JP2003270759A - Silver halide photographic sensitive material for photographing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion for photographing excellent in sensitivity to fog ratio and having high sensitivity and improved resistance to harmful gas produced in combustion, such as automobile exhaust gas. <P>SOLUTION: In a silver halide photographic sensitive material for photographing having on a support at least one photosensitive silver halide emulsion layer and at least one protective layer, ≥0.1 mass% polysaccharide originating from a microorganism based on the amount of gelatin in the protective layer is contained. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a silver halide photographic sensitivity.
Optical material (hereinafter also referred to as photosensitive material or photosensitive material) and its packaging
It is related to the body. For more information
Improved storability by reducing fluctuations in photographic properties (sensitivity, fogging)
Related to silver halide photographic light-sensitive materials for photography
The [0002] 2. Description of the Prior Art Sensitivity / grain ratio of silver halide photographic emulsion
The tabular grains that increase the light absorption efficiency
Use is known in US Pat. No. 4,956,269, etc.
It is. [0003] SUMMARY OF THE INVENTION In such tabular grains,
Increase the aspect ratio and increase the spectral sensitizing dye
Although the sensitivity is improved, the present inventors have particularly improved the above particles.
Combustion gas generated in the environment of the contained photosensitive material
(For example, exhaust gas from automobiles, etc.)
I found it big. Also known as a method for increasing quantum sensitivity.
When the reduction sensitization method is applied to the above particles, automobiles etc.
The phenomenon of fogging due to exhaust gas is further aggravated and improved
Was strongly desired. The present invention provides a high sensitivity with excellent sensitivity / fogging ratio.
It is an object to provide a silver halide photographic material for photographing.
It is what. At the same time, the present invention
Improved resistance to harmful gases generated during combustion
It is an object to provide a silver halide photographic material for photographing.
It is what. [0006] [Means for Solving the Problems] The present inventors have intensively studied.
As a result, the sensitivity of silver halide emulsion grains was improved.
Maintaining and covering with the combustion gas generated in the environment
In order to suppress the increase, the
Contains product-producing polysaccharide in the protective layer of silver halide photosensitive material
It was found that this can be achieved.
That is, the present invention provides the following silver halide photographic light-sensitive material:
I will provide a. (1) At least one on each support
Photography with photosensitive silver halide emulsion layer and protective layer
In the silver halide photographic light-sensitive material for use, contained in the protective layer
Microbial yield of 0.1% by mass or more based on gelatin
Silver halide photographic light-sensitive material containing saccharides
material. (2) A small amount of the photosensitive silver halide emulsion layer
Including a silver halide emulsion that has been subjected to reduction sensitization at least in one layer.
The photographic halo as described in (1) above,
Silver halide photographic material. (3) A small amount of the photosensitive silver halide emulsion layer
At least 50% of the total projected area of all silver halide grains
% Of silver halide emulsion grains with an aspect ratio of 8 or more
(1) or (2) above, characterized by containing
Silver halide photographic light-sensitive material for photography. [0010] The present invention will be described in detail below.
The protective layer of the light-sensitive material of the present invention will be described in detail. Protection
The protective layer is located farthest from the support. Protective layer
It can be a single layer, but usually consists of two or more layers.
The Basically gelatin is used as the binder for the protective layer
Yes. As gelatin, lime-processed gelatin and acid treatment
Gelatin, chemically modified gelatin and Bull. Soc. S
ci. Photo. Japan. No. 16, P30
(1966) used for enzyme-treated gelatin
May be. The protective layer of the light-sensitive material of the present invention has a high yield of microorganisms.
Contains sugars. The microbially-produced polysaccharide here is
Refers to water-soluble polysaccharides produced by living organisms, and general animals
And polysaccharides not found in plants are produced by microbial fermentation
It refers to what is done. Typical examples are pullulan and de
Examples include kisstran and xanthan gum (Shinji Nagatomo)
“Application and Market of New Water-soluble Polymers”, p. 20-2
1, p. 256-258 (1988), Shie Co., Ltd.
(See Musie). Pullulan is sucrose, glucose, maltose
And ferment monosaccharides and disaccharides with Pullularia pullulans
The weight average molecular weight is about 50,000 to about
200,000. Dextran is Lactovacil
D- made from sucrose by bacteria belonging to luse
A polymer based on glucopyranose having a degree of polymerization of 10
It is 00 to 10000th place. Xanthan gum, xant
Monas spp.
A neutral viscous polysaccharide with a degree of polymerization of about 1,000 to
10,000. These water-soluble microbially produced polysaccharides are
It is already known to have rear ability. Also these
Is compatible with gelatin and is a conventional silver halide photograph
Can be added as an additive to the protective layer of the photosensitive material.
It can also be used as an alternative to As described above, the present invention
The microbially produced polysaccharides used in
The microbially produced polysaccharide described above and
If it is equivalent, it is not necessarily produced by microorganisms
For example, those obtained by chemical synthesis
But you can. Microorganisms contained in the protective layer in the present invention
The amount of polysaccharide produced is relative to the gelatin contained in the protective layer.
Used at 0.1% by mass or more. The upper limit is 100 mass
% Or less is preferable. More preferably 1% by mass
It is 90 mass% or less. Even more preferably 2 quality
The amount is 80% by mass or more. Containing microbially produced polysaccharides
The higher the content, the higher the effect of the present invention, but the content is too high
However, the surface state of the applied protective layer may deteriorate. here
Gelatin is acid-treated gelatin in addition to lime-treated gelatin.
Chin, chemically modified gelatin and Bull. Soc. Sc
i. Photo. Japan. No. 16, P30 (1
966) containing enzyme-treated gelatin.
This refers to all gelatin derived from latin. In the light-sensitive material of the present invention, the production of microorganisms
Thickness of protective layer containing saccharides (when there are multiple protective layers
Is not particularly limited, but is preferably
Is 0.1 μm to 5 μm, more preferably 0.3 μm to 3
μm. The thicker the protective layer, the higher the effect of the present invention.
However, if it is too thick, other photographic performance problems arise. Protective layer
Protective layer containing microbially produced polysaccharide
Is preferably the top layer or the next layer after the top layer
Yes. The photosensitive material of the present invention contains a microbially produced polysaccharide.
The protective layer has a matting agent, UV absorber, slip agent, belt
Antistatic agent, antifoggant, stabilizer, dye, hardener, plastic
It may contain coating aids such as agents, lubricants, and surfactants.
You can. These additives are more specifically researched.
Disclosure Item 17643 (1978, 12
Month), Item 18716 (November 1979) and
Described in Item 308119 (December 1989)
It is. The photosensitive material of the present invention contains a microbially produced polysaccharide.
Hydrophilic properties other than gelatin as binder for protective layer
Colloids can also be used. For example, gelatin induction
Body, gelatin and other polymer graft polymer, al
Proteins such as bumine and casein, hydroxyethyl cellulose
Cellulose, carboxymethylcellulose, cellulose sulfate
Cellulose derivatives such as stealth, sodium alginate
Sugar derivatives such as starch and starch derivatives, poly-N-vinyl pyrrole
Don, polyacrylic acid, polymethacrylic acid, polyacrylic
Luamide, polyvinyl imidazole, polyvinyl pyrazo
Various synthetic hydrophilic properties such as mono- or copolymers such as
It is possible to use a polymer substance. Next, the halo used in the light-sensitive material of the present invention.
The silver halide emulsion grains will be described in detail. Sense of the present invention
The silver halide emulsion grains used in the light material are flat with each other.
In addition to so-called twin grains with a twin plane,
Well, the grain shape is also tabular grains, cubes, octahedrons, high
Polyhedral particles with the following surface, spherical shape, rod shape or any other shape
It may be. The halogen composition of silver halide is also the salt
Silver halide, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, etc.
There is no limit, and any silver halide composition may be used. In the present invention, silver iodobromide or chloroiodobromide
Since it is preferable to use a silver tabular grain emulsion, details will be described below.
Explained. Tabular grain emulsions have opposite (111) major surfaces
And side surfaces connecting the main surfaces. Tabular grain emulsions are iodine
It consists of silver bromide or silver chloroiodobromide. Including silver chloride
Preferably, the silver chloride content is preferably 8 mol% or less, more preferably
Preferably, it is 3 mol% or less or 0 mol%. Iodination
Regarding the silver content, the grain size distribution of the tabular grain emulsion
Is preferably 25% or less.
The silver halide content is preferably 20 mol% or less. Silver iodide content
By reducing the grain size of tabular grain emulsions.
It becomes easy to make the coefficient of variation of the cloth small. Especially flat plate
Variation coefficient of grain size distribution of grain emulsion should be less than 20%
The silver iodide content is preferably 10 mol% or less. Regardless of silver iodide content, silver iodide between grains
The variation coefficient of the content distribution is preferably 20% or less, particularly 1
0% or less is preferable. Tabular grain emulsions have an intragranular distribution of silver iodide.
It is preferable to have a structure. In this case, silver iodide
The distribution structure is double, triple, quadruple or even so.
There can be more structures. Tabular grain emulsions have more than 50% of the total projected area.
Occupied by particles having an aspect ratio of 3 or more. Flat grain here
The projected area and aspect ratio of the child are the Latec for reference.
By carbon replica method with shadow
It can be measured from an electron micrograph. Tabular grain
Is usually hexagonal when viewed from the direction perpendicular to the main surface,
It has a triangular or circular shape, but the projected area
The equivalent diameter of a circle with an area equal to
The ratio is The higher the ratio of hexagonal tabular grains, the higher the ratio
Preferably, the ratio of the lengths of adjacent sides of the hexagon is
It is preferably 1: 2 or less. The effect of the present invention is greater when the aspect ratio is higher.
Tabular grain emulsions have a total projected area of
50% or more preferably occupied by particles with an aspect ratio of 5 or more
It is More preferably, the aspect ratio is 8 or more
The If the aspect ratio becomes too large,
The coefficient of variation of the particle size distribution becomes larger
Therefore, the aspect ratio is usually preferably 50 or less. In the present invention, tabular grain emulsions face each other.
(111) It consists of a main surface and a side surface connecting the main surface.
There is at least one twin plane between the main surfaces.
The The tabular grain emulsion used in the light-sensitive material of the present invention includes
Usually two twin planes are observed. Between these two twin planes
The gap is 0.01 as described in US 5,219,720.
It is possible to make it less than 2 μm. Furthermore, JP-A-5
-Distance between (111) major surfaces as described in -249585
The value obtained by dividing the separation by the twin plane spacing may be 15 or more.
Noh. In the present invention, tabular grain emulsions face each other.
(111) Sides connecting main surfaces are 75% or less of all side surfaces
It is remarkably preferred that is composed of (111) planes
Yes. Here, 75% or less of all sides are composed of (111) planes
Is said to be higher than 25% of all sides (11
1) There is a crystallographic plane other than the plane
The Usually, the plane can be understood as the (100) plane
But other surfaces, ie (110) surface and higher fingers
It may also include the case of numbers. All aspects in the present invention
70% or less is composed of (111) planes
Is remarkable. 70% or less of all sides are composed of (111) planes.
Whether or not it is formed depends on the shadow of the host tabular grain
From an electron micrograph of the carbon replica method
Can be easily judged. More than 75% of the normal side is (11
1) in the case of hexagonal tabular grains
The six sides that connect directly to the (111) main surface are
On the other hand, it makes contact with the (111) main surface at an acute angle and an obtuse angle.
Continue. On the other hand, 70% or less of all sides are from the (111) plane
In the case of hexagonal tabular grains, (1
11) The six side faces directly connected to the main surface are (111) main
Connect all at an obtuse angle to the surface. Shadowing
Side to main surface by applying at an angle of 50 ° C or less
The obtuse angle and acute angle of the surface can be judged. Preferably 30 ° or less
Obtuse angle by shadowing at an angle of 10 ° or more
It is easy to judge the acute angle. Furthermore, the ratio of the (111) plane to the (100) plane
There is a method using adsorption of a sensitizing dye as a method for obtaining the rate.
It is effective. The Chemical Society of Japan, 1984, Volume 6, Page 94
(111) plane using the technique described in 2-947
And (100) plane ratio can be obtained quantitatively.
Using the ratio and the equivalent circle diameter and thickness of the tabular grains described above
Calculate the ratio of (111) planes on all sides
You can. In this case, the tabular grain has the equivalent circle diameter and thickness.
Is assumed to be a cylinder. This assumption makes the total table
The ratio of the side surface to the area can be obtained. The above
Increase the ratio of the (100) plane obtained using adsorption of sensitizing dye
The value divided by the ratio of the side mentioned above multiplied by 100 is all sides
(100) plane ratio. 100 to that value
The ratio of the (111) plane in all sides can be found
It becomes. In the present invention, (111) in all aspects
It is more preferable that the surface ratio is 65% or less. In the present invention, 7% of all sides of the tabular grain emulsion are used.
A method for setting 5% or less to the (111) plane will be described.
Most commonly, silver iodobromide or silver chloroiodobromide tabular grain milk
The ratio of the (111) face on the side of the agent is the same as that for preparing the tabular grain emulsion
PBr can be determined. Where pBr is the Br of the system^-
It is the logarithm of the reciprocal of the ion concentration. Total silver content of tabular grain emulsion
Is preferably at least 7 of the total silver amount.
After 0% or more is added, the ratio of (111) faces on the side is
Decrease, that is, increase the ratio of (100) sides
Set to pBr. Most preferably at least all silver
Of the (100) side surface after 90% or more of the amount has been added
PBr is set so that the ratio increases. 70 of total silver
% Of the side (100) plane before% is added
When the pBr is set such that the rate increases, the host tabular grains
Less preferred because the emulsion aspect ratio is reduced
Yes. Also, after 98% or more of the total silver is added,
PBr is set so that the ratio of the (100) plane increases.
And (100) side surface for obtaining the effect of the present invention.
It becomes difficult to achieve the ratio. Therefore most preferred
Or after at least 90% of the total silver has been added
The side surface until 98% or less of the total silver is added.
PBr is set so that the ratio of the (100) plane increases.
The effects of the invention are remarkably obtained. However, another one
(100) side of the side after the total amount of silver is added as a method
Set to pBr so that the ratio of
It is also possible to increase the ratio. The ratio of the (100) side surface is increased.
PBr is a protective roller for system temperature, pH, gelatin, etc.
Id agent type, concentration, presence or absence of silver halide solvent, type,
The value can vary widely depending on the concentration. Usually preferred
Specifically, pBr is 2.0 or more and 5 or less. More preferred
Is pBr2.5 or more and 4.5 or less. However,
As described above, the value of this pBr is, for example, a silver halide solution.
It can be easily changed by the presence of the agent. Preferably this departure
In light, it is better not to use silver halide solvents. Silver halide that can be used in the present invention
As the solvent, US Pat. No. 3,271,157,
3,531,289, 3,574,628, JP,
Described in Sho 54-1019, 54-1558917, etc.
(A) Organic thioethers, JP-A-53-824
08, 55-77737, 55-2982, etc.
(B) Thiourea derivatives described in JP-A-53-14
(C) oxygen or sulfur atom and nitrogen described in No. 4319
Halogen having a thiocarbonyl group sandwiched between elemental atoms
Silver halide solvent, described in JP-A-54-100717
(D) Imidazoles, (e) Ammonia, (f) Thio
Examples include cyanate. As a particularly preferred solvent
Are thiocyanate, ammonia and tetramethylthio
There is urea. The amount of solvent used depends on the type.
For example, in the case of thiocyanate, the preferred amount is
1 x 10 per mole of silver halide^-Four1 x 10 moles or more^-2
It is below the mole. Change the face index of the side face of a tabular grain emulsion.
Refer to EP515894A1 etc. as a method.
it can. In addition, poly, as described in US Pat. No. 5,252,453, etc.
An alkylene oxide compound can also be used. Yes
As an effective method, US 4,680,254, US 4,68
0,255, US 4,680,256 and US 4,
Use the surface index modifier described in 684,607, etc.
Can do. Normal photographic spectral sensitizing dyes have the same aspect as above.
It can be used as an index modifier. The present invention satisfies the above requirements.
As far as silver iodobromide or silver chloroiodobromide tabular grain emulsions are concerned
It can be prepared by various methods. Tabular grain
The preparation of the emulsion is usually the basis for nucleation, ripening and growth.
It consists of three steps. US4 in the nucleation process
713, 320 and US 4,942,120
Using gelatin with low methionine content, US
Nucleation at high pBr described in US Pat. No. 4,914,014
In a short time as described in JP-A-2-222940
The tabular grains used in the light-sensitive material of the present invention
It is extremely effective in the nucleation process of the emulsion. Aging
In the process, the low concentration described in US Pat. No. 5,254,453
In the presence of a base of US5013641
That is carried out at a high pH described in the above
Effective in the ripening process of tabular grain emulsions used in
There may be. In the growth process, US 5,248,
Growing at low temperature described in No. 587, US 4,6
72,027 and US 4,693,964
The use of silver iodide fine grains in the light-sensitive material of the present invention.
Especially effective in the growth process of tabular grain emulsion
The In addition, silver bromide, silver iodobromide, silver chloroiodobromide fine grain milk
It is also preferred to grow by adding aging agents and aging
Used. The stirring described in JP-A-10-43570
It is also possible to supply the fine grain emulsion using a stirrer
It is. The emulsion used in the light-sensitive material of the present invention is:
Hole capturing silver nuclei are formed on the surface of particles by intentional reduction sensitization.
It is preferable to introduce. What is intentional reduction sensitization?
Means reduction sensitization performed by adding sensitizers
The A hole-capturing silver nucleus is a small silver nucleus with low development activity.
This means that the silver nuclei prevent recombination loss during the exposure process.
It is possible to increase the sensitivity. Hole capture on the particle surface
For the detection of silver nuclei, the emulsion is coated with an emulsion before chemical ripening.
This can be determined by performing development processing. Gold reinforcement is PS
A Journal 14: 349, page 194
8), T.M. H. Intended for the gold booster described by James et al.
2 together with the emulsion coating sample that was not subjected to reduction sensitization
Can be done by treating for 10 minutes at 0 ° C
The After the coated sample was washed with water for 30 minutes, PSA Jo
urnal 19B, page 170 (1953),
T.A. H. A surface developer, MAA-1, described by James et al.
At 20 ° C. for 10 minutes. Cover of developed coating sample
Measure the optical density of the part. With intentional reduction sensitization
The optical density of the fogged part is smaller than the emulsion coating sample.
If it is high, there is a hole-capturing silver nucleus on the particle surface.
Become. As a method for introducing hole-trapping silver nuclei into the particle surface
Deliberate reduction in the grain formation of silver halide emulsions
This is possible by applying sensitization. As a reduction sensitizer, stannous salt, ascorbine
Acids and their derivatives, amines and polyamines, hydrazides
Derivatives, formamidinesulfinic acid, silane compounds
And borane compounds are known. In the present invention, reduction
For the sensitization, it is necessary to select and use these known reduction sensitizers.
In addition, two or more compounds can be used in combination.
Reduction sensitizers stannous chloride, thiourea dioxide, dimethyl
Luamine borane, ascorbic acid and its derivatives are preferred.
New compound. The amount of reduction sensitizer added is the emulsion production conditions.
It is necessary to select the addition amount because it depends on
10 per silver mole ^-7-10^-3A molar range is suitable.
Reduction sensitizers are water or alcohols, glycols,
Dissolved grains in solvents such as ketones, esters and amides
Added during child growth. In the present invention, it is preferable to form particles.
Add reduction sensitizer after 50% of total silver is added
To form hole-trapping silver nuclei on the particle surface.
The More preferably, 70% of the total silver amount required for grain formation
By adding a reduction sensitizer after the
Hole trapping silver nuclei are formed on the surface of the child. Since the end of particle formation
A reduction sensitizer is added to the surface to form hole-capturing silver nuclei on the particle surface.
It is also possible to introduce it in the present invention. Particle formation
Sometimes when a reduction sensitizer is added, some of the silver nuclei formed
It can stay inside the particles, but some
Finally, silver nuclei are formed on the surface of the grains. In the present invention
The nucleated silver nuclei are referred to as hole-capturing silver nuclei on the particle surface.
It is preferable to use it. The formation of hole-capturing silver nuclei on the particle surface is preferred.
Or at the time of intentional reduction sensitization, the general formula (V-1) or
Preferably in the presence of a compound of general formula (V-2)
That's right. General formula (V-1) [Chemical 1] General formula (V-2) [Chemical 2] In the general formulas (V-1) and (V-2)
W₅₁, W₅₂Represents a sulfo group or a hydrogen atom. However
W₅₁, W₅₂At least one of represents a sulfo group. The
Rufo group is generally an alkenyl such as sodium and potassium.
Water-soluble salts such as lithium metal salts or ammonium salts
The Specifically, a preferred compound is 3,5-disulfur
Jocatechol disodium salt, 4-sulfocatechola
Ammonium salt, 2,3-dihydroxy-7-sulfonaphth
Talen sodium salt, 2,3-dihydroxy-6,7-
And disulfonaphthalene potassium salt. Like
The amount added is the temperature of the system to be added, pBr, pH, gelatin
Protective colloid agent type, concentration, silver halide solvent
It may vary depending on the presence, type, concentration, etc.
0.0005 mol to 0.5 mol per mol of silver halide
More preferably 0.003 mol to 0.02 mol
Used. Tabular grains used in the light-sensitive material of the present invention
There is no limitation on the silver iodide content on the grain surface of the emulsion. The present invention
The silver iodide content of the grain surface used in the photosensitive material of
XPS (X-ray Photoelectron S
measured using spectroscopy. Haloge
Used for analysis of silver iodide content near the surface of silver halide grains
Regarding the principle of the XPS method, Aihara et al., “Electron Spectroscopy”
(Kyoritsu Library-16, published by Kyoritsu Publishing, 1978)
Can be helpful. XPS standard measurement method
Uses Mg-Kα as the excitation X-ray
Iodine (I) and silver released from the modified silver halide
(Ag) photoelectrons (usually I-3d5 / 2, Ag-3d
This is a method of observing the intensity of 5/2). Find iodine content
Several standard samples with known iodine content.
Intensity ratio (strength of photoelectrons of iodine (I) and silver (Ag))
(I) / Intensity (Ag)) calibration curve was created, and this calibration curve
Can be found from. Halo in silver halide emulsions
Proteolytic enzyme from gelatin adsorbed on the surface of silver halide grains
XPS measurement must be performed after disassembly and removal
I have to. Halogen used in the light-sensitive material of the present invention
The silver iodide content on the grain surface is 5 mol% or less.
If listed as tabular grain emulsion below, one emulsion
When the emulsion grains contained in are analyzed by XPS
The silver content is 5 mol% or less. in this case,
When two or more emulsions are clearly mixed, centrifuge
Same type after appropriate pretreatment such as separation and filtration
It is necessary to perform analysis for each emulsion. In the present invention, the iodine in the layer inside the surface is
It is preferred that the silver iodide content is higher than the surface silver iodide content.
The silver iodide content of the layer inside the surface is preferably
5 mol% or more, more preferably 7 mol% or more
The efficiency of light becomes remarkable. In the present invention, the tabular grains are preferably converted.
Has a level line. The dislocation lines of tabular grains are described in, for example, J.A. F. H
amilton, Photo. Sci. Eng. , 11,
57, (1967) and T.W. Shiozawa, J. et al. So
c. Photo. Sci. Japan, 35, 213,
(1972), the transmission electron microscope at low temperature is used.
Can be observed by direct methods. Snow
Do not apply enough pressure to generate dislocation lines from the emulsion to the grains.
Take out the silver halide grains carefully and carefully
Damage on the mesh for mirror observation (pudding)
The permeation method with the sample cooled to prevent
Observe. At this time, the thicker the particle, the more the electron beam
High pressure type (with a thickness of 0.25μm)
Those who use an electron microscope of 200 kV or more for particles
Can be observed more clearly. In this way
From the photograph of the obtained particle, the direction perpendicular to the main plane
The position and number of dislocation lines for each particle as seen from
Can be sought. The number of dislocation lines is preferably the average per particle
10 or more. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present, or
When dislocation lines are observed crossing each other,
Sometimes the number of dislocation lines cannot be clearly counted.
is there. However, even in these cases,
It can be counted as about 10, 20, or 30
It is possible, and clearly there are only a few
Can be separated. For the average number of dislocation lines per particle
Count the number of dislocation lines for more than 100 grains,
And ask. For example, the dislocation line is introduced near the outer periphery of the tabular grain.
You can enter. In this case, the dislocation is almost perpendicular to the outer circumference.
Yes, the length of the distance from the center of tabular grains to the side (outer circumference)
The dislocation lines start from the position of x% and reach the outer periphery.
I'm alive. The value of x is preferably 10 or more and not 100
It is full, more preferably 30 or more and less than 99.
Also preferably, it is 50 or more and less than 98. At this time,
The shape created by connecting the position where the position line starts is the particle shape.
It is close to similarity, but it is not completely similar and may be distorted.
The This type of dislocation number is not found in the central region of the grain.
The direction of dislocation lines is crystallographically approximately (211).
Often meandering and crossing each other
There is also. Further, almost all over the outer periphery of the tabular grain.
Even if it has dislocation lines evenly,
You may have a dislocation line. That is, hexagonal flat plate halogen
Taking silver halide grains as an example, dislocations are only near the six vertices.
The line may be limited or near one of the vertices
The dislocation line may be limited only to the side. Conversely, the six peaks
It is possible that the dislocation line is limited to only the sides except near the point.
Noh. The center of two parallel major planes of the tabular grain
Dislocation lines may be formed over a region including. main
If dislocation lines are formed over the entire area of the plane,
The direction of the grid line is crystallographic when viewed from the direction perpendicular to the main plane.
It may be roughly (211) direction, but (110) direction
Or it may be randomly formed, and each
The length of the dislocation line is also random, and it is a short line on the main plane.
And reach the side (outer circumference) as a long line
May be observed. The dislocation line may be a straight line
It is often meandering. Also often exchange with each other
I'm not. The position of the dislocation line is as described above on the outer periphery or
It may be limited to the main plane or local position
And these may be combined and formed.
That is, it may exist on the outer periphery and the main plane at the same time.
Yes. In the present invention, the above-mentioned silver bromide, salt odor
Insoluble in silver halide, silver chloroiodobromide or silver iodobromide tabular grain emulsions
Dislocation lines are introduced by adding silver halide emulsions.
You can Here, the poorly soluble silver halide emulsion means ha.
Less soluble than tabular grain emulsion in the rogen composition
Preferably, it is a silver iodide fine grain emulsion. In the present invention, the above-described flat plate is preferable.
By rapidly adding silver iodide fine grain emulsion to grain emulsion
Introducing dislocation lines. This process is essentially two steps
A silver iodide fine grain emulsion was added rapidly to the tabular grain emulsion.
And then grow silver bromide or silver iodobromide
This is a step of introducing dislocation lines. These two processes
May be performed completely separate, each with duplicates
It can also be done at the same time. Preferably separated lines
Be made. A silver iodide fine grain emulsion is added to the first tabular grain emulsion.
The process of adding rapidly will be described. The rapid addition of silver iodide fine grain emulsion is:
The silver iodide fine grain emulsion is preferably added within 10 minutes.
Say. More preferably, it should be added within 7 minutes
Yeah. These conditions are the temperature of the system to be added, pBr, pH, gel
Types and concentrations of protective colloids such as tin, silver halide soluble
It may vary depending on the presence, type, concentration, etc. of the agent.
The shorter one is preferable. Nitric acid when added
It is preferable not to add an aqueous silver salt solution such as silver.
The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower,
50 ° C. or more and 80 ° C. or less is particularly preferable. Silver iodide fine milk
There is no particular limitation on the pBr when the agent is added. The silver iodide fine grain emulsion should be substantially silver iodide.
Silver bromide and / or as long as it can be mixed crystals
May contain silver chloride. Preferably 100% iodine
It is silver fossil. Silver iodide has β-form and γ-form in its crystal structure.
As well as in US Pat. No. 4,672,026
In other words, there can be an α-form or an α-form-like structure. In the present invention
However, there are no particular restrictions on the crystal structure, but β-form and γ
A mixture of bodies is more preferably used. Silver iodide
Addition of fine grain emulsion described in US Pat. No. 5,004,679
It may be formed just before the normal washing process
Any of them may be used, but is preferred in the present invention.
Or what passed through the normal water-washing process is used. Silver iodide
The fine grain emulsion is described in US Pat. No. 4,672,026 described above.
It can be easily formed by the method described. PI value during grain formation
Silver salt aqueous solution and iodide salt water to form grains with constant
A double-jet addition method of the solution is preferred. Where pI is
System I^-It is the logarithm of the reciprocal of the ion concentration. Temperature, pI,
pH, type and concentration of protective colloids such as gelatin, halo
There are no particular restrictions on the presence, type, concentration, etc. of silver halide solvent
However, the particle size is 0.1 μm or less, more preferably
0.08 μm or less is convenient for the present invention. Is fine
Therefore, the particle shape cannot be completely specified, but the particle size
The distribution variation coefficient is preferably 25% or less. 20% or less
In the following cases, the effect of the present invention is remarkable. Silver iodide fine here
The size and size distribution of the grain emulsion is determined by
Carbon replica method on mesh for microscopic observation
Rather than observing directly by the transmission method. this is
Due to the small particle size, the carbon replica method is used.
This is because the measurement error increases in observation. Particle size
Is the diameter of a circle with a projected area equal to the observed particle and
Define. This equal throw is also applied to the particle size distribution.
Calculated using the shadow area circle diameter. Most effective in the present invention
Silver iodide fine grains have a grain size of 0.07 μm or less 0.0
2 μm or more, particle size distribution coefficient of variation is 18%
It is as follows. The silver iodide fine grain emulsion is preferably used after the above grain formation.
The normal water described in US 2,614,929, etc.
Washing and concentration of protective colloids such as pH, pI, gelatin
Adjustment and concentration adjustment of contained silver iodide are performed. pH is
5 or more and 7 or less are preferable. The pI value is the highest solubility of silver iodide.
Set to a lower pI value or a higher pI value
It is preferable to do. For protective colloids, average
Normal gelatin with a molecular weight of about 100,000 is preferably used.
The Low molecular weight gelatin with an average molecular weight of 20,000 or less is also preferred
Used. Also mixed with gelatin with different molecular weight
It may be convenient to use it. Per kg of emulsion
The amount of gelatin is preferably 10 to 100 g
The More preferably, it is 20 g or more and 80 g or less. emulsion
Silver amount in terms of silver atom per kg is preferably 10g or more
100 g or less. More preferably 20g or more 80g
It is as follows. Gelatin amount and / or silver amount is silver iodide fine grain
Select a value that is suitable for rapid addition of the emulsion.
preferable. The addition amount of the silver iodide fine grain emulsion is preferably
1 mol% or more and 10 mol in terms of silver based on the tabular grain emulsion
% Or less. Most preferably 2 mol% or more and 7 mol% or less
It is below. By selecting this addition amount, dislocation lines are favored.
The effect of the invention becomes remarkable. Silver iodide fine grains
The emulsion is usually added after being dissolved in advance.
Therefore, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably
The stirring speed is set higher than usual. When stirring
It is effective to add an antifoaming agent to prevent foam formation.
The Specifically, Examples of US Pat. No. 5,275,929
Are used. A silver iodide fine grain emulsion is rapidly added to a tabular grain emulsion.
After addition, dislocation by growing silver bromide or silver iodobromide
Introduce a line. Before adding silver iodide fine grain emulsion
May start growing silver bromide or silver iodobromide at the same time
Preferably, however, the odor is added after the silver iodide fine grain emulsion is added.
Start growth of silver halide or silver iodobromide. Silver iodide fine particles
After the emulsion is added, the growth of silver bromide or silver iodobromide is started.
The time to start is preferably less than 10 minutes and more than 1 second
is there. More preferably, it is 3 seconds or more within 5 minutes. More
Preferably, it is within 1 minute. The shorter this time interval, the better.
Preferably, before the start of silver bromide or silver iodobromide growth
Yes. Growth after addition of silver iodide fine grain emulsion is favorable.
Preferably it is silver bromide. Silver iodobromide contains silver iodide
The rate is preferably within 3 mol% relative to the layer. this
The amount of silver in the layer grown after addition of the silver iodide fine grain emulsion is
When the total silver amount of the plate grain emulsion is 100, preferably 5
It is 50 or less. Most preferably 10 or more and 30 or less
It is. The temperature, pH and pBr when forming this layer are
Although there is no particular limitation, the temperature is 40 ° C. or more and 90 ° C. or less, and the pH is
2 or more and 9 or less are usually used. More preferably 50 ° C
The temperature is 80 ° C. or lower and the pH is 3 or higher and 7 or lower. p
Regarding Br, in the present invention, at the end of formation of the layer,
pBr is higher than pBr at the initial stage of formation of the layer
Is preferred. Preferably, the pBr at the initial stage of formation of the layer is 2.
9 or less, and pBr at the end of formation of the layer is 1.7 or more.
is there. More preferably, the pBr at the initial stage of formation of the layer is 2.
5 or less and pBr at the end of the formation of the layer is 1.9 or more
is there. Most preferably, the initial pBr formation is 2.3.
Below 1 or more. Most preferably the pB at the end of the layer
r is 2.1 or more and 4.5 or less. By the above method
Dislocation lines in the present invention are preferably introduced. Other dislocations
The introduction method is described in JP-A-7-219102.
There are dislocation introduction methods, among which iodide ions
The release agent method is particularly preferred. Halogen used in the light-sensitive material of the present invention
Silver halide emulsions are usually spectrally sensitized. Spectral sensitizing dye and
Therefore, a methine dye is usually used. For methine dyes
Usually cyanine dye, merocyanine dye, complex cyanine
Dye, complex merocyanine dye, holopolar cyanine color
Element, hemicyanine dye, styryl dye and hemioxono
Color pigments are included. These dyes include basic
What is a ring commonly used for cyanine dyes?
This is also applicable. Examples of basic heterocycles include pylori
Ring, oxazoline ring, thiazoline ring, pyrrole ring, o
Xazole ring, thiazole ring, selenazole ring, imida
Name the sol ring, tetrazole ring and pyridine ring
I can do it. In addition, the hetero ring is an alicyclic hydrocarbon ring or aromatic
A ring condensed with a hydrocarbon ring can also be used. As an example of a fused ring
Indolenine ring, benzimidazole ring, benz
Oxazole ring, naphthoxazole ring, benzimidazole
Sol ring, benzothiazole ring, naphthothiazole ring,
The benzoselenazole ring and quinoline ring can be mentioned.
come. Substituents are attached to the carbon atoms of these rings
Also good. Merocyanine dye or complex merocyanine
The dye contains a 5 or 6 membered ketomethylene structure
Heterocycles can be applied. Such heterocyclic
Examples include pyrazolin-5-one ring, thiohydantoy
Ring, 2-thiooxazolidine-2,4-dione ring,
-Danin ring and thiobarbituric acid ring
come. The addition amount of the sensitizing dye was 1 mol of silver halide.
Preferably it is 0.001 to 100 millimoles per unit
More preferably 0.01 to 10 mmol.
Yes. The sensitizing dye is preferably during or during chemical sensitization.
Added before sensitization (eg during grain formation or physical ripening)
The In addition to sensitizing dyes, they themselves have spectral sensitizing effects.
Dyes not shown or those that do not substantially absorb visible light
Quality and supersensitizing material into silver halide emulsions
It may be added. Examples of such dyes or substances include
Aminostil compounds substituted with nitrogen heterocyclic groups (US
No. 2,933,390 and 3,635,721
Described in each specification), aromatic organic acid formaldehyde condensation
(Described in US Pat. No. 3,743,510),
Cadmium salts and azaindene compounds are included. Sensitization
For combinations of dyes with the above dyes or substances,
U.S. Pat.Nos. 3,615,613 and 3,615,641
Nos. 3,617,295 and 3,635,721
There are descriptions in each specification. Halogen used in the light-sensitive material of the present invention
Silver halide grains are sulfur sensitized, selenium sensitized, gold sensitized, palladium
Silver halide at least one of sensitization or noble metal sensitization
It can be applied in any step of the emulsion production process. 2
It is preferable to combine sensitizing methods of more than seeds. Which process
Prepare various types of emulsions depending on whether they are chemically sensitized with
Can be. Incorporating chemical sensitization nuclei inside the particles
Type, embedding shallowly from the particle surface, or
Has a type that creates chemical sensitization nuclei on the surface. Photosensitivity of the present invention
The emulsion used in the material depends on the field of chemical sensitization depending on the purpose.
Can be selected, but it is preferable
This is the case when at least one kind of chemical sensitization nucleus is made. One of the chemical sensitizations that can be preferably carried out in the present invention.
One is chalcogenide sensitization and noble metal sensitization alone or in combination
The photograph by T.H.James
Fick Process, 4th edition, published by Macmillan, 197
7 years (T.H.James, The Theory of the Photographic P
rocess, 4th ed, Macmillan, 1977) 67-76
Can be performed using active gelatin as described
And Research Disclosure Volume 120, 1
April 974, 12008; Research Disclosure
34, June 1975, 13452, US Patent
Nos. 2,642,361, 3,297,446,
3,772,031, 3,857,711, the same
3,901,714, 4,266,018, and
3,904,415 and British Patent 1,31
PAg 5-10 as described in US 5,755, pH
5-8 and temperature 30-80 ° C., sulfur, selenium, te
Lulu, gold, platinum, palladium, iridium or these
It can be a plurality of combinations of sensitizers. Precious metal sensitization
In the case of gold, platinum, palladium, iridium, etc.
Metal salts can be used, especially gold sensitization and parasitism.
Umum sensitization and a combination of both are preferred. In case of gold sensitization
Chloroauric acid, potassium chloroaurate, potassium
-Well-known such as lithiocyanate, gold sulfide, gold selenide
Compounds can be used. Palladium compounds are para
It means a divalent salt or a tetravalent salt. Preferred para
The rhodium compound is R₂PdX₆Or R₂PdX_FourRepresented by
It is. Where R is a hydrogen atom, an alkali metal atom or an
Represents an ammonium group. X represents a halogen atom and is a salt
Represents an elemental, bromine or iodine atom. Specifically, K₂
PdCl_Four, (NH_Four)₂PdCl₆, Na₂PdCl_Four, (N
H_Four)₂PdCl_Four, Li₂PdCl_Four, Na₂PdCl₆Also
Is K₂PdBr_FourIs preferred. Gold compounds and palladiumation
Compound is used in combination with thiocyanate or selenocyanate
It is preferable to do. Hypo, thiourea based sulfur sensitizers
Compounds, rhodanine compounds and US Pat. No. 3,857,7
No. 11, No. 4,266,018 and No. 4,054,4
Use of sulfur-containing compounds described in No. 57
it can. Chemical sensitization in the presence of so-called chemical sensitization aids
You can also. Useful chemical sensitization aids include azaindene
Chemicals such as N, Azapyridazine, Azapyrimidine
Suppress fog in the process of feeling and increase sensitivity
Thus known compounds are used. Chemical sensitizer modifier
Examples of U.S. Pat. Nos. 2,131,038 and 3,412.
1,914, 3,554,757, JP-A-58-
No. 126526 and the above-mentioned “Photo Emulsion Chemistry” by Duffin,
138-143. The emulsion used in the light-sensitive material of the present invention is gold.
It is preferable to use sensitization in combination. Preferred amount of gold sensitizer
As 1 x 10 per mole of silver halide^-Four~ 1x10^-7
Mole, more preferably 1 × 10^-Five~ 5x10
^-7Is a mole. The preferred range of the palladium compound is 1 ×
10^-3To 5 × 10^-7It is. Thiocyanate compound or
The preferred range of selenocyan compounds is 5 × 10^-2From
1 × 10^-6It is. C used in the light-sensitive material of the present invention
Preferred amount of sulfur sensitizer to be used for silver halide grains
Is 1 x 10 per mole of silver halide^-Four~ 1x10^-7Mole
And more preferably 1 × 10^-Five~ 5x10^-7Mo
It is le. For the emulsion used in the light-sensitive material of the present invention,
A preferred sensitizing method is selenium sensitization. Selenium increase
For feeling, a known unstable selenium compound is used.
In particular, colloidal metal selenium, selenoureas (eg
For example, N, N-dimethylselenourea, N, N-diethyl
Selenourea, etc.), selenoketones, selenoamides, etc.
The selenium compound can be used. Selenium sensitization is sulfur
Combined with yellow sensitization or precious metal sensitization or both
May be preferable. In the present invention, preferably thiocyanic acid
Addition of the above-mentioned spectral sensitizing dye and chemical sensitizer
Added before. Preferably after grain formation, more preferably
Is added after the desalting step. Preferably during chemical sensitization
Since thiocyanate is also added to the
Addition will be performed more than once. As thiocyanate
For example, potassium thiocyanate, sodium thiocyanate
And ammonium thiocyanate are used. Normally
It is dissolved in an aqueous solution or a water-soluble solvent and added. Addition
The amount is 1 x 10 per mole of silver halide^-Five1x from mole
10^-2Mole, more preferably 5 × 10^-Five5 x 1 from mole
0^-3Is a mole. Preparation of emulsion used in the light-sensitive material of the present invention
As protective colloids used in manufacturing and other parents
Gelatin is used as the binder for the aqueous colloid layer.
It is advantageous to use other hydrophilic colloids.
Can. Eg gelatin derivatives, gelatin and others
Graft polymer, albumin, casein
Protein such as: hydroxyethyl cellulose, carboxy
Such as methylcellulose, cellulose sulfate, etc.
Cellulose derivatives, sodium alginate, starch derivatives, etc.
Sugar derivatives of polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol
Partial acetal, poly-N-vinylpyrrolidone, poly
Liacrylic acid, polymethacrylic acid, polyacrylamid
, Polyvinyl imidazole, polyvinyl pyrazole, etc.
Synthetic hydrophilic polymers such as mono- or copolymers of
Substances can be used. Lime processing as gelatin
In addition to gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16, described in P30 (1966)
Enzyme-treated gelatin such as
Chin hydrolyzate and enzyme degradation product can also be used. The emulsion used in the light-sensitive material of the present invention is a non-emulsion.
Wash with water for salt and prepare a new protective colloid dispersion
It is preferable to do. Washing temperature can be selected according to purpose
Is preferably selected in the range of 5 ° C to 50 ° C. During washing
PH can be selected according to the purpose, but between 2 and 10
Is preferred. More preferably, it is the range of 3-8. water
The pAg at the time of washing can be selected according to the purpose, but it is selected between 5 and 10.
It is preferable. Noodle washing method as a washing method,
Dialysis using a semipermeable membrane, centrifugation, coagulation sedimentation,
Can be selected and used. Coagulation sedimentation
In case of descending method, using sulfate, organic solvent
Method, method using water-soluble polymer, gelatin derivative
You can choose from the method you use. Preparation of emulsion for use in light-sensitive material of the present invention
At the time of particle formation, desalting process, chemical sensitization, before application
The presence of a metal ion salt is preferred depending on the purpose.
That's right. When doping a particle, the surface of the particle during particle formation
Particle formation when used as a chemical sensitizer or as a chemical sensitizer
Thereafter, it is preferably added before the completion of chemical sensitization. Whole particles
When doping the body and only the core part of the particle or
Only in the cell part or only in the epitaxial part
Can also choose the method of doping only the base particles. Mg, C
a, Sr, Ba, Al, Sc, Y, LaCr, Mn, F
e, Co, Ni, Cu, Zn, Ga, Ru, Rh, P
d, Re, Os, Ir, Pt, Au, Cd, Hg, T
l, In, Sn, Pb, Bi, etc. can be used.
The These metals are ammonium salts, acetates, nitrates,
Sulfate, phosphate, hydrate or hexacoordination complex salt, tetracoordination complex
A salt form that can be dissolved during particle formation, such as salt.
Can be added. For example, CdBr₂, CdCl₂, Cd
(NO_Three)₂, Pb (NO_Three)₂, Pb (CH_Three(COO)₂, K
_Three[Fe (CN)₆], (NH_Four)_Four[Fe (CN)₆], K_Three
IrCl ₆, (NH_Four)_ThreeRhCl₆, K_FourRu (CN)₆Such
Is 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 them after dissolving them in a solvent.
Hydrogen halide aqueous solution (eg HC) to stabilize the solution
l, HBr, etc.) or alkali halides (eg KC)
l, NaCl, KBr, NaBr, etc.)
Can be used. If necessary, acid / alkaline
You may add. Metal compound is a reaction vessel before particle formation
Even if it is added to, it can also be added during the grain formation. Ma
Water-soluble silver salt (eg AgNO_Three) Or halogenated a
Added to Lucari water soluble (eg NaCl, KBr, KI)
It can also be added continuously during silver halide grain formation.
The Furthermore, it is independent of water-soluble silver salt and alkali halide
Prepare a solution and add it continuously at appropriate times during particle formation.
May be. It is also preferable to combine various addition methods.
That's right. Described in US Pat. No. 3,772,031
Chalcogenide compounds such as
The method of adding may also be useful. Other than S, Se, Te
Also cyanate, thiocyanate, selenocyanic acid, carbonate,
Phosphate and acetate may be present. The emulsion used in the light-sensitive material of the present invention is the same.
It is preferred to use an oxidizer for silver during the manufacturing process
Yes. However, some hole-capturing silver nuclei on the particle surface remain.
It is necessary to An oxidizing agent for silver acts on metallic silver.
Refers to a compound having the effect of converting into silver ions.
Especially in the process of silver halide grain formation and chemical sensitization.
The minute silver particles produced as a by-product are converted into silver ions.
The compound to be used is effective. Silver ions generated here
Is hardly soluble in water such as silver halide, silver sulfide, and silver selenide.
A silver salt may be formed, or a silver salt that is readily soluble in water such as silver nitrate
May be formed. The oxidizer for silver is inorganic.
Or it may be organic. As an inorganic oxidizing agent,
Ozone, hydrogen peroxide and its adducts (eg NaBO)
₂・ H₂O ₂・ 3H₂O, 2NaCO_Three・ 3H₂O₂, Na_FourP
₂O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂O),
Peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K₂P₂
O₈), Peroxy complex compounds (for example, K₂[Ti
(O₂) C₂O_Four] 3H₂O, 4K₂SO_Four・ Ti (O₂) O
H ・ SO_Four・ 2H₂O, Na_Three[VO (O₂) (C₂H_Four)₂・
6H₂O), permanganate (eg KMnO)_Four)
Lomate (eg K₂Cr₂O₇Oxygenates such as), iodine
And halogen elements such as bromine and perhalogenates (e.g.
Potassium iodate) high valent metal salts (eg hexa
Potassium cyanoferrate) and thiosulfonate
There is. Moreover, as an organic oxidizing agent, p-quinone etc.
Quinones, organic peroxides such as peracetic acid and perbenzoic acid,
Compounds that release active halogens (eg N-bromosa
Examples are succinimide, chloramine T, chloramine B)
Can be mentioned. Preferred for use in the light-sensitive material of the present invention
Oxidizing agents include ozone, hydrogen peroxide and its adducts, halogens.
Element, inorganic oxidizer of thiosulfonate and quinones
Is an organic oxidizer. 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 salts, nitroimidazoles
, Nitrobenzimidazoles, chlorobenzimida
Zoles, Bromobenzimidazoles, Mercaptochi
Azoles, mercaptobenzothiazoles, mercap
Tobenzimidazoles, mercaptothiadiazole
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole)
Do; mercaptopyrimidines; mercaptotriazine
Thioketo compounds such as oxadrine thione
Azaindenes such as triazaindenes,
Traazaindenes (especially 4-hydroxy substituted (1,
3,3a, 7) tetraazaindenes), pentaazai
As antifoggant or stabilizer such as
Many known compounds can be added. for example
U.S. Pat. Nos. 3,954,474 and 3,982,9
47, the one described in Japanese Patent Publication No. 52-28660
Can be used. One of the preferred compounds
There are compounds described in 2-47225. Cover protection
Stopper and stabilizer are used before, during and after particle formation.
After, washing process, during dispersion after washing, before chemical sensitization, chemical sensitization
Medium, after chemical sensitization, at various times before application, depending on purpose
Can be added. Added during emulsion preparation
Besides exhibiting anti-fogging and stabilizing effect,
Control walls, reduce particle size, particle solubility
Control chemical sensitization, control dye sequence
It can be used for multiple purposes. The photosensitive material relating to the present technology includes the above-mentioned various types.
Other additives, but other than these,
Various additives can be used. These additives are
More details: Research Disclosure Item 176
43 (December 1978), Item 18716 (19
November 1979) and Item 308119 (1989)
December), and the corresponding locations are listed in the table below.
Shown together.   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 sensitizers, 23-24 pages, 648 pages, right column-996 right-998 right     Supersensitizer 649 pages, right column 4 Whitening agent 24 pages 998 right 5 Antifoggant 24-25 pages 649 right column 998 right-1000 right     And stabilizers 6 Light absorber, 25-26 pages, 649 pages, 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 pages 1002 right 9 Hardener 26 pages 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 pages 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     Inhibitor 14 Matting agent 1008 left to 1009 left If the emulsion is used in the light-sensitive material of the present invention,
It can be used for photographic materials using the emulsion.
Layer alignment technology, silver halide emulsions, dye-forming caps
Functional couplers such as couplers and DIR couplers, various additives
Regarding the agent and the development processing, European Patent No. 05650
96A1 (released October 13, 1993) and this
It is described in the cited patent. Below are each item and this
List the locations corresponding to. 1. Layer structure: 61 pages 23 to 35 lines, 61 pages 41 lines to 62 lines
Page 14 line, 2. Middle layer: 61 pages 36-40 lines, 3. Multilayer effect imparting layer: 62 pages 15 to 18 lines, 4). Silver halide halogen composition: 62 pages 21-25 lines, 5). Silver halide grain habit: page 62 lines 26-30, 6). Silver halide grain size: 62 pages 31 to 34, 7). Emulsion production method: 62 pages 35 to 40 lines, 8). Silver halide grain size distribution: 62 pages 41-42
line, 9. Tabular grains: 62 pages 43-46, Ten. Particle internal structure: 62 pages 47 lines to 53 lines, 11． Emulsion latent image formation type: 62 pages 54 lines to 63 pages 5
line, 12． Physical ripening / chemical ripening of emulsion: 63 pages, lines 6 to 9, 13. Emulsion mixed use: 63 pages, lines 10 to 13, 14. Kabaze emulsion: page 63, lines 14 to 31 15． Non-photosensitive emulsion: p. 63, lines 32-43, 16． Amount of coated silver: 63 pages 49-50 lines 17. Photo additives: Research Disclosure
-Ja (RD) Item 17643 (December 1978),
Item 18716 (November 1979) and Item 30
7105 (November 1989)
Shows each item and its related description.   Type of additive RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 page 648 right column page 866 2 Sensitivity increasing agent Page 648, right column 3 Spectral sensitizer, pages 23-24, page 648, right column, pages 866-868     Supersensitizer-page 649, right column 4 Whitening agent page 24 page 647 right column page 868 5 Antifoggant, 24-25 pages, 649 pages, right column, 868-870 pages     Stabilizer 6 Light Absorber, pages 25-26, page 649, right column, page 873     Filter dye, 650 pages, left column     UV absorber 7 Stain inhibitor page 25 right column 650 left column to right column 872 8 Dye image stabilizer page 25 page 650 left column page 872 9 Hardener 26 pages 651 left column 874-875 10 Binder page 26 page 651 left column pages 873-874 11 Plasticizer, lubricant page 27 page 650 right column page 876 12 Coating aid, pages 26-27, page 650, right column, pages 875-876     Surfactant 13 Static 27 pages 650 right column 876-877 pages     Inhibitor 14 Matting agent 878-879 pages 18. Formaldehyde scavenger: 6
Page 4, lines 54-57, 19. Mercapto-type antifogging agent: 65 pages, 1-2 lines, 20． Release agent such as fogging agent: page 65, lines 3 to 7, twenty one. Dye: 65 pages 7-10 lines, twenty two. Color couplers in general: 65 pages, lines 11-13 twenty three. Yellow, magenta and cyan couplers: page 65 1
4-25 lines, twenty four. Polymer coupler: page 65, lines 26 to 28, twenty five. Diffusible dye-forming coupler: page 65, lines 29-31, 26. Colored coupler: 65 pages 32 to 38 lines, 27. Functional couplers in general: 65 pages 39-44, 28. Bleach accelerator releasing coupler: 65 pages 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: page 65 line 54 to page 66 4
line, 31. Coupler dispersion method: page 66, lines 5 to 28, 32. Preservatives and fungicides: 66 page 29-33, 33. Type of photosensitive material: 66 page 34-36, 34. Photosensitive layer thickness and swelling speed: 66 pages 40 lines to 67 pages 1
line, 35. Back layer: 67 pages 3-8 lines, 36. General development processing: 67 pages 9-11 lines, 37. Developer and developer: 67 pages 12-30 lines, 38. Developer additive: page 67, lines 31-44, 39. Inversion processing: 67 pages 45 to 56 lines, 40. Treatment liquid opening ratio: 67 pages 57 lines to 68 pages 12 lines, 41. Development time: 68 pages 13-15 lines, 42. Bleach fixing, bleaching, fixing: 68 pages 16 lines to 69 pages 31
line, 43. Automatic processor: 69 pages 32-40 lines, 44. Washing, rinsing, stabilization: 69 pages 41 lines to 70 pages 18
line, 45. Treatment liquid replenishment, reuse: page 70, lines 19-23 46. Built-in developer sensitive material: page 70, lines 24 to 33, 47. Development processing temperature: page 70, lines 34-38, 48. Application to lens film: 70 pages 39-41 lines Also described in European Patent No. 602600.
2-pyridinecarboxylic acid or 2,6-pyridine
Ferric salts such as dicarboxylic acid and ferric nitrate, and persulfate
A bleaching solution containing an acid salt can also be preferably used. This bleach
In the use of liquid, it is between the color development process and the bleaching process.
It is preferable to intervene a stop process and a water washing process,
Stopper solution contains organic acid such as acetic acid, succinic acid, maleic acid
It is preferable to use it. In addition, this bleach solution contains p
Acetic acid, succinic acid, maleic for H adjustment and bleach fog
Organic acids such as acid, glutaric acid, adipic acid, etc.
2 mol / liter (hereinafter, liter is also expressed as “L”)
It is preferable to make it contain in the range of. [0078] Examples of the present invention will be described below. However, this
It is not limited to the examples. (Example 1) In this example, a photosensitive silver halide emulsion was used.
The aspect ratio of the silver halide grains is increased.
By increasing the area and increasing the amount of spectral sensitizing dye added
When the sensitivity is increased by increasing the amount of light absorption,
Of light-sensitive material containing silver halide emulsion
When exposed to gas (such as automobile exhaust)
Indicates that there is a problem that causes fogging, and at the same time this problem
Is remarkably solved by the means disclosed in the present invention.
Show. (Em-A Production Method / Aspect Ratio 6, Reduction)
No sensitization) Low molecular weight gelatin with a molecular weight of 25000 0.
1200 milliliters of aqueous solution containing 75g, KBr, 0.9g
Tuttle (Hereinafter, milliliter is also expressed as "mL")
At 35 ° C, adjust pH to 1.8 and stir vigorously
It was. AgNO_ThreeAn aqueous solution containing 0.45 g and 1.5 mo
1% aqueous KBr solution containing 1% KI
Added over 6 seconds. At this time, excess KBr concentration should be reduced.
Kept constant. The temperature was raised to 75 ° C. and aging was performed. 1 after maturing
1 molecular weight containing 35 μmol methionine per g
20 g of 00000 gelatin was added. PH 5.9
Then, 1.9 g of KBr was added. AgNO
_Three, 288 mL of aqueous solution containing 28.8 g and KBr aqueous solution
Was added over 53 minutes by the double jet method. this
When an AgI fine grain emulsion having a grain size of 0.03 μm was added
Simultaneously added so that the silver halide content is 4.1 mol%
And the silver potential is -30 mV to the saturated calomel electrode.
Kept. After adding KBr, 1.5 g, AgN
O_Three, Double the aqueous solution containing 87.7g and KBr aqueous solution
The final flow rate is 1.2 times the initial flow rate by the jet method.
The flow rate was accelerated to 57 minutes and added over 57 minutes. At this time,
AgI fine grain emulsion having a silver iodide content of 8.5 mol%
And add the silver potential
It was kept at -30 mV. AgNO_ThreeWater containing 41.8g
132mL of solution and KBr aqueous solution are 2
Added over 5 minutes. + 20mV at the end of the addition
The addition of the aqueous KBr solution was adjusted so that benzene
After adding 2 mg of sodium thiosulfonate, KB
r was added to adjust the silver potential to -70 mV, and the above Ag
5.73 g of I fine grain emulsion was added in terms of KI mass. Attendant
Immediately after addition, AgNO_ThreeAqueous solution containing 66.4 g
609 mL was added over 10 minutes. 6 minutes at the beginning of addition
In the meantime, the silver potential was kept at -70 mV with an aqueous KBr solution. Flushing
After that, gelatin was added, pH 6.5 at 40 ° C., pA
g, adjusted to 8.2. (Em-B Manufacturing Method / Aspect Ratio 15, Return
No original sensitization) Low molecular weight gelatin with a molecular weight of 25000
1200 mL of an aqueous solution containing 75 g, KBr, and 0.9 g
While maintaining at 35 ° C., the pH was adjusted to 1.8 and vigorously stirred.
AgNO_ThreeAn aqueous solution containing 0.45 g and 1.5 mol%
KBr aqueous solution containing KI of 16 seconds by double jet method
Added in between. At this time, the excessive concentration of KBr is kept constant.
Kept. The temperature was raised to 75 ° C. and aging was performed. 1g after completion of aging
1000 molecular weight containing 5 μmol of methionine
20 grams of 00 phthalated gelatin was added. 4. PH
After adjusting to 9, KBr, 1.9 g was added. AgN
O_Three, 288 mL aqueous solution containing 28.8 g and KBr aqueous solution
The solution was added over 53 minutes by the double jet method. this
When an AgI fine grain emulsion having a grain size of 0.03 μm was added
Simultaneously added so that the silver halide content is 4.1 mol%
And the silver potential is -30 mV to the saturated calomel electrode.
Kept. After adding KBr, 3.5 g, AgN
O_Three, Double the aqueous solution containing 87.7g and KBr aqueous solution
The final flow rate is 1.2 times the initial flow rate by the jet method.
The flow rate was accelerated to 57 minutes and added over 57 minutes. At this time,
AgI fine grain emulsion having a silver iodide content of 8.5 mol%
And add the silver potential
It was kept at −50 mV. AgNO_ThreeWater containing 41.8g
132mL of solution and KBr aqueous solution are 2
Added over 5 minutes. +10 mV at the end of the addition
The addition of the aqueous KBr solution was adjusted so that benzene
After adding 2 mg of sodium thiosulfonate, KB
r was added to adjust the silver potential to -70 mV, and the above Ag
5.73 g of I fine grain emulsion was added in terms of KI mass. Attendant
Immediately after addition, AgNO_ThreeAqueous solution containing 66.4 g
609 mL was added over 10 minutes. 6 minutes at the beginning of addition
In the meantime, the silver potential was kept at -70 mV with an aqueous KBr solution. Flushing
After that, gelatin was added, pH 6.5 at 40 ° C., pA
g, adjusted to 8.2. (Em-C Manufacturing Method / Aspect Ratio 15, Return
Original sensitization) Low molecular weight gelatin with molecular weight 25000
1200m aqueous solution containing 0.75g, KBr, 0.9g
Keep L at 35 ° C, adjust pH to 1.8 and stir vigorously
It was. AgNO_ThreeAn aqueous solution containing 0.45 g and 1.5 mo
1% aqueous KBr solution containing 1% KI
Added over 6 seconds. At this time, excess KBr concentration should be reduced.
Kept constant. The temperature was raised to 75 ° C. and aging was performed. 1 after maturing
10 molecular weight containing 5 μmol methionine per g
20 g of 0000 phthalated gelatin was added. pH
After adjusting to 5.9, KBr, 1.9 g, was added. Return
Aqueous solution 20 containing 4 mg of original sensitizer and thiourea dioxide
After adding mL, AgNO_ThreeWater solution containing 28.8 g
288 mL of liquid and KBr aqueous solution were mixed 53 by the double jet method.
Added over a minute. At this time, the particle size is 0.03 μm.
AgI fine grain emulsion having a silver iodide content of 4.1 mol%
At the same time so that the silver potential is saturated calomel
It was kept at −30 mV with respect to the electrode. KBr, 3.5g
After addition, AgNO_ThreeAn aqueous solution containing 87.7 g and K
The final flow rate of Br aqueous solution is double jet method.
Accelerate the flow rate to 1.2 times and add over 57 minutes
did. At this time, the above AgI fine grain emulsion contains silver iodide.
At the same time, the flow rate is accelerated so that the rate is 8.5 mol%.
And the silver potential was kept at -50 mV. AgNO_Three,
Add 132 mL of aqueous solution containing 41.8 g and KBr aqueous solution.
It added over 25 minutes by the bull jet method. At the end of addition
Add the KBr aqueous solution so that the potential of the electrode becomes +10 mV.
It was adjusted. Sodium benzenethiosulfonate, 2mg
After adding KBr, the silver potential is -70 mV
4. Prepare the above-mentioned AgI fine grain emulsion in terms of KI mass.
73 g was added. Immediately after the addition, AgNO_Three, 6
Add 609 mL of aqueous solution containing 6.4 g over 10 minutes
did. The silver potential is -7 with KBr aqueous solution for the first 6 minutes of addition
It was kept at 0 mV. After washing with water, add gelatin and add 40 ℃
To pH 6.5, pAg, 8.2. Transmission type electricity at liquid nitrogen temperature of Em-A to C
From the microscopic observation, the dislocation lines in all the emulsions are free from grains.
Are observed at high density in the area of the
It had 20 or more level lines. The equivalent circle diameter of Em-A is
1.23 μm, its coefficient of variation is 17%, thickness is 0.2O5 μm
m, its coefficient of variation is 15%, and 99% of the total projected area is
Occupied by tabular grains. Em-B, C circular phase
This diameter is 1.67 μm, its coefficient of variation is 19%, thickness is 0.1
11 μm, its coefficient of variation is 15%, and 9% of the total projected area
9% was occupied by tabular grains. Em-A side
Is the (100) surface ratio of the surface a method using adsorption of a sensitizing dye?
20%. It was 14% in Em-B and C.
The particle cross-section obtained by cutting with a diamond cutter is also transparent.
From the observation with a scanning electron microscope, each particle has two twin planes.
The interval was 0.013 μm and the coefficient of variation was 19%. XP
When the silver iodide content on the grain surface was measured by the S method,
m-A is 3.1 mol%, and Em-B and Em-C are 4.5 mol.
Le%. (Chemical and spectral sensitization of Em-A to C) E
The temperature of m-A was raised to 56 ° C. Sensitizing dye Exs-1-1,
Halates Exs-1-2 and Exs-1-3
4.3 x 10 per mole of silver^-FourMol, 1.9 × 10^-FourMo
Le, 0.9 × 10^-FourMole was added. Then halogenated
3.3 × 10 potassium thiocyanate per mole of silver^-3Mo
And chloroauric acid 1.9 × 10^-6Mole, sodium thiosulfate
2.4 × 10^-6Mole, N, N-dimethylselenourea
3.9 × 10^-6Mole added and matured for optimal chemical sensitization
It was. At the end of chemical sensitization, compound 1 is further converted to 1 silver halide.
2.9 x 10 per ru^-FourMole was added. Em-B, C
For Em-A, sensitizing dye, chloroauric acid, sodium thiosulfate
Thorium, N, N-dimethylselenourea amount of 1.9
The procedure was the same except that the change was doubled. [0084] [Chemical Formula 3] [0085] [Formula 4] [0086] [Chemical formula 5] Compound 1 [Chemical 6] Cellulose triacetate film provided with an undercoat layer
The above film coating conditions are as shown in Table 1 below.
Emulsion Em-A to C with chemical sensitization applied with protective layer
Samples 101 to 103 were prepared. [0089] [Table 1]The protective layer gelatin is pullulan (average molecular weight).
50,000 to 100,000) in 0.1% by mass,
Emulsions Em-A to C in the same way, replacing 50, 100%
Apply and sample 111-113, 121-123, 131
-133 and 141-143 were made. These samples
Left at 40 ° C and 70% relative humidity for 14 hours
It was. After that, a gelatin filter manufactured by FUJIFILM Corporation
1/100 second exposure through SC-50 and continuous wedge
did. Further, these coated samples are generated by combustion.
For gas (exhaust gas from gasoline car in this example)
The degree of fog generated by exposure is as follows.
The method was evaluated. As a fuel, Showa Shell Sekiyu KK
Regular gasoline made by SITA, Nissan Motor
Co., Ltd. E-S14, engine is idling
(Motor speed 1000 rpm)
Gas collected from the outlet of the exhaust pipe
In addition, the temperature is adjusted to 25 ° C, 1 atm, and relative humidity 60%.
And unexposed in the space filled with the adjusted gas.
The coated sample was left for 20 hours. And then similarly
Exposed. Negative processor manufactured by Fuji Photo Film Co., Ltd.
Using FP-350, the method described below (cumulative solution compensation)
Process until the charge is 3 times the mother liquor tank capacity)
It was.   (Processing method)     Process Processing time Processing temperature Replenishment amount   Color development 3 minutes 15 seconds 38 ° C 45 mL   White drift 1 minute 00 seconds 38 ℃ 20mL                                               Bleach solution overflow                                               Full flow into bleach-fixing tank   Bleach fixing 3 minutes 15 seconds 38 ° C 30mL   Flushing (1) 40 seconds From 35 ℃ (2) to (1)                                                 Counterflow piping system   Washing with water (2) 1 min 00 sec 35 ° C 30 mL   Stable 40 seconds 38 ° C 20 mL   Drying 1 min 15 sec 55 ° C     * Replenishment amount is 35mm width per 1.1m length (equivalent to 24Ex.1) Next, the composition of the treatment liquid will be described.   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 1.0 1.1   1-hydroxyethylidene-1,1-diphosphonic acid                                              2.0 2.0   Sodium sulfite 4.0 4.4   Potassium carbonate 30.0 37.0   Potassium bromide 1.4 0.7   Potassium iodide 1.5mg −   Hydroxylamine sulfate 2.4 2.8   4- [N-ethyl-N- (β-hydroxyethyl) amino]     -2-Methylaniline sulfate 4.5 5.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.10 [0094]   (Bleaching solution) Common for tank solution and replenisher solution (Unit: g)   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 20.0   Ethylenediaminetetraacetic acid disodium salt 10.0   Ammonium bromide 100.0   Ammonium nitrate 10.0   Bleach accelerator 0.005 mol    (CH_Three)₂N-CH₂-CH₂-S-S-CH₂-CH₂-N (CH_Three)₂・ 2HCl   Ammonia water (27%) 15.0mL   1.0L with water   pH (adjusted with ammonia water and nitric acid) 6.3 [0095]   (Bleaching fixer) Tank solution (g) Replenisher (g)   Ethylenediaminetetraacetic acid ferric ammonium ammonium dihydrate                                             50.0 −   Ethylenediaminetetraacetic acid disodium salt 5.0 2.0   Sodium sulfite 12.0 20.0   Ammonium thiosulfate aqueous solution (700 g / L)                                           240.0 mL 400.0 mL   Ammonia water (27%) 6.0 mL −   Add water 1.0 L 1.0L   pH (adjusted with aqueous ammonia and acetic acid) 7.2 7.3 (Washing solution) Common to tank solution and replenisher solution Tap water is converted into an H-type strongly acidic cation exchange resin (Rohm and Ha
Amberlite IR-120B manufactured by Seuss Corporation and OH type
Filled with Nion exchange resin (Amberlite IR-400)
Calcium and Magnesium by passing water through a packed bed column
Treatment of um ion concentration to 3 mg / L or less, followed by dichloride
Sodium isocyanurate 20mg / L and sodium sulfate
0.15 g / L was added. The pH of this solution is 6.5-
It was in the range of 7.5. [0097]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether     (Average polymerization degree 10) 0.2   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 L   pH 8.5 Measure the concentration of the processed sample with a green filter
did. The obtained results are shown in Table 2 below. Sensitivity is foggy
It was displayed as a relative value of degree plus 0.2. [0099] [Table 2] As is apparent from Table 2, the photosensitive material of the present invention.
Remarkably burns by containing pullulan in the protective layer
Increased fog and decreased sensitivity to gas generated in
It is. The mass% of pullulan to gelatin is 10%.
% Or more, the effect is remarkable and there is almost no decrease in sensitivity.
However, in the samples 141 to 143 whose mass% is 100%
The sample after development was hazy. Also, Em-A to C
From the comparison of the results, the effect of the present invention is the high aspect ratio emulsion and the return
It is significantly larger than the original sensitized emulsion. Example 2 The following emulsion preparation was used as a dispersion medium.
Gelatin-1 to 4 used in the above are gelatins having the following attributes:
It is   Gelatin-1: Normal alkali-treated ossein gelatin made from beef bone                 -NH in gelatin₂No chemical modification of   Gelatin-2: Anhydrous gelatin-1 aqueous solution at 50 ° C. and pH 9.0                 After phthalic acid is added and chemically reacted, residual phthalic acid is removed                 Dried gelatin                 -NH in gelatin₂95% of the number of chemically modified groups   Gelatin-3: anhydrous in an aqueous solution of gelatin-1 at 50 ° C. and pH 9.0                 After trimellitic acid was added to cause a chemical reaction, the remaining trimelli                 Gelatin that has been dried by removing tutonic acid                 -NH in gelatin₂95% of the number of chemically modified groups   Gelatin-4: An enzyme is allowed to act on gelatin-1 to lower the molecular weight, and the average molecular weight is                 Gelatin after drying to 15000 after inactivating the enzyme                 -NH in gelatin₂No chemical modification of groups The above gelatin-1 to 4 were all deionized.
After that, the pH of the 5% aqueous solution at 35 ° C will be 6.0.
Adjustments were made. The silver halide emulsions D to R were prepared by the following process.
Was prepared. (Em-D production method) 97% phthalated fraction
31.7 g of low molecular weight gelatin with a molecular weight of 15000, KBr
Keep 42.2L of aqueous solution containing 31.7g at 35 ℃
Agitate. AgNO_Three, 316.7g containing aqueous solution 1
583mL and KBr, 221.5g, gelatin-4
Double solution of 1583 mL of aqueous solution containing 52.7 g of latin
It was added over 1 minute by the wet method. Immediately after the addition
Add KBr 52.8g and add AgNO_Three398.2 g
Aqueous solution containing 2485mL and KBr, 291.1g
2581 mL of aqueous solution passed over 2 minutes by the double jet method
Added. Immediately after the addition, 44.8 g of KBr
Added. Then, it heated up to 40 degreeC and matured. Matured
After completion, 923g of gelatin-2 and KBr, 79.2g
Add AgNO_ThreeAqueous solution 1594 containing 5103 g
The final flow rate of 7 mL and KBr aqueous solution by the double jet method
10 minutes after accelerating the flow rate to 1.4 times the initial flow rate
Was added over time. At this time, the silver potential is applied to the saturated calomel electrode.
On the other hand, it was kept at -60 mV. After washing with water, add gelatin.
PH 5.7, pAg, 8.8, per kg of emulsion
Silver equivalent mass 131.8g, gelatin mass 64.1g
A seed emulsion was prepared. 46 g of gelatin-2, KBr
Keep 1211 mL of an aqueous solution containing 1.7 g at 75 ° C.
Agitate. After adding 9.9 g of the above-mentioned seed emulsion,
Silicon oil (Nihon Unicar Co., Ltd. product, L760
0.3 g of 2) was added. H₂SO_FourTo adjust the pH
After adjusting to 5.5, AgNO_Three  Water solution containing 7.0g
67.6 mL of liquid and KBr aqueous solution
Accelerate the flow rate so that the final flow rate is 5.1 times the initial flow rate.
Added over 6 minutes. At this time, the silver potential is saturated with calomel.
It was kept at -20 mV to the electrode. Benzenethiosulfo
Add 2 mg sodium phosphate and 2 mg thiourea dioxide
After that, AgNO_ThreeAn aqueous solution containing 105.6 g, 328
The final flow rate of mL and KBr aqueous solution is the first by the double jet method.
Accelerates the flow rate to 3.7 times the initial flow rate, and in 56 minutes
Added over. At this time, the particle size of 0.037 μm
The silver iodide content of the AgI fine grain emulsion was 27 mol%.
So that the flow rate is accelerated at the same time and the silver potential is saturated.
It was kept at −50 mV with respect to the calomel electrode. AgN
O_Three, 45.6 g of aqueous solution containing 121.3 mL and KBr
The aqueous solution was added over 22 minutes by the double jet method.
At this time, the silver potential is +20 mV to the saturated calomel electrode.
Kept. Increase the temperature to 82 ° C and add KBr to increase the silver potential.
After adjusting to −80 mV, the aforementioned AgI fine grain emulsion was
6.33 g was added in terms of KI mass. Immediately after the addition
And AgNO_ThreeAn aqueous solution containing 66.4 g, 206.2 m
L was added over 16 minutes. KB for 5 minutes at the beginning of addition
The silver potential was kept at −80 mV with the aqueous r solution. After washing with water
Gelatin-1 was added and the pH was 5.8 at 40 ° C., pAg,
Adjusted to 8.7. After adding Compound 2 below, 60
The temperature was raised to ° C. Add sensitizing dyes Exs-2 and Exs-3
After addition, potassium thiocyanate, chloroauric acid, thiosulfate
Add sodium acid, N, N-dimethylselenourea
Optimum chemical sensitization. Compound 3 listed later at the end of chemical sensitization
And Compound 4 was added. Here, optimal chemical sensitization
Means sensitizing dye and each compound as silver halide 1mo
10 per l^-1To 10^-8Select from a range of mol addition
Means that Compound 2 [Chemical 7] Compound 3 [Chemical 8] Compound 4 [Chemical 9] [0106] Embedded image [0107] Embedded image (Method for producing Em-E) Gelatin-4 was changed to 0.9.
4 1192 mL of an aqueous solution containing 6 g, KBr, and 0.9 g
Maintained at 0 ° C. and stirred vigorously. AgNO_Three1.49g
Water containing 37.5 mL of aqueous solution containing 1.05 g of KBr
37.5 mL of solution over 30 seconds by double jet method
Added. After adding 1.2g of KBr, the temperature was raised to 75 ° C.
And matured. After ripening, add 35g of gelatin-3
And the pH was adjusted to 7. With 6mg of thiourea dioxide
Added. AgNO_Three116 mL of an aqueous solution containing 29 g
Final flow rate of KBr aqueous solution by double jet method is initial flow rate
The flow rate was accelerated so as to be 3 times as much as that. At this time, silver
The potential was kept at −20 mV with respect to the saturated calomel electrode.
AgNO_Three440.6 mL of an aqueous solution containing 110.2 g
And KBr aqueous solution with double jet method, final flow is initial flow
Accelerate the flow rate to be 5.1 times the amount for 30 minutes
Added. At this time, the AgI fine particles used in the preparation of Em-D
The grain emulsion has a silver iodide content of 15.8 mol%
At the same time, the flow rate is accelerated and added, and the silver potential is saturated
It was kept at 0 mV relative to the mel electrode. AgNO_Three24.
Double 16.5g aqueous solution containing 96.5mL and KBr aqueous solution
It added over 3 minutes by the jet method. At this time, the silver potential
It was kept at 0 mV. Sodium ethylthiosulfonate, 2
After adding 6 mg, the temperature was lowered to 55 ° C., and the KBr aqueous solution was added.
The silver potential was added to adjust to -90 mV. AgI mentioned above
8.5 g of the fine grain emulsion was added in terms of KI mass. End of addition
Immediately after completion, AgNO_Three  228m aqueous solution containing 57g
L was added over 5 minutes. At this time, the potential at the end of the addition
Was adjusted with an aqueous KBr solution so as to be +20 mV. E
It was washed with water in the same manner as m-D and chemically sensitized. (Method for producing Em-F) Gelatin-2 was changed to 1.0.
35 g of 1192 mL of an aqueous solution containing 2 g of KBr and 0.9 g of KBr
Keep at ℃ and stir vigorously. AgNO_Three4.47g
Aqueous solution containing 42mL and KBr, 3.16g water solution
Add 42 mL of liquid over 9 seconds by double jet method
It was. After adding 2.6 g of KBr, the temperature was raised to 63 ° C.
Made. After ripening, 41.2g of gelatin-3 and Na
Cl, 18.5 g was added. The pH was adjusted to 7.2
Later, 8 mg of dimethylamine borane was added. AgN
O_Three, 26 mL of an aqueous solution containing 26 g and an aqueous KBr solution
The final flow rate is 3.8 times the initial flow rate with the double jet method.
Were added as such. At this time, silver potential is saturated with calomel electrode
Against -30 mV. AgNO_Three110.2
Double the aqueous solution 44g mL containing g and the aqueous KBr solution
The final flow rate is 5.1 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 24 minutes. At this time, Em
-AgI fine grain emulsion used in preparation of -D contains silver iodide
At the same time, the flow rate is accelerated so that the rate is 2.3 mol%.
And a silver potential of −20 m with respect to the saturated calomel electrode
V kept. 1N aqueous potassium thiocyanate solution10.
After adding 7 mL, AgNO_ThreeWater containing 24.1 g
153.5mL of solution and KBr aqueous solution are double jet
For 2 minutes 30 seconds. At this time, the silver potential is 10
It was kept at mV. Add KBr aqueous solution to reduce silver potential to -70
Adjusted to mV. The above-mentioned AgI fine grain emulsion is KI mass
6.4 g was added in terms of conversion. Immediately after the addition, AgNO
_Three, And added 404 mL of an aqueous solution containing 57 g over 45 minutes
Added. At this time, the potential at the end of the addition becomes -30 mV.
As described above, it was adjusted with a KBr aqueous solution. Almost the same as Em-D
Washed with water and chemically sensitized. (Method for producing Em-G) In the preparation of Em-F
AgNO during nucleation_ThreeThe addition amount was changed to 2.3 times.
And the final AgNO_ThreeAqueous solution 404 containing 57 g
KB so that the potential at the end of the addition of mL is +90 mV
Changed to adjust with aqueous solution. Otherwise, Em-
Prepared in substantially the same manner as F. (Method for producing Em-H) Gelatin-4 was changed to 1.1.
g, 35 mL of 1200 mL of an aqueous solution containing 0.97 g of KBr
The temperature was maintained at 0 ° C., the pH was adjusted to 6.0 and the mixture was vigorously stirred. Ag
NO_Three, Aqueous solution containing 1.85 g and KBr, 1.52 g
Add the aqueous solution containing for 30 seconds by the double jet method
did. At this time, the excessive concentration of KBr was kept constant. 75
The temperature was raised to ° C and aging was performed. After ripening, add 3 gelatin-3
5 g was added. After adjusting the pH to 5.9, KBr,
6.5 g was added. AgNO_ThreeWater containing 30.0g
144 mL of solution and 1 KBr aqueous solution are added by double jet method.
Added over 1 minute. Continue to AgNO_Three109.
340 mL of an aqueous solution containing 5 g and 3.29 mol% KI
Contains KBr aqueous solution for 35 minutes by double jet method
Added. Furthermore, AgNO_ThreeAqueous solution containing 27 g and KBr
Aqueous solution with double jet method and saturated calomel with silver potential
It was kept at −20 mv with respect to the electrode. Then drop the temperature to 40 ℃
4-iodoacetamidobenzenesulfonic acid sodium
Um and sodium sulfite per mole of silver
4.0 × 10^-2Mol, 4.8 × 10^-2Mole added, Na
OH was added to adjust the pH to 9.0. After this, 55 ° C
And the pH was adjusted to 5.5. Immediately after that, Ag
NO_Three200 mL of an aqueous solution containing 70.0 g for 20 minutes
Was added over time. During the addition, the silver potential is adjusted to 35 with an aqueous KBr solution.
It was kept at mV. In addition, 0.2g of yellow blood salt is included during this addition
100 mL of an aqueous solution was added. After washing with water, gelatin-1
And adjusted to pH 6.5, pAg, 8.2 at 40 ° C.
It was. Chemical sensitization was carried out in substantially the same manner as Em-C in Example 1. Na
The amount of sensitizing dye used is as follows:
Exs-1-1 is 1.08 × 10^-3Mole, Exs-4
2.56 × 10^-FourMole, Exs-5 is 9.16 × 10^-Five
Is a mole. [0112] Embedded image [0113] Embedded image(Preparation of Em-I) Gelatin-4 was changed to 0.7
3 mL of aqueous solution containing 5 g, KBr, 0.9 g
While maintaining at 9 ° C., the pH was adjusted to 1.8 and stirred vigorously. A
gNO_ThreeAn aqueous solution containing 1.85 g and 1.5 mol%
KBr aqueous solution containing KI for 16 seconds by double jet method
Was added over time. At this time, the excessive concentration of KBr is kept constant.
It was. The temperature was raised to 54 ° C. and aging was performed. After aging, gelatin
-2 was added in an amount of 20 g. After adjusting the pH to 5.9,
KBr, 2.9 g was added. AgNO_Three27.4g
Double-jet solution containing 288 mL of aqueous solution and KBr aqueous solution
Added over 53 minutes. At this time, the particle size
0.03 μm AgI fine grain emulsion with silver iodide content
4.1 mol% at the same time and silver potential
Was kept at -60 mV to a saturated calomel electrode. KB
After adding 2.5 g of r, AgNO_Three, 87.7g
Final flow of aqueous solution containing KBr and aqueous solution of KBr
The flow rate is accelerated so that the amount becomes 1.2 times the initial flow rate.
Added over a minute. At this time, the above-mentioned AgI fine grain emulsion
At the same time so that the silver iodide content is 10.5 mol%
Added at an accelerated flow rate and the silver potential is kept at -70 mV.
It was. AgNO_Three132 mL of an aqueous solution containing 41.8 g
Add KBr aqueous solution over 25 minutes by double jet method
did. KB so that the potential at the end of the addition is +20 mV
The addition of aqueous r solution was adjusted. Adjust the pH to 7.3 and
1 mg of oxidized thiourea was added. Add KBr to silver
After adjusting the potential to -70 mV, the above AgI fine particle milk
5.73 g of the agent was added in terms of KI mass. After the addition,
Immediately AgNO_Three, 609 mL of an aqueous solution containing 66.4 g
Was added over 10 minutes. KBr for the first 6 minutes of addition
The silver potential was kept at -70 mV with an aqueous solution. After washing with water
Add latin-1 to pH 6.5 at 40 ° C., pAg, 8.
Adjusted to 2. Chemical sensitization was performed in substantially the same manner as Em-H. Na
The amount of sensitizing dye used is as follows:
Exs-1-1 is 1.08 × 10^-3Mole, Exs-4
2.56 × 10^-FourMole, Exs-5 is 9.16 × 10^-Five
Is a mole. (Method for producing Em-J) Gelatin-4 was changed to 0.7.
0g, KBr, 0.9g, KI, 0.175g, Em-
Contains 0.2 g of modified silicone oil used in the preparation of D
Maintain 1200 mL of aqueous solution at 33 ° C and adjust pH to 1.8
And stirred vigorously. AgNO_Three, 1.8g water-soluble
Solution and KBr aqueous solution containing 3.2 mol% KI
It was added over 9 seconds by the jet method. At this time, KBr
The excess concentration was kept constant. The temperature was raised to 62 ° C. and aging was performed. Ripe
After completion of the synthesis, 27.8 g of gelatin-3 was added. pH
Was adjusted to 6.3, and then KBr, 2.9 g, was added.
AgNO_Three270 mL of an aqueous solution containing 27.58 g and K
Add Br aqueous solution over 37 minutes by double jet method
It was. At this time, an aqueous solution of gelatin-4 and AgNO_ThreeAqueous solution
And KI aqueous solution described in Japanese Patent Application No. 8-207219
In a separate chamber with a coupling induction stirrer
Particle size prepared by mixing immediately before addition 0.008 μm
AgI fine grain emulsion having a silver iodide content of 4.1 mol%
At the same time so that the silver potential is saturated calomel
It was kept at −60 mV with respect to the electrode. KBr 2.6g
After addition, AgNO_ThreeAn aqueous solution containing 87.7 g and K
The final flow rate of Br aqueous solution is double jet method.
3. Accelerate the flow rate so that it is 1 time and add over 49 minutes
did. At this time, Ag prepared by mixing immediately before the above addition
I fine grain emulsion has a silver iodide content of 7.9 mol%
The flow rate is accelerated at the same time and the silver potential is kept at -70 mV.
It was. After adding 1 mg of thiourea dioxide, AgNO
_Three132mL aqueous solution containing 41.8g and KBr aqueous solution
Was added over 20 minutes by the double jet method. End of addition
Add the KBr aqueous solution so that the electric potential at the end is +20 mV.
Adjusted. Raise the temperature to 78 ° C and adjust the pH to 9.1
After that, KBr was added to bring the potential to −60 mV. Em
-IgI fine grain emulsion used in preparation of -D was converted to KI mass
5.73 g was added. Immediately after the addition, AgN
O_Three321 mL of an aqueous solution containing 66.4 g
Added. For the first 2 minutes of addition, use a KBr aqueous solution with silver potential.
Was kept at -60 mV. Wash with water in the same way as Em-H,
Chemical sensitization. The amount of sensitizing dye used is halogenated.
Exs-1-1 is 1.25 x 10 per mole of silver.^-3Mo
Le, Exs-4 is 2.85 × 10^-FourMole, Exs-5
3.29 × 10^-FiveIs a mole. (Method for producing Em-K)
Aqueous solution containing 8g, KBr, 6.2g, KI, 0.46g
The liquid was kept at 45 ° C. and stirred vigorously. AgNO_Three11.
An aqueous solution containing 85 g and an aqueous solution containing 3.8 g of KBr
It added over 45 seconds by the bull jet method. Rise to 63 ° C
After warming, 24.1 g of gelatin-1 was added and aged.
After aging, AgNO_ThreeAn aqueous solution containing 133.4 g;
Final flow rate of KBr aqueous solution by double jet method is initial flow rate
It was added over 20 minutes to 2.6 times the amount. This
The silver potential is +40 mV to the saturated calomel electrode
Kept. 10 minutes after the start of addition ₂IrCl₆0.1
mg was added. After adding 7 g of NaCl, AgNO_Three
An aqueous solution containing 45.6 g and a KBr aqueous solution
Over 12 minutes. At this time, the silver potential is +
It was kept at 90 mV. Also, yellow for 6 minutes from the start of addition
100 mL of an aqueous solution containing 29 mg of blood salt was added. KB
After adding 14.4 g of r, it was used in the preparation of Em-D
6.3 g of AgI fine grain emulsion was added in terms of KI mass.
Immediately after the addition, AgNO_ThreeWater solution containing 42.7 g
Liquid and KBr aqueous solution for 11 minutes by double jet method
Added. At this time, the silver potential was kept at +90 mV. Em
It was washed with water and chemically sensitized in the same manner as -H. Sensitizing dye
Exs-1 is used per 1 mol of silver halide.
5.79 × 10^-FourMole, Exs-4 is 1.32 × 10^-Four
Mole, Exs-5 is 1.52 × 10^-FiveIs a mole. (Preparation of Em-L) Preparation of Em-K
Almost the same except that the temperature during nucleation was changed to 35 ° C.
Prepared. The amount of sensitizing dye used is halogenated.
Exs-1-1 is 9.66 × 10 6 per mole of silver.^-FourMo
Le, Exs-4 is 2.20 × 10^-FourMole, Exs-5
2.54 × 10^-FiveIs a mole. (Method for producing Em-M) Gelatin-4 was changed to 0.7.
3 mL of aqueous solution containing 5 g, KBr, 0.9 g
While maintaining at 9 ° C., the pH was adjusted to 1.8 and stirred vigorously. A
gNO_ThreeAn aqueous solution containing 0.34 g and 1.5 mol%
KBr aqueous solution containing KI for 16 seconds by double jet method
Was added over time. At this time, the excessive concentration of KBr is kept constant.
It was. The temperature was raised to 54 ° C. and aging was performed. After aging, gelatin
-2 was added in an amount of 20 g. After adjusting the pH to 5.9, K
Br, 2.9 g was added. Thiourea dioxide, 3mg
After addition, AgNO_ThreeAqueous solution 28 containing 28.8 g
8mL and KBr aqueous solution in 58 minutes by double jet method
Added over. At this time, Ag having a particle size of 0.03 μm
I fine grain emulsion has a silver iodide content of 4.1 mol%
And simultaneously add the bulk emulsion solution in the reaction vessel.
Keep silver potential at -60 mV to saturated calomel electrode
It was. After adding KBr, 2.5 g, AgNO
_Three, An aqueous solution containing 87.7 g and an aqueous KBr solution
The final flow rate is 1.2 times the initial flow rate by the jet method.
The flow rate was accelerated and added over 69 minutes. At this time,
AgI fine grain emulsion with silver iodide content of 10.5 mol%
At the same time, the flow rate is accelerated so that
Was maintained at -70 mV. AgNO_Three41.8
Double solution of 132mL aqueous solution containing g and aqueous KBr solution
Over the course of 27 minutes. Benzenethiosulfo
Sodium acetate 2 mg was added pH. Add KBr
After adjusting the silver potential to -70 mV, the above AgI fine
5.73 g of the grain emulsion was added in terms of KI mass. End of addition
Immediately after completion, AgNO_ThreeAn aqueous solution 60 containing 66.4 g
9 mL was added over 10 minutes. During the initial 6 minutes
The silver potential was kept at -70 mV with an aqueous KBr solution. Washed with water
Thereafter, gelatin-1 was added, pH 6.5 at 40 ° C., pA
g, adjusted to 8.2. Then, add compound 2 above
The temperature was raised to 56 ° C. Add sensitizing dyes Exs-1 and Exs-6
And then potassium thiocyanate, chloroauric acid, thiosulfur
Sodium acid, N, N-dimethylselenourea added
Aged and optimally chemically sensitized. At the end of chemical sensitization
Compound 3 and Compound 4 were added. Use of sensitizing dye
The dose is 3. Exs-1 per mol of silver halide.
69 × 10^-FourMole, Exs-6 is 8.19 × 10^-FourMole
It is. [0121] Embedded image (Method for producing Em-N) Gelatin-2 was changed to 0.3.
6 of 1200 mL of an aqueous solution containing 8 g, KBr, and 0.9 g
While maintaining at 0 ° C., the pH was adjusted to 2 and stirred vigorously. AgN
O_Three, 1.03 g of aqueous solution and KBr, 0.88 g,
An aqueous solution containing KI and 0.09 g is obtained by the double jet method.
Added over 0 seconds. After completion of aging, gelatin-3 is 1
2.8 g was added. After adjusting the pH to 5.9, KB
r, 2.99 g, NaCl₆6.2 g was added. A
gNO_Three60.7 mL of an aqueous solution containing 27.3 g and KB
Add the aqueous solution over 39 minutes by the double jet method.
It was. At this time, the silver potential is -50 with respect to the saturated calomel electrode.
It was kept at mV. AgNO_ThreeAn aqueous solution containing 65.6 g;
Final flow rate of KBr aqueous solution by double jet method is initial flow rate
Accelerate the flow rate to be 2.1 times that of 50 minutes
Added. At this time, AgI fine particles used in the preparation of Em-D
So that the silver iodide content is 6.5 mol%.
At the same time, the flow rate is accelerated and added, and the silver potential is set to -50 mV.
Kept. After adding 1.5 mg of thiourea dioxide, A
gNO_ThreeAqueous solution 132mL containing 41.8g and KBr
The aqueous solution was added over 16 minutes by the double jet method.
KBr water so that the silver potential at the end of the addition is +40 mV
Solution addition was adjusted. Benzenethiosulfonic acid sodium
After adding 2 mg of um, add KBr to increase the silver potential.
Adjusted to -100 mV. The above AgI fine grain emulsion was changed to K.
6.2 g in terms of I mass was added. Immediately after the addition, A
gNO_Three300 mL of an aqueous solution containing 88.5 g for 10 minutes
Added in between. The potential at the end of the addition is +60 mV
It adjusted by addition of KBr aqueous solution so that. After washing with water
Gelatin-1 was added, pH 6.5 at 40 ° C., pAg,
Adjusted to 8.2. After adding compound 2 above, 58
The temperature was raised to ° C. Sensitizing dyes Exs-7, Exs-8, Ex
After adding s-9, K₂IrCl₆, Potassium thiocyanate
Um, chloroauric acid, sodium thiosulfate, N, N-dimethyl
Ruselenourea was added for optimal chemical sensitization. Chemical sensitization
Upon completion, Compound 3 and Compound 4 listed above were added. [0123] Embedded image (Method for producing Em-O) Preparation of emulsion N
AgNO added during nucleation_ThreeTo 1.96 g, K
Br amount to 1.67g and KI amount to 0.172g.
The temperature during chemical sensitization was changed from 58 ° C to 6 ° C.
Changed to 1 ° C. Other than that, almost the same as Emulsion N
Prepared. (Method for producing Em-P) Gelatin-4 was 4.9.
g, KBr, 5.3 mL of aqueous solution 1200 mL 40
The mixture was kept at ℃ and stirred vigorously. AgNO_Three, Including 8.75g
Aqueous solution 3 containing 27 mL of aqueous solution and 6.45 g of KBr
6 mL was added by the double jet method over 1 minute. 7
After heating to 5 ° C, AgNO_Three, An aqueous solution containing 6.9 g
21 mL was added over 2 minutes. NH_FourNO_Three, 26
g After adding 1N, NaOH and 56 mL sequentially,
Made. After completion of aging, the pH was adjusted to 4.8. AgNO
_Three, 438 mL of an aqueous solution containing 141 g and 10 KBr
A double jet method was used to transfer 458 mL of an aqueous solution containing 2.6 g.
The final flow rate was added so as to be 4 times the initial flow rate. 55 ° C
After cooling down to AgNO_Three, 7.1g containing aqueous solution 24
Double jet of aqueous solution containing 0 mL and 6.46 g of KI
For 5 minutes. 7.1 g of KBr was added
After, sodium benzenethiosulfonate, 4mg and K₂
IrCl₆0.05 mg was added. AgNO_Three57.
Contains 177 mL of aqueous solution containing 2 g and KBr, 40.2 g
Aqueous solution, 223mL double jet over 8 minutes
Added by the method. Wash with water in the same way as Em-N and chemically sensitize
did. (Method for producing Em-Q and R) Em-K and E
Prepared in substantially the same manner as m-L. However, chemical sensitization is emulsion
This was carried out in substantially the same manner as O. Table 3 shows the characteristic values of the silver halide emulsion.
Shown together. Surface iodine content is below by XPS
It can be investigated as follows. Transfer sample to 1 × 10 torr
Cool to −115 ° C. in the vacuum of the tube and use as probe X-ray
MgKα is irradiated with an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
To Ag3d5 / 2, Br3d, I3d5 / 2 electrons
And the integrated intensity of the measured peak is the sensitivity factor.
And calculate the iodine content of the surface from these intensity ratios.
It was. The silver halide grains of the above emulsions D to R are special.
Dislocation lines as described in Kaihei 3-237450
Has been observed using a high voltage electron microscope. [0128] [Table 3-1][0129] [Table 3-2] 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 and stretch 3.3 times at 140 ° C, then
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, Salicy
Luric acid 0.04 g / m², P-chlorophenol 0.2g
/ M², (CH₂= CHSO₂CH₂CH₂NHCO)₂C
H₂0.012 g / m², Polyamide-epichlorohydride
Polycondensate 0.02 g / m²Apply a primer solution (10
cc / m², Bar coater used), the primer layer is stretched at high temperature
Provided on the surface side. Drying was performed at 115 ° C. for 6 minutes (dry drying
All rollers and conveyors in the machine are at 115 ° C
) 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) Application 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
0.05g / m², (CH₂= CHSO₂CH₂CH₂N
HCO)₂CH₂0.02 g / m², Poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
m²And coated with resorcin. 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 aluminum oxide
Treated with 2% by mass of iron oxide with silicon oxide) 0.0
6g / m²Diacetylcellulose 1.2 g / m²(Oxidation
Iron dispersal is carried out with an open kneader and sand mill.
C) as a curing agent₂H_FiveC (CH₂OCONH-C₆H
_Three(CH_Three) NCO)_Three0.3 g / m²As a solvent.
T, methyl ethyl ketone, and cyclohexanone
A magnetic recording layer with a thickness of 1.2 μm is applied with a bar coater
Obtained. Silica particles (0.3 μm) and 3-
Poly (degree of polymerization 15) oxyethylene-propyloxyto
Polishing coated with limethoxysilane (15% by mass)
10 mg / ml of aluminum oxide (0.15 μm)
m²It added so that it might become. Drying at 115 ° C for 6 minutes
(All the rollers and conveyors in the drying zone are 115
° C). Magnetic recording layer with X-light (blue filter)
D^BThe increase in color density is about 0.1, and the saturation of the magnetic recording layer
Sum magnetization moment is 4.2 Am²/ Kg, coercivity 7.3
× 10^FourA / m, the squareness ratio was 65%. 3-3) Adjustment of sliding layer Diacetylcellulose (25mg / m²), C₆H₁₃CH
(OH) C_TenH₂₀COOC₄₀H₈₁(Compound a, 6 mg /
m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (compound b,
9mg / m²) The mixture was applied. This mixture
Xylene / propylene monomethyl ether (1 /
1) Propylene monomethyl melted at 105 ° C in room temperature
After pouring and dispersing in ruether (10 times amount),
After making dispersion (average particle size 0.01μm) in seton
Added. Silica particles (0.3 μm) as a matting agent
Abrasive 3-poly (degree of polymerization 15) oxyethylene propylene
Coated with ruoxytrimethoxysilane (15% by mass)
15 mg / m each of aluminum oxide (0.15 μm)
²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes.
(All the rollers and conveyors in the drying zone are 115
° C). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ step).
Nres hard ball, load 100g, speed 6cm / min), static
Coefficient of friction 0.07 (clip method), emulsion surface described later
The coefficient of dynamic friction of the sliding layer was also excellent at 0.12.
It was. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, the following composition
Each layer was applied in multiple layers to produce a color negative film. (Photosensitive layer composition) The main materials used for each layer are as follows.
Are classified as:     ExC: Cyan coupler UV: UV absorber     ExM: Magenta coupler HBS: High boiling point organic solvent     ExY: Yellow coupler H: Gelatin hardener     ExS: Sensitizing dye (Specific compounds are described below.
The chemical formula is listed behind) The number corresponding to each component is g / m²Application amount expressed in units
For silver halide, the coating amount in terms of silver is shown.
The However, for sensitizing dyes, silver halide in the same layer
The coating amount with respect to 1 mol is shown in mol units. First layer (first antihalation layer) Black colloidal silver Silver 0.155 0.07 μm AgBrI (1) Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver 0.011 Gelatin 0.407 ExM-1 0.050 ExF-1 0.002 Cpd-2 0.001 HBS-1 0.074 Solid disperse dye ExF-2 0.014 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) 0.07 μm AgBrI (2) Silver 0.020 ExC-2 0.022 Polyethyl acrylate latex 0.085 Gelatin 0.294 Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-R Silver 0.65 Em-Q Silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (medium sensitivity red-sensitive emulsion layer) Em-P Silver 0.21 Em-O Silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 Sixth layer (high-sensitivity red-sensitive emulsion layer) Em-N Silver 1.47 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84 Eighth layer (layer that gives a layered effect to the red-sensitive layer) Em-M Silver 0.560 Cpd-3 0.020 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58 Ninth layer (low sensitivity green-sensitive emulsion layer) Em-L Silver 0.39 Em-K Silver 0.28 Em-J Silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 Cpd-3 0.010 HBS-1 0.28 HBS-3 0.01 HBS-4 0.27 Gelatin 0.73 [0145]   10th layer (medium sensitive green sensitive emulsion layer)     Em-I Silver 0.45     ExC-6 0.009     ExM-2 0.031     ExM-3 0.029     ExY-1 0.006     ExM-4 0.028     ExG-1 0.005     Cpd-3 0.006     HBS-1 0.064     HBS-3 2.1 × 10^-3     Gelatin 0.44 Eleventh layer (high-sensitivity green-sensitive emulsion layer) Em-I Silver 0.30 Em-H Silver 0.69 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1.11 12th layer (yellow filter layer) Yellow colloidal silver silver 0.010 Cpd-1 0.16 Solid disperse dye ExF-5 0.010 Solid disperse dye ExF-6 0.020 HBS-1 0.082 Gelatin 1.057 [0148]   13th layer (low sensitivity blue-sensitive emulsion layer)     Em-G Silver 0.18     Em-E Silver 0.20     Em-F Silver 0.07     ExC-1 0.041     ExC-8 0.012     ExY-1 0.035     ExY-2 0.71     ExY-3 0.10     ExY-4 0.005     Cpd-2 0.10     Cpd-3 4.0 × 10^-3     HBS-1 0.24     Gelatin 1.41 [0149]   14th layer (high sensitivity blue-sensitive emulsion layer)     Em-D Silver 0.75     ExC-1 0.013     ExY-2 0.013     ExY-3 0.05     ExY-6 0.062     Cpd-2 0.075     Cpd-3 1.0 × 10^-3     HBS-1 0.10     Gelatin 0.91 [0150]   15th layer (first protective layer)     0.07 μm AgBrI (2) Silver 0.30     UV-1 0.21     UV-2 0.13     UV-3 0.20     UV-4 0.025     F-18 0.009     F-19 0.005     F-20 0.005     HBS-1 0.12     HBS-2 5.0 × 10^-2     Gelatin 1.8 [0151]   16th layer (second protective layer)     H-1 0.40     B-1 (diameter 1.7 μm) 5.0 × 10^-2     B-2 (diameter 1.7 μm) 0.15     B-3 0.05     S-1 0.20     Gelatin 0.75 Furthermore, preservability, processability and pressure are appropriately applied to each layer.
Improve resistance, antibacterial and antibacterial properties, antistatic properties and coatability
For W-1 to W-5, B-4 to B-6, F
-1 to F-18 and iron salt, lead salt, gold salt, platinum salt,
Palladium salt, iridium salt, ruthenium salt, rhodium
Contains salt. In addition, the coating solution for the eighth layer is halogenated.
8.5 x 10 per silver mole^-36. Gram, 7th layer
9x10^-3Gram calcium to calcium nitrate aqueous solution
As shown in Table 4 and maintained in the same manner as in Example 1.
Replacing the protective layer gelatin partly with pullulan, sample 201-
205 was created. Preparation of dispersion of organic solid disperse dye ExF-2 was dispersed by the following method. That is, 21.7m of water
P-octylphenoxyethoxy ester in L and 5% aqueous solution
3 mL of sodium toxiethane sulfonate and 5% aqueous solution
P-octylphenoxy polyoxyethylene ether
(Polymerization degree 10) 0.5g to a 700mL pot mill
And 5.0 g of dye ExF-2 and zirconium oxide
(1mm diameter) 500mL is added and the contents are 2 o'clock
Dispersed. For this dispersion, the BO-type vibration bow manufactured by Chuo Koki
Lumil was used. After dispersion, the contents are removed and 12.5
Add to 8 g of aqueous gelatin solution and filter out beads.
A gelatin dispersion of the dye was obtained. Average particle size of dye fine particles
The diameter was 0.44 μm. Similarly, ExF-3, ExF-4, E
A solid dispersion of xF-5 was obtained. The average particle size of the dye fine particles is
0.24 μm, 0.45 μm, and 0.52 μm, respectively
Met. ExF-6 is based on European Patent No. 549,489A
Microprecipitation as described in Example 1 (Microprecip
tation) Dispersed by a dispersion method. Average particle size is
It was 0.06 μm. Below, the compound used to create each layer
Showing things. [0155] Embedded image [0156] Embedded image[0157] Embedded image[0158] Embedded image[0159] Embedded image[0160] Embedded image[0161] Embedded image[0162] Embedded image[0163] Embedded image[0164] Embedded image [0165] Embedded image[0166] Embedded image[0167] Embedded image[0168] Embedded image[0169] Embedded image These samples were placed at 40 ° C. and 70% relative humidity.
It was left under conditions for 14 hours. Then Fujifilm
Gelatin filter SC-39 and continuous wedge
And exposed for 1/100 second. Development is Fuji Photo Hui
Using Rum's automatic processor FP-360B:
went. In addition, let the overflow solution of the bleaching bath flow to the back bath.
Instead, all modifications were made to discharge to the waste liquid tank. this
FP-360B is disclosed in the Invention Association Open Technique 94-4992.
The evaporation correction means described is mounted. The treatment process and the treatment liquid composition are shown below.   (Processing process)     Process Processing time Processing temperature Replenishment amount^*     tank capacity   Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L   Whitening 50 seconds 38.0 ℃ 5 mL 5L   Fixing (1) 50 seconds 38.0 ℃ -5L   Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L   Washing with water 30 seconds 38.0 ℃ 17 mL 3L   Stable (1) 20 seconds 38.0 ℃ -3L   Stable (2) 20 seconds 38.0 ℃ 15 mL 3L   Dry 1 min 30 sec 60.0 ° C   * Replenishment amount per photosensitive material 35mm width 1.1m (24Ex. 1 equivalent) 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.
2.5 mL, 2.0 mL, and 2.0 mL. Ma
The crossover time is 6 seconds.
The time is included in the processing time of the previous process. Open the above processor
Mouth area is 100cm with color developer²120c with bleach
m²Other processing solutions are about 100cm²Met. The composition of the treatment liquid is shown below.   (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 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18 [0173]   (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 1.0L 1.0L   pH [adjusted with aqueous ammonia] 4.6 4.0 (Fixing (1) Tank liquid) Bleaching tank liquid
And 5 to 95 (volume ratio) of the following fixing tank solution (pH)
6.8) [0175]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   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
Thorium 20mg / L and sodium sulfate 150mg / L
Was added. The pH of this solution is in the range of 6.5 to 7.5.
It was. [0177]   (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 1.0L   pH 8.5 Measure the concentration of the processed sample with a green filter
did. The results obtained are shown in Table 4 below. Sensitivity is foggy
It was displayed as a relative value of degree plus 0.2. Sample generated by combustion
Fog and sensitivity change caused by exposure to gas
The degree of was evaluated by the same method as in Example 1. Result in Table 4
Show fruit. [0179] [Table 4] As is apparent from Table 4, the photosensitive material of the present invention.
Containing modified polyvinyl alcohol in the protective layer
And fog increase with respect to gas generated by combustion
Sensitivity degradation is improved. Especially against pullulan gelatin
The effect is remarkable when the mass% is 10% or more. However, quality
In the sample 205 whose amount% is 100%, the developed sample is cloudy.
I was tinged. (Example 3) Em-A to C of Example 1
The aspect ratio was changed by changing the growth conditions of Em-H
Emulsions with modified chemical sensitization conditions, Em-S (As
Pect ratio 6, no reduction sensitization), T (aspect ratio 16,
No reduction sensitization), U (16 aspect ratio, with reduction sensitization)
When the same evaluation as in Example 2 was performed,
As in Example 1, the effect of the present invention on the combustion gas is
Significant for spect-ratio and reduction-sensitized emulsions
It was big. Example 4 In Example 2, pullulan
The same as in Example 2 except that the additive layer was replaced with the first protective layer
When the test was conducted, the same result was obtained.
It was. (Example 5) Implementation of Japanese Patent Laid-Open No. 9-5912
17th layer gelatin of sample 201 described in Example 2
30% by mass is replaced with the pullulan used in Example 1 of the present application.
A silver halide color reversal photographic light-sensitive material was prepared and
Colors described in Example 1 of Kaihei 9-5912
If the inversion process is performed, the same effect as in the first embodiment can be obtained.
It is. (Embodiment 6) As in Embodiment 1, except for pulling
Orchid into xanthan gum (weight average molecular weight about 1 million)
When the test was conducted instead, the combustion gas
The effect of the present invention was observed. (Embodiment 7) Dextst instead of pullulan
Replaced with run (polymerization degree about 5,000), same as Example 1.
As with pullulan, the effects of the present invention were observed.
It was. (Example 8) Pullulan and xanthan gum
1: 1 mass ratio, but the total mass of these two polysaccharides is zero
0.1, 10, 50, 100% to Chin
The same test as in Example 1 was conducted.
The effect of the present invention was observed as in the case of the single substance. (Embodiment 9) Pull evaluation similar to that in Embodiment 2
Xanthan gum (weight average molecular weight of about 10
The effect of the present invention is similar to that of pullulan.
It was seen. (Example 10) Evaluation similar to that in Example 2 was performed.
When I went to Dextran instead of Luran, Pullula
Similar to the above, the effect of the present invention was observed. (Example 11) Evaluation similar to that in Example 3 was performed.
When I went to Xanthan Gum instead of Luran,
The effect of this invention was seen like a run. (Example 12) Evaluation similar to that in Example 3 was performed.
When I went to Dextran instead of Luran, Pullula
Similar to the above, the effect of the present invention was observed. (Example 13) The same evaluation as in Example 4 was performed.
When I went to Xanthan Gum instead of Luran,
The effect of this invention was seen like a run. (Embodiment 14) Evaluation similar to that in Embodiment 4 was performed.
When I went to Dextran instead of Luran, Pullula
Similar to the above, the effect of the present invention was observed. [0193] According to the present invention, high sensitivity and an automobile can be obtained.
Covers against harmful gases generated during combustion of exhaust gas, etc.
Halogen for photography with significantly improved resistance to increase
A silver halide photographic light-sensitive material can be provided.

Claims (1)

What is claimed is: 1. A photographic silver halide photographic material having at least one photosensitive silver halide emulsion layer and a protective layer, respectively, on a support, wherein the gelatin contained in the protective layer comprises A silver halide photographic light-sensitive material for photography, comprising 10% by mass or more of a microbially produced polysaccharide.