rapid processing of the light-sensitive material as well as in storage stability.
In a silver halide color photographic light-sensitive material comprising a support bearing thereon a red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, the foregoing objects have been attained by the silver halide color photographic light-sensitive material characterized in that one or both of the red-sensitive emulsion layer and green-sensitive layer have the three-layered structure in which the low speed silver halide emulsion layer, medium speed silver halide emulsion layer and high speed silver halide emulsion layer are coated on a support in this order and that the amount of silver used in at least one of said three-layer-structured layer of the red-sensitive and green-sensitive emulsion layer increases in the order of the medium speed layer, low speed layer and high speed layer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is hereunder described in more details.
The silver halide color photographic light-sensitive material of the invention has on a support the red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, and at least one of these emulsion layers consists of the low speed silver halide emulsion layer, medium speed silver halide emulsion layer and high speed silver halide emulsion layer. Particularly, the green-sensitive layer consists at least of the low speed silver halide emulsion layer, medium speed silver halide emulsion layer and high speed silver halide emulsion layer, and the coating amount of silver of these emulsion layers increases in order of the medium speed silver halide emulsion layer, low speed silver halide emulsion layer, and high speed silver halide emulsion layer. With these features, the silver halide color photographic light-sensitive material of the invention can exhibit an excellent graininess and a wide latitude in a high exposure portion.
In the silver halide color photographic light-sensitive material of the invention, the green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer are preferably of three-layered structure in which the low speed layer, medium speed layer and high speed layer are coated on a support in this sequence.
Further, in the silver halide color photographic light-sensitive material of the invention, the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer are of three-layered structure in which the low speed layer, medium speed layer and high speed layer are coated on a support in this sequence.
The total coating amount of silver in the silver halide color photographic light-sensitive material is desirably 100 mg/dm.sup.2 to 20 mg/dm.sup.2, more desirably 80 mg/dm.sup.2 to 40 mg/dm.sup.2.
The amount of silver contained in each of the low speed, medium speed and high speed layers may be arbitrarily selected within the limit of the total silver amount of 100 mg/dm.sup.2 to 20 mg/dm.sup.2 and in a manner to increase in the order of the medium speed silver halide emulsion layer, low speed silver halide emulsion layer and high speed silver halide emulsion layer.
The coating amount of silver of the high speed silver halide emulsion layer of the red-sensitive silver halide emulsion layer is preferably larger than the total silver amount in the low speed silver halide emulsion layer and medium speed silver halide emulsion layer, and ranges from 51 wt % to 75 wt %, preferably from 60 wt % to 70 wt %.
When the silver amount in the upper layer or the high speed layer of the red-sensitive emulsion layer is 50 wt % or less of the total silver amount in the red-sensitive layer, the graininess deteriorates on a shadow portion of a portrait, one of the most important photographic subjects, particularly on the neck and its vicinity. Deterioration in graininess is also caused in a blue sky portion of a picture photographed in the daytime of fine weather, leaving an unfavorable finish of images.
When the foregoing silver amount exceeds 75 wt %, a wide exposure latitude, a feature of the negative light-sensitive material, is deteriorated; thus, a large difference in luminance of subjects photographed by amateur photographers cannot be covered and inevitably causes deterioration in graininess or quality of images.
The low speed silver halide emulsion layer, medium speed silver halide emulsion layer and high speed silver halide elusion layer used in the invention may be any of those which are conventionally used in the photographic art.
In the invention, a good graininess and a wide latitude in a high exposure portion can be imparted to the light-sensitive material by increasing the silver amount in each of the low speed, medium speed and high speed silver halide emulsion layer in the order of the medium speed, low speed and high speed emulsion layer.
The silver halide color photographic light-sensitive material of the invention is usable not only as a light-sensitive material for the negative but as a light-sensitive material for the positive.
In the silver halide color photographic light-sensitive material of the invention, any of the conventional silver halide emulsions can be used.
Said emulsion may be chemically sensitized by conventional methods and spectrally sensitized to a desired wavelength range with the addition of a sensitizing dye.
An antifogging agent, stabilizer and the like may be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.
The emulsion layers and other hydrophilic colloid layers can be hardened. A plasticizer and latex of a water-insoluble or sparingly solulble synthetic polymer may be also incorporated.
Further, there may be contained a colored coupler having a function of color correction, a competing coupler and a compound which releases a useful photographic fragment such as development accelerator, bleach accelerator, developer, solvent for silver halide, toning agent, hardener, fogging agent, antifogging agent, chemical sensitizing agent, spectral sensitizing agent or desensitizing agent upon coupling reaction with an oxidation product of a developing agent.
In the light-sensitive material, there may be provided auxiliary layers such as a filter layer, antihalation layer, anti-irradiation layer, etc. In these auxiliary layers and/or the emulsion layers, there may be contained a dye capable of being bleached or discharged from the light-sensitive material during processing.
Further, there may be added to the light-sensitive material of the invention a formalin scavenger, fluorescent brightening agent, slipping agent, image stabilizer, surfactant, antistain agent, development accelerator, development retarder, bleach accelerator, etc.
Materials for the support are polyethylene laminated paper, polyethylene terephthalate film, baryta paper, cellulose triacetate film, etc.
To form dye images on the light-sensitive material of the invention, conventional color photographic processes can be used.

EXAMPLES
The present invention is hereunder described in more details with the examples, but the scope of the invention is not limited to these examples.
The addition amount of each material in the following examples is g/m.sup.2, unless otherwise specified. The amount of silver halide and colloidal silver is a value converted into an equivalent amount of silver. The amount of sensitizing dyes is given in mol/mol Ag.
EXAMPLE 1
On a triacetyl cellulose film support were coated in order the layers of the following composition to prepare Sample 1 of a multilayered color photographic light-sensitive material.
Sample 1 (comparison)
______________________________________1st layer: antihalation laterBlack colloidal silver (coating weight) 0.2Gelatin 0.4UV-1 0.3High boiling solvent (Oil-1) 0.32nd layer: intermediate layerGelatin 1.03rd layer: low speed red-sensitive silver halide emulsionlayerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.6grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.10Coupler (C-3) 0.25Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.454th layer: medium speed red-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 1.0grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.10Coupler (C-3) 0.30Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.07High boiling solvent (Oil-1) 0.505th layer: high speed red-sensitive silver halide emulsionlayerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.6grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.406th layer: intermediate layerGelatin 0.80SC-1 0.03SC-2 0.02High boiling solvent (Oil-2) 0.057th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.4grain size as converted into cube: 0.3 .mu.m)Gelatin 0.8Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.05Coupler (M-3) 0.25Colored coupler (CM-1) 0.04DIR coupler (D-1) 0.06High boiling solvent (Oil-2) 0.408th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.8grain size as converted into cube: 0.7 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.05Coupler (M-3) 0.20Colored coupler (CM-1) 0.03DIR coupler (D-1) 0.05High boiling solvent (Oil-2) 0.309th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.3010th layer: yellow filter layerYellow colloidal silver 0.05Gelatin 1.0SC-1 0.03SC-2 0.02High boiling solvent (Oil-2) 0.0511th layer: low speed blue-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.2grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-7) 1 .times. 10.sup.-3Coupler (Y-1) 0.80DIR coupler (D-2) 0.10High boiling solvent (Oil-2) 0.2812th layer: medium speed blue-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.50grain size as converted into cube: 0.7 .mu.m)Gelatin 0.50Sensitizing dye (S-7) 5 .times. 10.sup.-4Coupler (Y-1) 0.60DIR coupler (D-2) 0.08High boiling solvent (Oil-2) 0.2513th layer: high speed blue-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 0.70grain size as converted into cube: 1.0 .mu.m)Gelatin 0.70Sensitizing dye (S-7) 2 .times. 10.sup.-4Coupler (Y-1) 0.20DIR coupler (D-2) 0.01High boiling solvent (Oil-2) 0.0714th layer: 1st protective layerSilver bromoiodide 0.3(AgI: 1 mol %, average grain size: 0.08 .mu.m)Gelatin 1.0UV absorbent (UV-1) 0.1UV absorbent (UV-2) 0.1Formalin scavenger (HS-1) 0.5Formalin scavenger (HS-2) 0.2High boiling solvent (Oil-1) 0.1High boiling solvent (Oil-3 0.115th layer: 2nd protective layerGelatin 0.7Alkali-soluble matting agent 0.12(average particle size: 2 .mu.m)Polymethylmethacrylate particle 0.02(average particle size: 3 .mu.m)Slipping agent (wax-1) 0.04Static control agent (Su-1) 0.004______________________________________
In addition to the above compounds, a coating aid (Su-2), dispersing agents (Su-2 and Su-3), gelatin hardeners (H-1 and H-2), a stabilizer (Stab-1), antifogging agents (AF-1 and AF-2) and a antiseptic agent (D1-I) were added to each layer.
Chemical structures of the compounds contained in Sample 1 are as follows: ##STR1##
Samples 2 to 11 were prepared by varying the compositions of 7th, 8th and 9th layers of green-sensitive silver halide emulsion layers, each a low, medium, high speed layer, respectively, in Sample 1 as follows:
Sample 2 (comparison)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.4grain size as converted into cube: 0.3 .mu.m)Gelatin 0.8Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.05Coupler (M-3) 0.25Colored coupler (CM-1) 0.04DIR coupler (D-1) 0.06High boiling solvent (Oil-2) 0.408th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron,grain size as converted into cube: 0.7 .mu.m) 1.0Gelatin 1.3Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.06Coupler (M-3) 0.24Colored coupler (CM-1) 0.04DIR coupler (D-1) 0.06High boiling solvent (Oil-2) 0.369th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.0grain size as converted into cube: 1.0 .mu.m)Gelatin 1.0Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.04Coupler (M-3) 0.09Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 3 (comparison)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.6grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.08Coupler (M-3) 0.40Colored coupler (CM-1) 0.06DIR coupler (D-1) 0.09High boiling solvent (Oil-2) 0.608th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 0.8Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.04Coupler (M-3) 0.15Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.04High boiling solvent (Oil-2) 0.259th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 4 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.7grain size as converted into cube: 0.3 .mu.m)Gelatin 1.4Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.09Coupler (M-3) 0.44Colored coupler (CM-1) 0.07DIR coupler (D-1) 0.11High boiling solvent (Oil-2) 0.708th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.5grain size as converted into cube: 0.7 .mu.m)Gelatin 0.7Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.03Coupler (M-3) 0.13Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.03High boiling solvent (Oil-2) 0.199th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 5 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.9grain size as converted into cube: 0.3 .mu.m)Gelatin 1.8Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.11Coupler (M-3) 0.56Colored coupler (CM-1) 0.09DIR coupler (D-1) 0.14High boiling solvent (Oil-2) 0.908th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.5grain size as converted into cube: 0.7 .mu.m)Gelatin 0.7Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.03Coupler (M-3) 0.13Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.03High boiling solvent (Oil-2) 0.199th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.0grain size as converted into cube: 1.0 .mu.m)Gelatin 0.9Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.04Coupler (M-3) 0.08Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.25______________________________________
Sample 6 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.9grain size as converted into cube: 0.3 .mu.m)Gelatin 1.8Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.11Coupler (M-3) 0.56Colored coupler (CM-1) 0.09DIR coupler (D-1) 0.14High boiling solvent (Oil-2) 0.908th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.4grain size as converted into cube: 0.7 .mu.m)Gelatin 0.6Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.03Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.03High boiling solvent (Oil-2) 0.179th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.0grain size as converted into cube: 1.0 .mu.m)Gelatin 0.9Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.04Coupler (M-3) 0.08Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.25______________________________________
Sample 7 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.9grain size as converted into cube: 0.3 .mu.m)Gelatin 1.8Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.11Coupler (M-3) 0.56Colored coupler (CM-1) 0.09DIR coupler (D-1) 0.14High boiling solvent (Oil-2) 0.908th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.5grain size as converted into cube: 0.7 .mu.m)Gelatin 0.7Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.03Coupler (M-3) 0.13Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.03High boiling solvent (Oil-2) 0.199th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 8 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 2.0Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.13Coupler (M-3) 0.63Colored coupler (CM-1) 0.10DIR coupler (D-1) 0.15High boiling solvent (Oil-2) 1.08th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.8grain size as converted into cube: 0.7 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.05Coupler (M-3) 0.20Colored coupler (CM-1) 0.03DIR coupler (D-1) 0.05High boiling solvent (Oil-2) 0.309th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 9 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 2.0Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.13Coupler (M-3) 0.63Colored coupler (CM-1) 0.10DIR coupler (D-1) 0.15High boiling solvent (Oil-2) 1.08th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 0.8Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.04Coupler (M-3) 0.15Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.04High boiling solvent (Oil-2) 0.239th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.05Coupler (M-3) 0.10Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.30______________________________________
Sample 10 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 2.4Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.19Coupler (M-3) 0.94Colored coupler (CM-1) 0.15DIR coupler (D-1) 0.23High boiling solvent (Oil-2) 1.58th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.05Coupler (M-3) 0.20Colored coupler (CM-1) 0.03DIR coupler (D-1) 0.05High boiling solvent (Oil-2) 0.309th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.04Coupler (M-3) 0.08Colored coupler (CM-1) 0.02DIR coupler (D-1) 0.02High boiling solvent (Oil-2) 0.28______________________________________
Sample 11 (invention)
______________________________________7th layer: low speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron,grain size as converted into cube: 0.3 .mu.m) 1.0Gelatin 2.4Sensitizing dye (S-4) 6 .times. 10.sup.-4Sensitizing dye (S-5) 1 .times. 10.sup.-4Sensitizing dye (S-6) 1 .times. 10.sup.-4Coupler (M-1) 0.19Coupler (M-3) 0.94Colored coupler (CM-1) 0.15DIR coupler (D-1) 0.23High boiling solvent (Oil-2) 1.58th layer: medium speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 3 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-5Sensitizing dye (S-6) 5 .times. 10.sup.-5Coupler (M-1) 0.05Coupler (M-3) 0.20Colored coupler (CM-1) 0.03DIR coupler (D-1) 0.05High boiling solvent (Oil-2) 0.309th layer: high speed green-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.2grain size as converted into cube: 1.0 .mu.m)Gelatin 1.1Sensitizing dye (S-4) 2 .times. 10.sup.-4Sensitizing dye (S-5) 5 .times. 10.sup.-4Sensitizing dye (S-6) 5 .times. 10.sup.-4Coupler (M-2) 0.06Coupler (M-3) 0.12Colored coupler (CM-1) 0.03DIR coupler (D-1) 0.03High boiling solvent (Oil-2) 0.35______________________________________
Samples 1 to 11 prepared as above were subjected to imagewise exposure to white light, and color-developed by the following process [I].
______________________________________Color developing 3 min 15 secBleaching 6 min 30 secWashing 3 min 15 secFixing 6 min 30 secWashing 3 min 15 secStabilizing 1 min 30 secDrying______________________________________
Composition of each processing solution was as follows:
______________________________________(Color developer)4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)- 4.75 ganiline sulfateAnhydrous sodium sulfite 4.25 gHydroxylamine 1/2 sulfate 2.0 gAnhydrous potassium carbonate 37.5 gSodium bromide 1.3 gTrisodium nitrilotriacetate monohydrate 2.5 gPotassium hydroxide 1.0 gWater was added to make 1 l.(Bleacher)Ammonium ferric ethylenediamine tetracetate 100.0 gDiammonium ethylenediamine tetracetate 10.0 gAmmonium bromide 150.0 gGlacial acetic acid 10.0 mlWater was added to make 1 l, and pH was adjusted to6.0 with aqueous ammonia.(Fixer)Ammonium thiosulfate 175.0 gAnhydrous sodium sulfite 8.5 gSodium metasulfite 2.3 gWater was added to make 1 l, and pH was adjusted to6.0 with acetic acid.(Stabilizer)Formalin (37% solution) 1.5 mlKoniducks (made by Konica Corp.) 7.5 mlWater was added to make 1 l.______________________________________
On the processed samples, the magenta dye densities yielded by varied exposures were measured to obtain a photographic sensitometry characteristic curve.
The exposure necessary to give a density of the minimum magenta density (Dmin)+0.15 is defined as S1 by photographic sensitometry. Further, S.sub.2 to S.sub.5 were defined as follows, and these characteristic points were determined on each sample:
S.sub.2 =Dmin+0.80
S.sub.3 =Dmin+1.5
S.sub.4 =S.sub.1 +2.0log E
S.sub.5 =S.sub.1 +2.8log E
At the density points of S.sub.2 and S.sub.3, the densities were measured with a microdensitometer having an aperture area of 250 .mu.m.sup.2, thereby the RMS granularities were determined. The results are shown in Table 1 as S.sub.2 RMS and S.sub.3 RMS, respectively.
Next, the color density difference (D) between the exposure points of S.sub.4 and S.sub.5 was determined on each sample. The results are also shown in Table 1.
The relative RMS granularities are expressed by values relative to S.sub.2 RMS and S.sub.3 RMS of Sample 1 both of which are set at 100.
TABLE 1______________________________________ Sample Granularity Density in high No. S.sub.2 RMS S.sub.3 RMS exposure portion (.DELTA. D)______________________________________Comparison 1 100 100 0.15 2 95 120 0.10 3 120 95 0.15Invention 4 95 85 0.20 5 90 70 0.30 6 95 75 0.30 7 90 70 0.30 8 85 65 0.40 9 90 70 0.40 10 80 65 0.55 11 90 65 0.55______________________________________
As apparent from the results in Table 1, the samples of the invention exhibit smaller RMS granularities than the comparative samples at the points of S.sub.2 and S.sub.3, this indicates that the graininess is improved in the samples of the invention. Further, the density differences in high exposure portions are larger in the samples of the invention; therefore, the difference in image density can be expressed more distinctively in a high exposure portion, and thus high details in a highlight portion can be obtained.
EXAMPLE 2
Sample 12 of a multilayered color photographic light-sensitive material was prepared by coating the same layers as in Sample 1 of Example 1 in like manner on a triacetyl cellulose film support, except that the red-sensitive layers of the 3rd, 4th and 5th layers of Sample 1, each a low, medium and highspeed layer, respectively, were changed as follows:
Sample 12 (comparison)
______________________________________3rd layer: low speed red-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 1.0grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.10Coupler (C-3) 0.30Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.07High boiling solvent (Oil-1) 0.505th layer: high speed red-sensitive silver halideemulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.6grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.40______________________________________
Samples 13 to 21 were prepared by varying the red-sensitive silver halide emulsion layers of the 3rd, 4th and 5th layers in Sample 12.
Sample 13 (comparison)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.2grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 1.2grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.10Coupler (C-3) 0.30Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.07High boiling solvent (Oil-1) 0.505th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.8grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.40______________________________________
Sample 14 (comparison)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.2grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.70Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 1.5grain size as converted into cube: 0.7 .mu.m)Gelatin 2.0Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.15Coupler (C-3) 0.45Colored coupler (CC-1) 0.05DIR coupler (D-2) 0.10High boiling solvent (Oil-1) 0.755th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.8grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing de (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.40______________________________________
Sample 15 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 0.9grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.8grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.10Coupler (C-3) 0.30Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.07High boiling solvent (Oil-1) 0.505th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.8grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.40______________________________________
Sample 16 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 1.8grain size as converted into cube: 1.0 .mu.m)Gelatin 1.6Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.10Coupler (C-1) 0.20Colored coupler (CC-1) 0.02DIR coupler (D-2) 0.05High boiling solvent (Oil-1) 0.40______________________________________
Sample 17 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 2.2grain size as converted into cube: 1.0 .mu.m)Gelatin 2.2Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.12Coupler (C-1) 0.24Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.06High boiling solvent (Oil-1) 0.49______________________________________
Sample 18 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 2.5grain size as converted into cube: 1.0 .mu.m)Gelatin 2.5Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.14Coupler (C-1) 0.28Colored coupler (CC-1) 0.03DIR coupler (D-2) 0.06High boiling solvent (Oil-1) 0.55______________________________________
Sample 19 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 3.0grain size as converted into cube: 1.0 .mu.m)Gelatin 3.0Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing de (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.20Coupler (C-1) 0.40Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.10High boiling solvent (Oil-1) 0.80______________________________________
Sample 20 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.70Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 0.6grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 4.0grain size as converted into cube: 1.0 .mu.m)Gelatin 3.5Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.20Coupler (C-1) 0.40Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.10High boiling solvent (Oil-1) 0.80______________________________________
Sample 21 (invention)
______________________________________3rd layer: low speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 7 mol %, octahedron, 1.0grain size as converted into cube: 0.3 .mu.m)Gelatin 1.2Sensitizing dye (S-1) 8 .times. 10.sup.-4Sensitizing dye (S-2) 5 .times. 10.sup.-4Sensitizing dye (S-3) 3 .times. 10.sup.-5Coupler (C-1) 0.17Coupler (C-3) 0.42Colored coupler (CC-1) 0.07DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.754th layer: medium speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 8 mol %, octahedron, 1.0grain size as converted into cube: 0.7 .mu.m)Gelatin 1.3Sensitizing dye (S-1) 3 .times. 10.sup.-4Sensitizing dye (S-2) 2 .times. 10.sup.-4Sensitizing dye (S-3) 2 .times. 10.sup.-5Coupler (C-1) 0.12Coupler (C-3) 0.36Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.08High boiling solvent (Oil-1) 0.605th layer: high speed red-sensitive silver halide emulsion layerSilver bromoiodide (AgI: 6 mol %, octahedron, 4.5grain size as converted into cube: 1.0 .mu.mGelatin 4.5Sensitizing dye (S-1) 1 .times. 10.sup.-4Sensitizing dye (S-2) 1 .times. 10.sup.-4Sensitizing dye (S-3) 1 .times. 10.sup.-5Coupler (C-2) 0.20Coupler (C-1) 0.40Colored coupler (CC-1) 0.04DIR coupler (D-2) 0.10High boiling solvent (Oil-1) 0.80______________________________________
Samples 12 to 21 prepared as above were subjected to imagewise exposure to white light, followed by color development according to the process [I] in Example 1.
The cyan dye densities yielded by varied exposures were measured on each of the processed samples to obtain a photographic sensitometry curve. Then, the point S defined by the following expression was determined with respect to the density of cyan images,
S=D min+0.5
where Dmin is the minimum density.
At the point S, the density was measured with a microdensitometer having an aperture area of 250 .mu.m.sup.2 to determine the RMS granularity. Further, after conditioning at 60% RH, each sample was put into a moisture-proof bag and subjected to heat treatment at 40.degree. C. for 50 days, followed by color development by the process [I]. Then, the difference in minimum cyan density between before and after the heat treatment (.DELTA.d) was determined.
Moreover, the samples undergone the imagewise exposure to white light were color-developed according to the following process [II].
______________________________________Processing [II]Color developing 3 min 15 sec 38.degree. C.Bleach-fixing 2 min 00 sec 38.degree. C.Washing 1 min 40 sec 38.degree. C.Fixing 40 sec 38.degree. C.(Color developer)Diethylenetriamine pentacetate 1.0 g1-hydroxyethylidene-1,1-diphosphonic acid 2.0 gSodium sulfite 4.0 gPotassium carbonate 30.0 gPotassium bromide 1.4 gPotassium iodide 1.3 mgHydroxylamine sulfate 2.4 g4-(N-ethyl-N-.beta.-hydroxyethylamino)-2- 4.5 gmethylaniline sulfateWater to make 1 l pH 10.00(Bleach-fixer)Ammonium ferric ethylenediamine 80.0 gtetracetateDisodium ethylenediamine tetracetate 10.0 gBleaching accelerator 1.5 gSodium sulfite 12.0 gAqueous solution of ammonium thiosulfate 240 ml(70%)Water to make 1 lWith aqueous ammonia (28%) pH 6.8(Stabilizer)Formalin (37% wt) 2.0 mlPolyoxyethylene-p-monononylphenolether 0.3 g(average polymerization degree: 10)Disodium ethylenediamine tetracetate 0.05 gWater to make 1 l pH 6.0______________________________________
The infrared density (1,000 nm) at the maximum density portion of each processed film was measured to evaluate desilverizing property.
The results are shown in Table 2, which summarizes the evaluation results on the RMS granularity, stability in high temperature storage and infrared absorption density.
TABLE 2______________________________________Sample No. RMS.sup.1) .DELTA.D.sup.2) IR Density.sup.3)______________________________________12 Comparison 100 100 2013 Comparison 80 200 10014 Comparison 75 250 16015 Invention 60 80 2016 Invention 60 40 1017 Invention 55 50 518 Invention 50 55 1019 Invention 75 80 1020 Invention 80 90 4021 Invention 105 110 180______________________________________ .sup.1) Expressed by a value relative to RMS granularity of Sample 12 which is set at 100 (a smaller value means better granularity). .sup.2) Expressed by a value relative to .DELTA.d of Sample 12 which is set at 100 (a smaller value means better storage stability). .sup.3) Expressed by a value relative to infrared density of Sample 13 which is set at 100 (a smaller value means better desilverizing property)
It can be understood from the results in Table 2 that the samples of the invention are lower in RMS granularity and better in graininess than the samples for comparison and cause less change in the minimum density even after the heat treatment, besides having an excellent desilverizing property in a rapid processing.

Number	Date	Country	Kind
1-272046	Oct 1989	JPX
1-272048	Oct 1989	JPX

Number	Name	Date
4746601	Mihayashi et al.	May 1988
4780399	Urata	Oct 1988
4880726	Shiba et al.	Nov 1989
4946767	Yamagami	Aug 1990
4952485	Shibahara et al.	Aug 1990

Silver halide color photographic light-sensitive material having a wide latitude

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