JP2002258426A - Silver halide color photographic sensitive material and color image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material giving a good image under various light source conditions and excellent in color reproduction, sharpness and processing dependency. SOLUTION: The silver halide color photographic sensitive material has a silver halide emulsion layer containing a coupler and having the spectral sensitivity maximum at 400-490 nm, a silver halide emulsion layer containing a coupler and having the spectral sensitivity maximum at 500-600 nm, a silver halide emulsion layer containing a coupler and having the spectral sensitivity maximum at 600-700 nm and a non-photosensitive layer on the base. The emulsion layer having the spectral sensitivity maximum at 500-600 nm comprises one average grain diameter minimum emulsion layer in which the average grain diameter (equivalent spherical diameter) of all silver halide grains is smallest and two or more coarse emulsion layers in which the average grain diameter of all silver halide grains is larger than the average grain diameter of the average grain diameter minimum emulsion layer. One or more of the two or more coarse emulsion layers are disposed on each of the sides close to and remote from the base with respect to the average grain diameter minimum emulsion layer. The non-photosensitive layer is not situated nearer the base than the silver halide emulsion layer having the spectral sensitivity maximum at 600-700 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a color photographic light-sensitive material for photographing. The present invention relates to a silver halide color photographic material having excellent sharpness and processing dependence.

The present invention also relates to a color image forming method using the above-mentioned silver halide color photographic light-sensitive material.

[0003]

2. Description of the Related Art In recent years, silver halide color photographic materials have been developed according to ISO. The demand in the ultra-high sensitivity region represented by color negative films such as 800 and 1600 has been increasing, and the demand for higher image quality of these photographic materials for high sensitivity has been increasing. As these color negative films become more sensitive, the number of cases where exposure is performed without much effort in setting the light source for photography has been increasing. Color negative films that can be used are preferred in principle. For the purpose of reproducing colors close to the human eye, a technique of providing a photosensitive layer that gives a negative layering effect to the red photosensitive layer (US
-4705744, JP-A-2000-105445, etc.)
Also, a number of techniques (for example, Japanese Patent Application Laid-Open No. 62-160449) have been disclosed in which the spectral sensitivity distribution is adjusted to approximate the spectral sensitivity of the human eye. However, when these techniques are simply applied to a conventional color negative film, although the color reproducibility is improved, the change in the development density due to the fluctuation of the developing solution is large, and the spectral sensitivity has a maximum at 500 to 600 nm in particular. The problem that the change in the development density of the photosensitive layer becomes large newly occurred. The worsening of the development density fluctuation due to the fluctuation of the processing solution means that under various processing conditions in the market, the original characteristics of the photosensitive material may not be sufficiently exhibited, and thus an improvement is required. Further, when scanning and exposing these photosensitive materials using a CRT, LED, or laser as a light source based on the digitized image information,
It has also been found that this processing dependency is further deteriorated.
Conventionally, measures to solve these problems have been taken by improving the method of producing silver halide emulsion grains to improve processing dependency, changing the materials of couplers and the like to be used, changing additives, and searching for optimal combinations. Was not enough.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which gives a good image even under various light source conditions, is excellent in color reproduction and sharpness, and is excellent in processing dependence. It is.

Another object of the present invention is to provide a color image forming method which gives good images even under various light source conditions, is excellent in color reproduction and sharpness, and is excellent in processing dependence.

[0006]

Means for Solving the Problems The object of the present invention was able to be solved by the following means as a result of intensive studies.

(1) 400 to 490 containing a coupler
a silver halide emulsion layer having a spectral sensitivity maximum in a region of nm, a coupler, containing a coupler, and a silver halide emulsion layer having a spectral sensitivity maximum in a region of 500 to 600 nm; In a silver halide color photographic material having a silver halide emulsion layer having a maximum spectral sensitivity and a non-photosensitive layer on a support,
There are three or more silver halide emulsion layers having a spectral sensitivity maximum in the range of 00 to 600 nm, and the three or more emulsion layers are the average grain size (equivalent to sphere) of all silver halide grains in the layer (a). One layer having the smallest average particle size).
(B) two or more “large emulsion layers” in which the average grain size (equivalent sphere diameter) of all silver halide grains in the layer is larger than the average grain size of the minimum emulsion grain size emulsion layer; One or more large emulsion layers are disposed on the side closer to and farther from the support with respect to the minimum emulsion layer, and
A silver halide color photographic light-sensitive material having no non-light-sensitive layer on the side closer to the support than a silver halide emulsion layer having a spectral sensitivity maximum in a region of from about 700 nm.

(2) A coupler containing 400 to 490
a silver halide emulsion layer having a spectral sensitivity maximum in a region of nm, a coupler, containing a coupler, and a silver halide emulsion layer having a spectral sensitivity maximum in a region of 500 to 600 nm; In a silver halide color photographic material having a silver halide emulsion layer having a maximum spectral sensitivity and a non-photosensitive layer on a support,
There are three or more silver halide emulsion layers having a spectral sensitivity maximum in the range of 00 to 600 nm, and the three or more emulsion layers are the average particle diameter (equivalent sphere diameter) of all silver halide grains in the layer. (C) a silver halide emulsion layer other than the minimum average grain size emulsion layer, and (c) contained in the minimum average grain size emulsion layer. Of the development inhibitor releasing compound (mol / m ² ) (DI
R _L ) and (d) the total coating amount (DIR _H ) of the development inhibitor releasing compound contained in any one of the silver halide emulsion layers other than the average grain size minimum emulsion layer. (DI
R _H ) / (DIR _L )> 2, that there is at least one silver halide emulsion layer,
A silver halide color photographic light-sensitive material having no non-light-sensitive layer on the side closer to the support than a silver halide emulsion layer having a spectral sensitivity maximum in a range of 0 to 700 nm.

(3) 400 to 490 containing a coupler
Silver halide emulsion layer having spectral sensitivity maximum in nm range
And a coupler, and divided into regions of 500 to 600 nm.
A silver halide emulsion layer having a maximum light sensitivity and a coupler
And has a spectral sensitivity maximum in the 600-700 nm region
Silver halide emulsion layer and non-photosensitive layer on a support
Silver halide color photographic light-sensitive material having
Halogen having spectral sensitivity maximum in the range of 00 to 600 nm
Three or more silver halide emulsion layers, and the three or more emulsion layers
Layer is the average particle size (sphere) of all silver halide grains in layer (a).
One layer having the smallest average grain size),
(B) Average grain size of all silver halide grains in the layer (equivalent to sphere)
Diameter) is larger than the average particle diameter of the emulsion layer having the minimum average particle diameter.
A "large emulsion layer" consisting of two or more layers,
Layer is closer to and farther from the support than the average grain size minimum emulsion layer
(C) said average grain
Of the development inhibitor releasing compound contained in the emulsion layer having the smallest diameter.
Total application amount (mol / m^Two) (DIR_L) And (d) the average particle size
In any one of the silver halide emulsion layers other than the small emulsion layer
The total amount of the development inhibitor-releasing compound contained (DIR
_H) And (DIR)_H) / (DIR_L)> 2
At least one silver halide emulsion layer in which
And a spectral sensitivity in the range of 600 to 700 nm.
Closer to the support than the silver halide emulsion layer having the maximum
Halogen having no non-photosensitive layer on the side
Silver halide color photographic material.

(4) a blue-sensitive silver halide emulsion layer containing at least one yellow coupler on a support,
A green-sensitive silver halide emulsion layer containing a magenta coupler and a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer containing a cyan coupler,
The center-of-gravity sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm ≦ λ _G ≦ 580 nm, and at least one cyan-sensitive red-sensitive silver halide emulsion layer has a range of 500 nm to 600 nm. And the center-of-gravity wavelength (λ _-R ) of the distribution of the magnitude of the multilayer effect received from other layers is 500 nm <λ
_-R <560 nm and λ _G -λ- _R ≧ 5 nm, and further comprising no non-photosensitive layer closer to the support than the red-sensitive silver halide emulsion layer. Color photographic light-sensitive material.

(5) Any one of (1) to (4), wherein a resin-back layer containing carbon is provided on the surface of the support opposite to the surface having the photosensitive layer.
2. The silver halide color photographic light-sensitive material described in 1. above.

(6) The silver halide emulsion layer having a spectral sensitivity maximum in the range of 600 to 700 nm is a cyan coloring layer, and the maximum spectral sensitivity wavelength λ _R ^max in the spectral sensitivity distribution of cyan coloring is 639 nm or less. The silver halide color as described in (5), wherein the wavelength λ _R ⁸⁰ (using a wavelength shorter than λ _R ^max ) at which the sensitivity is 80% of the sensitivity at the maximum spectral sensitivity wavelength is 585 nm or more and 615 nm or less. Photosensitive material.

(7) Any one of (1) to (6)
After exposing the silver halide color photographic light-sensitive material described in
A color image forming method, comprising developing with a developing solution containing -amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline.

(8) The color image forming method according to the above (7), wherein the exposure is scanning exposure of 10 ^-3 seconds or less per pixel using digital image information.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The light-sensitive material of the present invention contains a coupler and has a content of 400 to 490.
a silver halide emulsion layer having a spectral sensitivity maximum in a region of nm, a silver halide emulsion layer containing a coupler and having a spectral sensitivity maximum in a region of 500 to 600 nm, and a spectral sensitivity in a region of 600 to 700 nm containing a coupler. This is a silver halide color photographic material having a silver halide emulsion layer having a maximum and a non-light-sensitive layer on a support. Especially 500
There are a plurality of silver halide emulsion layers each having a spectral sensitivity maximum in the range of
It contains silver halide emulsion grains having a spectral sensitivity maximum in the nm region, couplers and the like.

The number of silver halide emulsion layers having a spectral sensitivity maximum in the range of 500 to 600 nm is preferably within 6 layers from the viewpoint of production cost and the like. Particularly preferably, there are three to five layers. In the present invention, the position of the photosensitive layer in which the average particle diameter (equivalent sphere diameter) of all the silver halide grains contained in each layer is the smallest (hereinafter, also referred to as the "average grain size minimum emulsion layer") or the average grain size. It defines the total coating amount of the development inhibitor releasing compound contained in the minimum diameter emulsion layer. In the present specification, “average grain size” means that when one layer contains a plurality of silver halide emulsions having different average grain sizes,
It means the average value of the particle diameters of all the grains contained in those emulsions.

More specifically, in the present invention, the average
The side closer to and farther from the support with respect to the smallest emulsion layer
Has an average grain size larger than that of the minimum emulsion grain size emulsion layer.
Halogen having a spectral sensitivity maximum in the range of 0 to 600 nm
The presence of a silver halide emulsion layer; and / or
The total coating amount of the development inhibitor releasing compound in the small emulsion layer (mol / m
^Two) (DIR_L) And the other 500-600 nm region
Any one of the silver halide emulsion layers having the maximum spectral sensitivity
Total coating amount of development inhibitor releasing compound in the layer (DIR_H)
(DIR_H) / (DIR_L)> 2
At least one silver halide emulsion layer
is necessary. DIR_HAnd DIR_LThe relationship of (DIR_H)
/ (DIR_L)> 4 is preferred. For the smallest average grain size emulsion layer
Coating amount of DIR compound contained (DIR_L) Is photosensitive
Can be set as appropriate according to the material composition, purpose, etc.
But usually 0-5 × 10^-Fourmol / m^TwoCan be added
You. 500-600nm region other than the smallest average grain size emulsion
Any one of the silver halide emulsion layers having the maximum spectral sensitivity
Coating amount of DIR compound contained in the layer (DIR_H)Also,
It can be set as appropriate according to the composition and purpose of the photosensitive material.
Yes, usually 1 × 10 ^-6~ 1 × 10^-3mol / m^TwoAdded
be able to. (DIR_H) / (DIR_L)> 2
DIR where_HOf silver halide emulsion layers satisfying
Is preferably 5 layers or less from the viewpoint of manufacturing cost and the like.
And more preferably 1 to 3 layers.

One of the embodiments of the present invention, 600 to 700
The absence of the non-photosensitive layer on the side closer to the support than the silver halide emulsion layer having the spectral sensitivity maximum in the region of
On the side closer to the support than the silver halide emulsion layer spectrally sensitized to the region of 00 to 700 nm, the photosensitive silver halide emulsion grains containing any of colloidal silver, a development inhibitor, a coupler, and a dye are prepared. It means that there is no substantially free hydrophilic colloid layer. Here, the term "hydrophilic colloid layer substantially free of photosensitive silver halide emulsion particles" refers to a very small amount of hydrophilic colloid layer containing photosensitive silver halide emulsion particles that does not affect photographic characteristics. However, this means that it is in the category of the non-photosensitive layer defined in the present invention.

The gradation of the light-sensitive material of the present invention is not particularly limited, but the following ranges are more preferable. The range will be described. The exposure is performed by white light exposure or green light exposure through a wedge which can adjust the amount of light applied to the light-sensitive material by changing the density commonly used in the art stepwise or continuously. The exposure time is 1/100 sec. After this exposure, color development processing is performed, and the color transmission density for each exposure amount is measured to obtain a Log E versus color density curve. In this transmission density measurement, an interference filter having a λmax of 550 nm and a half width of 10 nm is used for the measurement of magenta density. In this Log E versus color density curve, the slope of a straight line connecting the point of D _min +0.2 and the density point at a light quantity 1.5 Log E higher than the light quantity giving this density is obtained. That is, the inclination γ _M of the magenta coloring layer obtained by white exposure is Γ _{M in} green exposure.
Is obtained. In the present invention, γ _M is 0.7 or less, Δ _M / γ
_M is preferably 1.3 or less. More preferably gamma _M / gamma _M 1.2
It is as follows.

The center-of-gravity sensitivity wavelength λ _G defined in the present invention is given by the following equation. λ _G = [∫ ₅₀₀ ⁶⁰⁰ λ · S _G (λ) · dλ] / [∫ ₅₀₀ ⁶⁰⁰
_{S G (λ) · dλ]} S G (λ) is the spectral sensitivity distribution curve of the green-sensitive layer. When there are two or more green sensitive layers, the relationship between the center-of-gravity sensitivity wavelengths refers to the entirety of the green sensitive layers. In the present invention, 52
Preferably, 0 nm ≦ λ _G ≦ 580 nm, and 52
More preferably, 5 nm ≦ λ _G ≦ 570 nm.

The red-sensitive silver halide emulsion layer of 500
The center-of-gravity wavelength λ- _R of the wavelength distribution of the magnitude of the multilayer effect received from another layer in the range of nm to 600 nm is obtained as follows. When the number of red-sensitive layers is two or more, the above-mentioned 500
The relationship between the center-of-gravity wavelengths of the wavelength distribution of the magnitude of the multilayer effect received from other layers in the range of nm to 600 nm refers to the center-of-gravity wavelength of the multilayer effect obtained from the plurality of red-sensitive layers as a whole.

First, a red filter that transmits a specific wavelength or more or an interference filter that transmits only a specific wavelength is used so that a red-sensitive layer that emits cyan at a wavelength of 600 nm or more is exposed and other layers are not exposed. And apply a uniform exposure to cover the red-sensitive layer which develops cyan so as not to have substantial light sensitivity. Next, when a spectral exposure is applied, the blue-sensitive layer and the green-sensitive layer act on the fogged emulsion by a layering effect of development suppression to give a reversed image. From this inverted image, the spectral sensitivity distribution S as an inverted photosensitive material is shown.
_-R (λ) is calculated. The center-of-gravity wavelength λ- _R of the multilayer effect is calculated by the following equation. λ _-R = [∫ ₅₀₀ ⁶⁰⁰ λ · S _-R (λ) · dλ] / [∫ ₅₀₀
⁶⁰⁰ S _-R (λ) · dλ].

In the present invention, 500 nm <λ _−R <56
0 nm, and 510 nm <λ _−R <55
More preferably, it is 0 nm.

In the present invention, λ _G -λ _-R ≧ 5n
m, preferably 10 nm ≦ λ _G −λ _−R ≦ 50
More preferably, it is nm.

In the light-sensitive material of the present invention, the above 600 to
When the silver halide emulsion layer having a spectral sensitivity maximum at 700 nm is a cyan coloring layer, the maximum spectral sensitivity wavelength λ _R ^max in the spectral sensitivity distribution of cyan coloring is preferably 639 nm or less, and the maximum spectral sensitivity wavelength 80% of sensitivity
Sensitivity wavelength λ _R ⁸⁰ (Use a wavelength shorter than λ _R ^max )
Is preferably 585 nm or more and 615 nm or less.
λ _R ^max is more preferably 605 nm or more and 635 nm or less. lambda _R ⁸⁰ is more preferably 585 or more 610nm or less.

In the present invention, it is preferable to use a solid dispersion dye in the photographic material. In particular, it is preferable to use a solid dispersion dye having an absorption maximum in a blue region (range of 400 nm to 500 nm) and having a small absorption in a region exceeding 500 nm. This means that, if there is unnecessary absorption in the region exceeding 500 nm, not only light in the blue region but also light in the red region from the green region will be absorbed, and the substrate side will be closer to the support than the layer containing the solid dispersion dye. This is because the quantity of light of a wavelength component necessary for the located green-sensitive emulsion layer and red-sensitive emulsion layer is reduced, causing low sensitivity. As the solid dispersion dye having an absorption maximum in the blue region, a dye described in JP-A-11-305395 is preferably used.

In addition to those having absorption in the blue region, solid disperse dyes having absorption in the green and red regions or solid dispersion dyes having absorption over the entire visible region are used depending on the purpose. .

The dispersion of these dyes is described in JP-A-52-9271.
6, a dispersing machine such as a ball mill, a sand mill, a colloid mill, or a dispersing machine such as a vibrating ball mill, a planetary ball mill, a jet mill, a roll mill, a manton gauulin, a microfluidizer, and a disk impeller mill. Can be arbitrarily selected, but a vertical or horizontal medium disperser is preferable.

In each case, it is preferable to use a solvent (for example, water), and it is more preferable to use a dispersing surfactant. As the surfactant for dispersion, JP-A-52
Anionic surfactants can be used as described in JP-A-92716 and WO 88/04794, and an anionic polymer can be used as described in JP-A-4-324858. Although cationic surfactants can be used, anionic polymers or anionic surfactants are preferred.

After dissolving the dye in an appropriate solvent, a poor solvent for the dye may be added to precipitate microcrystals. In this case, the above-mentioned surfactant for dispersion may be used. . Alternatively, it may be dissolved first by controlling the pH in a solvent, and then the pH may be changed to cause microcrystallization.

The dye in the dispersion has an average particle size of 0.005.
μm to 10 μm, preferably 0.01 μm to 1 μm
m, more preferably 0.01 μm to 0.5 μm, and in some cases, preferably 0.01 μm to 0.1 μm.

In dispersing the dye used in the present invention, the solid dye may be dispersed without any pretreatment. At this time, it is preferable to use the dye solid in a wet state obtained in the synthesis process of the dye for dispersion.

If necessary, the heat treatment may be performed before and / or after the dispersion. For more effective heat treatment, it is preferable to perform the heat treatment at least after the dispersion. The heating method is not particularly limited as long as heat is applied to the dye solid. The temperature is preferably 40 ° C. or higher, and the upper limit may be any number as long as the dye is not decomposed.
It is below ° C. More preferably, it is 50 ° C to 150 ° C. The heating time is not particularly limited as long as the dye is not decomposed, and is 15 minutes to 1 week, preferably 1 hour to 4 days. In order to effectively perform the heat treatment, it is preferable to perform the treatment in a solvent, and the type of the solvent is not limited as long as the dye used in the present invention is not substantially dissolved.
For example, water, alcohols (eg, methanol, ethanol, isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol,
Diethylene glycol, ethyl cellosolve), ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate, butyl acetate), alkyl carboxylic acids (eg, acetic acid, propionic acid), nitriles (eg, acetonitrile), ethers (For example, dimethoxyethane, dioxane, tetrahydrofuran) and the like.

It is more effective to coexist an organic carboxylic acid during the heat treatment. Examples of the organic carboxylic acids include alkyl carboxylic acids (for example, acetic acid and propionic acid), carboxymethyl celluloses (CMC), and aryl carboxylic acids (for example, benzoic acid and salicylic acid). When used as a solvent, the amount of the organic carboxylic acid is from 0.5 to the mass of the dye used in the present invention.
100 times the amount can be used. When an organic carboxylic acid is added and used using a solvent other than the organic carboxylic acids, the dye used in the present invention is used in an amount of 0.05 to 1%.
It can be used at a mass ratio of 00%. The timing of adding the dye may be any step before coating.

These dyes can be used in any of the emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, back layer, etc.). May be used for a plurality of layers. Addition to a non-photosensitive layer is preferred. It is more preferably used for a filter layer, and particularly preferably used for a yellow filter layer.

The emulsion used in the present invention is preferably tabular silver halide grains. The tabular grains have two parallel main planes and side surfaces connecting these main planes as outer surfaces. Tabular grains are grains having one twin plane or two or more parallel twin planes. In this case, the twin plane is a mirror image of all lattice point ions on both sides of the (111) plane. Refers to the (111) plane. When viewed from a direction perpendicular to the main plane of the grains, the main surface of the tabular grains has a triangular shape, a hexagonal shape, or a round shape in which these are rounded.

In the tabular grains, the aspect ratio means the ratio of the diameter to the thickness of the silver halide grains. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the silver halide grain when observed with a microscope or an electron microscope, and is referred to as a circle equivalent diameter. Therefore, that the aspect ratio is 5 or more means that the circle equivalent diameter is 5 times or more with respect to the particle thickness.

As an example of the method of measuring the aspect ratio,
There is a method in which a transmission electron micrograph is taken by a replica method to determine the equivalent circle diameter and thickness of each particle. In this case, the thickness is calculated from the length of the shadow of the replica.

In the tabular grains used in the present invention, 60% or more of the total projected area is tabular grains having an aspect ratio of 5 or more, preferably 7 or more, more preferably 10 or more. The upper limit of the aspect ratio can be up to about 150. The proportion occupied by the tabular grains is preferably at least 60%, more preferably at least 80% of the total projected area. When the proportion of the tabular grains is less than 60%, the photographic performance is greatly deteriorated, which is not preferable.

The tabular grains used in the present invention are preferably monodispersed. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-151618. The shape is briefly described as follows: 70% or more of the total projected area of silver halide grains is: The ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less, and is occupied by tabular grains having a hexagonal shape and having two parallel surfaces as main planes. Has been
Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular grains (a value obtained by dividing the variation (standard deviation) of the grain size represented by the circle equivalent diameter of the projected area) by the average grain size.
Has a monodispersity of 20% or less. Preferably, the coefficient of variation of the particle size distribution is 18% or less.

The average grain size (equivalent sphere diameter) of the silver halide emulsion used in the present invention is preferably from 0.2 μm to 2.5 μm. Further, the average grain size of the silver halide grains of the “average grain size minimum emulsion layer” of the present invention is preferably from 0.2 μm to 0.9 μm, and the average grain size of the silver halide grains of the “large emulsion layer” is “ The average grain size of the silver halide grains in the “average grain size minimum emulsion layer” is preferably at least 0.1 μm or more.

The thickness of the tabular grains is preferably less than about 0.8 μm, more preferably 0.03 μm to
0.6 μm, more preferably 0.05 μm to 0.4 μm
It is. In this case, it is preferable that the coefficient of variation of the thickness distribution has a monodispersity of 20% or less.

The average silver iodide content of the tabular grains is preferably from 1 mol% to 12 mol%. The halogen composition of the tabular grains of the present invention is preferably silver iodobromide or silver chloroiodobromide. The average silver iodide content was measured using an X-ray microanalyzer, one by one.
It can be measured by analyzing the composition of individual particles. The average silver iodide content is an arithmetic average when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. A method for determining the silver iodide content of individual emulsion grains is described, for example, in EP 147868A.

The tabular silver halide grains preferably have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F.
Hamilton, Photo. Sci. Eng. , 11, 57, (196
7) and T. Shiozawa, J .; Soc. Photo. Sci, Japan, 3
5, 213 (1972) by a direct method using a low-temperature transmission electron microscope. That is, silver halide grains taken out of the emulsion are placed on a mesh for electron microscopic observation, taking care not to apply enough pressure to cause dislocations in the grains, so as to prevent damage (for example, printout) by electron beams. Observation by a transmission method is performed while the sample is cooled. In this case, the larger the thickness of the particles, the more difficult it is for an electron beam to penetrate. Therefore, it is possible to more clearly observe using a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm). . The dislocation lines may be visible or invisible depending on the tilt angle of the sample with respect to the electron beam.Therefore, in order to observe the dislocation lines, take a photograph of the same particle at as many sample tilt angles as possible and sample the dislocation lines. It is necessary to confirm the location. The number of dislocation lines in the tabular grains is preferably 10 or more per grain.

The dislocation lines may be located almost uniformly over the entire outer periphery of the tabular grains, or may be located at local positions on the outer periphery. That is, taking hexagonal tabular grains as an example, they may be limited to only near six vertices. The dislocation line may be limited to only one of the vertices. Conversely, dislocation lines may be limited to only sides excluding the vicinity of the six vertices. Further, dislocation lines may be formed on the main surface of the tabular grains.

The tabular grains are preferably reduction sensitized. Here, reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, or pAg1 to silver ripening.
7, a method of growing particles in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening, can be selected. Further, two or more methods can be used in combination.

The method of adding a reduction sensitizer during the growth of silver halide grains is preferred because the level of reduction sensitization can be finely adjusted. Known reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination.
As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but it is preferably in the range of 10 ^-7 to 10 ^-2 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but is preferably added at an appropriate time during the grain growth. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferable method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add them continuously for a long time.

The tabular silver halide grains used in the present invention preferably use an oxidizing agent for silver during grain formation.

The oxidizing agent for silver acts on metallic silver
A compound having an action of converting into silver ions. Special
During the formation and chemical sensitization of silver halide grains
To convert very small silver particles that are by-produced into silver ions.
Compounds to be effective are effective. Silver ions generated here
Is poorly soluble in water such as silver halide, silver sulfide, silver selenide, etc.
A silver salt may be formed, and silver which is easily soluble in water such as silver nitrate may be used.
Salts may be formed. The oxidizing agent for silver is inorganic.
Or organic matter. As inorganic oxidants,
Ozone, hydrogen peroxide and its adducts (eg, NaB
O_Two・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_Four
P_TwoO₇・ 2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO _Two・ 2H
_TwoO), peroxyacid salts (eg, K_TwoS_TwoO₈, K_TwoC
_TwoO₆, K_TwoP_TwoO₈), Peroxy complex compounds (eg, K_Two
｛Ti (O_Two) C_TwoO_Four｝ ・ 3H_TwoO, 4K_TwoSO _Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three｛VO (O_Two)
(C_TwoH_Four)_Two・ 6H_TwoO｝, permanganate (eg, K
MnO_Four), Chromates (eg, K_TwoCrO₇) Etc. oxygen
Acid salts, halogen elements such as iodine and bromine, perhalates
(Eg potassium periodate) High valent metal salts (eg
Potassium ferric hexacyano) and thiosulfone
Acid salts).

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).

Preferred oxidizing agents for the tabular grains used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents for thiosulfonates and organic oxidizing agents for quinones. It is a preferred embodiment to use the above-mentioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of performing reduction sensitization after the use of an oxidizing agent, a method of coexisting the two methods, or a method of coexisting the two. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion used in the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. .

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
No. 16, P30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin can also be used.

The silver halide emulsion used in the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose,
It is preferable to select in the range of 5 ° C to 50 ° C. P at the time of washing
H can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

The silver halide emulsion grains used in the present invention are:
It is preferable to add a metal ion salt during the preparation, for example, during grain formation, in a desalting step, during chemical sensitization, and before coating, depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. When doping the whole grain and only the core of the grain,
Alternatively, a method of doping only the shell portion, only the epitaxial portion, or only the base particle can be selected.
Mg, Ca, Sr, Ba, Al, Sc, Y, LaCr,
Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, R
h, Pd, Re, Os, Ir, Pt, Au, Cd, H
g, Tl, In, Sn, Pb, Bi and the like can be used. These metals can be added in the form of a salt which can be dissolved at the time of particle formation, such as an ammonium salt, an acetate, a nitrate, a sulfate, a phosphate, a hydroxide, a six-coordinate complex, and a four-coordinate complex. For example, CdBr ₂ , CdCl ₂ , C
d (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ ,
K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K
₃ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent. In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). Further, if necessary, an acid or an alkali may be added. The metal compound can be added to the reaction vessel before the formation of the particles or during the formation of the particles. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or a water-soluble alkali halide (eg, NaCl, KBr, KI) and added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The silver halide grains used in the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization at any time during the production of a silver halide emulsion. It can be applied in the process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the preferred chemical sensitizations of the silver halide emulsion grains used in the present invention is chalcogenide sensitization and noble metal sensitization alone or in combination.
H. James), The Photographic Process, 4th Edition, Macmillan, 1977, (TH James, Th
e Theory of the Photographic Process, 4th ed, Mac
millan, 1977), pages 67-76, and can be performed using active gelatin, and is also described in Research Disclosure, Vol. 120, April 1974, 12
008; Research Disclosure, 34, 19
June 75, 13452, U.S. Pat. No. 2,642,36
No. 1, 3,297,446, 3,772,031
No. 3,857,711, No. 3,901,714
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 3 as described in GB 1,315,755.
At 0 to 80 ° C, sulfur, selenium, tellurium, gold, platinum,
It can be palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium. Preferred palladium compounds are R
It is represented by ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group.
X represents a halogen atom, and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
_{l 6, Na 2 PdCl 4,} (NH 4) 2 PdCl 4, Li 2 P
dCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
S ". ) 3,857,711, 4,26
The sulfur-containing compounds described in 6,018 and 4,054,457 can be used. Further US
Specific tetrasubstituted thioureas described in 4,810,626 (for example, carboxymethyltrimethylthiourea, dicarboxymethyldimethylthiourea, etc.) can also be preferably used.

The chemical sensitization can also be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog during chemical sensitization and increase sensitivity are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat. Photographic emulsion chemistry ", pp. 138-143.

The silver halide emulsion used in the present invention is preferably used in combination with gold sensitization. As the gold sensitizer, other than known gold compounds such as chloroauric acid, so-called mesoionic gold described in US-5049485 (for example, bis (1,
4,5-trimethyl-1,2,4-triazolium-3
-Thiolate gold) (1) tetrafluoroborate and the like are preferably used. In particular, specific tetrasubstituted thioureas (for example, carboxymethyltrimethylthiourea and dicarboxymethyldimethylthiourea) and mesoionic gold (for example, bis (1,4,5-trimethyl-1,2,4-triazolium-3-) It is preferably used in combination with thiolate gold) (1) tetrafluoroborate).

The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. . The preferred range of the palladium compound is 1 × 10 ⁻³ to 5 × 10
^-7 . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ .
The preferred amount of sulfur sensitizer used for the silver halide grains used in the present invention is 1 × 10 ^-4 per mol of silver halide.
To 1 × 10 ⁻⁷ mol, more preferably 1 × 10 ⁻⁷ mol.
^{−5 to} 5 × 10 ⁻⁷ mol.

Selenium sensitization is a preferred sensitizing method for the silver halide emulsion used in the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. The preferred amount of the selenium sensitizer is 1 × 10 5 per mole of silver halide.
^-9 mol to 1 × 10 ^-3 mol, more preferably 1 × 10 ^-3 mol
It is 10 ⁻⁸ to 1 × 10 ⁻⁴ . It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,94
No. 7, JP-B No. 52-28660 can be used. One of the preferred compounds is disclosed in
There are compounds described in U.S. Pat. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effect by adding during emulsion preparation, control the crystal wall of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is spectrally sensitized by a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene Imidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, 5 such as rhodanine nucleus and thiobarbituric acid nucleus
A 6-membered heterocyclic nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
Nos. 2-110618 and 52-109925.

The timing at which the sensitizing dye is added to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder may be chemically sensitized. It is also possible to add the silver halide grains after the formation of the silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
It can be used at 10 ^-6 to 8 × 10 ^-3 mol.

The light-sensitive material of the present invention is coated on a support in the range of 400 to 4
A silver halide emulsion layer having a spectral sensitivity maximum in the region of 90 nm, a silver halide emulsion layer having a spectral sensitivity maximum in the region of 500 to 600 nm, and a silver halide emulsion having a spectral sensitivity maximum in the region of 600 to 700 nm One or more silver halide emulsion layers are provided. 50
In the constitution of the present invention, two or three or more silver halide emulsion layers having a spectral sensitivity maximum in the range of 0 to 600 nm are required. The number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited as long as they are included in the definition of the present invention. A silver halide emulsion layer having a spectral sensitivity maximum in a 400 to 490 nm region,
In a silver halide emulsion layer having a spectral sensitivity maximum in a region of 00 nm, a plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent 1,121,470 or British Patent 923,045. As described in the above, a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-light-sensitive layer may be provided between the halogen emulsion layers having the same color sensitivity. Also, JP-A-57-112751, 62
-200350, 62-206541, 62-
As described in No. 206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers (layers having different color sensitivity) and as the uppermost layer. The intermediate layer is disclosed in
-43748, 59-113438, 59-1
No. 13440, No. 61-20037, No. 61-200
A coupler and a DIR compound as described in No. 38 may be contained, and a color mixing inhibitor may be contained as usually used.

The above-mentioned various additives are used in the light-sensitive material according to the present invention. In addition, various additives can be used according to the purpose. Emulsions used in the light-sensitive material of the present invention and techniques such as layer arrangement that can be used in the photographic light-sensitive material of the present invention, silver halide emulsions,
Functional couplers such as dye-forming couplers and DIR couplers, various additives, and development processing are described in EP 056596 A1 (published on Oct. 13, 1993) and patents cited therein. .
The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening / chemical ripening of emulsion: p. 63, lines 6-9, 13. Mixed use of emulsion: p. 63, lines 10 to 13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Photo Additives: Research Disclosure Item
17643 (December 1978), Item 18716
(November 1979) and Item 308119 (1
(December 989), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer 649 right column 4 Brightener 24 page 998 right 5 Antifoggant 24-25 page 649 right column 998 right 1000 right and stabilizer 6 light absorber, 25-26 page 649 right column 1003 Left to 1003 right Filter dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardening agent 26 page 651 left column 1004 right to 1005 left 10 Binder 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Antistatic agent Page 27 Same as above 1006 right to 1007 left 14 Matting agent 1008 left to 1009 left.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. 23. Yellow, magenta and cyan couplers: p. 65, lines 14-25; Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming coupler: page 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5 to 28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. Sensitive material with built-in developer: page 70, lines 24-33, 47. Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and US Pat.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654 and 4,556,630, and WO 88/04795 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers and are described in US Pat.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622 and 4,333,99.
No. 9, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,29
No. 6,199, JP-A-61-42658 and the like are preferable.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084,820.
Nos. 0,211, 4,367,282, 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No. U.S. Pat. No. 4,366,237 discloses a coupler in which a coloring dye has an appropriate diffusibility.
No. 2,125,570, EP 9
No. 6,570, West German Patent (Published) No. 3,234,533
Those described in the above item are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII-G of 307105
Item, U.S. Pat. No. 4,163,670, JP-B-57-3
No. 9413; U.S. Pat. Nos. 4,004,929 and 4,138,258; British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler that releases the development inhibitor is RD1 described above.
No. 7643, Section VII-F and No. VII-F. 307105, VII-
Patents described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950 and JP-A-62-24252.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat.
55,477 and the like; couplers releasing leuco dyes described in JP-A-63-75747; and couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , Decyl phthalate, bis (2,4-di-ter
t-amylphenyl) phthalate, bis (2,4-di-
tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p- Hydroxybenzoate); amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N
-Tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-
Di-tert-amylphenol); aliphatic carboxylic esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N , N-dibutyl-2-butoxy-5-tert-octylaniline);
Hydrocarbons (eg, paraffin, dodecylbenzene,
Diisopropylnaphthalene).
As the auxiliary solvent, for example, the boiling point is about 30 ℃ or more,
Preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
No. 9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

The light-sensitive material of the present invention may be prepared from phenethyl alcohol or JP-A-63-257747 and JP-A-62-27224.
No. 8, and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-
It is preferable to add various preservatives or fungicides such as chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means the film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, and is described, for example, by A. Green et al. In Photographic Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129 can be used for measurement. In addition, T _1/2 is 30 in the color developing solution.
℃, the maximum swelling film thickness of 9 reached when treated for 3 minutes 15 seconds
0% is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

The light-sensitive material of the present invention has a total dry film thickness of 0.5 μm on the side opposite to the support having the emulsion layer.
It is preferable to provide a back layer having a thickness of about 20 μm. In the back layer, for example, the above-described light absorber, carbon black, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surfactant.

In the present invention, a carbon black powder kneaded into a polymer is provided on the side opposite to the side having the emulsion layer with respect to the support so that the optical transmission density (in white light) becomes 2.0 or less. It is preferable to provide an applied layer (resin back layer). In this back layer, a light absorber,
It is preferable to contain a filter dye, an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surfactant, and the like. The thickness of the resin back layer is preferably 0.5 to 20 μm. This resin back layer is dissolved in an alkali bath (pre-bath) during the development processing, and is washed away by rinsing in the next step.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3-methyl-4-amino-N-ethyl-β-methoxy Ethyl aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof are exemplified. Among them, a sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds can be used in combination of two or more depending on the purpose.

The effect of the present invention is greatest when 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline is used as a developing agent. The optimum amount of the developing agent varies greatly depending on the setting of the pH, temperature, and other additives of the developing solution. However, a preferable range is 0.5 g / L to 10 g.
/ L.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or an antifoggant such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid; ethylene glycol; Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Representative examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process) or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As a bleaching agent, for example, iron (III)
And polyacids, such as peracids (particularly, sodium persulfate is suitable), quinones, and nitro compounds.
Representative bleaching agents include organic complex salts of iron (III), for example,
Complex salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid And a complex salt with malic acid. Among these, aminopolycarboxylate iron (III) complexes such as ethylenediaminetetraacetate (III) complex salt and 1,3-diaminopropanetetraacetate (III) complex salt are useful for rapid treatment and prevention of environmental pollution. Is preferred. Further, the iron (III) complex of aminopolycarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be performed at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: for example, U.S. Pat. No. 3,893,858, German Patent 1,290,812, and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95763, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A-51-140129; a thiazolidine derivative described in JP-A-51-140129;
No. 32, No. 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644;
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 8, West German Patent No. 1,290,812,
Compounds described in No. 95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable.
These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

It is preferable that the bleaching solution and the bleach-fixing solution contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methyl for adjusting pH. It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / L.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. Furthermore, a method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid and making the emulsion surface turbulent, and increasing the circulation flow rate of the entire processing liquid There is a method to make it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, thereby increasing the desilvering speed. Further, the means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Unexamined Patent Publication No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, and further, for example, the replenishment such as the rinsing water temperature, the number of rinsing tanks (number of stages), countercurrent, and forward flow. It can be set in a wide range according to the method and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal.
of the Society of Motion
Picture and Television E
nginers 64, p. 248-253 (19
May, 1980).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of the water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, for example, benzotriazole, written by Hiroshi Horiguchi "The Chemistry of Bactericidal and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Bactericidal and Fungicide Society, Ed. A fungicide described in "Encyclopedia of fungicides" (1986) can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is 4 to 9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on, for example, the characteristics of the photosensitive material and the application, but are generally at 15 to 45 ° C for 20 seconds to
A range of 10 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543 is disclosed.
And all known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. For example, in the case of processing using an automatic developing machine, when the above processing solutions are concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color photographic light-sensitive material to which the present invention is applied, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent.
For example, indoaniline compounds described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599
No., Research Disclosure No. 14,850
And the same No. No. 15, 159; An aldol compound according to 13,924,
Metal salt complexes described in U.S. Pat. No. 3,719,492;
Urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material to which the present invention is applied may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described, for example, in JP-A-56-6433.
No. 9, No. 57-144547 and No. 58-115
No. 438. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually 33 ° C
A temperature of ~ 45 [deg.] C is standard, but higher temperatures can accelerate processing to reduce processing time, and conversely lower temperatures to improve image quality and improve processing solution stability.

The silver halide photographic light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1.
No. 33449, No. 59-218443, No. 61-23
No. 8056, European Patent No. 210,660A2, and the like. Further, the silver halide color photographic light-sensitive material to which the present invention is applied exhibits more effects when applied to a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784. Easy and effective.

[0117]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. (Example 1) 1. Preparation of Emulsion A silver halide emulsion was prepared by the following method. The structures of the compounds used in the preparation are listed below.

(Production method of emulsion Em-Ro1) 2.0 g of low molecular weight gelatin having a weight average molecular weight of 15,000, KBr1.
1300 mL of an aqueous solution containing 1 g was maintained at 45 ° C., the pH was adjusted to 9, and the mixture was vigorously stirred. An aqueous solution containing 1.1 g of AgNO ₃ and an aqueous solution containing 1.1 g of KBr and 1.0 g of low molecular weight gelatin having a weight average molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. KBr
Was added and the mixture was heated to 75 ° C. and aged. After completion of ripening, 20.0 g of gelatin obtained by chemically modifying alkali-treated gelatin having a weight average molecular weight of 100,000 with succinic anhydride was added, and then the pH was adjusted to 5.2 (up to this point, the formation of internal nuclei). An aqueous solution containing the AgNO ₃ 29.3g 230m
An aqueous solution containing L, 15.8 g of KBr and 1.92 g of KI was added over 40 minutes by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. Further, the aqueous solution containing 64.5 g of AgNO ₃ and 233 mL of an aqueous solution containing 42.3 g of KBr and 5.14 g of KI were accelerated by a double jet method so that the final flow rate was 1.33 times the initial flow rate and accelerated for 57 minutes. Added throughout. At this time, during the addition, the silver potential was set to -25.
mV (up to this point after the formation of internal nuclei, the first coating phase was formed). Next, an aqueous solution containing 47.2 g of AgNO ₃ and an aqueous KBr solution were brought to a silver potential of −20 m by a double jet method.
The V was added over 25 minutes while maintaining V.

After lowering the temperature to 40 ° C., Compound 1 was
3.9 g was added, and 0.8 M aqueous sodium sulfite was added.
25.6 mL of the solution was added. Then use NaOH aqueous solution
The pH was adjusted to 9.0 and maintained for 5 minutes. 55 ℃
And then H_TwoSO_FourThe pH was adjusted to 5.5 with.
1.5 mg sodium benzenethiosulfonate
Lime-treated gelatin with a calcium concentration of 1 ppm
6 g were added. After the addition is completed, AgNO_ThreeIncluding 94.6g
The aqueous solution of 250 mL and the aqueous solution of KBr were brought to a silver potential of +7.
The addition was performed over 30 minutes while maintaining the voltage at 5 mV. At this time,
2.0 × 10 5 yellow blood salt per mole of silver^-FiveMole and K
_TwoIrCl₆Is 1.5 × 10 ^-8Molar addition
did.

After washing with water, gelatin was added, and p
H5.6 and pAg8.8 were adjusted. After the temperature was raised to 56 ° C., Compound 2 and sensitizing dyes ExS-1, ExS-2,
After adding ExS-3, potassium thiocyanate, chloroauric acid, sodium thiosulfate, hexafluorophenyldiphenylphosphine selenide, compound F-11, and compound 3 were added to perform optimal chemical sensitization. At the end of the chemical sensitization, compound F-2 was added.

This emulsion had an average equivalent sphere diameter of 1.30 μm.
m, average circle equivalent diameter 2.74 μm, average aspect ratio 1
It was 4.0 tabular grains. As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, 10 or more dislocation lines per particle were observed in the periphery of the particles having a projected area of 30% from the periphery of the particles.

(Production method of Em-Go1) Em-Go1 was produced in the same production method as Em-Ro1, except that the sensitizing dye used in Em-Ro1 was changed to ExS-5, 6, 7, 8, and 9. did.

(Preparation of Em-Bo1) (Preparation of Seed Emulsion) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight oxidized gelatin having a weight average molecular weight of 15,000 and 0.9 g of KBr was maintained at 35 ° C. and stirred vigorously. AgN
40 mL of an aqueous solution containing 1.05 g of O ₃ and KBr, 1.
Low molecular weight gelatin having a molecular weight of 2 g and a molecular weight of 15,000
35 mL of an aqueous solution containing 2 g was added by a double jet method for 30 seconds to perform nucleation. Immediately after the addition, KBr
5.4 g was added, the temperature was raised to 75 ° C., and ripening was performed. After ripening, 35 g of gelatin obtained by chemically modifying alkali-treated gelatin having a weight average molecular weight of 100,000 with succinic anhydride was added, and then the pH was adjusted to 5.5. AgNO ₃ , 36
g of an aqueous solution containing 250 g of KBr, 21.2 g of KBr and K
282 mL of an aqueous solution containing 2.21 g of I
The solution was added over a period of 25 minutes by the double jet method while maintaining the mV. Then, an aqueous solution 6 containing 200 g of AgNO ₃
A flow rate of 900 mL of an aqueous solution containing 50 mL, 134.1 g of KBr, and 13.9 g of KI was accelerated by a double jet method so that the final flow rate was 1.5 times the initial flow rate, and 150
Added over minutes. At this time, the silver potential was kept at +5 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, the pAg to 8.8, the silver equivalent weight per emulsion to 139.0 g, and the gelatin weight to 56 g to obtain a seed emulsion.

1200 mL of an aqueous solution containing 33 g of lime-processed gelatin having a calcium concentration of 1 ppm and 3.4 g of KBr
Was kept at 75 ° C. and stirred vigorously. 89 seed emulsion
After the addition, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. The pH was adjusted to 5.8 by adding H ₂ SO ₄ , 3 mg of sodium benzenethiosulfonate and 3 mg of thiourea dioxide were added, and then 600 mL of an aqueous solution containing 51.0 g of AgNO ₃ , 36.2 g of KBr and KI3. An aqueous solution (600 mL) containing 49 g was accelerated by a double jet method so that the final flow rate was 1.1 times the initial flow rate, and added over 85 minutes. At this time, the silver potential was -3 with respect to the saturated calomel electrode.
It was kept at 5 mV. Further, 300 mL of an aqueous solution containing 44.7 g of AgNO ₃ , 30.6 g of KBr and KI3.
300 g of an aqueous solution containing 0.6 g was accelerated by a double jet method so that the final flow rate was 1.1 times the initial flow rate, and added over 56 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode.

Next, 180 mL of an aqueous solution containing 36.9 g of AgNO ₃ and an aqueous KBr solution were mixed with 40 mL of a double jet method.
Added over minutes. At this time, the silver potential was kept at +10 mV with respect to the saturated calomel electrode. After adding KBr to adjust the silver potential to -70 mV, 1.38 g of an AgI fine grain emulsion having a grain size of 0.037 µm was added in terms of KI mass. Immediately after the addition is completed, AgNO ₃ , 17.4 g
Was added over 15 minutes. After washing with water, gelatin was added and pH 5.8 at 40 ° C., pA
g was adjusted to 8.7. After the temperature was raised to 60 ° C., Compound 2 and sensitizing dyes ExS-10, ExS-11, ExS-1
2. Add ExS-13, add potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold) (1) tetrafluoroborate, dicarboxymethyldimethylthiourea, hexa Fluorophenyldiphenylphosphine selenide, compound F
-11 and Compound 3 were added for optimal chemical sensitization. At the end of the chemical sensitization, compound F-3 was added.

This emulsion has an average equivalent sphere diameter of 1.90 μm.
m, an average equivalent circle diameter of 3.58 μm, a coefficient of variation of equivalent circle diameter of 20%, and an average aspect ratio of 10.0 were tabular grains. The obtained particles were observed with a transmission electron microscope while cooling with liquid nitrogen.
About 97% of all grains had no dislocation lines within 10%, and 10 or more dislocation lines per grain were observed from the periphery of the grains to the periphery of the grains having a projected area of 20% from the grain periphery.

(Production method of Em-Rm1) Mass average molecular weight 1
3.0 g of 5000 low molecular weight gelatin, 1.1 g of KBr
Was maintained at 35 ° C. and stirred vigorously. Aqueous solution containing 3.1 g of AgNO ₃ and 2.1 g of KBr
And low molecular weight gelatin 2.0 having a mass average molecular weight of 15,000
An aqueous solution containing g was added over 40 seconds by a double jet method to form nuclei. 5.6 g of KBr was added, and 75
The temperature was raised to ℃ to ripen. After aging, the mass average molecular weight is 1
25.0 g of gelatin obtained by chemically modifying 100,000 alkali-treated gelatin with succinic anhydride was added, and then the pH was adjusted to 5.2.
Was adjusted. Aqueous solution 230 containing 29.3 g of AgNO ₃
An aqueous solution containing mL and 20.8 g of KBr was added over 20 minutes by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode (up to this point, the formation of internal nuclei). Further, the aqueous solution containing 64.5 g of AgNO ₃ and 233 mL of an aqueous solution containing 41.4 g of KBr and 6.42 g of KI were accelerated by a double jet method so that the final flow rate was 1.33 times the initial flow rate, and was accelerated for 57 minutes. Added throughout. At this time, the silver potential was kept at −25 mV during the addition (the formation of the first coating phase up to and including the internal nucleation). Next, an aqueous solution containing 47.2 g of AgNO ₃ and an aqueous KBr solution were brought to a silver potential of 0 m by a double jet method.
The V was added over 15 minutes while maintaining the V.

After the temperature was lowered to 55 ° C., the silver potential was lowered to −5.
The pressure was adjusted to 5 mV, 1.5 mg of sodium benzenethiosulfonate was added, and 16 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. Then, AgNO
_{3 An} aqueous solution of (7.1 g), an aqueous solution of KI (6.9 g) and an aqueous solution of gelatin having a molecular weight of 20,000 are disclosed in JP-A-10-4357.
In a separate chamber with a magnetic coupling induction stirrer as described in No. 0, mixed immediately before addition and added over 5 minutes.

After the addition was completed, 250 mL of an aqueous solution containing 94.6 g of AgNO ₃ and an aqueous KBr solution were brought to a silver potential of +55.
The addition was performed over 30 minutes while maintaining the mV. At this time, the yellow blood salt was added in an amount of 2.0 × 10 ⁻⁵ mol per mol of silver and K ₂
1.5 × 10 ⁻⁸ mol of IrCl ₆ was added per 1 mol of silver.

After washing with water, gelatin was added, and p
H5.6 and pAg8.8 were adjusted. After the temperature was raised to 53 ° C., Compound 2 and sensitizing dyes ExS-1, ExS-2,
After adding ExS-3, potassium thiocyanate, chloroauric acid, sodium thiosulfate, hexafluorophenyldiphenylphosphine selenide, compound F-11, and compound 3 were added to perform optimal chemical sensitization. At the end of the chemical sensitization, compound F-2 was added.

This emulsion had an average sphere equivalent diameter of 0.70 μm.
m, tabular grains having an average equivalent circle diameter of 1.22 μm and an average aspect ratio of 8.0. As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, 10 or more dislocation lines per particle were observed from the periphery of the particles to the periphery of the particles having a projected area of 20%.

(Preparation of Em-Rm2, Ru1, 2) The size and sensitivity can be changed by appropriately changing the temperature, pH, silver potential, silver nitrate amount, KI amount, compound amount, etc. in the preparation of the above-mentioned emulsion Em-Rm1. It was prepared.

(Production method of Em-Gm1) Mass average molecular weight 1
2.0 g of 5000 low molecular weight oxidized gelatin, KBr
1300 mL of an aqueous solution containing 1.1 g was kept at 40 ° C.
H was adjusted to 9 and stirred vigorously.

An aqueous solution containing 3.1 g of AgNO ₃ and KBr
An aqueous solution containing 3.1 g and 1.0 g of low molecular weight oxidized gelatin having a mass average molecular weight of 15,000 was added over 45 seconds by a double jet method to form nuclei. KBr.
6 g was added, and the temperature was raised to 78 ° C. to ripen. After aging,
35.0 g of gelatin obtained by chemically modifying alkali-processed gelatin having a mass average molecular weight of 100,000 with succinic anhydride was added, and then the pH was adjusted to 6.0 (this is the end of the formation of internal nuclei). 230 mL of an aqueous solution containing 29.3 g of AgNO ₃ and an aqueous solution containing 12.7 g of KBr were mixed by a double jet method.
Added over 0 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added to a silver iodide content of 7 mol.
% At the same time, and the silver potential was kept at -25 mV with respect to the saturated calomel electrode (the formation of the first coating phase up to this point after the internal nucleation). Furthermore, AgN
An aqueous solution containing 64.5 g of O ₃ and 233 mL of an aqueous solution containing 42.3 g of KBr were added over a period of 57 minutes by double jet method with the flow rate accelerated so that the final flow rate was 1.33 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 8 mol%, and the silver potential was reduced to −3.
It was kept at 0 mV. Next, an aqueous solution containing 82.6 g of AgNO ₃ and an aqueous KBr solution were brought to a silver potential of 0 m by a double jet method.
The V was added over 30 minutes while maintaining the V.

After the temperature was lowered to 35 ° C., 2.5 g of Compound 1 was added, and 20.6 mL of a 0.8 M aqueous sodium sulfite solution was further added. Next, the pH was adjusted to 9.0 using an aqueous NaOH solution, and held for 5 minutes. 45 ° C
Then, the pH was adjusted to 5.5 with H ₂ SO ₄ .
1.5 mg of sodium benzenethiosulfonate was added, and 1 g of lime-processed gelatin having a calcium concentration of 1 ppm was added.
6 g were added. After the addition, 250 mL of an aqueous solution containing 59.1 g of AgNO ₃ and an aqueous KBr solution were brought to a silver potential of −2.
The addition was performed over 30 minutes while maintaining the voltage at 5 mV. At this time,
K ₄ [Ru (CN) ₆ ] was added to 1.0 × 10
^-5 mol and 3.0 × the K ₂ IrCl ₆ per mol of silver
10 ^-8 mol was added.

After washing with water, gelatin was added, and p
H5.6 and pAg8.8 were adjusted. After the temperature was raised to 56 ° C., Compound 2 and sensitizing dyes ExS-5, ExS-6,
After adding ExS-7, ExS-8 and ExS-9, potassium thiocyanate, bis (1,4,5-trimethyl-
1,2,4-triazolium-3-thiolate gold)
(1) Tetrafluoroborate, carboxymethyltrimethylthiourea, hexafluorophenyldiphenylphosphine selenide, compound F-11 and compound 3 were added for optimal chemical sensitization. Compound F- at the end of chemical sensitization
2 was added.

This emulsion had an average equivalent sphere diameter of 1.10 μm.
m, average circle equivalent diameter 2.52 μm, average aspect ratio 1
It was a tabular grain of 8.0. As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, 10 or more dislocation lines per particle were observed in the periphery of the particles having a projected area of 30% from the periphery of the particles.

(Preparation of Em-Gm2, Gu1, 2) Size and sensitivity can be changed by appropriately changing the temperature, pH, silver potential, silver nitrate amount, KI amount, compound amount, etc. in the preparation of the above-mentioned emulsion Em-Gm1. It was prepared.

(Production method of Em-Gs1) Emulsion Em-G
It was prepared by changing the sensitizing dye in the preparation of m1 to ExS-4,5. This emulsion was prepared using the above Em-Gu1, Gu
The sensitivity was higher than that of No. 2.

(Preparation of Em-Bm1, Bu1) The size and sensitivity were changed by appropriately changing the temperature, pH, silver potential, silver nitrate amount, KI amount, compound amount, etc. in the preparation of the above-mentioned emulsion Em-Bo1. did.

(Preparation of Em-Bu2) 1250 mL of an aqueous solution containing 48 g of deionized gelatin and 0.75 g of KBr
Was kept at 70 ° C. and stirred vigorously. AgN in this solution
An aqueous solution of KBr having an equimolar concentration of 276 mL of an aqueous solution containing 12.0 g of O ₃ was p-jetted over 7 minutes by a double jet method.
Ag was added while keeping it at 7.5. Next, AgNO ₃ 1
KB with an equimolar concentration of 600 mL of an aqueous solution containing 08.0 g
A mixed aqueous solution of r and KI (2.2 mol% KI) was added by a double jet method over 28 minutes and 30 seconds while maintaining the pAg at 7.30. At this time, 5 minutes before the end of the addition, 24.0 mL of a 0.1% by mass aqueous solution of thiosulfonic acid was added.
Was added. After re-dispersion by performing desalting and washing with a normal flocculation method, the pH is 6.2 at 40 ° C., and pA
g was adjusted to 7.6. After controlling the temperature to 40 ° C., Compound 2 and sensitizing dyes ExS-10, ExS-11, ExS
After adding S-12 and ExS-13, potassium thiocyanate, chloroauric acid, sodium thiosulfate, hexafluorophenyldiphenylphosphine selenide, compound F-1
1. After adding compound 3 and then raising the temperature to 65 ° C., optimal chemical sensitization was performed. At the end of the chemical sensitization, compound F-2 was added. This emulsion was cubic grains having an equivalent sphere diameter of 0.20 μm and a coefficient of variation of the equivalent sphere diameter of 16%.

Table 1 shows a list of the emulsions thus prepared.

[Table 1]

(Preparation of fine grain silver iodide emulsion M)
1700 mL of an aqueous solution containing 23 g and 23 g of gelatin
The mixture was kept at 0 ° C and stirred. An aqueous solution containing 153 g of silver nitrate and K
An aqueous solution containing 149.5 g of I was 13
Added over minutes. After desalting, 78 g of gelatin was added, and the pH was adjusted to 5.8 at 40 ° C. The silver iodide fine particles contained 0.72 mol of Ag and 31 g of gelatin per kg of the emulsion, and had an average equivalent circle diameter of 0.047 μm and a variation coefficient of the equivalent circle diameter of 20%.

2. Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 used in the eleventh layer of the following photosensitive material 101 was dispersed by the following method.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg 4.020 kg of water 7.210 kg in total (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was roughly dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm. Similarly, solid dispersions of ExF-4 and ExF-8 were obtained. The average particle size of the fine dye particles is 0.28 μm, respectively.
It was 0.49 μm.

[0147] 3. Preparation of Coating Sample Multilayer Color Photosensitive Material 101 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 which was a multilayer color photosensitive material.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler ExF: dye ExS: sensitizing dye Cpd: additives H: number corresponding to a gelatin hardener components showed a coating amount represented in × 10 ^-5 mol / m ² unit. Regarding silver halide, the coating weight (g / m ² ) in terms of silver, HBS-1 to 4 (dispersion solvent) and polymer compounds (gelatin, latex, B
-1 to B-6) and the hardener (H-1) were applied in an amount of (g / g).
m ² ). However, as for the sensitizing dye (ExS),
The coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

(Specific compounds are described in the following, in which numerical values are given after symbols and chemical formulas are listed after). The DIR compound in the silver halide emulsion layer (green-sensitive emulsion layer) having a spectral sensitivity maximum at 500 to 600 nm is *
Shown by a mark.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.077 Gelatin 0.560 ExM-1 5.750 Cpd-2 0.300 F-8 0.400 HBS-1 0.120 HBS- 2 0.015.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.088 Gelatin 0.830 ExM-1 6.800 ExF-1 0.350 F-8 0.400 HBS-1 0.090 HBS- 2 0.010.

Third layer (intermediate layer) ExC-2 1.100 Cpd-1 11.70 UV-2 10.80 UV-3 16.10 UV-1 3.100 HBS-1 0.100 Gelatin 0.580 .

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Em-Ru2) Silver content 0.17 Silver iodobromide emulsion (Em-Ru1) Silver content 0.65 Gelatin 1.00 ExS- 1 5.20 × 10 ^-4 ExS-2 2.20 × 10 ^-5 ExS-3 7.10 × 10 ^-4 ExC-1 30.0 ExC-4 20.0 ExC-2 3.90 ExC-5 1 .10 ExC-11 0.70 ExC-8 0.70 Cpd-2 7.50 HBS-1 0.150.

Fifth layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion (Em-Rm2) Silver amount 0.04 Silver iodobromide emulsion (Em-Rm1) Silver amount 0.14 Gelatin 0.90 ExS- 1 8.50 × 10 ^-5 ExS-2 0.50 × 10 ^-5 ExS-3 1.20 × 10 ^-4 ExC-1 6.50 ExC-3 6.00 ExC-2 0.45 ExC-5 1 .50 ExC-9 0.20 ExC-8 1.10 Cpd-2 2.00 HBS-1 0.070.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Em-Ro1) Silver amount 1.10 Gelatin 1.00 ExS-1 2.20 × 10 ^-4 ExS-2 1.00 × 10 ^-5 ExS-3 3.20 × 10 ^-4 ExC-1 2.40 ExC-3 2.40 ExC-10 2.40 ExC-6 2.40 ExC-8 1.70 Cpd-4 3.00 HBS -1 0.150 HBS-2 0.020.

Seventh layer (intermediate layer) Gelatin 0.90 Cpd-1 8.20 Cpd-5 400.0 Solid disperse dye ExF-4 2.50 HBS-1 0.040 Polyethyl acrylate latex 0.150.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Em-Gu2) Silver content 0.50 Silver iodobromide emulsion (Em-Gu1) Silver content 0.20 Gelatin 1.20 ExS- 5 1.90 × 10 ⁻⁵ ExS-6 4.80 × 10 ⁻⁵ ExS-7 1.90 × 10 ⁻⁴ ExS-8 1.00 × 10 ⁻⁴ ExS-9 4.30 × 10 ⁻⁴ ExM− 1 7.00 ExM-2 20.0 ExM-3 5.50 ExM-6 ^* 0.70 ExY-1 ^* 2.00 ExC-11 ^* 1.50 HBS-1 0.200 HBS-3 0.008.

Ninth layer (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion (Em-Gm2) Silver content 0.75 Silver iodobromide emulsion (Em-Gm1) Silver content 0.30 Gelatin 1.50 ExS- 5 3.90 × 10 ^-5 ExS-6 6.00 × 10 ^-5 ExS-7 9.00 × 10 ^-5 ExS-8 1.70 × 10 ^-4 ExS-9 7.50 × 10 ^-4 ExM- 2 15.0 ExM-3 4.00 ExM-6 ^* 0.50 ExY-1 ^* 2.00 ExY-5 ^* 3.50 ExC-11 ^* 1.80 HBS-1 0.230 HBS-3 0.009 .

Tenth Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion (Em-Go1) Silver Amount 1.00 Gelatin 1.00 ExS-5 4.50 × 10 ^-5 ExS-6 6.00 × 10 ^-5 ExS-7 1.10 × 10 ^-4 ExS-8 1.20 × 10 ^-4 ExS-9 5.30 × 10 ^-4 ExM-8 3.20 ExM-6 ^* 0.20 ExM-7 1 .00 ExM-1 0.30 ExM-3 0.30 Cpd-3 4.50 HBS-1 0.140.

Eleventh layer (yellow filter layer) Solid disperse dye ExF-2 45.0 Solid disperse dye ExF-8 10.0 Gelatin 0.55 Cpd-1 11.0 HBS-1 0.600.

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Em-Bu1) Silver amount 0.07 Silver iodobromide emulsion (Em-Bu2) Silver amount 0.07 Gelatin 0.35 ExS- 10 8.5 × 10 ^-5 ExS-11 7.4 × 10 ^-4 ExS-12 9.5 × 10 ^-5 ExS-13 3.0 × 10 ^-4 ExY-2 8.00 ExY-3 8.00 ExY-1 3.00 ExC-1 1.50 Cpd-2 12.0 HBS-1 0.080.

Thirteenth Layer (Medium Speed Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion (Em-Bm1) Silver Content 0.26 ExS-10 6.5 × 10 ^-5 ExS-11 5.4 × 10 ^-4 ExS -12 7.5 × 10 ^-5 ExS-13 2.0 × 10 ^-4 gelatin 0.60 ExS-7 52.0 ExY-2 35.0 ExY-3 35.0 Cpd-2 2.00 HBS-1 0.140.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Em-Bo1) Silver content 1.15 Gelatin 1.10 ExS-10 5.5 × 10 ⁻⁵ ExS-11 4.0 × ^10-4 ExS-12 6.5 x ^10-5 ExS-13 1.5 x ^10-4 ExY-2 13.0 Cpd-3 7.50 Cpd-4 7.50 HBS-1 0.070.

Fifteenth Layer (First Protective Layer) Fine Particle Silver Iodobromide Emulsion M Silver Content 0.33 Gelatin 1.24 UV-4 56.0 UV-2 25.0 UV-3 25.0 UV-15 .50 ExF-1 0.35 ExF-5 0.300 ExF-6 0.150 ExF-7 0.200 HBS-4 0.080.

Sixteenth layer (second protective layer) Gelatin 0.90 H-1 0.30 B-1 (1.7 μm in diameter) 0.04 B-2 (1.7 μm in diameter) 0.09 B-30 .10 S-1 10.0.

Further, the storage stability, processing property, pressure resistance,
W-1 to W-6, B-4 to B-6, F-1 to F
-17 and iron, lead, gold, platinum, palladium, iridium and rhodium salts. or,
The center of gravity sensitivity wavelength λ _G of the green sensitive layer of the light-sensitive material 101 λ _G = 548 n
m, the center-of-gravity wavelength λ _-R = 545 nm of the wavelength distribution affected by the layer effect from the other layer of the red-sensitive layer.

Preparation of Multilayer Color Photosensitive Material 102 A multilayer color photosensitive material prepared on an undercoated cellulose triacetate film support was newly provided between the seventh layer and the eighth layer of the sample 101, which is the following 7.5 layer. A multilayer color photosensitive material 102 similar to 101 was prepared except that the layers were inserted and the constitution of the eighth layer was changed as described below.

7.5th Layer (Additional Green Sensitive Emulsion Layer: Gs Layer) Silver Iodobromide Emulsion (Em-Gs1) Silver 0.92 Cpd-4 6.00 ExM-2 30.0 ExM-3 0.60 ExM-4 8.50 ExY-1 ^* 2.00 ExY-4 ^* 5.50 ExC-7 ^* 1.50 ExS-4 7.8 × 10 ^-4 ExS-5 3.5 × 10 ^-4 HBS-1 0.400 HBS-3 0.006 HBS-5 0.020 Gelatin 1.550.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Em-Gu2) Silver content 0.15 Silver iodobromide emulsion (Em-Gu1) Silver content 0.15 Gelatin 0.75 ExS- 5 1.90 × 10 ⁻⁵ ExS-6 4.80 × 10 ⁻⁵ ExS-7 1.90 × 10 ⁻⁴ ExS-8 1.00 × 10 ⁻⁴ ExS-9 4.30 × 10 ⁻⁴ ExM− 1 5.00 ExM-2 12.0 ExM-3 3.50 ExM-6 ^* 0.20 ExY-1 ^* 0.00 ExC-11 ^* 0.75 HBS-1 0.160 HBS-3 0.005.

The center-of-gravity sensitivity wavelength λ _G of the green-sensitive layer of the light-sensitive material 102 was 549 nm, and the center-of-gravity wavelength λ _{-R of the} wavelength distribution receiving the layer effect from the other layers of the red-sensitive layer was 525 nm.

Preparation of Multilayer Color Photosensitive Materials 103 and 104 The above multilayer color photosensitive materials 101 and 102 were coated with the first to third layers without coating the first to third layers, and the fourth layer on an undercoated cellulose triacetate film support. 103 and 104 were prepared in the same manner except that the subsequent steps were applied.

Preparation of Multilayer Color Photosensitive Materials 201-204 On a subbed cellulose triacetate film support,
As the photosensitive layer, a multilayer color photosensitive material 201 to 204 similar to 101 to 104 was prepared except that a back layer having the following composition was applied to the back surface.

(Coating of Back Layer) A back layer having the following composition was coated on one surface of the support. Methyl methacrylate-methacrylic acid copolymer (copolymerization molar ratio 1: 1) 1.5 parts by mass Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%, phthalyl group 36%) 1.5 50 parts by weight of acetone 50 parts by weight of methanol 25 parts by weight of methanol 25 parts by weight of methyl cellosolve 1.2 parts by weight of colloidal carbon A coating solution was prepared at a ratio of not less than 1.0, and applied so that the concentration with respect to white light became 1.0.

The compounds used for each layer are shown below.

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[0177]

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[0178]

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[0187]

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[0192]

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[0193]

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The obtained multilayer color photographic materials 101 to 10
Table 2 summarizes the contents of 4, 201-204.

[0195]

[Table 2]

Each of the samples 101 to 104 and 201 to 204 was exposed to white light for 1/100 second through a wedge. The exposed sample was subjected to the development processing described below, and the density was measured by the method described in JP-A-63-226650.

The development was performed by an automatic developing machine F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. In addition, the remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath, but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Publication Technique No. 94-4992 (issued by the Invention Association).

To confirm the effect of improving the processing dependence of the present invention, the developing agent (2-methyl-4- [N
Two types of tank solutions were prepared with different amounts of -ethyl-N-([beta] -hydroxyethyl) amino] aniline sulfate (Treatment 1, Treatment 2). Further, for this experiment only, the test was performed without replenishing the color developing solution tank.

The processing steps and the composition of the processing solution are shown below. (Processing process) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C-11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L fixing (2) 50 seconds 38.0 ° C 8mL 5L Washing with water 30 seconds 38.0 ° C 17mL 3L stable (1) 20 seconds 38.0 ° C-3L stable (2) 20 seconds 38.0 ° C 15mL 3L Drying 1 minute 30 seconds 60.0 ° C Per 1.1m width (equivalent to 24 shots per 24).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.
2.5mL, 2.0mL, 2.0m / m
L. The crossover time was 6
Seconds, and this time is included in the processing time of the previous step.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing liquid is shown below. (Color developing solution; tank solution (g)) Processing. 1 Processing. 2 Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 3.9 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 1.5 Potassium bromide 1.3 1.3 Potassium iodide 1.3 mg 1.3 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazain Den 0.05 0.05 Hydroxylamine sulfate 2.4 2.4 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 3.0 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.05.

(Bleaching solution) Tank solution (g) Replenishment solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with aqueous ammonia] 4.6 4.0.

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixed solution (pH 6.8) of the bleaching tank liquid and the following fixing tank liquid.

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.)
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L.
L was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

The magenta density fog of the sample obtained after the processing is defined by the minimum density (DMmin) of the density of the processing, and the magenta density DM of the processing 2 at the exposure amount giving the density of DMmin + 1.0 when the processing is performed in the processing 1. , And ΔDM = (DMmin
+1.0) -DM was calculated and used as a measure of the change in properties due to the change in the processing solution. It can be said that the larger the ΔDM, the more sensitive the processing dependency is.

Next, samples 101 to 104 and 201 to 2
After taking a Macbeth color chart with daylight tungsten light under the same conditions using all of No.04, development processing was performed. From this color negative, hand-baked printing was performed on a color paper so that the gray color would be the same, and 18 colors of the obtained print were represented by L *, a *, b * color system. The deviation of each of these points from the original chromaticity point of the Macbeth chart was calculated as an average color difference ΔEa, b defined by the following equation.

ΔEa, b = Σ ｛(Lpi−Loi) ² + (api-aoi)
² + (bpi-boi) ² ｝ ^(1/2) / n where Lpi, api, and bpi are the i-th colors of L, a, b Loi, aoi, and boi of the Macbeth chart on the color print. Color L,
The smaller a, b ΔEa, b indicates that the color reproduction is more faithful to the original. Table 2 summarizes the obtained results.

As is evident from the results obtained, a sample having a non-photosensitive layer closer to the support than the red-sensitive layer such as the AH layer. Performance is improved, but on the contrary, processing dependency is increased (101 →
102). In contrast, by eliminating the non-photosensitive layer on the side closer to the support than the red-sensitive layer such as the AH layer and adopting the structure of the present invention, the processing dependency is greatly improved, and the color fidelity is improved. It can be seen that both are compatible (102 → 104). on the other hand,
For samples that have not been improved in color reproducibility, such as conventional photographic materials, even if the non-photosensitive layer is removed closer to the support than the red-sensitive layer, such as the AH layer, processing-dependent There is no improvement effect (101 → 103), and it can be seen that it is specifically effective only in the configuration of the present invention.

Example 2 Samples 101 to 104 and 2
01-204 were exposed in the same manner as in Example 1, and then 4-amino-3-methyl-N-ethyl-N
Development processing was performed using a color developing solution containing-(β-methanesulfonamidoethyl) aniline (Kodak Color Development Agent CD-3) as a developing agent. The development was carried out using a KODAK ECN-2 (standard development processing for developing cinema film) developer as follows.
As in Example 1, the amount of the developing agent was 4.0 g / L (processing 1).
Two kinds of 3.0 g / L (processing 2) were performed to determine ΔD.

[Development process] Time Temperature (° C) Pre-bath 10 seconds 27 Rinse 20 seconds 30 Color development 3 minutes 41.1 Stop 30 seconds 30 Wash 30 seconds 30 Bleaching 3 minutes 27 Wash 1 minute 30 Fix 2 minutes 38 Wash 2 minutes 30 rinse 10 seconds 30 dry 5-7 minutes 32-47 (30-50% relative humidity).

<Composition of pre-bath> H ₂ O 800 mL Borax (decahydrate) 20 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1 g Water was added to add 1 L pH 9.25 ± 0.10.

<Composition of color developer> H ₂ O 850 mL Kodak Anticalcium No. 4 2 mL Sodium sulfite (anhydrous) 2 g Eastman Antifog No. 9 0.22 g Sodium bromide (anhydrous) 1.2 g Sodium carbonate (anhydrous) 25.6 g Sodium bicarbonate 2.7g Kodak color developing agent CD-3 4g / 3g Add water to 1L pH 10.20 ± 0.5.

<Bleach Composition> H ₂ O 700 mL Proxel GXL 0.07 mL Kodak Chelating Agent No. 1 24.2 g 28% ammonium hydroxide solution 30 mL ammonium bromide 32.5 g glacial acetic acid 10 mL ferric nitrate (9-hydrate) 28.8 g Add water and add 1L.

<Composition of Stop Solution> H ₂ O 900 mL 7.0 N sulfuric acid 50 mL Water was added to make 1 L.

<Composition of Fixing Solution> 700 mL of H ₂ O ₂ mL of Kodak Anticalcium No. 4 58 mL of 58% ammonium thiosulfate 185 mL Sodium sulfite (anhydrous) 10 g Sodium metabisulfite (anhydrous) 8.4 g Add 1 L of water.

Next, samples 101 to 104 and 201 to 2
After a Macbeth color chart was photographed under the same conditions and using a white fluorescent lamp, the image was subjected to the development processing described above. From this color negative, a print was made on a cinema color positive film so that the gray color became the same, and 18 of the resulting print was obtained.
The color was represented by the L *, a *, b * color system. The deviation of each of these points from the original chromaticity point of the Macbeth chart was calculated for the average color difference ΔEa, b in the same manner as in Example 1. Table 3 shows the obtained results.
Put together.

[0219]

[Table 3]

From the obtained results, it is understood that the sample of the present invention has good processing dependency and improved color fidelity by the constitution of the present invention. Further, the effect of the improvement is that the development agent containing 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline used in Example 2 was compared with the developing agent used in Example 1. Was more prominent.

(Example 3) An LUT (look-up table) was prepared from the sample prepared in Example 1 using an ARRI laser digital film recorder system using an RGB semiconductor laser, and gray step exposure was performed. In this system, the exposure of 2 million pixels requires 4 seconds, so the exposure time per pixel is 2 ×
10 ^-6 seconds. The obtained exposure sample was subjected to the processing of Example 1 or 2, and the same evaluation was performed. The processing dependency tends to be deteriorated as a whole by short-time exposure with a laser, and the improvement effect of the present invention was more remarkable.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03C 7/413 G03C 7/413

Claims (5)

[Claims] Claims: 1. A coupler, comprising 400 to 490 nm.
A silver halide emulsion layer having a spectral sensitivity maximum in the region of
A silver halide emulsion layer containing a coupler and having a spectral sensitivity maximum in a region of 500 to 600 nm, a silver halide emulsion layer containing a coupler and having a spectral sensitivity maximum in a region of 600 to 700 nm, and a non-photosensitive layer And a silver halide color photographic light-sensitive material having on a support, there are three or more silver halide emulsion layers having a spectral sensitivity maximum in the range of 500 to 600 nm. a) one layer having the smallest average particle size (average particle size minimum emulsion layer) having the smallest average particle size (equivalent sphere diameter) of all silver halide grains in the layer;
(B) two or more “large emulsion layers” in which the average grain size (equivalent sphere diameter) of all silver halide grains in the layer is larger than the average grain size of the minimum emulsion grain size emulsion layer; One or more large emulsion layers are disposed on the side closer to and farther from the support with respect to the minimum emulsion layer, and
A silver halide color photographic light-sensitive material having no non-light-sensitive layer on the side closer to the support than a silver halide emulsion layer having a spectral sensitivity maximum in a region of from about 700 nm. 2. It contains a coupler and has a wavelength of 400 to 490 nm.
A silver halide emulsion layer having a spectral sensitivity maximum in the region of
A silver halide emulsion layer containing a coupler and having a spectral sensitivity maximum in a region of 500 to 600 nm, a silver halide emulsion layer containing a coupler and having a spectral sensitivity maximum in a region of 600 to 700 nm, and a non-photosensitive layer A silver halide color photographic light-sensitive material having on a support, three or more silver halide emulsion layers having a spectral sensitivity maximum in the range of 500 to 600 nm, and the three or more emulsion layers are One "average grain size minimum emulsion layer" having the smallest average grain size (equivalent sphere diameter) of all silver halide grains in the layer, and two or more silver halide emulsion layers other than the smallest average grain size emulsion layer. (C) the total coating amount (mol / m ² ) of the development inhibitor releasing compound contained in the average grain size minimum emulsion layer (DIR
_L ) and (d) the total coating amount (DIR _H ) of the development inhibitor releasing compound contained in any one of the silver halide emulsion layers other than the average grain size minimum emulsion layer. DIR _H )
/ (DIR _L )> 2 that at least one silver halide emulsion layer is satisfied;
A silver halide color photographic light-sensitive material comprising no non-light-sensitive layer closer to the support than a silver halide emulsion layer having a spectral sensitivity maximum in a region of 700 nm. 3. The composition according to claim 1, further comprising a coupler,
A silver halide emulsion layer having a spectral sensitivity maximum in the region of
Contains coupler and has spectral sensitivity in the range of 500-600nm
Contains silver halide emulsion layer with maximum degree and coupler
And has a spectral sensitivity maximum in the range of 600 to 700 nm
Having a silver halide emulsion layer and a non-photosensitive layer on a support
A silver halide color photographic light-sensitive material having a spectral sensitivity maximum in the range of 500 to 600 nm.
There are three or more silver halide emulsion layers, and
The emulsion layer has an average grain size of all silver halide grains in the layer (a).
One layer with the smallest average grain size emulsion layer with the smallest (sphere equivalent diameter)
And the average particle size of all silver halide grains in the layer (b) (spherical phase).
(Equivalent diameter) is larger than the average particle size of the average grain size minimum emulsion layer.
A "large emulsion layer" consisting of two or more layers,
Layer is closer to and farther from the support than the average grain size minimum emulsion layer
(C) said average grain
Of the development inhibitor releasing compound contained in the emulsion layer having the smallest diameter.
Total application amount (mol / m^Two) (DIR_L) And (d) the average particle size
In any one of the silver halide emulsion layers other than the small emulsion layer
The total amount of the development inhibitor-releasing compound contained (DIR
_H) And (DIR)_H) / (DIR_L)> 2
At least one silver halide emulsion layer in which
And a spectral sensitivity in the range of 600 to 700 nm.
Closer to the support than the silver halide emulsion layer having the maximum
Halogen having no non-photosensitive layer on the side
Silver halide color photographic material. 4. A blue-sensitive silver halide emulsion layer containing at least one layer of a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide containing a cyan coupler on a support. In a silver halide color photographic light-sensitive material having an emulsion layer, the center-of-gravity sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm ≦ λ _G ≦ 580 nm, and at least one cyan color is formed. The center-of-gravity wavelength (λ _-R ) of the distribution of the magnitude of the layering effect that the red-sensitive silver halide emulsion layer receives from other layers in the range of 500 nm to 600 nm is 500 nm <λ _-R <
A silver halide color photographic light-sensitive material characterized by satisfying λ _G -λ _-R ≧ 5 nm and having no non-light-sensitive layer closer to the support than the red-sensitive silver halide emulsion layer. material. 5. The silver halide color photographic light-sensitive material according to claim 1, which is exposed to 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl). A) a color image forming method, which comprises developing with a developer containing aniline;