JPH05173302A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material superior in graininess and small in disturbance of the gradation of each same color sensitive layer and also small in rise of fog during storage. CONSTITUTION:The silver halide photographic sensitive material has at least silver halide color-sensitive emulsion layers sensitive to the same color comprising >=3 layers and it is characterized by satisfying the following expression: A+5>=B>=A>=8, where A is the average silver iodide content of the lowest sensitive layer of the >=3 same color sensitive layers and B is that of the highest sensitive layer of them, and regulating the total coated silver amount of these layers to 1.4g/m<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent graininess and
The present invention relates to a multi-layered silver halide photographic light-sensitive material in which the gradation of each layer having the same color-sensitive layer when developed is small and the fog increase during storage is small.

[0002]

2. Description of the Related Art In recent years, the image quality of silver halide photographic light-sensitive materials in any field has been remarkably improved, and in order to obtain higher image quality, emulsion layers having substantially the same color sensitivity are multi-layered. Is being done. In particular, it is one of the indispensable means for improving graininess in color photographic light-sensitive materials.

JP-B-49-15495 discloses that at least one of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer is a top layer, an intermediate layer and a bottom layer. Described is a color light-sensitive material having a sensitivity that decreases in order, and the maximum color density of the uppermost layer and the intermediate layer is 0.6 or less. There is a problem that it becomes high and that the processing dependency of gradation change in the middle density range is large.

Further, in JP-A-61-289349, at least one emulsion layer has a three-layer structure of a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer and a high-sensitivity silver halide emulsion layer. Among these silver halide emulsion layers, the maximum color density of the medium-speed silver halide emulsion layer is 0.
It is described that a color photographic material having good graininess and less processing dependence of gradation can be obtained by setting it to more than 6. From the viewpoint of the demand for image quality, the processing dependence of gradation is still insufficient.

When three or more layers having the same color-sensing property are used in this manner, each of the high-sensitivity silver halide emulsion layer, the medium-sensitivity silver halide emulsion layer and the low-sensitivity silver halide emulsion layer is developed. It is difficult to match the gradations of the above, and especially the gradation change with respect to the processing standard in many laboratories is a cause of deteriorating the finished image quality.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide excellent graininess, less breakage in gradation of each layer of the same color-sensitive layer when developed, and less increase in fog during storage. It is to provide a multilayered silver halide photographic light-sensitive material.

[0007]

As a result of earnest research, the present inventors achieved the above object by the following.

(1) In a silver halide photographic light-sensitive material in which any one of the color-sensitive emulsion layers has three or more layers having different sensitivities, the average iodide of all emulsions used in each of the three or more emulsion layers The silver content (mol%) satisfies the relation of the following [1], and the total coated silver amount of the three or more emulsion layers is
Silver halide photographic light-sensitive material characterized by being 1.4 g / m ² or less [1] A + 5 ≧ B ≧ A ≧ 8 A: average silver iodide content of the layer having the lowest sensitivity among three or more layers B: Among the three or more layers, the average silver iodide content of the layer having the highest average silver iodide content (2) In a silver halide photographic light-sensitive material comprising any of three or more color-sensitive emulsion layers having different sensitivities, The silver halide photographic light-sensitive material according to (1), wherein the emulsion layer having the highest sensitivity among the three or more emulsion layers contains a reduction-sensitized emulsion.

The present invention will be described in more detail below.

The average silver iodide content of all emulsions referred to in the present invention is a value obtained by arithmetic mean from the average silver iodide content of all emulsion species contained in one constituent layer.

In the present invention, the total iodine content of silver halide grains was measured by the fluorescent X-ray analysis method (WDX) as follows.

1. Predetermined amounts of high-purity powder AgBr and AgI were measured and dissolved in a potassium cyanide solution.

2. After that, the solution having a known concentration was sampled with a microsyringe and dropped on a drip filter paper.

3. The sample was dried and A
The fluorescent X-ray intensities of g and I were measured, and the intensity ratio was correlated with the AgI concentration to prepare a calibration curve.

4. Next, the emulsion particles to be measured were enzymatically decomposed into gelatin and centrifuged to remove the supernatant.

5. The emulsion as the precipitate was dissolved in a potassium cyanide solution, the fluorescent X-ray intensity of AgI was similarly measured by WDX, and this was compared with a calibration curve to determine the iodine content of the sample to be measured.

For measuring WDX, Fluorescent X manufactured by Rigaku Denki Kogyo
The accuracy was improved by repeating the measurement twice using the line analyzer system 3080.

The average silver iodide content in the present invention is preferably in the range of [2] below, and more preferably [3].
The range is.

[2] 20 ≧ A + 5 ≧ B ≧ A ≧ 8 [3] 16 ≧ A + 3 ≧ B ≧ A ≧ 8 Within the range of the constitution of the present invention, even one kind of emulsion is contained in one constitution layer, You can have more than one. In the case of plural grains, a normal crystal and a twin crystal may be mixed, or grains having different silver iodide contents may be mixed.

The silver halide emulsion used in the present invention is not particularly limited, but it is preferable to apply at least one emulsion containing twinned grains.

Among twinned grains, an emulsion as disclosed in JP-A-3-241336 is more preferable.

The emulsion of the present invention is preferably reduction-sensitized with a reducing substance such as ascorbic acid.

In the present invention, the emulsion layer having the highest silver iodide content is preferably the highest sensitivity layer among the same color-sensitive layers, but at least one layer other than the highest sensitivity layer and the highest sensitivity layer have an average iodide content. The silver halide content may be the same and the average silver iodide content of the two or more layers may be the highest.

The constitution of the present invention can be applied to any color-sensitive layer, but most preferably to the blue-sensitive emulsion layer.

In the present invention, the total coating silver amount of the emulsion layer consisting of three or more layers is 1.4 g / m ² or less, preferably 1.2 g / m ² or less.

When the present invention is applied to a multi-layer color light-sensitive material, the color-sensitive layers may be arranged in order from the support side, that is, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer. Depending on the purpose, the installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are
Disclosure No.17643, No.18716 and No.308119
(Respectively abbreviated to RD17643, RD18716 and RD308119 below).

The locations of description are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known compounds usable in the present invention Photographic Additives are also described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (contained in light-sensitive material) 1011 XXB Item Various couplers can be used in the present invention, Specific examples thereof are described in the above-mentioned Research Disclosure. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-G item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR Coupler 1001 Item VII-F Item VIIF Item BAR Coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Additives used in the present invention Can be added by the dispersion method described in RD308119XIV.

In the present invention, the above-mentioned RD17643 page 28, RD
The supports described in 18716 pages 647-8 and RD308119, XVII can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119VII.
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided.

The light-sensitive material of the present invention is the above-mentioned RD308119VII-
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section K can be adopted.

The present invention is preferably applied to various color photographic light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. You can

The light-sensitive material of the present invention has the above-mentioned RD17643 28-29.
Development can be carried out by a usual method described in pp. RD18716, page 615 and RD308119, XIX.

[0037]

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

In all the following examples, the addition amount to the silver halide photographic light-sensitive material was 1 m ² unless otherwise specified.
The number of grams per unit is shown. Further, silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver halide.

Example 1 A light-sensitive material sample 101 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample 101 First layer: Antihalation layer (HC) Black colloidal silver 0.14 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer (IL-1) Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol%) 0.49 Silver iodobromide emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.12 Sensitizing dye (SD-1) 2.4 × 10 ^-4 Sensitizing dye (SD-2) 1.6 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 8.7 × 10 ^-5 Cyan coupler (C-1) 0.48 (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D -1) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: Medium sensitivity red-sensitive emulsion layer (RM) Silver iodobromide emulsion (average grain size 0.52 μm, AgI content 10.0 mol%) 0.54 (average) Particle size 0. 38μm, AgI content 10.0 mol%) 0.23 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Dye-sensitizing agent (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.15 (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) ) 0.30 Gelatin 0.93 Fifth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 1.0 μm, AgI content 16.0 mol%) 1.1 Sensitizing dye (SD-1) 1.1 × 10 ^-4 Sensitizing dye (SD-2) 1.1 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) ) 0.14 Gelatin 0.91 6th layer: Intermediate layer (IL-2) Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 7th layer: Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide Emulsion (Average grain size 0.38μm, AgI included 8.0 mol%) 0.58 Silver iodobromide emulsion (average particle diameter 0.27 [mu] m, AgI content of 2.0 mol%) 0.12 Sensitizing dye (SD─4) 6.4 × ^{10 -5} Sensitizing dye (SD─5) 5.7 × 10 ^{- 4} Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 Eighth layer: Medium sensitivity green sensitive emulsion layer (GM) Silver iodobromide emulsion (average grain size 0.59 μm, AgI content 8.0 mol%) 0.75 Sensitizing dye (SD-6) 2.1 × 10 ^-4 Sensitizing dye (SD-7) 9.5 × 10 ^-5 Magenta coupler (M -1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.07 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.0 9th layer: High sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 1.0 μm, average silver iodide content 10 mol%) 1.1 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-7) 1.2 × 10 ^-4 Magenta coupler (M-2) 0.84 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil-1) 0.27 (Oil-2) 0.012 Gelatin 1.0 10th layer: Yellow filter layer (YC) Yellow colloidal silver 0.07 Color stain inhibitor (SC-2) 0.15 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 Formalin scavenger (HS-1) 0.20 11th Layer: Intermediate layer (IL-3) Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol) %) 0.16 Silver iodobromide emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.115 Sensitizing dye (SD-8) 5.25 × 10 ^-4 Yellow coupler (Y-1) 0.75 High boiling solvent (Oil-- 2) 0.30 Gelatin 1.20 Formalin scavenger (HS-1) 0.073 13th layer: Medium Every time the blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 .mu.m, AgI content of 8.0 mol%) 0.33 Sensitizing dye (SD-8) 1.75 × 10 -4 Sensitizing dye (SD-9) 7.75 × 10 -5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.01 High boiling solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em-A (average Grain size 1.25 μm Average silver iodide content 11.0 mol%) 0.93 Sensitizing dye (SD-8) 7.88 × 10 ^-5 Sensitizing dye (SD-9) 3.0 × 10 ^-5 Yellow coupler (Y-1) 0. 11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.8 14th or 15th layer: 1st protective layer (Pro-1) Silver iodobromide emulsion (average grain size 0.08 μm, AgI content 1.0 mol%) 0.35 UV light Absorber (UV-1) 0.065 Ultraviolet absorber (UV-2) 0.10 High-boiling solvent (Oil-1) 0.07 High-boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 15th layer or Is the 16th layer: the second protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 The above textures In addition, coating aid Su-1, dispersion aid Su-2, viscosity modifier, hardeners H-1 and H-2, stabilizer ST-1, antifoggant AF-1, weight average molecular weight: 1
Two kinds of AF of 0,000 and weight average molecular weight: 1,100,000
2, and preservative DI-1 was added. The amount of DI-1 added was 9.4 mg / m ² .

Next, the sample 102, which is the 12th layer and the 13th layer in place of the 12th to 14th layers of the sample 101, is changed to the 12th layer to the 13th layer of the sample 101.
Samples 103 to 106 were prepared by changing 14 layers of emulsion.

Sample 102 12th layer: low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.4 μm, average silver iodide content 8.0 mol%) 0.3 Silver iodobromide emulsion (average grain size) 0.7 μm, average silver iodide content 8.0 mol%) 0.3 sensitizing dye (SD-8) 3.1 × 10 ^-4 sensitizing dye (SD-9) 1.1 × 10 ^-5 yellow coupler (Y-1) 0.78 DIR compound (D-1) 0.03 High boiling point solvent (Oil-2) 0.31 Gelatin 1.3 Formalin scavenger (HS-1) 0.073 13th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em-A (average grain Diameter 1.25 μm, average silver iodide content 11.0 mol%) 0.6 Sensitizing dye (SD-8) 1.1 × 10 ⁻⁴ Sensitizing dye (SD-9) 4.7 × 10 ⁻⁵ Yellow coupler (Y-1) 0.18 High Boiling point solvent (Oil-2) 0.067 Gelatin 1.3 Sample 103 12th layer: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol) %) 0.09 Silver iodobromide emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.13 Sensitizing dye (SD-8) 4.2 × 10 ^-4 Yellow coupler (Y-1) 0.75 High boiling solvent (Oil- 2) 0.30 Gelatin 1.20 Formalin scavenger (HS-1) 0.073 13th layer: Medium sensitive blue sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, AgI content 8.0 mol%) 0.26 Sensitizing dye (SD-8) ) 1.4 × 10 ^-4 Sensitizing dye (SD-9) 6.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.01 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em-B (average grain size 1.25 μm, average silver iodide content 9.0 mol%) 0.74 Sensitizing dye (SD-8) 6.3 × 10 ^-5 sensitization Dye (SD-9) 2.4 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) 0.046 Gelatin 0.8 Sample 104 12th layer: Low sensitivity blue Sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol%) 0.13 Silver iodobromide emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.09 Sensitizing dye ( SD-8) 4.2 × 10 ^-4 Yellow coupler (Y-1) 0.75 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 Formalin scavenger (HS-1) 0.073 Layer 13: Medium sensitivity blue-sensitive layer Silver iodobromide Emulsion (average particle size 0.59 μm, AgI content 8.0 mol%) 0.26 Sensitizing dye (SD-8) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-9) 6.2 × 10 ⁻⁵ Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.01 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em-C (average grain size 1.25 μm, average iodide Silver content 15.0 mol%) 0.74 Sensitizing dye (SD-8) 6.3 × 10 ^-5 Sensitizing dye (SD-9) 2.4 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.8 Sample 105 12th layer: Low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol%) 0.13 Iodobromide Silver emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.09 Sensitizing dye (SD-8) 4.2 × 10 ^-4 Yellow coupler (Y-1) 0.75 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 Formalin Scavenger (HS-1) 0.073 13th layer: Medium-sensitive blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, AgI content 8.0 mol%) 0.26 Sensitizing dye (SD-8) 1.4 × 10 ^-4 Sensitizing dye (SD-9) 6.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.01 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em-A (average grain size 1.25 μm, average silver iodide content 11.0 mol%) 0.74 Sensitizing dye (SD 8) 6.3 × 10 ^-5 Sensitizing dye (SD-9) 2.4 × 10 -5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) 0.046 Gelatin 0.8 Samples 106 12th layer: low sensitivity blue-sensitive emulsion Layer (BL) Silver iodobromide emulsion (average grain size 0.38 μm, AgI content 12.0 mol%) 0.13 Silver iodobromide emulsion (average grain size 0.27 μm, AgI content 2.0 mol%) 0.09 Sensitizing dye (SD- 8) 4.2 × 10 ^-4 Yellow coupler (Y-1) 0.75 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 Formalin scavenger (HS-1) 0.073 13th layer: Medium sensitive blue sensitive layer Silver iodobromide emulsion ( Average particle size 0.59 μm, AgI content 11.0 mol%) 0.26 Sensitizing dye (SD-8) 1.4 × 10 ^-4 Sensitizing dye (SD-9) 6.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.01 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion Em D (average particle size 1.25 .mu.m, the average silver iodide content of 8.0 mol%) 0.74 Sensitizing dye (SD-8) 6.3 × 10 -5 Sensitizing dye (SD-9) 2.4 × 10 -5 Yellow coupler (Y- 1) 0.11 high-boiling solvent (Oil-2) 0.046 gelatin 0.8 Emulsions Em-A to D used in the high-sensitivity blue-sensitive emulsion layer are Ag-2 fine particles of Em-2 used in the examples of JP-A-3-241336. Other than changing the halogen composition by changing the amount, etc., Em
-2 was prepared according to the preparation method.

The contents of the above samples 101 to 106 are summarized in Table 1.

[0044]

[Table 1]

The structures of the compounds used in each of the above samples are as follows.

[0046]

[Chemical 1]

[0047]

[Chemical 2]

[0048]

[Chemical 3]

[0049]

[Chemical 4]

[0050]

[Chemical 5]

[0051]

[Chemical 6]

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

The gradation properties, graininess, and fog during storage of the samples 101 to 106 produced as described above were evaluated. Each evaluation method is as follows.

[Gradation Test] (1) Test Conditions The test is conducted in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%.
The light-sensitive material to be tested is left in this state for 1 hour or more before use.

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

[0059]

[Table 2]

The illuminance change on the exposed surface is performed by using a chemical wedge. The chemical wedge used has a spectral transmission density variation of 360% to 700 nm in any region, within 10% in a region of less than 400 nm, and in a region of 40 nm or more in a region of 40 nm or more. Use within 5%.

The exposure time is 1/100 second.

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

The development treatment is completed within 30 minutes to 6 hours after the exposure.

The development process is performed as follows.

1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Fixing 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stable 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the treatment liquid used in each step is shown below.

(Color developer) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.
Add 0 g water to make 1 liter. (PH = 10.1) (Bleach) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1 liter and use ammonia water pH
Adjust to 6.0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Natrium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 cc. Conidax (manufactured by Konica Corp.) 7.5 cc. Add water to make 1 liter.

(4) Concentration measurement The concentration is represented by log ₁₀ (φ ₀ / φ). φ ₀ is an illumination light flux for density measurement, and φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. Also, during the measurement, the emulsion film surface shall face the light receiving device side. Density measurement is blue,
The status M densities of green and red are used, and the spectral characteristics thereof are set to the values shown in Table 3 as the overall characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.

[0070]

[Table 3]

The blue, green, and red densities obtained by plotting the densities obtained by the exposure, development, and density measurement as described above against the common logarithmic value (logE) of the exposure were plotted as the density function curve D (log
E) is determined.

Next, the ji value defined by the equation (3) described later is set to the density function curve D (log of yellow, magenta, and cyan).
Obtained in E). That is, the exposure dose that gives a density do of Dmin + 0.15
Exposure range logEi for every ΔlogE = 0.5 unit in the range from logE ₀ to logE ₅ at ΔlogE = 2.5
(I = 0,1,2,3,4,5) and density di (i = 0,1,2,3,4,5) given by each logEi, equation (1) gi is defined below.

Gi = di-di _-1 / logEi-logEi _-1 (1) Further, h is defined below in the expression (2).

H = d ₅ −d ₀ / logE ₅ −logE ₀ (2) Then, the ratio ji of gi and h is obtained.

Ji = gi / h (3) This ratio gi / h is taken as a ji value, and this is used as a parameter representing gradation. Evaluation was made based on the difference between the maximum value and the minimum value among J1 to J5. The smaller the difference, the better the gradation.

[Evaluation of Graininess] Regarding the graininess, RMS is used.
The value was evaluated.

With respect to the samples 101 to 106 after the development processing, the density of the minimum density +0.3 of the green density of the sample was determined by the aperture scanning area 1800 μm ² (slit width 10 μm, slit length 180 μm).
Scan with a micro densitometer to measure the standard deviation of the fluctuations of the density value of sampling number 1000 or more.
RMS value of was shown as a relative value with 100.

[Preservation Test] 55 ° C. for Samples 101 to 106
After leaving under the condition of 20 RH% for 7 days, the same exposure and development process as in the above gradation test was carried out to obtain a density function curve. The minimum yellow density value on the density function curve was determined and compared to that of the untreated sample. The difference from the value of the untreated sample was expressed as Δfog. The smaller this value is, the better the storage stability is. Table 4 shows the evaluation results of gradation, graininess, storability and the like.

[0079]

[Table 4]

From Table 4, it can be seen that Samples 105 and 106 according to the present invention have excellent graininess, good gradation and comparatively little increase in fog during storage, as compared with Comparative Samples 101 to 104.

Example 2 A sample 107 was prepared in the same manner as the sample 105 except that the emulsion Em-A of the high-sensitivity blue-sensitive emulsion layer in the sample 105 of the example 1 was changed to the following Em-E.

[Em-E] In Em-A, particles were formed in the presence of 1 × 10 ⁻³ mol / mol AgX of ascorbic acid.

When the sample 107 was evaluated in the same manner as in Example 1, the effect of the present invention was obtained.

[0084]

According to the present invention, a silver halide photographic light-sensitive material having excellent graininess, less breakage in gradation of each color layer of the same color when developed, and less increase in fog during storage was obtained. ..

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising any one of three color-sensitive emulsion layers having different sensitivities,
The average silver iodide content (mol%) of all emulsions used in each of the three or more emulsion layers satisfies the relationship of the following [1], and all the three or more emulsion layers are coated. 1.4g silver
/ m ² or less, a silver halide photographic light-sensitive material. [1] A + 5 ≧ B ≧ A ≧ 8 A: average silver iodide content of the layer having the lowest sensitivity among three or more layers B: average iodide of the layer having the highest average silver iodide content among the three or more layers Silver content 2. A silver halide photographic light-sensitive material in which any one of the color-sensitive emulsion layers comprises three or more layers having different sensitivities,
2. The silver halide photographic light-sensitive material according to claim 1, wherein the emulsion layer having the highest sensitivity among the three or more emulsion layers contains a reduction-sensitized emulsion.