JP2003302730A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in graininess and sharpness in spite of high sensitivity. <P>SOLUTION: In the silver halide color photographic sensitive material having on a support unit blue-, green- and red-sensitive layers each consisting of two or more color-sensitive layers different from each other in sensitivity, an emulsion layer disposed farthest from the support in each unit sensitive layer satisfies the following requirements (a)-(c); (a) ≥50% of the total projected area of all silver halide grains in a silver halide emulsion contained in the emulsion layer is occupied by tabular grains having (111) faces as principal surfaces, ≥3.5 equivalent circular diameter and an aspect ratio of ≥8.0, (b) the volume fraction of all silver halide grains in the emulsion layer is ≤20%, (c) the silver coating weight of silver halide (expressed in terms of silver) contained in the emulsion layer is ≤1.0 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a silver halide color.
-This is related to photographic photosensitive materials.
Photosensitive material with excellent graininess and sharpness despite its sensitivity
It is about. [0002] [0002] Silver halide color photographic light-sensitive materials have been used in recent years.
Specific color sensitivity (ISO) for color negative film
Sensitivity) Regular use of high-sensitivity film of 800 or more is definitely immersed
It is transparent. On the other hand, in the past few years,
CCD (Charge Coupl) without using silver halide photosensitive material
ed Device) as a photosensitive element
A so-called digital camera for image formation to each household
PC penetration, conventional halogenation
The reason that no development processing is required for silver photosensitive materials.
It ’s also true that the reason is that it ’s starting to be used suddenly.
is there. However, a general-purpose digital camera for consumer use
Compared to conventional silver halide color negative photosensitive materials
Although there has been steady progress in sensitivity / image quality,
Assuming that general users enjoy images easily and easily
Therefore, CCD size, cost, S / N ratio
Sensitivity / image quality / exposure latitude
Much more in the silver halide color, especially in high sensitivity areas
The current situation is not as good as that for photosensitive materials. Therefore, the conventional silver halide color photographing feeling
The high sensitivity of the film in the optical material is the result of the scan in a dark room.
Telephoto lenses for shooting without using a trobo, sports photos, etc.
Shooting with a high-speed shutter using an astronomical photographer
Shooting with photosensitive materials, such as shooting that requires time exposure
Allows the expansion of the area, so that
It will bring great benefits. Therefore, film
Sensitivity is one of the eternal themes imposed on the industry
is there. The former high-sensitivity film has an absolute sensitivity.
In pursuit of, the user far exceeds the limit of patience
That can only provide low-quality film
Because of the situation, users
You are forced to choose one, and as a result you have to choose image quality rather than sensitivity
Did not get. In the industry, the sensitivity of photosensitive materials has been increased.
To increase the size of the silver halide grains that are photosensitive elements,
In addition, it is common practice to use it in combination with other high-sensitivity technologies.
It has become. Increasing the grain size of silver halide
The sensitivity increases to a certain extent, but the silver halide
As long as the content is constant, inevitably silver halide grains
Decrease in the number of children, i.e., the number of development start points, and graininess
It has the disadvantage of being greatly damaged. In order to compensate for this disadvantage as much as possible, a simple
Design to increase the number of silver halide grains per unit area
If this is done, the thickness of the photosensitive layer increases accordingly.
Incident light induced by silver halide grains
As a result, the sharpness of the film is sufficiently increased by scattering etc.
The balance between graininess and sharpness
It becomes difficult. Furthermore, such halo per unit area
Design to increase the number of silver halide grains, ie in photosensitive materials
When the amount of silver halide applied to the coating increases,
As described in JP-A-226650,
Increased fogging, reduced sensitivity,
The problem of photographic performance degradation such as graininess degradation
Arise. To solve such problems, the industry
Study of improved technology to achieve both high sensitivity and high image quality
Has been done. Halogen as an element for recording by exposure to light
For silver halide grains, efforts to increase sensitivity to light
Power has been made. Each wavelength range of blue, green and red
As a method for selectively absorbing silver on the surface of silver halide grains
Methods for adsorbing spectral sensitizing dyes are widely known. Feeling
In order to increase the degree, the silver halide grains are tabular and the ratio table
Increasing the area and increasing the amount of sensitizing dye adsorption
In recent years, tabular grains have been further reduced in thickness.
(Ultrathin tabular grains) have been used. However, when ultrathin tabular grains are used, these
Reported a significant drop in sensitivity due to large particle reflections
((I) Research Disclosure, 25330,
1985, (ii) A.E.Bohan, G.L.House, J.Imag.Sci.38, 32
(1994)). Therefore, such ultrathin tabular grains are
If it is used as a light sensitive material, the sensitivity will decrease, and other
It is anticipated that the true characteristics will decline.
It is described in. On the other hand, a design approach for color light-sensitive materials.
For example, Japanese Patent Application Laid-Open No. 62-17747 discloses:
Defines silver density and dry film thickness of blue-sensitive silver halide emulsion layers
And techniques for improving sharpness and graininess are disclosed.
The U.S. Pat. No. 5,322,766 discloses image formation.
Unit silver amount, film thickness, silver halide grain flatness, silver
/ Coupler ratio is specified, and the technology of image quality improvement by low silver amount is
It is disclosed. Further, in the above-mentioned JP-A-63-226650,
Is a color negative photosensitivity with a specific photographic sensitivity of 800-6400
Define the total silver content of the material and the silver amount of the most sensitive layer,
Technologies that improve image quality, storage stability and pressure are disclosed
The Photosensitive materials can be used for development processing after exposure.
Chemically treated silver halide grains by photoresponse
In order to finally form the latent image formed in
It is a well-known fact. In general, color negative photography
In the case of shadow light-sensitive materials, development-bleaching-fixing process (including washing process)
Including). Liquid composition used in each development process
And each process time is the same condition, the development speed is
Swelling speed of gelatin-containing layer of photosensitive material to be developed,
Used depending on the diffusion rate of chemical species
Details about the effects based on silver halide grains are clear
It was not. However, in the prior art, silver halide is used.
Especially when using ultrathin tabular grains as grains.
In areas where the fixed-photo sensitivity is 1000 or higher, the sensitivity and graininess
And the image quality level of sharpness is insufficient and satisfactory
New research has revealed that this is not the case
It was. As described above, the high sensitivity of the film is as follows.
In order to expand the shooting area of the photosensitive material,
A silver halide alloy that has both high sensitivity and high image quality.
There is a demand for development of a light-sensitive material. [0018] The object of the present invention is to provide high sensitivity.
Silver halide with excellent graininess and sharpness
An object of the present invention is to provide a photographic material. [0019] [Means for Solving the Problems] The above problems are the result of earnest research.
As a result, achieved by the present invention having the following configuration
I was able to. (1) Two layers having different sensitivities on the support.
Unit blue-sensitive silver halide composed of the above color-sensitive layers
Emulsion layer, unit green sensitive silver halide emulsion layer and unit red sensitivity
Silver halide color photograph having a silver halide emulsion layer
In the light-sensitive material, in each unit photosensitive layer, the most
The emulsion layers located far away from each other satisfy the following requirements (a) to (c)
Silver halide color photograph characterized by satisfying all
Photosensitive material. (A) Halogenation contained in the emulsion layer
Silver emulsion is at least 50% of the projected area of all silver halide grains
With an equivalent circle diameter of 3.5 μm or less with the (111) plane as the main surface
Above, occupied by tabular grains having an aspect ratio of 8.0 or more
It is. (B) The volume fraction of all silver halide grains in the emulsion layer is 2
0% or less. (C) In terms of silver of silver halide contained in the emulsion layer
Silver application amount in 1.0g / m²It is as follows. (2) The volume fraction is 15% or less.
The silver halide color photograph described in (1)
Photosensitive material. (3) The silver coating amount is 0.8 g / m.²Less than
The halo as described in (1) or (2),
Silver halide color photographic light-sensitive material. (4) The tabular silver halide grains are coagulated.
The silver salt epitaxy is selectively bonded to the inner part.
(1) to (3) characterized in that
The silver halide color photographic light-sensitive material listed. (5) Specific photo sensitivity is 1000 or more
In any one of (1) to (4)
The silver halide color photographic light-sensitive material described. [0026] BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in further detail below.
explain. The color photographic light-sensitive material of the present invention is provided on a support.
Blue sensitive halogens of at least two layers with different sensitivities
Silver halide emulsion layer, green sensitive silver halide emulsion layer, red sensitive halogen
Must have a silver halide emulsion layer. In addition to the photosensitive emulsion layer, for example, a protective layer, a mixed layer
Color prevention layer, yellow filter layer (also serves as a color mixture prevention layer)
Various non-photosensitive layers of the antihalation layer are provided.
It is preferable. The order of layer arrangement is not particularly limited, but is typical.
As a typical example, support from a position farthest from the support side
Protective layer, multiple blue-sensitive emulsion layers,
Yellow filter layer (also serves as a color mixing prevention layer), multiple green
Sensitive emulsion layer, anti-color mixing layer, multiple red sensitive emulsion layers, anti-color mixing
Color photograph arranged in order of stop layer and antihalation layer
A photosensitive material can be mentioned. The same color-sensitive layer comprising a plurality of layers is
Consists of different emulsion layers, especially restricted in the order of arrangement of these layers
No, but more sensitive milk on the side farther from the support
It is common to arrange an agent layer. For the purpose of increasing sensitivity, the typical arrangement described above is used.
In addition to blue, green and red sensitive emulsion layers with different color sensitivities
The most sensitive layer is located farthest from the support
You can also I.e.
In order from the position, the protective layer, the highest sensitivity blue-sensitive emulsion layer,
Color mixing prevention layer, highest sensitivity green sensitive emulsion layer, color mixing prevention layer, highest
Sensitive red sensitive emulsion layer, anti-color mixing layer, multiple blue sensitive emulsion layers,
Yellow filter layer (also serves as a color mixing prevention layer), multiple
Green sensitive emulsion layer, anti-color mixing layer, multiple red sensitive emulsion layers, color mixing
It is like the prevention layer and the antihalation layer. For the purpose of increasing the sensitivity, the “highest sensitivity blueness”
Emulsion layer, (color mixing prevention layer if necessary), maximum sensitivity green sensitivity
Emulsion layer, (Color mixing prevention layer, if necessary) Maximum sensitivity red sensitive milk
The highest sensitivity unit consisting of an agent layer (and a color mixing prevention layer if necessary)
Arrange the knit layer as the emulsion layer farthest away from the support,
Furthermore, toward the support, one or more blue layers
Sensitive emulsion layer, color mixing prevention layer, consisting of one or more layers
Green sensitive emulsion layer, color mixing prevention layer, one or more layers
The order of the red-sensitive emulsion layer, the color mixing prevention layer, and the antihalation layer
It can also be arranged. Furthermore, for the purpose of increasing the sensitivity, it is incident on the photosensitive material.
In order to efficiently use the emitted light, a light reflection layer is appropriately provided.
Can be placed. A reflective material contained in the light reflecting layer;
For example, fine silver halide grains and TiO₂Cost
Inorganic crystals represented are mentioned. In these cases, for example
When using fine silver halide grains, change the wavelength of the incident light.
Particles depending on the desired wavelength of light for the purpose of selective reflection
It is preferable to set the thickness. In the high-sensitivity color negative photosensitive material,
As mentioned above, for example, Japanese Patent Laid-Open No. 58-147744.
Improved graininess even a little as described in the issue
In order to obtain a silver halide grain in a silver halide emulsion,
The industry practice is to design as much content as possible.
It was. However, as described in JP-A-63-226650
As you can see, deterioration of image quality performance after storage of photosensitive materials.
From a viewpoint, even if the silver amount is increased beyond a certain amount,
The effect of improving the shape is small, but rather the image quality by storage after coating
A new side effect of severe degradation of performance
It becomes. In addition, the amount of silver used in the photosensitive material is reduced.
If set too high, the desired specific sensitivity can be maintained and
It is impossible to secure the degree. Therefore, it is included in the color photographic light-sensitive material of the present invention.
The total silver content is 3.0 g / m as the coating amount.²
-8.5 g / m²Preferably, it is 5.0.
g / m²~ 8.0 g / m²Is more preferable. Specific photographic feeling of the color photographic light-sensitive material of the present invention
The degree is not particularly limited, but is preferably 1000 or more.
It is particularly preferable to be used for expressing the effect of the present invention.
Yes. Here, the specific photo sensitivity will be described in detail.
The The sensitivity of photographic materials is generally an international standard, I.
Although SO sensitivity is used, photosensitive material is used for ISO sensitivity.
Is developed on the 5th day after exposure, and the development process is
In the present invention, after the exposure,
Reduce time to image processing and perform certain development processing
I am doing so. The method for determining the specific photo sensitivity is JIS
Different from K 7614-1981
30 minutes or more after exposure for sensitometry at 6 o'clock
The point to be completed within a short time and the development process will be described later
To the point according to Fuji Color Processing Formula CN-16 shown in Example 1
is there. Others are substantially JIS measurement methods. The silver halide photosensitive material in the present invention is:
Unit blue sensitive layer, unit green sensitive layer, unit red sensitive layer color sensitive layer
Each consisting of two or more emulsion layers with different sensitivities.
Emulsion layers that are farthest from the support among the photosensitive layers
More than 50% of the projected area of all silver halide grains
An equivalent circle diameter of 3.5 μm or more with the (111) plane as the main surface,
Tabular silver halide grains having an aspect ratio of 8.0 or more
Hereinafter, it is also referred to as “tabular grain of the present invention”. )
Emulsion is contained. In the following, in each unit photosensitive layer
This emulsion layer is also referred to as “emulsion layer of the present invention”. The flat of the present invention
A detailed description of the plate particles will be described later. On the other hand, the silver halide photosensitive material of the present invention.
Other than the emulsion layer of the present invention in each unit photosensitive layer
The silver halide grains used in the
The normal crystal particles such as octahedron and tetrahedron, and the main surface (11
1) Tabular grains having a plane, the main surface is from the (100) plane
Tabular grains, epitaxial grains, etc.
Although there is no restriction | limiting in it, It is preferable that it is a tabular grain. So
The tabular grains are silver iodobromide or silver chloroiodobromide
It preferably has dislocation lines.
Good. The equivalent circle diameter of 3.5 used in the present invention.
A tabular silver halide grain of μm or more
For the purpose of improving the absolute sensitivity, simply apply the silver coating amount.
Increasing the photosensitivity of the photographic material on the support side
The present inventors have newly introduced a phenomenon of lowering the sensitivity in the adhesive layer.
It was found. This phenomenon is caused by the research disk described above.
Reported by Roger (25330, 1985) and Bohan et al.
Due to light reflection at the grain surface due to the thickness of the tabular grains
As a result of experiments, it is clear that this is a different problem
It became. When tabular grains are coated on a support, the characteristics
Due to its unique shape, it can be applied to the support from different shapes.
Align along the fabric direction (perpendicular to the thickness direction of the emulsion layer)
Therefore, as the equivalent circle diameter of the tabular grains increases,
Seen from the direction perpendicular to the cloth surface, i.e.
The overlap in the projected area of the main surface increases
The As a result, a large tabular grain having an equivalent circle diameter is sensed.
By placing it in the light material, to the emulsion layer of the light-sensitive material
The rate of penetration of the developer is slow, especially away from the support
When the tabular grains are arranged on the side to be placed, development delay is remarkable.
Therefore, low sensitivity and softening may occur in standard processing development.
And became a new problem. As a result of diligent research, the present inventors have found that a photosensitive material.
To satisfy both of the above issues with satisfactory sensitivity / image quality
Surprisingly, the equivalent circle diameter and
Spectral ratio and the layer containing the grains, contained in the emulsion layer
Volume fraction of all silver halide grains to be produced, and the total halogen
The amount of silver used in the silver halide grains should be defined within the scope of the present invention.
I found it. The silver halide photographic light-sensitive material of the present invention
Of each unit photosensitive layer of each emulsion layer farthest from the support
(Ie, the emulsion layer of the present invention)
The volume fraction of all silver halide grains in the emulsion layer is 20%
It is as follows. Here, the volume fraction is the amount contained in the emulsion layer.
Of hydrophilic colloids and total silver halide grains
The volume of all silver halide grains relative to the total volume
It is expressed as a fraction. That is, as shown below
It is. Volume fraction (%) = (Amount of silver halide coated /
(Silver halide density) ÷ {(silver halide coating amount / halogen)
Silver halide density) + (hydrophilic colloid coating amount / hydrophilic colloid)
Density)} × 100 The silver halide density mentioned here is, for example, the theory of Iwanami Publishing.
AgBr, AgI, AgCl described in the chemical dictionary
Crystal density values, 6.47, 5.71, 5.56, respectively
Is used. However, regarding AgI, depending on the state
It can take any of α, β, or γ structures, but here
Use the density of the β isomer. The silver halide grains effective in the present invention are iodine.
Halogen mixtures such as silver bromide, silver chlorobromide, silver chloroiodobromide
In this case, the silver halide density is the grain size.
Use the sum of the products of the average halogen composition ratio and the above density.
To calculate the average density. For example, if the average halogen composition is A
The average density of the particles with gBr0.7I0.2Cl0.1 is the average
Density = (0.7 × 6.47 + 0.2 × 5.71 + 0.1
× 5.56) = 6.23. Further, hydrophilic colloid is usually used.
Used in combination with gelatin and other hydrophilic colloids
Can be. For example, gelatin derivatives, gelatin
And other polymer graft polymers, albumin, casein
Protein such as in; hydroxyethyl cellulose, potassium
Ruboxymethylcellulose, cellulose sulfate esters
Cellulose derivatives such as sodium alginate, starch inducer
Sugar derivatives such as conductors; polyvinyl alcohol, polyvinyl chloride
Nyl alcohol partial acetal, poly-N-vinyl pyro
Redone, polyacrylic acid, polymethacrylic acid, polyacrylic acid
Rilamide, polyvinyl imidazole, polyvinyl pyra
Various synthesis such as single or copolymer such as sol
A hydrophilic polymer substance can be used. In the above volume fraction formula, (hydrophilic colloid coating
Cloth amount / hydrophilic colloid density) is a number of hydrophilic colloids
Each of the hydrophilic colloids (hydrophilic core
(Lloyd coating amount / hydrophilic colloid density)
Sum. Total halogen contained in the emulsion layer of the present invention
As mentioned above, when the volume fraction of silver halide grains exceeds 20%
In addition, when viewed from the direction perpendicular to the coated surface, that is, tabular grains
Overlap in projected area of main surface in child increases
As well as between grains in the thickness direction of the emulsion layer.
Reduced distance and extremes in developer penetration and diffusivity
It works against disadvantages and causes low feeling and softness. Preferably, it is 5% or more and 18% or less,
More preferably, it is 8% or more and 15% or less. The volume fraction becomes extremely low because the present invention
The number of silver halide grains contained in the emulsion layer is extremely small.
Or the hydrophilic colloid content of the emulsion layer is
The former has problems with sensitivity and graininess.
The latter occurs when the film thickness of the emulsion layer of the present invention is increased,
Both of them cause sharpness problems and deterioration of film quality. Total halogen contained in the emulsion layer of the present invention
The silver coating amount of silver halide grains in terms of silver is 1.0 g / m.²After
It is below. Preferably 0.3 g / m²1.0 g / m or more
²Or less, more preferably 0.5 g / m²that's all
0.8g / m²It is as follows. The silver coating amount contained in the emulsion layer is 1.0 g.
/ M²Exceeding the above range, as described above, the penetration of the developer and
Work extremely disadvantageous to diffusion and low sensitivity and softening
Invite. On the other hand, if the silver coating amount is extremely small,
Works well for penetration, but in terms of sensitivity and graininess
Problems arise. The light-sensitive material of the present invention is based on the support.
Total dry film thickness of all hydrophilic colloid layers on the side with emulsion layers
The sum is preferably 28 μm or less, and 23 μm or less
Is more preferable, 18 μm or less is more preferable, and 16 μm
m or less is particularly preferable. The dry film thickness of the emulsion layer of the present invention is as follows.
The volume fraction of all silver halide grains contained
If you look at the regulations, there is no particular regulation, but 3μm or less is preferred
More preferably, it is 2.5 μm or less. What is dry film thickness?
Measured after holding for 2 days or more at 25 ° C and 55% relative humidity
Thickness. Film swelling film thickness is well known in the art.
Can be measured according to the technique, eg A
Photographic support by A. Green et al.
Jens and Engineering (Photog
r. Sci. Eng. ), 19, 2, 124-12
Use a serometer of the type described on page 9
Can be measured. The water swelling rate is determined by the gelatin as a binder.
Add a hardener to the skin, or
It can be adjusted by changing. Hardeners are inorganic or organic gelatin hardeners.
Used alone or in combination, and multi-layer coating
The swelling speed can be controlled by adding it appropriately to each layer of material.
You can. Such hardeners are those described above, and
Kenneth Mason Publications, Ltd., Dudley Annex,
12 North Street, Emsworth, Hampshire P010 7DQ, ENG
Research disk published in September 1996 by LAND
Roger (ResearchDisclosure) No. 38957 from 599
See page 600. In the present invention, it is preferable.
A new hardener is a vinylsulfonyl compound. So
Such compounds contain multiple vinylsulfonyl groups
It is characterized by that. In divinyl sulfone, simple
One sulfonyl group is bonded to two vinyl groups.
Multiple vinylsulfonylalkyl groups such as vinylsulfur
Honylmethyl, vinylsulfonylethyl, vinylsulfo
Nylpropyl or vinylsulfonylbutyl group intervenes
Through ether, amine, diamine or hydrocarbon bonds
Are connected to each other. Bis (vinylsulfonyl) ether
Such as bis (vinylsulfonylmethyl) ether
And bis (vinylsulfonylethyl) ether, N, N-
Tylene-bis ((β-vinylsulfonyl) propionamide
Is particularly preferred. Typical vinylsulfonyl hardener
As well as procedures for their synthesis and use.
No. 3,490,911, U.S. Patent 3,539,644, U.S. Patent
No. 3,642,486. Blistering of photosensitive layer
Another way to control the moisture rate is to put a hydrophilic polymer
Increase its swelling rate or polymer hardener, or
Is a hardener-reactive polymer or modified gelatin, for example
Control by adding amine-modified gelatin
You can also. Water on the side having the emulsion layer of the light-sensitive material of the present invention
The swelling rate is preferably 20% or more and 300% or less, and 50% or less.
More preferably, the upper limit is 200% or less. The following is a description of the present invention.
The plate-like silver halide grains will be described in detail. The present invention
The composition of tabular silver halide grains in is silver iodobromide,
Silver iodochlorobromide is preferred. In the present invention, tabular silver halide grains (hereinafter referred to as
Is called two tabular grains (111)
A silver halide grain having a main surface. Flat plate of the present invention
A particle has one twin plane or two or more parallel twin planes.
Have. The twin plane is all lattices on both sides of the (111) plane.
If the ions at the point are mirror images of this (111) plane
That means. This tabular grain has three grains when viewed from above.
Square shape, hexagonal shape or round shape with rounded shape
Have outer surfaces parallel to each other
The The equivalent circle diameter and thickness of tabular grains are determined by the replica method.
By taking a transmission electron micrograph, the projection surface of each particle
Diameter (projected area diameter) and thickness of a circle with an area equal to the product
Ask for. In this case, the thickness is the shadow of the replica (shadow)
Calculated from the length of The tabular silver halide grain of the present invention has a circular phase.
The diameter is 3.5 μm or more. Preferably, 3.5 μm
Although it is 20.0 μm or more, it is 4.0 μm or more and 10.
More preferably 0 μm or less. Sphere equivalent diameter is 1.0 μm or more and 5.0 μm or less.
Lower is preferable, more preferably 1.2μm or more and 4μm or less
That's right. The equivalent sphere diameter is the volume equal to the volume of each particle.
The diameter of the sphere it has. The aspect ratio is 8 or more
200 or less is preferable, and 10 or more and 200 or less is more preferable.
Good. The aspect ratio is the equivalent circle diameter of a particle.
The value divided by the thickness. The emulsion contained in the emulsion layer of the present invention is monodispersed.
Preferably all silver halide grains in the emulsion.
The coefficient of variation of the equivalent sphere diameter is preferably 30% or less, more preferably
Preferably it is 25% or less. In the case of tabular grains,
The coefficient of variation of the equivalent circle diameter is also important, and
Coefficient of variation of equivalent circle diameter of silver halide grains is 30% or less
Is more preferable, and 25% or less is more preferable. Also,
The coefficient of variation of the tabular grain thickness is preferably 30% or less.
More preferably 25% or less. The coefficient of variation is an individual
The standard deviation of the distribution of equivalent diameter of silver halide grains is the average equivalent diameter.
The value divided by 100 multiplied by 100 or the individual halo
The average thickness is the standard deviation of the thickness distribution of silver halide tabular grains.
The value divided by 100 is multiplied by 100. Silver halide contained in the emulsion layer of the present invention
The silver iodide content in the grain is relative to the total silver in the grain.
0.5 mol% or more and less than the solid solution limit is preferable, and 1 mol%
More preferred is 20 mol% or less. Silver chloride content
Is 0 mol% or more and 10 mol% or less with respect to the total silver amount in the grain.
Below is preferred. Halogen contained in the emulsion in the emulsion layer of the present invention
The silver iodide tabular grains preferably have a silver iodide content of each other.
Are composed of a different core part and a shell surrounding the core part.
You may have what is called a core / shell structure. Shi
The shell portion may surround the entire core portion, and the core portion flat plate
It may surround only the side of the particle, or only the main plane
It may be surrounded. Even if the number of shells is one, two or more
It may be above. Silver halide contained in the emulsion layer of the present invention
The particles are within 20% in area from the outer periphery of the particle projection part,
Preferably, dislocation lines may be present within 10%.
Yes. Even if the dislocation line exists along the outer periphery in the vicinity of the outer periphery
It may be good or may be localized near the corner. Corner section
The neighborhood is x from the center of the straight line connecting the center of the particle and each vertex.
When a perpendicular line is drawn from the point at% to the edge that makes each vertex
The three-dimensional part surrounded by the perpendicular and the side
It is. The value of x is preferably 50 or more and less than 100,
More preferably, it is 75 or more and less than 100. Exist
The average number of dislocation lines is 10 or more per particle. Better
The average number is 20 or more per particle. The tabular silver halide grains of the present invention
Protruding part (hereinafter referred to as epitaxial) outside the particle
May exist. Junction to epitaxial tabular grains
There are few corners, edges, and main planes of tabular grains.
At least a part may be sufficient, and it may be spread over several places.
Yes. The junction position to the epitaxial tabular grain is the corner
More preferably, it is a part. "Corner" here
Is when the tabular grains are viewed from the direction perpendicular to the main surface.
1 of the length of the shorter side of the two sides adjacent to the vertex.
This means the part in a circle with a radius of / 3. Epita
One or more Kishals must be joined per particle.
Preferably, it is 3 or more. Epita
Depending on the formation conditions of the Kishal, two pieces above and below the corner
Two epitaxial layers grow on the main surface
In some cases, it becomes one, and such a grown and fused
We will count as one Pitataxal. D
The composition of the pitaxial is AgBr, AgCl, AgBrC
l, AgBrClI, AgBrI, AgI, AgSCN
Etc. are preferred. Further, the epitaxial portion is disclosed in JP-A-8-6.
"Dopant (metal) as described in 9069
Complex) ”may be introduced. Next, a method for preparing silver halide grains is described.
This will be described in more detail. The preparation process of the present invention includes a base part forming process.
Step ((a) step) and the subsequent outer portion forming step
(Step (b)). Basically (a) only process
Although it is good, the step (b) can be performed following the step (a).
More preferred. (B) Process is (b1) Dislocation introduction
(B2) Corner part dislocation limited introduction process, (b3) D
This is the Pitaxial joining process, which process is used.
May be. First, the base part will be described. Base part
May be 100% of the total silver used for grain formation.
However, it is preferably 50% or more and 95% or less,
More preferably, it is 0% or more and 90% or less. In addition, the base part silver
The average iodine content with respect to the amount is 5 mol% or more.
The following is preferable, but 7 mol% or more and 30 mol% or less are further
preferable. In addition, the base part has a core / shell structure as necessary.
You may take a structure. At this time, the core part of the base part
50% or more and 90% or less of the total silver amount is preferred
The average iodine composition of the core is 5 mol% or more and less than the solid solution limit.
Lower is preferable, and more preferably 7 mol% or more and 30 mol% or less.
Good. On the other hand, the iodine composition of the shell part is 0 mol% or more and 5 mol%.
% Or less is preferable, and 3 mol% or less is more preferable. Next, (a) the process of forming the base portion
The process will be described. The formation process of the base part is generally
Processes well known in the field, i.e. Nucleation process-ripening process-growth process It can be manufactured through the process. Nucleation, ripening
For example, Japanese Unexamined Patent Publication No. 2001-9
No. 2057 is described in detail. Preparation of the emulsion of the present invention
As the protective colloid used in manufacturing, the above-mentioned gelatin
Is advantageous, but other hydrophilic colloids
Can also be used. For example, gelatin derivatives, gelatin and other
Of graft polymer with polymer, albumin, casein
Such as protein; hydroxyethyl cellulose, carbox
Like methylcellulose and cellulose sulfates
Cellulose derivatives, sodium alginate, starch derivatives
Sugar derivatives such as polyvinyl alcohol, polyvinyl alcohol
Lucol partial acetal, poly-N-vinylpyrrolide
, Polyacrylic acid, polymethacrylic acid, polyacrylic
Amide, polyvinyl imidazole, polyvinyl pyrazo
Various synthetic hydrophilics such as mono- or copolymers such as
Can be used. The emulsion of the present invention was washed with water for desalting, and was renewed.
It is preferable to disperse in a prepared protective colloid.
Gelatin is used as the protective colloid, but zera
Natural polymers and synthetic polymers other than tin are also used.
The The types of gelatin include alkali-treated gelatin,
Oxidation of methionine group in gelatin molecule with hydrogen peroxide
Oxidized gelatin (methionine content 40μmol / g or less)
Lower), amino group-modified gelatin of the present invention (eg, phthalate)
Gelatin, trimellitated gelatin, succinylated gelatin
, Maleated gelatin, esterified gelatin)
It is done. If necessary, JP-A-11-237704
Molecules measured by the paggy method
30% or more of components with a molecular weight of 280,000 or more in the quantity distribution
You may use the lime processing bone gelatin which contains. Also, compare
For example, European Patent No. 758758 and US Patent No. 57
Starch described in No. 33718 may be used. So
In addition, natural polymer is Japanese Patent Publication No.7-111550, Lisa
J Disclosure Vol.176, No.17643 (1978 1
(February) in section IX. Washing temperature depends on purpose
However, it is preferable to select in the range of 5 ° C to 50 ° C.
That's right. The pH at the time of washing can be selected according to the purpose, but it is between 2 and 10.
Is preferable. More preferably in the range of 3-8
It is. The pAg at the time of washing can also be selected according to the purpose, but 5-10
It is preferable to choose between. Noodles as a washing method
Washing method, dialysis method using semipermeable membrane, centrifugal separation method, coagulation sedimentation
Method, ion exchange method, ultrafiltration method
be able to. In the case of coagulation sedimentation, use of sulfate
Method, using organic solvent, using water-soluble polymer
Method, method using gelatin derivatives, etc.
Yes. When forming the particles of the present invention, for example,
Kaihei 5-173268, 5-173269, 5
-173270, 5-173271, 6-20
Polyamides described in Nos. 2258 and 7-175147
Lucylene oxide block copolymer or for example
Polyalkylene described in Japanese Patent No. 3089578
Oxide copolymers may be present. The compound is
It can be any time during particle preparation,
The effect is great when used at an early stage of formation. When preparing the emulsion of the present invention, for example, during grain formation,
During the desalting process, chemical sensitization, there is a metal ion salt before coating.
It is preferable depending on the purpose. Dope particles
In some cases, during particle formation, particle surface modification or chemical sensitization
When used as an agent, added after grain formation and before chemical sensitization
It is preferable to do. When doping the whole particle and the particle
Doping only the core part or the shell part
You can also choose the law. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals are ammo
Nitric acid salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrochloride salt
Or 6-coordinate complex salt, 4-coordinate complex salt, etc.
Any salt form that can be added can be added. For example,
CdBr₂, CdCl₂, Cd (NO₃)₂, Pb (N
O₃)₂, Pb (CH₃COO)₂, K₄[Fe (C
N)₆], (NH₄)₄[Fe (CN)₆], K₂Ir
Cl₆, (NH₄)₃RhCl₆, K₄Ru (CN)₆
Can be given. As ligands for coordination compounds, halo, a
Co, cyano, cyanate, thiocyanate, nitros
Selected from thio, thionitrosyl, oxo and carbonyl
You can These use only one metal compound
You can use 2 or more types in combination.
Yes. The metal compound is water or methanol, aceto
It is preferable to add it in a suitable organic solvent such as
That's right. Hydrogen halide aqueous solution to stabilize the solution
(Eg HCl, HBr) or halogenated alk
(For example, KCl, NaCl, KBr, NaBr)
The method of adding can be used. Also acid if necessary
・ Alkali may be added. Metal compounds form particles
Even if it is added to the previous reaction vessel, it must be added in the middle of particle formation.
You can also. There is also a water-soluble silver salt (for example, AgNO3)
Or an aqueous alkali halide solution (for example, NaCl, K
Br, KI) added continuously during silver halide grain formation
It can also be added. Further water-soluble silver salt, halogenated
Prepare a solution independent of the alkali at an appropriate time during particle formation
You may add continuously in a period. Furthermore, various addition methods
It is also preferable to combine them. Described in US Pat. No. 3,772,031
Add chalcogen compounds such as those mentioned during emulsion preparation
This method may be useful. In addition to S, Se, Te
Ansalt, thiocyanate, selenocyanic acid, carbonate, phosphorus
Acid salts and acetate salts may be present. The silver halide grains of the present invention have sulfur sensitization,
Chalcogen sensitization such as ren sensitization and tellurium sensitization;
Noble metal sensitization such as radium sensitization; at least one of reduction sensitization
One step in the silver halide emulsion production process
be able to. It is good to combine two or more sensitization methods
Good. Depending on the process of chemical sensitization,
Emulsions can be prepared. Chemical increase inside the particle
Type that embeds the nucleus, embeds shallow from the particle surface
Type that creates chemical sensitization nuclei on the surface.
The In the emulsion of the present invention, the location of the chemical sensitization nucleus is selected according to the purpose.
But generally less preferred is near the surface.
This is the case when at least one kind of chemical sensitization nucleus is made. In the present invention
One of the chemical sensitization that can be preferably performed is chalcogen sensitization and
Noble metal sensitization alone or in combination with James (T.
H. James), The Photographic Process
Su, 4th edition, published by McMillan, 1977, (TH
James, The Theory of the P
photographic Process, 4th e
d, McMillan, 1977), pages 67-76.
Can be performed using active gelatin as described
Research Disclosure, Volume 120, 1
April 974, 12008; Research Disclosure
34, June 1975, 13452, US Patent
No. 2,642,361, No. 3,297,446,
No. 3,772,031, No. 3,857,711,
No. 3,901,714, No. 4,266,018
And 3,904,415, as well as British patents
PAg 5-1 as described in 1,315,755
0, pH 5-8 and temperature 30-80 ° C., sulfur,
Ren, tellurium, gold, platinum, palladium, iridium or
Can be a plurality of combinations of these sensitizers. You
For metal sensitization, gold, platinum, palladium, iridium
Precious metal salts such as
Sensation, palladium sensitization and a combination of both are preferred. In gold sensitization, P.I. Grafkide
by s, Chimie et Physique Pho
tografique (Paul Momtel)
Published, 1987, 5th edition), Research Dis
Closure magazine 307 Volume 307105 etc.
The gold salt that is used can be used. Specifically, chloroauric acid, potassium chloroo
In addition to -rate, potassium aurithiocyanate,
US Pat. No. 2,642,361 (such as gold sulfide and gold selenide)
No. 3503749 (thiolate having a water-soluble group)
Gold), 5049484 (bis (methylhydanto)
Inert) gold complex, etc.), No. 5049485 (Mesoi)
Onicthiolate gold complexes such as 1,4,5-trime
Til-1,2,4-triazolium-3-thiolate gold
Complex), 5252455 and 5391727.
Macrocyclic gold complex of No. 5620841, 57
No.00631, No.5759760, No.5759761
No., 5912111, 5912112, 59
39245, JP-A-1-147537, 8-690
74, 8-69075, 9-269554,
Japanese Patent Publication No. 45-29274, East German Patent DD-264
524A, 264525A, 265474A, 2
98321A, JP 2001-75214 A, 200
1-75215, 2001-75216, 20
01-75217, 2001-75218
The listed gold compounds can also be used. The palladium compound is a divalent palladium salt or
Means a tetravalent salt. Preferred palladium compounds are
R2 PdX6 or R2 PdX4
The Where R is a hydrogen atom, an alkali metal atom or an
Represents a monium group. X represents a halogen atom, chlorine,
Represents a bromine or iodine atom. Specifically, K₂PdC
l₄, (NH₄)₂PdCl₆, Na₂PdCl₄,
(NH₄)₂PdCl₄, Li₂PdCl₄, Na₂P
dCl₆Or K₂PdBr₄Is preferred. Gold compound
And palladium compounds are thiocyanate or seleno
It is preferable to use in combination with cyanate. In sulfur sensitization, unstable sulfur compounds are added.
Used, P.P. By Grafkides, Chimie et
  Physique Photographic
(Paul Momtel, published in 1987, No. 5
Edition), Research Disclosure Magazine 30
Unstable sulfurization described in Vol. 7, No. 307105, etc.
A compound can be used. Specifically, thiosulfate (for example, high
Po), thioureas (eg, diphenylthiourea, tri
Ethylthiourea, N-ethyl-N ′-(4-methyl-2
-Thiazolyl) thiourea, dicarboxymethyl-dimethyl
Ruthiourea, carboxymethyl-trimethylthiourine
Element), thioamides (eg, thioacetamide),
-Danines (eg, diethyl rhodanine, 5-benzidine)
Reden-N-ethylrhodanine), phosphine sulf
(E.g., trimethylphosphine sulfiphy)
Do), thiohydantoins, 4-oxo-oxazolid
N-2-thiones, disulfides or polysulfides
(E.g., dimorpholine disulfide, cystine
, Hexathiocanthion), mercapto compounds (eg
For example, cysteine), polythionate, elemental sulfur, etc.
Also known sulfur compounds and active gelatin can be used.
You can. Especially thiosulfates, thioureas, phosphies
N-sulfides and rhodanines are preferred. In selenium sensitization, unstable selenium compounds
No. 43-13489, 44-157
48, JP-A-4-25832, and 4-109340.
No., No. 4-271341, No. 5-40324, No. 5
-11385, 6-51415, 6-1752
58, 6-180478, 6-208186
No., No. 6-208184, No. 6-317867, No.
7-92599, 7-98483, 7-140
Use selenium compounds described in No. 579 etc.
You can. Specifically, colloidal metal selenium,
Noureas (eg, N, N-dimethylselenourea, tri
Fluoromethylcarbonyl-trimethylselenourea, a
Cetyl-trimethylselenourea), selenoamides (eg
For example, selenoamide, N, N-diethylphenylseleno
Amide), phosphine selenides (e.g.
Nylphosphine selenide, pentafluorophenyl
Triphenylphosphine selenide), selenophosf
(E.g., tri-p-tolylselenophosphate)
, Tri-n-butylselenophosphate), selenium
No ketones (eg, selenobenzophenone), isose
Lenocyanates, selenocarboxylic acids, selenoeste
(E.g., methoxyphenylselenocarboxy-
2,2-dimethoxycyclohexane ester)
Ruselenides may be used. In addition, Shoko
46-4553, 52-34492, etc.
Non-labile selenium compounds such as selenite, selenasia
Acids (eg, potassium selenocyanate), selenazo
And selenides can also be used. In particular,
Phosphine selenides, selenoureas, selenoeste
And selenocyanic acids are preferred. In tellurium sensitization, unstable tellurium compounds
JP-A-4-224595, 4-2713
No. 41, No. 4-3333043, No. 5-303157
No. 6-27573, No. 6-175258, No. 6
-180476, 6-208186, 6-20
No. 8184, No. 6-317867, No. 7-14057
Use unstable tellurium compounds described in No. 9 etc.
be able to. Specifically, phosphine tellurides (eg,
For example, butyl-diisopropylphosphine telluride,
Tributylphosphine telluride, tributoxyphos
Fintellide, ethoxy diphenylphosphine
Lurid), diacyl (di) tellurides (eg bis
(Diphenylcarbamoyl) ditelluride, bis (N-fu
Enyl-N-methylcarbamoyl) ditelluride, bis
(N-phenyl-N-methylcarbamoyl) telluride,
Bis (N-phenyl-N-benzylcarbamoyl) tel
Lido, bis (ethoxycarbonyl) telluride), telluro
Ureas (for example, N, N′-dimethylethylenetellurourine
Elemental, N, N'-diphenylethylenetellurourea) telluro
Amides, telluroesters, and the like may be used. Useful chemical sensitization aids include azaindene,
Chemical sensitization such as azapyridazine and azapyrimidine
To suppress fog and increase sensitivity in the process
Known compounds are used. Examples of chemical sensitization aid modifiers
U.S. Pat. Nos. 2,131,038 and 3,412.
1,914, 3,554,757, JP 58
-126526 and the above-mentioned "Daffin", "photographic emulsion
Science, pp. 138-143. Gold sensitizer and chalcogen used in the present invention
The amount of sensitizer used depends on the silver halide grains used and the chemical intensifier.
Depending on the sensitivity conditions, but per mole of silver halide
10 ^-8-10^-2Moles, preferably 10^-7-10
^-3It is about a mole. During grain formation of the silver halide emulsion of the present invention,
After grain formation and before or during chemical sensitization
Alternatively, reduction sensitization after chemical sensitization is preferred. here
Reduction sensitization means adding a reduction sensitizer to a silver halide emulsion.
A low pAg atmosphere with a pAg of 1-7, called silver ripening
A method of growing or aging in the atmosphere, called high pH aging
Grow or mature in a high pH atmosphere of pH 8-11
You can choose any of the methods. More than one way
Can also be used together. How to add a reduction sensitizer
Preferred method in that the level of reduction sensitization can be finely adjusted
It is. Examples of reduction sensitizers include stannous salt and asthma.
Corbic acid and its derivatives, amines and polyamines
, Hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and borane compounds are known. Return of the present invention
Select and use these known reduction sensitizers for source sensitization
Can also be used in combination with two or more compounds
The Reduction sensitizers include stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives
The body is a preferred compound. The amount of reduction sensitizer added is emulsion.
It is necessary to select the amount of addition because it depends on the manufacturing conditions.
10 per mole of silver halide^-7-10^-3The molar range is
Is appropriate. The reduction sensitizer is, for example, water or alcohol.
, Glycols, ketones, esters, amides
It is dissolved in an organic solvent such as No. 1 and added during grain growth.
It may be added to the reaction vessel in advance,
A method of adding at an appropriate time is preferable. Also water-soluble silver salt
Or in advance to the water solubility of water-soluble alkali halide
Add a reduction sensitizer and use these aqueous solutions.
Silver halide grains may be precipitated. Also for particle growth
Along with this, the reduction sensitizer solution can be added several times.
It is also a preferable method to add it for a long time. Acid for silver during the production process of the emulsion of the present invention
It is preferable to use an agent. What is an oxidizing agent for silver?
Acts on metallic silver and converts it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very fine silver particles by-produced during chemical sensitization
A compound capable of converting to silver ions is effective. here
The silver ions produced in
It may form a slightly soluble silver salt in water such as silver or silver selenide
It is also possible to form a readily soluble silver salt in water such as silver nitrate.
Yes. The oxidizing agent for silver is organic, even if it is inorganic.
There may be. Examples of inorganic oxidizing agents include ozono
, Hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, N
a₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂
・ 2H₂O), peroxyacid salts (eg K₂S
₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex
Body compounds (eg, K₂[Ti (O₂) C₂O₄] ・ 3
H₂O,₄K₂SO₄・ Ti (O₂) OH / SO₄・ 2
H₂O, Na₃[VO (O₂) (C₂H₄)₂] 6H
₂O), permanganate (eg KMnO)₄),Black
Mumate (eg, K₂Cr₂O₇) Oxylate,
Halogen elements such as iodine and bromine, perhalogenates (eg
For example, potassium periodate), high valent metal salts (eg
For example, potassium hexacyanoferric acid) and thiosulfur
There is oxalate. Further, as an organic oxidizing agent, p-quinone is used.
Quinones, such as peracetic acid and perbenzoic acid.
Oxides, compounds that release active halogens (eg N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidizing agents of the present invention are ozone and peracid.
Hydrogen fluoride and its adducts, halogen elements, thiosulfo
Inorganic oxidizers of phosphates and organic oxidants of quinones.
It is preferable to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.
This is a new aspect. Those who apply reduction sensitization after using an oxidizing agent
Method, the reverse method, or the method of coexisting both at the same time
You can choose from among them. These methods are grain
It can be selected and used in both the child formation process and the chemical sensitization process.
Yes. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the production process, storage, or photo processing
To stop or stabilize photographic performance,
Compounds can be included. Ie thiazole
Such as benzothiazolium salt, nitroimidazole
, Nitrobenzimidazoles, chlorobenzimi
Dazoles, bromobenzimidazoles, mercapto
Thiazoles, mercaptobenzothiazoles, merca
Putobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; examples
For example, a thioketo compound such as oxadrine thione;
Zaindenes such as triazaindenes, tetraa
Zaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Chitraazaindene), Pentaazaindene
Known as antifoggants or stabilizers, such as
Many compounds can be added. For example, US patents
3,954,474, 3,982,947,
Use the one described in Japanese Patent Publication No. 52-28660.
You can. One preferred compound is disclosed in JP-A-63-21.
There are compounds described in No. 2932. Antifogging agent
And stabilizers before and during particle formation, after particle formation,
During the washing process, after dispersion with water, before chemical sensitization, during chemical sensitization,
After sensitization, add according to purpose at various times before application
can do. Add to the original fog during emulsion preparation
In addition to preventing and stabilizing,
Control, reduce particle size, reduce particle solubility
Control, chemical sensitization, control dye sequence
It can be used for various purposes. The photographic emulsion used in the present invention has a methine color.
The effect of the present invention is spectral sensitization by elements and others
Is preferable. The dye used is cyani
Dye, merocyanine dye, composite cyanine dye, composite dye
Russianine dye, holopolar cyanine dye, hemicia
Nin dye, styryl dye and hemioxonol dye
Is included. Particularly useful dyes are cyanine dyes, merosi
Dyes belonging to anine dyes and complex merocyanine dyes
It is. These dyes have a basic heterocyclic nucleus as
Any of the nuclei normally used for anine pigments can be applied.
The That is, for example, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole
Nucleus, selenazole nucleus, imidazole nucleus, tetrazole
Nucleus, pyridine nucleus; alicyclic hydrocarbon ring fused to these nuclei
Nuclei; and aromatic nuclei fused to these nuclei
Nucleus, for example, indolenine nucleus, benzoindoleni
Nucleus, indole nucleus, benzoxador nucleus, naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, benzimidazole nucleus, key
Norin nucleus is applicable. These nuclei are substituted on carbon atoms
It may have a group. Merocyanine dyes or complex merocyanines
As a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thio
Oxazolidine-2,4-dione nucleus, thiazolidine-
2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid
A 5-6 membered heterocyclic nucleus of the nucleus can be applied. These sensitizing dyes may be used alone.
However, combinations of these may be used, and combinations of sensitizing dyes
Is often used for the purpose of supersensitization. That generation
Examples are U.S. Pat. Nos. 2,688,545 and 2,973.
No. 7,229, No. 3,397,060, No. 3,5
22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No.
3,666,480, 3,672,898,
No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
No. 7, British Patent No. 1,344,281, No. 1,50
7,803, Japanese Examined Sho 43-4936, 53-12
No. 375, JP-A 52-110618, 52-10
No. 9925. Spectral sensitization by itself with sensitizing dye
Dyes that do not absorb or that do not substantially absorb visible light
May contain in the emulsion a material that is high in quality and exhibits supersensitization.
Yes. The time when sensitizing dye is added to the emulsion is useful
At any stage of emulsion preparation known to be
Also good. Most commonly, after completion of chemical sensitization and before application
US Pat. No. 3,628,969.
And No. 4,225,666.
Spectral sensitization is added at the same time as the chemical sensitizer.
It can also be performed simultaneously with Japanese Patent Application Laid-Open No. 58-113928.
Can also be done prior to chemical sensitization as described
Can be added before silver halide grain precipitation completes.
Spectral sensitization can also be started. Furthermore, US Patent No.
As taught in US Pat. No. 4,225,666.
Adding the compounds separately, ie these compounds
Part of the chemical is added prior to chemical sensitization, and the remainder is added for chemical sensitization.
It can also be added later, US Pat. No. 4,18.
Including the method disclosed in US Pat. No. 3,756.
Any time during the formation of silver halide grains may be used. The amount added was 4 × per mole of silver halide.
10^-6~ 8x10^-3Can be used in moles. Fragmentable electron donating sensitizer
It is also good to use. An electron donating sensitizer is disclosed in US Pat.
No. 747235, No. 5747236, No. 605426
No. 0, 5940551, European Patent No. 786692A
1, 893732 A1, JP 2000-18100 A.
No. 1, 2000-180999, 2000-18
1002, 2000-181000, 2000
Described in -221626, 2000-221628
Has been. Fragmentable electron donating sensitizers
It may be used in any case during the photosensitive material manufacturing process.
For example, during particle formation, desalting process, chemical sensitization, before application, etc.
It is. Also add in multiple steps during these steps
You can also The compound of the present invention contains water, methanol, ethanol.
In water-soluble solvents such as tanol or mixed solvents
It is preferable to add after dissolving. When dissolved in water,
Higher or lower pH makes the compound more soluble
For this reason, dissolve at a high or low pH and add it.
You may add. Fragmentable electron donating sensitizer
Is preferably used in the emulsion layer, but together with the emulsion layer
Even if it is added to the protective layer or intermediate layer and diffused during application
Good. The timing of addition of the compound of the present invention may be before or after the sensitizing dye.
Preferably, each is preferably 1 per mole of silver halide.
× 10^-9~ 5x10^-2Mole, more preferably 1 × 1
0^-8~ 2x10^-3Silver halide emulsion layer in mole ratio
Contained. Fragmentable electron donating sensitizer
When used, it is preferable to use a preservability improving agent. Protection
JP-A-11-119364 and JP-A-20
Use compounds described in 01-42466
Are preferred. The photosensitive material according to the present invention includes the above-mentioned species.
Various additives are used, but other than that, depending on the purpose
Various additives can be used. These additives are more specifically researched.
Disclosure Item 17643 (1978)
December), Item 18716 (1979 1
January) and Item 308119 (1989)
December), and the corresponding locations are listed in the table below.
Shown together. [0107]     Additive type RD17643 RD18716 RD308119    1 Chemical sensitizer page 23 page 648 right column page 996    2 Sensitivity increasing agent Same as above    3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right       Supersensitizer 649, right column on page 649    4 Brightener 24 pages 647 right column 998 right    5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right       And stabilizer    6 Light absorber, pages 25-26, page 649, right column-1003 left-1003 right       Filter dye, page 650, left column       UV absorber    7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right    8 Dye image stabilizer 25 page 1002 right    9 Hardener page 26 page 651 left column 1004 right to 1005 left   10 Binder page 26 Same as above 1003 right to 1004 right   11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right   12 Application aid, pages 26-27 Same as above 1005 left-1006 left       Surfactant   13 Static 27 pages Same as above 1006 Right to 1007 Left       Anti-blocking agent   14 Matting agent 1008 left to 1009 left It also prevents photographic performance deterioration due to formaldehyde gas.
To stop, U.S. Pat. No. 4,411,987 and
Formaldehyde described in US Pat. No. 4,435,503
A compound that can react and be immobilized is added to the photosensitive material.
Are preferred. In the present invention, various color couplers are used.
An example of this can be found in the previous research disc.
Roger No. 17643, VII-CG, and N
o. 307105, described in the patents described in VII-CG
It is listed. As a yellow coupler, for example,
Allowed 3,933,501, 4,022,620
No. 4,324,024 No. 4,401,75
No. 2, No. 4,248,961, JP-B 58-107
No. 39, British Patent No. 1,425,020, No. 1,4
76,760, US Pat. No. 3,973,968, the same
No. 4,314,023, No. 4,511,649,
Preferred are those described in European Patent No. 249,473A, etc.
That's right. As a magenta coupler, 5-pyrazolone
And pyrazoloazole-based compounds are preferred.
Allowed 4,310,619, 4,351,897
No., European Patent No. 73,636, US Patent No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (1984, 6
Moon), JP-A-60-33552, Research Disc
Roger No. 24230 (June 1984), JP
60-43659, 61-72238, 60-
35730, 55-118034, 60-18
No. 5951, US Pat. No. 4,500,630, No.
No. 4,540,654, No. 4,556,630, country
Particularly preferred are those described in International Publication WO88 / 04795.
That's right. Cyan couplers include phenolic and cyan couplers.
Naphthol couplers, US Pat. No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No.
2,369,929, 2,801,171,
Nos. 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent
121,365A, 249,453A, US
Patents 3,446,622 and 4,333,999
Nos. 4,775,616, 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212, 4,296,
No. 199, JP-A 61-42658, etc.
preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. Nos. 3,451,820 and 4,084.
No. 0, 211, No. 4,367, 282, No. 4, 4
09,320, 4,576,910, British patent
No. 2,102,137, European Patent No. 341,188A
In the issue. Couplers in which coloring dyes have appropriate diffusibility
US Patent 4,366,237, British Patent
No. 2,125,570, European Patent No. 96,570,
Those described in West German Patent (Public) No. 3,234,533
Is preferred. Color for correcting unwanted absorption of coloring dyes
Coupler is a Research Disclosure No.
No. 17643, VII-G, no. 307105 VII-
G, U.S. Pat. No. 4,163,670, JP-B-57-
No. 39413, US Pat. No. 4,004,929, No.
No. 4,138,258, British Patent No. 1,146,368
Are preferred. U.S. Pat.
Fluorescence emitted during coupling described in No. 4,181
Couplers that correct unnecessary absorption of coloring dyes with dyes,
The developing agent described in US Pat. No. 4,777,120
A dye precursor group capable of forming a dye in response to a leaving group
It is also preferable to use a coupler having Residues that are photographically useful with coupling
Compounds that release can also be preferably used in the present invention.
The DIR coupler that releases the development inhibitor is the RD1 described above.
7643, VII-F and No. 307105, VII −
Patents described in Section F, Japanese Patent Application Laid-Open No. 57-151944,
57-154234, 60-184248,
63-37346, 63-37350, US Patent
Nos. 4,248,962 and 4,782,012
What has been described is preferred. Nucleating agent or development acceleration in the form of an image during development
As a coupler for releasing the agent, British Patent No. 2,09
7,140, 2,131,188, JP 59
-157638, 59-170840
Is preferred. JP-A-60-107029, the same as above.
60-252340, JP-A-1-44940, 1
-Redox with an oxidized form of the developing agent described in No. -45687
Depending on the reaction, fogging agent, development accelerator, silver halide dissolved
Also preferred are compounds that release agents and the like. In addition, it can be used for the light-sensitive material of the present invention.
Possible compounds include US Pat. No. 4,130,427.
Competitive couplers described in US Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent couplers described in No. 618, etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound release coupler, DIR coupler release
Coupler, DIR coupler release redox compound
Is a DIR redox release redox compound, European Patent No.
173,302A and 313,308A
A coupler that releases a dye that recovers color after release, RD. No. 1
1449, 24241, JP-A-61-2012247
Bleach accelerator releasing couplers described in US Pat.
Patent application title: Ligand-releasing coupler described in Japanese Patent No. 55,477
A leuco dye releasing agent described in JP-A-63-75747
Fluor, described in US Pat. No. 4,774,181
Examples include couplers that release a dye. There are various known couplers used in the present invention.
It can be introduced into the light-sensitive material by the dispersion method. Oil-in-water dispersion
Examples of high boiling solvents used in the process are, for example, U.S. Pat.
No. 2,322,027. Boiling point at normal pressure used in oil-in-water dispersion method
Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher include
Talates (eg, dibutyl phthalate, disi
Chlohexyl phthalate, di-2-ethylhexyl phthalate
Rate, decyl phthalate, bis (2,4-di-ter
t-Amylphenyl) phthalate, bis (2,4-di-)
tert-amylphenyl) isophthalate, bis
(1,1-diethylpropyl) phthalate); phosphoric acid or
Or esters of phosphonic acid (e.g.
Sulfate, tricresyl phosphate, 2-ethyl
Xyldiphenyl phosphate, tricyclohexyl phosphate
Sulfate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate
, Trichloropropyl phosphate, di-2-e
Tilhexyl phenylphosphonate); benzoic acid ester
(E.g. 2-ethylhexyl benzoate, dode
Silbenzoate, 2-ethylhexyl-p-hydroxy
Cybenates); amides (eg, N, N-die)
Ludodecanamide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone); alcohols or alcohols
Enols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol); aliphatic carbo
Acid esters (eg, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tri
Butyrate, isostearyl lactate, trioctyl
Citrate); aniline derivatives such as N, N-dibu
Til-2-butoxy-5-tert-octylanily
Hydrocarbons (eg paraffin, dodecylben)
Zen, diisopropylnaphthalene)
Yes. As the auxiliary solvent, for example, the boiling point is about 30 ° C.
Above, preferably above 50 ° C and below about 160 ° C organic
Solvents can be used, and typical examples include, for example, ethyl acetate.
Butyl acetate, ethyl propionate, methyl ethyl ketone
T, cyclohexanone, 2-ethoxyethyl acetate
And dimethylformamide. Latex dispersion process steps, effects and impregnation
Specific examples of latexes for use are, for example, U.S. Pat. No. 4,19.
9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.
ing. In the color light-sensitive material of the present invention, phenethyl is used.
Alcohol, JP-A 63-257747, 62-
Described in No. 272248 and JP-A-1-80941
Of, for example, 1,2-benzisothiazoline-3-
N-butyl-p-hydroxybenzoate, phenol
4-chloro-3,5-dimethylphenol, 2-
Phenoxyethanol, 2- (4-thiazolyl) benzo
Add various preservatives or antifungal agents such as imidazole
It is preferable to add. The present invention is applied to various color light-sensitive materials.
be able to. For example, general or movie colors
Color film for negative film, slide or TV
Transfer film, color paper, color positive film and
And color reversal paper
The The present invention is also particularly preferred for color duplication films.
Can be used. Suitable supports that can be used in the present invention are, for example,
RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and
No. 307105, page 879. The light-sensitive material of the present invention has an emulsion layer side.
On the opposite side, hydrophilicity with a total dry film thickness of 2 μm to 20 μm
It is preferable to provide a colloid layer (called back layer)
Yes. The back layer includes, for example, the above-described light absorber and fibre.
Luther dye, UV absorber, antistatic agent, dura
Agent, binder, plasticizer, lubricant, coating aid, surface activity
It is preferable to contain an agent. Water swelling of this back layer
The rate is preferably 50 to 250%. The color photographic light-sensitive material according to the present invention is
RD. No. 17643, pp. 28-29, ibid.
No. 18716, page 651, left column to right column; 30
7105, pages 880-881 in the usual way
Therefore, it can be developed. Coloring used in the development processing of the light-sensitive material of the present invention
The developer is preferably an aromatic primary amine color developer
It is an alkaline aqueous solution mainly composed of a medicine. This color development
Aminophenol compounds are also useful as image agents.
However, p-phenylenediamine compounds are preferably used.
As a typical example, 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl
Tyl-4-amino-N-ethyl-N-β-methanesulfo
N-amidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and these
Sulfate, hydrochloride or p-toluenesulfonate
Is mentioned. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylanily
Sulfate is preferred. These compounds may be used depending on the purpose.
More than one species can be used in combination. The color developer is, for example, an alkali metal charcoal.
PH buffering agents such as acid salts, borates or phosphates,
Chloride salt, bromide salt, iodide salt, benzimidazole
Benzothiazoles or mercapto compounds
Such development inhibitors or antifogging agents are generally included.
is there. If necessary, hydroxylamine, diethyl
Hydroxylamine, sulfite, N, N-biscarbo
Hydrazines such as xylmethylhydrazine, phenyl
Micarbazides, triethanolamine, catechols
Various preservatives such as sulfonic acids; ethylene glycol, di
Organic solvents such as ethylene glycol; benzyl alcohol
, Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines; dye-forming couplers, competition
Couplers such as 1-phenyl-3-pyrazolidone
Auxiliary developing agent; Viscosifier; Aminopolycarboxylic acid, amino
Nopolyphosphonic acid, alkylphosphonic acid, phosphonocar
Use various chelating agents as represented by boric acid
Can do. Examples of chelating agents include ethylene dia
Mine tetraacetic acid, nitrile triacetic acid, diethylenetriamine five
Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl
Louisinodiacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N, N, N-trimethylene
Sphonic acid, ethylenediamine-N, N, N, N-tetra
Methylenephosphonic acid, ethylenediamine-di (o-hydride)
Roxyphenylacetic acid) and their salts are typical examples.
I can make it. When the inversion process is performed, it is usually black.
Color development is performed after white development. In this black and white developer
For example, dihydroxybens such as hydroquinone
Zens such as 1-phenyl-3-pyrazolidone
Such as 3-pyrazolidones or, for example, N-methyl-
Publicity of aminophenols such as p-aminophenol
Use known black and white developing agents alone or in combination
be able to. P of these color developers and black-and-white developers
H is generally 9-12. Also this
The replenishment amount of these developers is the color photographic material to be processed
However, generally 3 liters per square meter of photosensitive material
Torr or less, reducing bromide ion concentration in the replenisher
You can make it less than 500ml
The When reducing the replenishment amount, contact the processing solution with air.
By reducing the area, liquid evaporation and air oxidation are prevented.
It is preferable to stop. Contact area between photographic processing solution and air in processing tank
Can be expressed by the aperture ratio defined below. Immediately
The Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Process
Capacity of scientific liquid (cm³]] The opening ratio is preferably 0.1 or less, more
Preferably it is 0.001-0.05. Open like this
As a method to reduce the percentage, the photographic processing liquid level of the processing tank
In addition to providing a shield such as a floating lid
Using the movable lid described in JP-A-1-82033
The method described in Japanese Patent Application Laid-Open No. 63-2106050
Can be mentioned. Reduces aperture ratio
If only the color development and black and white development processes
And subsequent processes such as bleaching, bleach-fixing, fixing, water
It is preferable to apply in all steps of washing and stabilization.
Yes. Means to suppress accumulation of bromide ions in the developer
The amount of replenishment can also be reduced by using. The color development processing time is usually between 2 and 5 minutes.
Set at high temperature, high pH, and high color developing agent
By using it for concentration, the processing time is further shortened.
You can also. The photographic emulsion layer after color development is usually bleached.
It is. The bleaching process may be performed simultaneously with the fixing process.
(Bleaching and fixing treatment) may be performed individually. Further processing
In order to speed up the process, a bleach-fix process is performed after the bleach process.
It may be a rational method. In addition, two continuous bleach-fixing baths
Processing, fixing processing before bleach-fixing processing,
Depending on the purpose, it is also possible to perform bleaching after bleach-fixing.
Can be implemented arbitrarily. Examples of bleaching agents include iron (III)
Polyvalent metal compounds such as peracids (especially sodium persulfate)
Is suitable for color negative films for movies), quinones,
Toro compounds are used. Typical bleach is iron
(III) organic complex salts, such as ethylenediaminetetraacetic acid,
Diethylenetriaminepentaacetic acid, cyclohexanediamine
Tetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropa
Like tetraacetic acid, glycol ether diamine tetraacetic acid
Complex salts with aminopolycarboxylic acids or, for example,
Complex salts with enoic acid, tartaric acid, malic acid can be used
The Of these, ethylenediaminetetraacetic acid iron (III) complex
Salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt
And other aminopolycarboxylic acid iron (III) complex salts
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
Aminopolycarboxylic acid iron (III) complex salt
Are also particularly useful in bleach-fixing solutions. These a
Bleaching solution or drift using iron (III) complex salt of minopolycarboxylate
The pH of the white fixer is usually from 4.0 to 8, but the processing is quick
It can also be processed at a lower pH for conversion. For bleaching solutions, bleach-fixing solutions and their pre-baths
If necessary, a bleaching accelerator can be used.
Specific examples of useful bleach accelerators are described in the following specification:
For example: US Pat. No. 3,893,858, West Germany
Patent Nos. 1,290,812 and 2,059,988
, JP-A-53-32736, 53-57831
No., 53-37418, 53-72623,
53-95630, 53-95311, 53-
104232, 53-124424, 53-1.
41623, 53-18426, Research D
Closure No. No. 17129 (July 1978)
Having a mercapto group or disulfide group as described in
Compound: thiazolid described in JP-A No. 51-140129
Derivatives: Japanese Examined Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20
No. 832, No. 53-32735, US Pat. No. 3,70
A thiourea derivative described in US Pat. No. 6,561, West German Patent 1,
127,715, described in JP-A-58-16235
Iodide salt; West German Patent No. 966,410, No. 2,74
Polyoxyethylene compounds described in No. 8,430;
A polyamine compound described in JP-A-45-8836;
Other JP-A-49-40943, 49-59644,
53-94927, 54-35727, 55
-26506 and 58-163940
Bromide ions can be used. Among them, mercap
A compound having a thio group or a disulfide group has an accelerating effect
Preferred from a large standpoint, especially US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP 53
The compound described in -95630 is preferable. In addition, the United States
The compounds described in Japanese Patent No. 4,552,884 are also preferred.
Yes. These bleach accelerators may be added to the light-sensitive material. Shoot
When bleach-fixing color light-sensitive materials for shadows, these
Bleach accelerators are particularly effective. In the bleaching solution and bleach-fixing solution, in addition to the above compounds
To contain organic acid for the purpose of preventing bleach stain
It is preferable. Particularly preferred organic acids are acid dissociation constants.
A compound having (pKa) of 2 to 5, specifically,
For example, acetic acid, propionic acid, hydroxyacetic acid
Can do. Fixing agents used for fixing solutions and bleach-fixing solutions;
For example, thiosulfate, thiocyanate, thioe
List of ether compounds, thioureas, and large amounts of iodide salts
be able to. Of these, the use of thiosulfate is common
In particular, ammonium thiosulfate is the most widely used
Yes. Also, thiosulfate and, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferred. Constant
Preservatives for landing and bleach-fixing solutions include sulfites and bisulfites.
Acid salt, carbonyl bisulfite adduct or European Patent No. 2
94,769A is preferred sulfinic acid compound
Yes. In addition, fixing solutions and bleach-fixing solutions have the purpose of stabilizing the solutions.
Of various aminopolycarboxylic acids and organic phosphonic acids
Addition is preferred. In the present invention, a fixing solution or a bleach-fixing solution is used.
Has a pKa of 6.0 to 9.0 for pH adjustment.
Products, preferably imidazole, 1-methylimidazole
1-ethylimidazole, 2-methylimidazole
0.1 to 10 mol / liter of imidazole such as
It is preferable to add. The total time of the desilvering process is the result of desilvering failure.
It is preferable that the length is as short as possible. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Also processing temperature
Is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferred temperature range, the desilvering rate is improved and
Stain generation after treatment is effectively prevented. In the desilvering process, stirring is as strong as possible.
It is preferable that Specific method of strengthening stirring
As a photosensitive material described in JP-A-62-183460.
A method in which a jet of processing liquid collides with the emulsion surface
Use the rotating means in No. 62-183461 to increase the stirring effect
The method to get off is mentioned. Furthermore, a wire provided in the liquid
Move photosensitive material while contacting par blade and emulsion surface
And more stirring effect by making the emulsion surface turbulent
Increase the circulation flow rate of the entire processing solution
Method. Such a stirring improving means is bleaching
Effective in any of solution, bleach-fixing solution and fixing solution
The Stirring is improved by bleaching agent and fixing agent in emulsion film.
To speed up the supply of silver and consequently increase the desilvering speed
It is done. Also, the above stirring improvement means uses a bleach accelerator.
It is more effective when the
Or to eliminate fixing problems with bleach accelerators
Can do. Automatic used for developing the light-sensitive material of the present invention
Developing machines are disclosed in JP-A-60-191257 and 60-19.
Photosensitive materials described in Nos. 1258 and 60-191259
It is preferable to have a conveying means. The above-mentioned JP-A-6
Such a carrier as described in 0-191257
The stage significantly reduces the amount of processing solution brought from the pre-bath to the post-bath.
Therefore, the effect of preventing the performance deterioration of the processing liquid is high. like this
The main effects are shortening of processing time and replenishment of processing solution in each process.
This is particularly effective for reducing the amount. The silver halide color photographic light-sensitive material of the present invention
After desilvering, it is recommended to go through water washing and / or stabilization process.
It is common. The amount of water washed in the washing process is a characteristic of the photosensitive material.
(For example, depending on the material used such as coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (number of stages),
Depending on replenishment methods such as counterflow and forward flow, and other various conditions
Can be set widely. Of these, the multistage countercurrent method
The relationship between the number of washing tanks and the amount of water is Journal of
  the Society of Motion Pi
cute and Television Engi
neers vol. 64, p. 248-253 (1955
In May). [0140] According to the multistage countercurrent system described in the above document,
Although the amount of washing water can be greatly reduced, the water in the tank
Increased residence time causes bacteria to propagate and
There arises a problem that the play material adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, such a problem.
As a solution to the problem, described in JP-A-62-288838
Reduces calcium and magnesium ions
The method can be used very effectively. In addition,
For example, isothiazolonation described in No. 57-8542
Compounds, siabendazoles, chlorinated isocyanuric acid
Chlorine disinfectants such as sodium, etc.
Horiguchi Hiroshi “Non-Triazole”
Science (1986) Sankyo Publishing, Hygienic Technology Society
Sterilization, sterilization and fouling technology "(1982) Japan Industrial Technology Association, Japan
This edition of the Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antifungal and Antifungal Agents” (1986)
The described fungicides can also be used. P of washing water in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. Washing water temperature and
Depending on the characteristics and application of the photosensitive material,
Generally, it can be set, but in general, it is 20 seconds to 1 at 15 to 45 ° C.
0 minutes, preferably 25-40 ° C for 30 seconds to 5 minutes
Selected. Further, the light-sensitive material of the present invention can be used in place of the above water washing.
Alternatively, it can be treated directly with a stabilizing solution. this
In such stabilization treatment, JP-A-57-8543
No. 58-14834, 60-220345
All known methods described can be used. Further, following the water washing treatment, further stabilization.
Sometimes it is processed. An example of this is color photography for photography.
Dye stabilizers and surface activity used as the final bath of materials
Mention may be made of a stabilizing bath containing a sexing agent. Dye stability
Examples of the agent include formalin and glutaraldehyde.
Aldehydes, N-methylol compounds, hex
Samethylenetetramine or aldehyde sulfite addition
You can list things. In this stable bath,
Toning agents and fungicides can be added. The above-mentioned washing and / or replenishment of stabilizing solution
-The bar flow solution can be reused in other processes such as the desilvering process.
It can also be used. For example, processing using an automatic processor
In the case where each of the above processing liquids is concentrated by evaporation
It is preferable to correct the concentration by adding water. The silver halide color photographic light-sensitive material of the present invention
In order to simplify and speed up processing,
It may be built in. To incorporate, color developing agent
It is preferable to use various precursors. For example, rice
Indoaniline system described in Japanese Patent No. 3,342,597
Compound, for example, 3,342,599, Research
・ Disclosure No. 14,850 and No.
No. 15,159, Schiff base type compounds, 1
Aldol compounds described in US Pat. No. 3,924, US Pat.
719,492, a metal salt complex described in JP-A-53-1
Examples include urethane compounds described in No. 35628
it can. The silver halide color light-sensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may be incorporated. Typical
Examples of such compounds are disclosed in, for example, JP-A-56-64339.
57-144547 and 58-115438
It is described in. The various processing solutions in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually a temperature between 33 ° C and 38 ° C
Is standard, but at higher temperatures, the process is accelerated and processed.
To improve the image quality and process
An improvement in the stability of the liquid can be achieved. The silver halide photosensitive material of the present invention is
U.S. Pat. No. 4,500,626, JP-A-60-133
449, 59-218443, 61-2380
56, European Patent No. 210,660A2, etc.
The present invention can also be applied to photothermographic materials. In addition, the silver halide color photographic feel of the present invention
The optical materials are Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication 3-397.
Film unit with lens described in No. 84 etc.
When applied to the
The [0149] EXAMPLES The present invention will be specifically described below with reference to examples.
Light up. However, the present invention is limited to these examples.
It is not a thing. Example 1 (Seed emulsion) described in Example 1 of JP-A-11-174606
In emulsion 1C, AgI fine particles during the growth process
Is added to the total amount of silver in the grains after the growth process.
Halogenation by adjusting the silver halide content to 10 mol%
Silver tabular grains were prepared. After washing with water, add gelatin and p
H, 5.7, pAg, 8.8, silver exchange per kg of emulsion
Adjusted to a total mass of 131.8 g and a gelatin mass of 64.1 g
A seed emulsion was obtained. In the resulting emulsion, the silver iodide content
10 mol%, sphere equivalent diameter 0.7μm, aspect ratio 28 grains
The child accounted for 97% of the total projected area. (Em-A1) A trimellitization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 ml of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Co., Ltd. product, L7602) 0.3g
Added. H₂SO₄To adjust the pH to 5.5
After that, AgNO ₃67.6 ml of an aqueous solution containing 7.0 g
Dub mixed aqueous solution of KBr and KI containing 10 mol% KI
The final flow rate is 5.1 times the initial flow rate by the Lujet method.
The flow rate was accelerated and added over 6 minutes. At this time,
The position was kept at +0 mV to a saturated calomel electrode. Ben
Sodium zenthiosulfonate 2mg and thiourea dioxide
After adding 2 mg, AgNO₃Aqueous solution containing 170 g
Mixed water of KBr and KI containing 762 ml and 10% KI
The final flow rate of the solution is 3.7 by the double jet method.
Accelerate the flow rate to double and add over 120 minutes
It was. At this time, the silver potential is +10 with respect to the saturated calomel electrode.
It was kept at mV. AgNO₃Aqueous solution 75 containing 23.4 g
Deliver ml and KBr aqueous solution for 11 minutes by double jet method
Added. At this time, the silver potential is applied to the saturated calomel electrode.
And kept at -10 mV. Increase the temperature to 82 ° C and add KBr
After adjusting the silver potential to −80 mV, 0.037 μm
1. An AgI fine grain emulsion having a grain size of 2.
28 g was added. Immediately after the addition, AgNO₃2
100.2 ml of an aqueous solution containing 3.4 g over 10 minutes
Added. For 5 minutes at the beginning of the addition, apply silver potential with aqueous KBr solution.
It was kept at −80 mV. After washing with water, add gelatin 4
The pH was adjusted to 5.8 and pAg 8.7 at 0 ° C. At 60 ° C
After raising the temperature, sensitizing dyes ExS-1 and ExS-2 are added.
In addition, potassium thiocyanate, chloroauric acid, thiosulfuric acid
Add sodium, N, N-dimethylselenourea
Chemical sensitization was performed appropriately. Compound F- described later at the end of chemical sensitization
2 was added. Here, optimal chemical sensitization means sensitization
10 dyes per mole of silver halide
^-1To 10^-8Selected from a range of molar additions
means. [0152] [Chemical 1] [0153] [Chemical 2] (Em-A2) A trimellitization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 ml of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Co., Ltd. product, L7602) 0.3g
Added. H2SO4 was added to adjust the pH to 5.5.
After, AgNO₃67.6 ml of an aqueous solution containing 7.0 g and K
Double mixed aqueous solution of KBr and KI containing 10 mol% I
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 6 minutes. At this time, silver potential
Was kept at +0 mV to a saturated calomel electrode. Benze
Sodium thiosulfonate 2mg and thiourea dioxide 2
After adding mg, AgNO₃Aqueous solution 7 containing 170 g
Final flow rate of 62ml and KBr aqueous solution by double jet method
The flow rate is increased to 120 times the initial flow rate to 120 times.
Added over a minute. At this time, 0.037 μm at the same time
A grain-size AgI fine grain emulsion having a silver iodide content of 10
At the same time, the flow rate is accelerated so as to be mol% and silver is added.
The potential was kept at -30 mV with respect to the saturated calomel electrode.
AgNO₃75ml aqueous solution containing 23.4g and KBr water
The solution was added over 11 minutes by the double jet method. This
The silver potential is +10 mV to the saturated calomel electrode
Kept. Increase the temperature to 82 ° C and add KBr to reduce the silver potential.
After adjusting to 80 mV, the particle size of 0.037 μm
Add 2.28 g of AgI fine grain emulsion in terms of KI mass
It was. Immediately after the addition, AgNO₃Contains 23.4g
100.2 ml of aqueous solution was added over 10 minutes. Addition
For the first 5 minutes, keep the silver potential at -80 mV with aqueous KBr solution.
It was. After washing with water, gelatin is added and the pH is 5.degree.
8, adjusted to pAg 8.7. After that, the same as Em-A1
Like, chemical sensitization. (Em-A3) Trimeritization rate of 97%
Contains 46g of trimellitated gelatin and 1.7g of KBr
1211 ml of the aqueous solution was kept at 75 ° C. and stirred vigorously. Previous
After adding 48g of the seed emulsion described above, modified silicone oil
(Nihon Unicar Co., Ltd. product, L7602) 0.3g
Added. H₂SO₄To adjust the pH to 5.5
After that, AgNO ₃67.6 ml of an aqueous solution containing 7.0 g
Dub mixed aqueous solution of KBr and KI containing 10 mol% KI
The final flow rate is 5.1 times the initial flow rate by the Lujet method.
The flow rate was accelerated and added over 6 minutes. At this time,
The position was kept at +0 mV to a saturated calomel electrode. Ben
Sodium zenthiosulfonate 2mg and thiourea dioxide
After adding 2 mg, the stirring device installed outside the reaction vessel
AgNO₃, 170g aqueous solution, 762ml and KB
107.1 g of r and 16.6 g of KI and weight average molecule
Aqueous solution 76 containing 76.2 g of 20,000 amount of gelatin
2ml was added at the same time and the silver iodide content was 10mol% Ag
BrI fine grain emulsion (average size: 0.015 μm)
This AgBrI emulsion is placed in a reaction vessel for 120 minutes while making
Added in between. At this time, the silver potential is adjusted to the saturated calomel electrode.
Against -30 mV. AgNO₃58.5g
131 ml of an aqueous solution containing KBr and 10 mol% of KBr containing KI
KI mixed solution for 30 minutes by double jet method
Added. At this time, the silver potential is set to the saturated calomel electrode.
+ 20mV for the first 20 minutes, 12 for the remaining 10 minutes
It was kept at 0 mV. After cooling to 50 ° C, 0.3% KI water
55 ml of solution was added over 10 minutes. Immediately thereafter,
AgNO₃18.8 ml of an aqueous solution containing 8.4 g and NaC
11 ml of aqueous solution containing 1.44 g and KBr 2.35 g
And a solution containing 0.005 mol of AgI fine particles are added simultaneously.
Added. At this time, AgNO to be added₃For 1 mol
8.0 × 10^-4mol K₄[RuCN₆Exist
Let Then sensitized color for epitaxial stabilization
Elementary ExS-1 was added. After washing with water, add gelatin
The pH was adjusted to 5.8 and pAg 8.7 at 40 ° C. 50
After raising the temperature to 0 ° C., sensitizing dyes ExS-1 and ExS-2
In addition, potassium thiocyanate, bis (1,4,5
-Trimethyl-1,2,4-triazolium-3-thio
Rate gold) (1) Tetrafluoroborate, carboxy
Methyltrimethylthiourea, hexafluorophenyldi
Phenylphosphine selenide, compound F-11 shown below
Added and optimally chemically sensitized. When chemical sensitization is complete,
Compounds F-3 and F-3 were added. Where optimized
Scientific sensitization means that sensitizing dyes and compounds are halogenated.
10 per mole of silver halide^-1To 10^-8Addition range of mole
Means you have selected from the box. (Em-J1) Weight average molecular weight 15000
Low molecular weight oxidized gelatin 1.6g, KBr 1.0g
1300 mL of an aqueous solution containing benzene was kept at 58 ° C. and the pH was adjusted to 9.
Adjusted and stirred vigorously. AgNO₃An aqueous solution containing 1.3 g and KBr
Low molecular weight oxidation treatment with 1.1g and weight average molecular weight 15000
An aqueous solution containing 0.7g of physical gelatin is obtained by the double jet method.
Nucleation was carried out over 30 seconds. KBr is 6.
6 g was added and the mixture was heated to 78 ° C. and aged. After aging,
Alkali-treated gelatin with a weight average molecular weight of 100,000
Add 15.0 g of gelatin chemically modified with succinic acid,
Thereafter, the pH was adjusted to 5.5. AgNO₃29.3g
230ml of aqueous solution containing 15.8g of KBr and KI
An aqueous solution containing 1.92 g by a double jet method for 30 minutes
Added in between. At this time, the silver potential is adjusted to the saturated calomel electrode.
Against -20 mV. Furthermore, AgNO₃, 6
An aqueous solution containing 4.5 g, KBr 42.3 g and KI
Double jet 233 mL of aqueous solution containing 5.14 g
So that the final flow rate is 1.33 times the initial flow rate
Accelerated and added over 37 minutes. At this time, added
The silver potential was kept at -20 mV during the time. Next, AgNO
₃, 70.8g containing aqueous solution and KBr aqueous solution
In 35 minutes while maintaining the silver potential at -10 mV
Added over time. After the temperature was lowered to 40 ° C., Compound 1 was
4.9g was added and 0.8M sodium sulfite water was added.
32 mL of the solution was added. Next, using NaOH aqueous solution
The pH was adjusted to 9.0 and held for 5 minutes. Raise temperature to 55 ° C
After warming, H₂SO₄The pH was adjusted to 5.5. Be
1 mg of sodium zenthiosulfonate is added
Add 13g of lime-processed gelatin with 1ppm calcium concentration
did. After the addition, AgNO₃Aqueous solution containing 71.0 g
250 mL and KBr aqueous solution to silver potential +75 mV
It was added over 20 minutes while keeping. At this time, the yellow blood salt
1.0 x 10 per mole of silver^-5Mole and K₂Ir
Cl₆1 × 10 for 1 mole of silver^-8Mole was added. After washing with water, add gelatin and p at 40 ° C.
Adjusted to H6.5, pAg, 8.8. Raise the temperature to 56 ℃
And then compound 2 and sensitizing dye ExS-3, ExS-
4, after adding ExS-5, potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, N, N-dimethylsel
Optimum addition of Nourea and Compound F-11, Compound 3
Chemically sensitized. Compound F-2 described later at the end of chemical sensitization
Was added. This emulsion has an average equivalent sphere diameter of 1.33 μm.
m, average equivalent circle diameter 2.63 μm, aspect ratio 11.
4 tabular grains. The obtained particles were cooled while being cooled with liquid nitrogen.
As a result of observation with an over-electron microscope, the projected area from the center of the particle
About 90% of the particles have no dislocation lines within 80%.
%, Around 20% of the projected area from the outer periphery of the particle
In the part, 10 or more dislocation lines per particle were observed. [0162] [Chemical 3] [0163] [Formula 4] [0164] [Chemical formula 5] [0165] [Chemical 6] [0166] [Chemical 7] [0167] [Chemical 8] (Em-J2) Weight average of 97% phthalation rate
Phthalated gelatin with an average molecular weight of 100,000, 0.38
6 of 1200 ml of aqueous solution containing g, KBr, and 0.99 g
While maintaining at 0 ° C., the pH was adjusted to 2 and vigorously stirred. AgN
O₃, 1.96 g of aqueous solution and KBr, 1.97 g,
An aqueous solution containing KI, 0.172 g by the double jet method
Added over 30 seconds. 35 per gram after completion of aging
Weight average molecular weight of 100 containing μmol methionine
000 amino group chemically modified with trimellitic acid
12.8 g of meritified gelatin was added. pH is 5.
After adjusting to 9, KBr, 2.99 g, NaCl 6.2
g was added. AgNO₃, 27.3g in aqueous solution 6
0.7 ml and KBr aqueous solution for 35 minutes by double jet method
Added in between. At this time, the silver potential is adjusted to the saturated calomel electrode.
Against -30 mV. Next, install it outside the reaction vessel.
AgNOG₃, 65.6g aqueous solution
, KBr and KI and weight average molecular weight 20000
Silver iodide content by simultaneously adding an aqueous solution containing tin
While preparing a 6.5 mol% AgBrI fine grain emulsion,
Add this AgBrI emulsion to the reaction vessel over 62 minutes.
It was. At this time, the silver potential is ± 0 m with respect to the saturated calomel electrode.
V kept. Thiourea dioxide, 1.5 mg was added
After, AgNO₃132 ml of an aqueous solution containing 41.8 g,
Add KBr aqueous solution over 13 minutes by double jet method
did. K so that the silver potential at the end of the addition is +40 mV
Addition of Br aqueous solution was adjusted. Benzenethiosulfonic acid
After adding 2 mg of sodium, add KBr to add silver
The potential was adjusted to -100 mV. AgI fine particle milk
The agent was added in an amount of 6.2 g in terms of KI mass. Directly after addition
AgNO₃300 ml of an aqueous solution containing 88.5 g
Added over 8 minutes. The potential at the end of the addition is +60 mV
It adjusted by addition of KBr aqueous solution so that it might become. Washed with water
After that, gelatin was added and pH 6.5, pAg,
Adjusted to 8.2. After heating to 58 ° C, compound 2 increased
Add dye Sens ExS-3, ExS-4, ExS-5,
Furthermore K₂IrCl₆, Potassium thiocyanate, gold chloride
Acid, sodium thiosulfate, compound 3, compound F-11,
Hexafluorophenyl diphenylphosphine selenide
For optimum chemical sensitization. Compound at the end of chemical sensitization
F-2 was added. The obtained particles were permeated while being cooled with liquid nitrogen.
As a result of observation with an over-electron microscope, the projected area from the center of the particle
About 90% of the total number of particles having no dislocation line within 80%.
%, Around 20% of the projected area from the outer periphery of the particle
In the part, 10 or more dislocation lines per particle were observed. (Em-J3) Reaction to Em-J2
AgBrI fine particles using a stirrer installed outside the container
The conditions of the process of adding the emulsion into the reaction vessel while preparing the emulsion
All adjustments were made in the same manner except for changes as appropriate. (Em-P1) Sensitization to Em-J1
Change the dye to ExS-6, ExS-7, ExS-8,
Chemical sensitization was optimally performed to obtain Em-P1. (Em-P2) Sensitization to Em-J2
Change the dye to ExS-6, ExS-7, ExS-8,
Chemical sensitization was optimally performed to obtain Em-P2. (Em-P3) Sensitization to Em-J3
Change the dye to ExS-6, ExS-7, ExS-8,
Chemical sensitization was optimally performed to obtain Em-P3. [0175] [Chemical 9] [0176] Embedded image [0177] Embedded image The silver halide emulsion thus obtained
Features of Em-A1-A3, J1-J3, and P1-P3
The properties are shown in Table 1. Also, emulsions Em-B to I and K to O
Are described in Examples of JP-A-2001-92057.
Implementation of Em-A to P and JP-A-2001-92059
Grain formation conditions based on the em-A to O emulsion preparation method described in the examples
Are adjusted as appropriate, and the characteristics are shown in Table 1.
doing. [0179] [Table 1][0180] Embedded image [0181] Embedded image [0182] Embedded image 1) Support The support used in this example was prepared by the following method.
It was. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.I. 3
26 (Ciba-Geigy Ciba-Geigy) 2 quality
After drying the part and melting at 300 ° C,
Extrude, 3.3 times longitudinal stretch at 140 ° C,
The film is stretched 3.3 times at 130 ° C, and then 250 ° C
PEN (polyethylene with a thickness of 90 μm was fixed by heat for 6 seconds.
Nnaphthalate) film was obtained. This PEN fi
Lum has blue, magenta and yellow dyes
(Public technique: I-1, described in public technical number 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
An appropriate amount of 5) was added. Furthermore, stainless steel with a diameter of 20 cm
Wrapped around a loess core and heat history at 110 ° C for 48 hours
To provide a support that is difficult to curl. 2) Application of undercoat layer The above support has corona discharge treatment and UV discharge treatment on both sides.
Then, after further glow discharge treatment,
Latin 0.1g / m²Sodium α-sulfodi-2-
Ethylhexyl succinate 0.01g / m², Salici
Luric acid 0.04g / m²P-chlorophenol 0.2
g / m², (CH₂= CHSO₂CH ₂CH₂NHC
O)₂CH₂0.012 g / m², Polyamide-epic
Lorhydrin polycondensate 0.02 g / m²Apply primer solution
Cloth (10cc / m², Using bar coater), undercoat
Was provided on the high temperature side during stretching. Drying at 115 ° C for 6 minutes
(All the rollers and conveyors in the drying zone are 115
℃). 3) Coating of back layer The following set as a back layer on one side of the support after undercoating
An antistatic layer, a magnetic recording layer, and a sliding layer were coated. 3-1) Coating of antistatic layer Tin oxide-antimony oxide composite with an average particle size of 0.005 μm
The specific resistance of the compound is a dispersion of fine powder of 5 Ω · cm (secondary
Aggregated particle diameter of about 0.08 μm) is 0.2 g / m², Gelatin
0.05 g / m², (CH₂= CHSO₂CH₂CH
₂NHCO)₂CH₂ 0.02 g / m², Poly (polymerization
Degree 10) Oxyethylene-p-nonylphenol 0.
005 g / m²And resorcin 0.22 g / m²With
It was applied to. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization 15) oxyethylene-propyloxy
Coated with citrimethoxysilane (15% by mass)
Cobalt-γ-iron oxide (specific surface area 43m²/ G, long axis
0.14 μm, uniaxial 0.03 μm, saturation magnetization 89 Am²
/ Kg, Fe⁺²/ Fe⁺³= 6/94, the surface is oxidized
(Treated with 2% by mass of iron oxide with lumi silicon oxide)
0.06 g / m²Diacetylcellulose 1.2 g / m
²(Dispersion of iron oxide was performed using an open kneader and a sand mill.
C) as a curing agent₂H₅C (CH₂OC ON
HC₆H₃(CH₃) NCO)₃0.3 g / m²The
As solvents, acetone, methyl ethyl ketone, cyclohexane
Coated with a bar coater using xanon and a film thickness of 1.2μ
m magnetic recording layers were obtained. Silica particles as matting agent
(0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene
N-propyloxytrimethoxysilane (15% by mass)
Abrasive coated aluminum oxide (0.15μm)
10 mg / m each²It added so that it might become. Dry
Was conducted at 115 ° C for 6 minutes (rollers in the drying zone
All conveyors are 115 ° C). X-Light (Blue Fi
The increase in the color density of the magnetic recording layer DB is approximately
0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2.
Am²/ Kg, coercive force 7.3 × 10⁴A / m, squareness ratio is
65%. 3-3) Preparation of sliding layer Diacetylcellulose (25mg / m²), C₆H₁₃
CH (OH) C₁₀H ₂₀COOC₄₀H₈₁(Compound
a, 6 mg / m²) / C₅₀H₁₀₁O (CH ₂CH₂
O)₁₆H (Compound b, 9 mg / m²) Apply the mixture
It was. This mixture is made up of xylene / propylene mono
Melt at 105 ° C in methyl ether (1/1)
Added to 10 ml of propylene monomethyl ether
After dispersion, the dispersion (average particle size 0.
01 μm) and then added. Silica as matting agent
Particles (0.3 μm) and abrasive 3-poly (degree of polymerization 15)
Oxyethylenepropyloxytrimethoxysilane (1
5 mass%) coated with aluminum oxide (0.15 μm)
15mg / m each²  It added so that it might become. Dry
Was carried out at 115 ° C. for 6 minutes (dry zone roller and transport
All equipment is 115 ° C). The sliding layer has a coefficient of dynamic friction of 0.0
6 (5mmφ stainless hard ball, load 100g, speed
6cm / min), coefficient of static friction 0.07 (clip method),
The dynamic friction coefficient between the emulsion surface and the sliding layer described later is also 0.12.
Excellent characteristics. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, the following composition
Each layer of is applied in layers, and a sample that is a color negative photosensitive material is applied.
Created. That is, the sixth layer, the eleventh layer, and the fourteenth layer
Place each emulsion as shown in (Table 2).
Change the volume fraction and applied silver amount as shown in the table
As a result, samples 101 to 108 were prepared.
The volume fraction can be changed as appropriate by changing the gelatin coating amount of the emulsion layer.
A sample was prepared. [0190] [Table 2] (Composition of photosensitive layer) Main materials used for each layer
Are classified as follows:     ExC: Cyan coupler UV: UV absorber     ExM: Magenta coupler HBS: High boiling point organic solvent     ExY: Yellow coupler H: Gelatin hardener (hardener) (Specific compounds are described below.
The chemical formula is listed behind) The number corresponding to each component is the coating amount expressed in units of g / m2.
For silver halide, the coating amount in terms of silver is shown.
The [0192]   First layer (first antihalation layer)   Black colloidal silver Silver 0.07   Gelatin 0.660   ExM-1 0.048   Cpd-2 0.001   F-8 0.001   HBS-1 0.090   HBS-2 0.010. [0193]   Second layer (second antihalation layer)   Black colloidal silver Silver 0.09   Gelatin 0.830   ExM-1 0.057   ExF-1 0.002   F-8 0.001   HBS-1 0.090   HBS-2 0.010. [0194]   Third layer (intermediate layer)   ExC-2 0.010   Cpd-1 0.086   UV-2 0.029   UV-3 0.052   UV-4 0.011   HSB-1 0.100   Gelatin 0.580. [0195]   4th layer (low sensitivity red sensitive emulsion layer)   Em-M Silver 0.47   Em-N Silver 0.37   Em-O Silver 0.20   ExC-1 0.222   ExC-2 0.010   ExC-3 0.072   ExC-4 0.148   ExC-5 0.005   ExC-6 0.008   ExC-8 0.071   ExC-9 0.010   UV-2 0.036   UV-3 0.067   UV-4 0.014   Cpd-2 0.010   Cpd-4 0.012   HBS-1 0.240   HBS-5 0.010   Gelatin 1.630. [0196]   5th layer (medium sensitivity red emulsion layer)   Em-K Silver 0.43   Em-L Silver 0.23   ExC-1 0.111   ExC-2 0.039   ExC-3 0.018   ExC-4 0.074   ExC-5 0.019   ExC-6 0.024   ExC-8 0.010   ExC-9 0.021   Cpd-2 0.020   Cpd-4 0.021   HBS-1 0.129   Gelatin 0.900. [0197]   6th layer (high-sensitivity red-sensitive emulsion layer)   Em-J1 Silver 1.27   ExC-1 0.122   ExC-6 0.032   ExC-8 0.110   ExC-9 0.005   ExC-10 0.159   Cpd-2 0.068   Cpd-4 0.015   HBS-1 0.440   Gelatin 1.610. [0198]   7th layer (intermediate layer)   Cpd-1 0.081   Cpd-6 0.002   Solid disperse dye ExF-4 0.015   HBS-1 0.049   Polyethyl acrylate latex 0.088   Gelatin 0.759. [0199]   Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))   Em-E silver 0.40   Cpd-4 0.010   ExM-2 0.082   ExM-3 0.006   ExM-4 0.026   ExY-1 0.010   ExY-4 0.040   ExC-7 0.007   HBS-1 0.203   HBS-3 0.003   HBS-5 0.010   Gelatin 0.570. [0200]   9th layer (low sensitivity green emulsion layer)   Em-G Silver 0.15   Em-H Silver 0.23   Em-I Silver 0.26   ExM-2 0.388   ExM-3 0.040   ExY-1 0.003   ExY-3 0.002   ExC-7 0.009   HBS-1 0.337   HBS-3 0.018   HBS-4 0.260   HBS-5 0.110   Cpd-5 0.010   Gelatin 1.470. [0201]   10th layer (medium sensitive green sensitive emulsion layer)   Em-F Silver 0.30   Em-G Silver 0.12   ExM-2 0.084   ExM-3 0.012   ExM-4 0.005   ExY-3 0.002   ExC-6 0.003   ExC-7 0.007   ExC-8 0.008   HBS-1 0.096   HBS-3 0.002   HBS-5 0.002   Cpd-5 0.004 Gelatin
  0.382. [0202]   11th layer (high sensitivity green emulsion layer)   Em-P1 Silver 1.200   ExC-6 0.002   ExC-8 0.010   ExM-1 0.014   ExM-2 0.023   ExM-3 0.023   ExM-4 0.005   ExM-5 0.040   ExY-3 0.003   Cpd-3 0.004   Cpd-4 0.007   Cpd-5 0.010   HBS-1 0.259   HBS-5 0.020   Polyethyl acrylate latex 0.099   Gelatin 1.110. [0203]   12th layer (yellow filter layer)   Cpd-1 0.088   Solid disperse dye ExF-2 0.051   Solid disperse dye ExF-8 0.010   HBS-1 0.049   Gelatin 0.593. [0204]   13th layer (low sensitivity blue-sensitive emulsion layer)   Em-B Silver 0.50   Em-C Silver 0.12   Em-D Silver 0.09   ExC-1 0.024   ExC-7 0.011   ExY-1 0.002   ExY-2 0.956   ExY-4 0.091   Cpd-2 0.037   Cpd-3 0.004   HBS-1 0.372   HBS-5 0.047   Gelatin 2.200. [0205]   14th layer (high sensitivity blue-sensitive emulsion layer)   Em-A1 Silver 1.22   ExY-2 0.235   ExY-4 0.018   Cpd-2 0.075   Cpd-3 0.001   HBS-1 0.087   Gelatin 1.156. [0206]   15th layer (first protective layer)   0.07 μm silver iodobromide emulsion Silver 0.28   UV-1 0.358   UV-2 0.179   UV-3 0.254   UV-4 0.025   F-11 0.008   S-1 0.078   ExF-5 0.0024   ExF-6 0.0012   ExF-7 0.0010   HBS-1 0.175   HBS-4 0.050   Gelatin 2.231. [0207]   16th layer (second protective layer)   H-1 0.400   B-1 (diameter 1.7 μm) 0.050   B-2 (diameter 1.7 μm) 0.150   B-3 0.050   S-1 0.200   Gelatin 0.711. Furthermore, storage stability, processability, and pressure are appropriately applied to each layer.
Improves resistance, antibacterial and antibacterial properties, antistatic properties, and coating properties
W1 to W6, B-4 to B-6, F
-1 to F-17, and iron salt, lead salt, gold salt, platinum salt,
Palladium salt, iridium salt, ruthenium salt, rhodium
Contains salt. Preparation of dispersion of organic solid disperse dye A solid dispersion of ExF-2 was dispersed by the following method. The water
4 to 2800g of ExF-2 wet cake containing 18%
Add 376 g of 000 g of water and 3% solution of W-2
The slurry was stirred to obtain a slurry having a concentration of ExF-2 of 32%. next
Ultra Viscomill (UVM-) manufactured by IMEX
2) 170 zirconia beads having an average particle size of 0.5 mm
Filled with 0 ml, the peripheral speed is about 10 m / se through the slurry.
c, It grind | pulverized for 8 hours with the discharge amount of 0.5 liter / min.
The average particle size was 0.45 μm. Similarly, ExF
-4, ExF-8 solid dispersion was obtained. Flat of dye fine particles
The average particle size was 0.28 μm and 0.49 μm, respectively.
It was. The compounds used to form each of the above layers are shown below.
It is. [0210] Embedded image [0211] Embedded image[0212] Embedded image[0213] Embedded image[0214] Embedded image[0215] Embedded image[0216] Embedded image[0217] Embedded image[0218] Embedded image[0219] Embedded image[0220] Embedded imageMethod for determining specific photographic sensitivity in the present invention
Is in accordance with JIS K 7614-1981
The difference is that the development process is performed after exposure for sensitometry 3
Complete the development process within 0 to 6 minutes
The point by the Fuji color processing method CN-16 shown below
The Others are substantially the same as the measurement method described in JIS.
is there. Except for the treatment method described below, JP-A-63-63.
-Test conditions, exposure and darkness described in No. 226650
The method was the same as that for determining the degree of light and determining the specific photosensitivity. Development is an automatic processor F manufactured by Fuji Photo Film Co., Ltd.
The following was performed using P-360B. In the bleaching bath
Drain all overflow liquid to the waste liquid tank without flowing it to the back bath.
Remodeled to make it out. This FP-360B
Evaporation correction means described in Association Technique 94-4992 is installed.
It is listed. The treatment process and the treatment liquid composition are shown below. [0224]   (Processing process)     Process Processing time Processing temperature Replenishment amount * Tank capacity   Color development 3 minutes 5 seconds 37.8 ° C 20 ml 11.5 liters   Whitening 50 seconds 38.0 ℃ 5 ml 5 liters   Fixing (1) 50 seconds 38.0 ℃ ─ 5 liters   Fixing (2) 50 seconds 38.0 ℃ 8 ml 5 liters   Washing with water 30 seconds 38.0 ℃ 17 ml 3 liters   Stable (1) 20 seconds 38.0 ℃ ─ 3 liters   Stable (2) 20 seconds 38.0 ℃ 15 ml 3 liters   Dry 1 min 30 sec 60.0 ° C   * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1) Stabilizer and fixer are countercurrent from (2) to (1)
In this case, all the overflow water of the washing water is led to the fixing bath (2).
I entered. The amount of developer brought into the bleaching process, bleach solution
To the fixing process and to the washing process of the fixing solution
The amount brought in is 35mm per photosensitive material and 1.1m wide.
2.5ml, 2.0ml, 2.0mm
It was a liter. Also, crossover time yes
The deviation is also 6 seconds, and this time is included in the processing time of the previous process.
Is done. The opening area of the processor is 10 with the color developer.
0cm²120cm with bleach solution², About other processing liquid
100cm²Met. The composition of the treatment liquid is shown below. [0226]   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3mg −   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-Methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0 liter 1.0 liter   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18. [0227]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-diaminopropanetetraacetic acid second     Iron ammonium monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0 liter 1.0 liter   pH [adjusted with aqueous ammonia] 4.6 4.0. (Fixing (1) Tank solution) Bleaching tank solution
And 5 to 95 (volume ratio) of the following fixing tank solution (pH)
6.8). [0229]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240ml 720ml   (750g / liter)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0 liter 1.0 liter   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45. (Washing water) Tap water is exchanged with H-type strongly acidic cation.
Replacement resin (Rum & Haas Amberlite IR-
120B) and OH type strongly basic anion exchange resin (same as above)
To a mixed bed column packed with mberlite IR-400)
Pass water and adjust calcium and magnesium ion concentration to 3m
g / l or less, followed by isocyanuric dichloride
Sodium Lurate 20mg / L and Sodium Sulfate 1
50 mg / liter was added. The pH of this solution is 6.5
It was in the range of ~ 7.5. [0231]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average polymerization degree 10)   1,2-Benzisothiazoline-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Add water and add 1.0 liter   pH 8.5 The relative sensitivity of each of the color-sensitive layers of Samples 101 to 108 is the above-mentioned characteristics.
For the value obtained from the method for measuring the constant photographic sensitivity, the sample 10
It is expressed as a relative value with a value of 1 as a reference 100. Regarding granularity, measurement of specific photographic sensitivity and
The same development processing is performed, and the conventional RMS (Root Mean Squa
re) method. At this time, the exposure is 0.005 Lux.
Second, RMS measurement using an aperture with a diameter of 48 μm
The regular method was performed. RMS ratio is each at a concentration of fog +0.15
Indicates the value obtained by dividing the RMS value of the sample by the RMS value of Sample 101
The higher the value, the worse the granularity
The Sharpness is evaluated by measuring MTF.
I was worth it. The measured value of MTF is “Journal of
"TOGRAPHIC ENGINEERING" Vol. 6 (1) 1-8
(1980). The value of MTF is a spatial frequency of 25 lines / mm.
And the relative value when the value of sample 101 is 100
expressed. Samples 101 to 108 obtained in this way.
The photographic performance is shown in (Table 3). [0236] [Table 3] From Table 3, that is, samples 101 to 104.
As described above, the emulsion is intended for high sensitivity and improvement in granularity.
When designing with a large amount of silver applied to the layer and a high volume fraction,
Deterioration of graininess of emulsion layer, and support side of emulsion layer
Sensitive degradation and MTF degradation in the photosensitive layer
It was. The deterioration of the granularity of the emulsion layer is caused by the density (aggregation) of grains.
Due to this, the sensitivity reduction in the photosensitive layer on the support side from the layer is
The deterioration of the permeability of the developer and the deterioration of the MTF
It is also thought to be due to optical scattering caused by concentrating children.
The On the other hand, as in samples 105 to 106, the flat
Even if the silver coating amount of the emulsion layer using plate grains is reduced, the volume
If the fraction is high, sensitivity improvement and lower sharpness degradation
I can't prevent it. Therefore, the samples 107 to 108 of the present invention.
Thus, it has a circle equivalent diameter of 3.5 μm or more and 8.0 or more.
An emulsion layer containing tabular grains having the above aspect ratio
It is coated at a specific position, and all the halogen in the emulsion layer
Set the volume fraction of silver halide grains and the amount of coated silver as in the present invention.
To achieve high sensitivity and excellent image quality.
It has become possible to provide a light-sensitive material.

Claims (1)

What is claimed is: 1. A unit blue-sensitive silver halide emulsion layer, a unit green-sensitive silver halide emulsion layer each comprising two or more color-sensitive layers having different sensitivities on a support; In a silver halide color photographic light-sensitive material having a unit red-sensitive silver halide emulsion layer, the emulsion layer located farthest from the support in each unit light-sensitive layer satisfies all the following requirements (a) to (c): A silver halide color photographic light-sensitive material characterized by satisfying. (A) The silver halide emulsion contained in the emulsion layer accounts for 50% or more of the projected area of all silver halide grains (111)
It is occupied by tabular grains having an equivalent circle diameter of 3.5 μm or more and an aspect ratio of 8.0 or more with the main surface as the surface. (B) The volume fraction of all silver halide grains in the emulsion layer is 2
0% or less. (C) The silver coating amount in terms of silver of the silver halide contained in the emulsion layer is 1.0 g / m ² or less.