JPH03239248A - Silver halide color photographic sensitive material having improved graininess - Google Patents

Abstract

PURPOSE:To improve graininess by specifying the coated amt. of silver in a blue sensitive silver halide emulsion layer. CONSTITUTION:The coated amt. of the silver in the blue sensitive silver halide emulsion layer is specified to 25 to 65wt.% of the total sum of the coated amt. of the silver of the sensitive silver halide emulsion layers. Both the sensitivity and the graininess are inferior and such is undesirable if the coated amt. of the silver of the blue sensitive silver halide emulsion layer is used at the amt. smaller than 25wt.% of the total sum. The effect does not change when the amt. exceeds 65wt.%. The images with which the graininess is inconspicuous when viewed by human eyes are obtd. in this way even when the images are printed onto monochromatic paper from the color photosensitive material.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color material having high sensitivity and improved graininess of a blue-sensitive silver halide emulsion layer. Regarding photographic materials.

[Background of the Invention] Silver halide negative color photographic photosensitive materials (hereinafter also referred to as negative color photosensitive materials) are usually used by being printed on color vapor, but in this case, green-sensitive halogenated materials are visible to the human eye. Graininess in the silver emulsion layer and the red-sensitive silver halide emulsion layer was noticeable. Therefore, in the past, it was necessary to use a large amount of silver in the green-sensitive layer and the red-sensitive layer, or to make each layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer multilayered. The graininess is improved by the following methods.

For example, British Patent No. 923,045 discloses that the layer is divided into a high-speed emulsion layer and a low-speed emulsion layer containing a diffusion-resistant coupler that develops substantially the same hue, and furthermore, the maximum color density in the high-speed emulsion layer is Although it is described that sensitivity can be increased without impairing graininess by adjusting the sensitivity to a low level, this technique does not have sufficient graininess.

Furthermore, in Japanese Patent Publication No. 49-15495, at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer is arranged in order of a top layer, an intermediate layer, and a bottom layer. A color light-sensitive material has been described which has such a sensitivity as to have a maximum color development density of the uppermost layer and an intermediate layer of 0.6 or less, and the graininess in the middle density region has been significantly improved.

On the other hand, in conventional news photography, monochrome negative photosensitive materials, that is, black and white negative films, are used exclusively, and after photography, these are printed onto monochrome paper.

However, in recent years, with the advancement of color photosensitive materials, there has been an increase in the use of negative color film in news photography, and as a result, opportunities to change camera film have increased.
Its complexity was a problem. In order to solve this problem, printing on monochrome vapor using negative color film has come to be done, but when printing from negative color film on color paper, the graininess of the blue-sensitive layer is noticeable to the human eye. Although it was not very noticeable, when printing from negative color film to monochrome vapor, the graininess of the blue-sensitive layer, which had not been a problem in the past, became noticeable, and a solution to this problem was desired.

In order to improve the graininess of the blue-sensitive silver halide emulsion layer, the inventors of the present invention have conducted various studies and found that by specifying the amount of silver coated in the emulsion layer, the graininess as seen by the human eye is ,
It was discovered that images with less noticeable graininess could be obtained, and the present invention was completed.

[Object of the Invention] The object of the present invention is to provide a silver halide color photographic light-sensitive material which, when printed from a negative color light-sensitive material to a light-sensitive material, especially a monochrome vapor, can produce an image in which graininess is not noticeable when viewed by the human eye. The goal is to provide the following.

[Structure of the Invention] The above object is to provide a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a support. This was achieved by a silver halide color photographic light-sensitive material characterized in that the amount of silver coated in the silver halide emulsion layer is 25% to 65% by weight of the total amount of silver coated in the light-sensitive silver halide emulsion layer.

The present invention will be explained in more detail below.

The silver halide color photographic light-sensitive material used in the present invention consists of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. Among these color-sensitive layers, Preferably, the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer have a three-layer structure. The three-layer structure herein refers to one in which the same color-sensitive layer consists of high-sensitivity, medium-sensitivity, and low-sensitivity layers. Therefore, the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer each consist of a high-speed, medium-speed, and low-speed layer.

More preferably, each color-sensitive layer has a three-layer structure, that is, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer consisting of high-speed, medium-speed, and low-speed layers. Become.

The amount of coated silver in the blue-sensitive silver halide emulsion layer used in the uninvention is 2 of the total amount of coated silver in the light-sensitive silver halide emulsion layer.
5% to 65% by weight, preferably 25% to 65% by weight
60% by weight is preferable, more preferably 30% by weight to 4% by weight.
It is 5% by weight.

The reason why the amount of silver coated in the blue-sensitive silver halide emulsion layer is limited as described above in the present invention is that if the total amount of silver coated is less than 25% by weight, both sensitivity and graininess are undesirable. Furthermore, if the total amount of coated silver exceeds 65% by weight, the effect of the present invention will not change, although the economical burden will increase.

As the silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention, any conventional silver halide emulsion can be used.

The emulsion can be chemically sensitized by a conventional method, and optically enhanced to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or emulsion layers may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Formalin scavenger-1 optical brightener, matting agent, lubricant, image stabilizer, surfactant, color fog preventive agent, development accelerator, development retarder, bleach accelerator, etc. are added to the photosensitive material of the present invention. be able to.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, commonly known color photographic processing can be performed after exposure.

In the following margin [Example] Next, the present invention will be described in more detail by showing examples, but the present invention is not limited to these examples.

In all the following examples, the amount added in the silver halide photographic light-sensitive material is g per 1 m2 unless otherwise specified.
Show the number. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

Example 1 Sample No. 1 of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

1st layer; antihalation layer black colloidal silver (coating amount of silver) 0.2 gelatin 0.4U V -10
,3 High boiling point solvent (Oil-1) 0.3 Second layer, intermediate layer gelatin 1.0 Third layer, first red-sensitive silver halide emulsion layer Silver iodobromide (Agl 7n+o1
%, octahedral, cubic equivalent particle size 0.3 μm) Gelatin sensitizing dye (s-i) Sensitizing dye (S-2) Sensitizing dye (S-3) Coupler (C-1) Coupler (C-3) Colored coupler (cc-1) DIR coupler (D-2) High boiling point solvent (Oil-1) 4th layer; 2nd red-sensitive silver halide emulsion layer Silver iodobromide (Ag
I 8mo1%, octahedral, cubic equivalent particle size 0.7 μm) Gelatin sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) 0.5 1.2 8 X 10- ' 5 X 10-' 3 X 10-5 0.10 0゜25 0.04 0.05 0.45 0.8 1.3 3 -1) Q, LO coupler (
C-3) 0.30 colored coupler (c
c-x) 0.03DIR coupler (D-2)
0.07 High boiling point solvent (Oil-1)
0.50 5th layer; 3rd red-sensitive silver halide emulsion layer Silver iodobromide (AgI 6mol1%, octahedral, cubic equivalent grain size 1.0 μm) 1.4 Gelatin
1.6 Sensitizing dye (S-1) l
Xl0-'sensitizing dye (S-2) txto
-' Sensitizing dye (S-3) 1x1o-'' coupler (C-2) 0.10 coupler (C
-1) 0.20 colored coupler (CG
-1) 0.02DIR coupler (D -2
) 0.05 high boiling point solvent (Oil-1)
0.40 6th layer; middle layer gelatin 0.803 C-10
,03 S C-20,02 High boiling point solvent (Oil-2) 0.05 No. 7
Layer; first green-sensitive silver halide emulsion layer silver iodobromide (AgI
7mo1%, octahedron, cubic equivalent particle size 0.3μm 1
0.3 gelatin 0.8 sensitizing dye (S-4) 6 x 10-' sensitizing dye (S-5) 1xlO-' sensitizing dye (s
-6) 1xto-' coupler (M-1)
0.05 coupler (M-3)
0.25 colored coupler (CM-1)
0.04DIR coupler (D-1) 0.06
High boiling point solvent (O11-2) 0.40 No. 8
Layer; second green-sensitive silver halide emulsion layer silver iodobromide (8gI
8mo1%, octahedron, cubic equivalent particle size 0.7μm)
0.7 Gelatin 1.1 Sensitizing dye (S-4) 3X10-' Sensitizing dye (
S-5) 5 X 10-'1 2 Sensitizing dye (S-6) 5 X 10-5
Coupler (M-1) 0.05 coupler (
M-3) 0.20 colored coupler (C
M-1) 0.03DIR coupler (D-1
) 0.05 high boiling point solvent (0il-2)
0.30 9th layer; 3rd green-sensitive emulsion layer Silver iodobromide (Agl 8 mo1%, octahedral, cubic equivalent grain size 1.0 μm) 1. t-gelatin
], 1 sensitizing dye (S-4)
2 X 10-' sensitizing dye (S-5) 5
X 10-' Sensitizing dye (S-6) 5X1
0-' coupler (M-2) 0.05 coupler (M-3) 0.10 colored coupler (CM-110,02DIR coupler (D-1)
0.02 high boiling point solvent (Oil-2)
0.30 10th layer; yellow filter layer yellow colloidal silver 0.05 gelatin
1. O3C-10,03 3C-20,02 High boiling point solvent (0il-2) 0.05 1st
1 layer; first blue-sensitive silver halide emulsion layer silver iodobromide (Agl
7mo1%, octahedron, cubic equivalent particle size 0.3μm l
0.15 gelatin 1.
3 sensitizing dye (S-7) 1xto-' coupler (Y-1) o, g.

DIR coupler (D-2) o, t.

High boiling point solvent (0ff-2) 0.28 1st
2nd layer; second blue-sensitive silver halide emulsion layer silver iodobromide (AgI
8mo1%, octahedron, cubic equivalent particle size 0.7μm)
0.25 Gelatin 0.
50 sensitizing dye (S-7) 5 X 10-
4 coupler (Y-1) 0.80 DIR coupler (D-2) 0.08 high boiling point solvent (0i
l-2) 0.25 13th layer; 2nd blue-sensitive silver halide emulsion layer Silver iodobromide (AgT 8mol%, 8
Hedron, cubic equivalent grain size 1.0μm) 0.50
Zeradin 070 sensitizing dye (s
-7) 2 X 10-' coupler (Y-1
) 0.20DIR coupler (D-2)
o, ot high boiling point solvent (0il-2)
0.07 14th layer: 1st protective layer Silver iodobromide (AgI 1 mol% average particle size 0.08 μm) 0.3 Gelatin 1.0 Ultraviolet absorber (U
V-1) 0.1 ultraviolet absorber (UV-2)
0.1 formalin scavenger (H5-1) 0
．． 5 Formalin scavenger (H5-2) 0.2 High boiling point solvent (oH-x) o, High boiling point solvent (Oil-3) 0.1 15th layer: 2nd protective layer gelatin 0.7-1 - 4 Alkali-soluble matting agent (average particle size 2 μm) 0.12 Polymethyl methacrylate particles (average particle size 3 μm) 0.02 Shelly agent (WAX-1) 0.04 Charge control agent (5u-1) 0. 004 In addition to the above composition, each layer contains a coating aid (Su-2) and a dispersion aid (Su-2).
Su-2, 5u-3), gelatin hardeners (H-1) and (++-2), stabilizers (Stab-1), antifoggants (AF-1, AF-21 and preservatives (DI-1) ) was added.

The compounds contained in each layer of Sample 1 are as follows.

6 -6 -7 Y-1 CM-1 aU35 -2 0 H5 M5-2 1-2 (C1(2-CH5O2CL)20 u-1 u-2 tab-1 F-1 AX 4 In the above sample No. 1 Sample No. 092.3.7.8 was prepared in which the amounts of silver halide (AgBrl) in the 11th layer, 12th layer, and 13th layer of the blue-sensitive silver halide emulsion layer were changed as shown in Table-1. did.

In addition, Sample No. 4 was prepared by omitting the 12th layer of Sample No. 1 and changing the 11th layer as follows.

11th layer: first blue-sensitive silver halide emulsion layer silver iodobromide (A
gI 7mo1%, octahedron, cubic equivalent particle size 0.3 μm
) 0.15 silver iodobromide (AgI 8mo1%,
Octahedron, cubic equivalent grain size 0.7 μm) 0.2
5 Gelatin 13 Sensitizing dye (S-7) 7xlO-' coupler (Y-1) o, g.

DIR coupler (D-2) 0.08 High boiling point solvent (Oil-2) 0.2 Sample No. 65 modified as shown
.

The ratio "in Table 1" is the ratio of the amount of silver coated in the blue-sensitive silver halide emulsion layer to the total amount of silver coated in the light-sensitive emulsion layer.

After the sample thus prepared was wedge exposed using white light, it was developed according to the following processing steps.

Margins below Table 1 7 8 Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Washing 3 minutes 15 seconds Fixing 6 minutes 30 minutes
Wash with water for 3 minutes 1 minute
Stabilization for 5 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

(color developer) Aniline/sulfate anhydrous sodium sulfite Hydroxylamine・ Anhydrous potassium carbonate sodium bromide 4.75g 4.25g 1/2 sulfate 2.0 g 37.5 g 1.3 g Nitrilotritriacetic acid trisodium salt (monohydrate salt) 2.5 g Add water and 1f1. shall be.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mj! Add water to bring the temperature to 1°C, and use aqueous ammonia to adjust pi (= 6.
Adjust to 0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1, and adjust to p)I=6.0 using acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 m
A Konidax (manufactured by Konica) 7.5mf
Add water and bring to 1°C.

Potassium hydroxide 1, Og The results of sensimetry using blue color (B) after development and the results of graininess are shown in Table 2.

Here, the sensitivity is the reciprocal of the exposure amount that gives a minimum density of 10, 1, and is expressed as a relative value with the sensitivity of sample No. 1 as 100.

Further, graininess was evaluated by RMS value. The RMS value is the minimum density of blue density +0.1, +0.5, +1.0 using Sakura Microdensitometer/Hidell PDM-5.
The standard deviation of the variation in concentration value when measuring 250 μm2 with Model AR (manufactured by Konica Corporation) was determined, and sample No.
The RMS value of 1 is expressed as a relative value of 100.

Regarding the sensitivity, a value larger than 100 indicates better sensitivity, and regarding the RMS value, a value smaller than 100 indicates good graininess.

Margin below 1 As is clear from Table 2, the present invention, in which the amount of silver coated in the blue-sensitive emulsion layer is 25% or more of the total amount of silver coated in the light-sensitive emulsion layer, has high sensitivity and extremely low graininess. I know it's good for you. In particular, the effect of sample No. 7 (the present invention) is
Although it has a superior effect compared to 3 (comparison), this effect cannot be explained simply by the amount of coated silver.

Also, one with three blue-sensitive layers (sample No. 7.8)
was more effective than the two-layered one (sample No. 9.10), especially in the high concentration area.

Example 2 Sample No. 1 to Sample No. 10 prepared in Example 1
was processed into a colored film of 13511II11 and photographed outdoors on a sunny day using a single-lens camera TT-1 (manufactured by Konica Corporation) and a Maches color chart (manufactured by Macbeth Corporation).

After the photographed samples were subjected to the development process described in Example 1, each developed sample was processed using Konica Color PC Vapor Type SR.
(manufactured by Konica Corporation), and then developed with process CPK-18A (manufactured by Konica Corporation).

Further, the same sample was carefully enlarged and printed on Fuji Pro Ortho WPFM-3 (manufactured by Fuji Photo Film Co., Ltd.), and then developed with Konicatone (manufactured by Konica Co., Ltd.).

The resulting prints were visually evaluated for graininess. The evaluation was made by averaging the evaluation results of 10 people on a scale of 1 to 10. 1
0 indicates the best graininess, and 1 indicates the worst graininess. The result is the third
Shown in the table.

Margin below No. 3 table Procedural amendment

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a support, the coating amount of silver in the blue-sensitive silver halide emulsion layer A silver halide color photographic light-sensitive material, wherein the silver halide color is 25% to 65% by weight of the total amount of silver coated in the light-sensitive silver halide emulsion layer.