JPH04348337A - Silver halide photographic sensitive material and production of same - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and superior in graininess and sharpness and improved in pressure resistance by introducing dislocation lines into 30% of normal crystals. CONSTITUTION:The silver halide emulsion contains the normal silver halide crystals having the dislocation lines in >=30% of the normal crystals, and are used for the photographic sensitive material having a silver halide emulsion layer on a support. It is preferred to prepare the silver halide grains having the dislocation lines by the manufacturing processes comprising: 1, preparation of the normal crystals as the basic crystals; 2, growth of fine epitaxial silver chloride or chlorobromide crystals on the normal crystals; 3, physical ripening of the fine epitaxial crystals on the normal crystals or conversion by halogen.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a silver halide photographic material.
It relates to materials with particularly good pressure resistance and spectral enhancement.
Uses a high-sensitivity silver halide photographic emulsion that is favorable for
This article concerns photographic materials and their manufacturing methods.
Ru. [Prior Art] Photographs generally coated with silver halide emulsion
Various pressures are applied to photosensitive materials. For example, general photographic negative film is
If it gets caught in the camera or when loading it into the camera,
be bent or pulled for frame-by-frame
. In addition, it is also used as printing sensitive materials and direct medical X-ray sensitive materials.
Eel sheet film is handled directly by hand, so
It often breaks or bends. Furthermore, all types of sensitive materials are subjected to great pressure during cutting and processing.
receive. [0004] In this way, various pressures are applied to photographic materials.
and zeolite, which is a support (binder) for silver halide grains.
Using latin or plastic film as a support medium
pressure is applied to the silver halide grains. silver halide grains
When pressure is applied to the photosensitive material, changes may occur in the photographic properties of the photosensitive material.
For example, K. B. Mather, J.
．． Opt. Soc. Am. , 38. 1054
(1948), P. Faelens and P. d
e Smet, Sci. et Ind. Photo
．． , 25. No. 5. 178 (1954),
P. Faelens, J. Photo. Sci.
2. 105 (1954), etc.
ing. [0005] For this reason, what happens to photographic properties under these pressures?
It is important to provide photographic materials that are not affected by
highly desired. [0006] Polymers are a means of improving pressure characteristics.
Methods of incorporating plasticizers such as emulsions and halogenated
Those who want to reduce the silver halide/gelatin ratio in silver emulsions, etc.
In the law, it is known what prevents pressure from reaching the particles.
It is. For example, in British Patent No. 738618,
738637 refers to heterocyclic cyclic compounds, and
The specification of 738639 describes kil phthalate as alkylphthalate.
U.S. Pat. No. 2,960,404 describes
The polyhydric alcohol is
Boxyalkyl cellulose, JP-A-49-5017
The official gazette describes paraffin and carboxylic acid salts,
No. 8086 discloses alkyl acrylate and organic acid,
Methods for using each as a plasticizer are disclosed. However, the method of adding a plasticizer does not affect the emulsion layer.
There is a limit to its usage as it reduces mechanical strength.
Disadvantages such as increasing the amount of gelatin slows down the processing speed
None of the methods can achieve sufficient effects due to
difficult to achieve. The requirements for silver halide emulsions for photography are
Tough, high sensitivity, high contrast and excellent graininess
It is required to have excellent pressure characteristics while maintaining
. Monodisperse emulsions are better for the former requirement.
is well known, but the pressure characteristics are at a satisfactory level.
However, the above plasticizers and silver halide/zeta
Various methods other than the latin ratio have been disclosed. For example, a method using iodide ions
JP-A-59-178447 discloses that locally iodine
A silver halide photographic emulsion containing oxide ions has been disclosed.
ing. U.S. Pat. No. 4,210,450 describes particle formation.
Halo that is converted into halogen by iodide ions on the way
A method for making silver germide grains is disclosed. However, this
The method of using iodide as in
Because it sometimes has a significant effect on photographic properties such as developability,
There are restrictions on its use. On the other hand, a US patent for a method using silver chloride
No. 4,495,277 describes the inner core of silver halide grains.
A silver halide emulsion having a single silver chloride layer is disclosed.
ing. However, if such a silver chloride layer is provided,
This method is problematic because it improves the pressure characteristics but at the same time deteriorates the graininess.
There is a problem. In recent years, the sensitivity of silver halide photosensitive materials has increased and
With the advancement of larger and smaller formats, higher sensitivity and improved image quality have been achieved.
There is a strong demand for color photosensitive materials with a high quality of color. Also, sensitivity and
In addition to image quality such as graininess, there are also
In contrast to so-called toughness such as strength,
requests have been made. With conventional silver halide emulsions, this
It is insufficient to meet the demands of
It is hoped that the capacity will be improved. [0013] The present invention is directed to the dislocation of normal crystal silver halide grains.
Regarding technology to introduce. Dislocations in silver halide tabular crystals
Regarding ■C. R. Berry, J. Appl. Phys. ，
27, 636 (1956) ■C. R. Berry,
D. C. Skillman, J. Appl. Phys.
．． , 35, 2165 (1964) ■J. F. Hamilton, Phot. Sci. E
ng. , 11, 57 (1967) ■T. Shioz
awa, J. Soc. Photo. Sci. Jpn. ，
34, 16 (1971) ■T. Shiosawa
, J. Soc. Photo. Sci. Jpn. , 35
, 213 (1972), etc., and the X-ray diffraction method
Alternatively, dislocations in the crystal can be detected using low-temperature transmission electron microscopy.
It is possible to observe and strain the crystal.
Due to this, various dislocations occur in the crystal.
It has been stated. On the other hand, the influence of dislocation on photographic performance is
G. C. Famell, R. B. Flint a
nd J. B. Chanter, J. Photo. Sc
i. , 13, 25 (1965),
In large size high aspect ratio tabular silver bromide grains
There is a close relationship between the location where the latent image nucleus is formed and the defects within the particle.
It has been shown that there is. [0015] JP-A-63-220238 and JP-A No.
1-201649 each publication intentionally introduced dislocations.
Tabular silver halide grains are disclosed. dislocation
Compared to tabular grains without dislocations, tabular grains with introduced
It has excellent photographic characteristics such as sensitivity and reciprocity, and is sensitive to these characteristics.
It has been shown that it has excellent sharpness and graininess when used in optical materials.
ing. However, in these disclosed examples, the flat plate
This is the introduction of dislocation lines in grains with
This technology for introducing dislocations has not been reported so far. [0017] An object of the present invention is to improve sensitivity.
In addition to having high graininess and sharpness, it also has low pressure resistance.
Silver halide containing improved normal crystal silver halide grains
To provide a photographic material and its manufacturing method
. [Means for Solving the Problems] The objects of the present invention are (1)
A photographic material having a silver halide emulsion layer on a support.
Therefore, the emulsion layer contains normal crystal silver halide grains.
and at least 30% of the normal crystal silver halide grains.
The upper grain is characterized by having dislocation lines inside the grain.
Silver halide photographic material and (2) dislocation inside the grains
Silver halide milk containing normal silver halide crystals with lines
The agent was prepared by the following three processes, and then the obtained
Characterized by coating a silver halide emulsion on a support
Manufacturing method for silver halide photographic materials: ■Basic
Normal crystal grains (hereinafter referred to as "base grains" or "host grains")
Also say. ) Preparation of
Formation of epitaxy of silver chloride or silver chlorobromide; and ■ positive
Physical ripening and/or haphazard micro epitaxy of ordinary crystal grains
The conversion was achieved by Rogen. [0019] The particle size of the base particles is 0.1μ.
Preferably, the thickness is from m to 3 μm. [0020] In this specification, "normal crystal grain" refers to
It means a particle that has no crystal planes. Furthermore, herein
"30% or more grains" refers to the number of silver halide grains.
It means a ratio in numbers. The present invention will be explained in detail below. The normal crystal grains of the present invention have dislocations. Dislocations of tabular grains are described, for example, in the above-mentioned J. F.
Hamilton, Phot. Sci. Eng. ，
11, 57 (1967) and T. Shiozaw
a, J. Soc. Photo. Sci. Jpn. , 3
Transmission electrons at low temperatures as described in 5, 213 (1972)
It can be observed directly using a microscope.
Ru. However, even if the thickness is 0.3 μm or more,
To tabular grains or normal crystal grains with a diameter of 0.3 μm or more
In some cases, the electron beam is difficult to penetrate, so the above-mentioned
Observation using a transmission electron microscope is difficult. For observation of dislocations in normal crystal grains as in the present invention
This can be done by the following method. That is, as dislocations occur from the emulsion to the grains,
Remove under safe light, being careful not to apply any pressure.
The silver halide grains are mixed with a suitable dilute silver halide solvent.
After soaking for a while and etching, the thickness is less than 0.3 μm.
Let's do it. As the silver halide solvent, KBr aqueous solution,
Sodium thiosulfate aqueous solution, potassium cyanide aqueous solution, etc.
Which is used. [0027] Thus obtained from normal silver halide crystals,
The thin plate crystals were damaged by the electron beam (printed out).
etc.), the sample is cooled to prevent the observation using the transmission method.
conduct an investigation. Images of particles obtained by this method
From the truth, dislocations can be confirmed for each particle. In other words, in particles without dislocations, the radius
You can see rounded black spots at random locations, but this
These may gradually increase in size during observation and may cause contamination.
by Nation or by printout silver.
It is seen as something that Also, using wet etching method
This is due to the fact that the thickness of the particles is not uniform due to
A gentle contrast is created. However, there is a clear change
The presence of rank is not seen. On the other hand, for particles with dislocations, the above
Similar black spot-like things and mildness depending on the thickness of the sample.
In addition to the sharp contrast, there are many clear linear contrasts.
, that is, many dislocation lines can be seen. Next, regarding the method for producing normal crystal particles of the present invention
state The normal crystal particles of the present invention are:
Preparation of crystal grains: ■Minute chlorination of normal crystal grains that serve as the base
Formation of epitaxy of silver or silver chlorobromide; and ■ normal crystals.
Physical ripening of microscopic epitaxy of particles and/or halogen
conversion through three processes.
Manufactured. [0032] Furthermore, silver halide shell formation is carried out.
The growth of dislocations may also occur. Rearrangement is minute chlorination
Generates where silver or silver chlorobromide epitaxy is attached
Therefore, the location of dislocations is the location of microepitaxy formation.
determined by control. By the way, if the surface iodine content is 10 mol% or more,
In the normal crystal grains of silver iodobromide below, micro-epitaxial
Sea preferentially attaches to (111) surfaces. therefore
, selectively introduces dislocations onto the (111) surface of normal crystal grains.
be able to. In Japanese Patent Publication No. 58-24772, there are ten
The second halogen is preferentially attached to the (111) surface of the tetrahedral crystal.
A method for producing hybrid silver halide crystals with added silver oxide is described.
ing. However, this is the (111) surface of the tetradecahedral crystal.
By preferentially adding a second silver halide to
In terms of ultimately creating a cubic crystal, it is important to
There is no apparent intention to enter. [0034] Also, for silver chloride or silver chlorobromide epitaxy,
Regarding that, C. R. Berry and D. C.
Skillman, J. Appl. Phys 35
:2165 (1964) and J. E. Maska
In Japanese Unexamined Patent Application Publication No. 59-133540 by Sky, there is a
Particles in which silver chloride is epitaxially grown on the surface of silver chloride grains.
It is shown. However, for any of these particles,
After micro-epitaxy growth, physical ripening and/or
Introducing dislocation through conversion with halogen
I can't see the diagram. Furthermore, silver chloride or silver chlorobromide epitaxy
The adhesion site can also be controlled using a site-indicating agent.
It is possible. As a site indicator, methine dye, etc.
dyes are used. Examples of dyes used include
Dianine pigment, merocyanine pigment, complex cyanine pigment,
Composite merocyanine dye, holopolar cyanine dye,
Mycyanin pigment, styryl pigment and hemioxonol color
Examples include elementary. [0036] These dyes can be used as site indicators.
silver chloride or silver chlorobromide epitaxy to normal crystal grains.
It is possible to selectively attach it to the top and/or ridge of the child.
Yes, therefore subsequent physical ripening and/or
Selective normal grains due to conversion by rogens
Dislocation lines can be introduced at the child crests and/or edges. Regarding the site indicator for silver chloride epitaxy
is J. E. Maskasky, J. Imag.
Sci. 32 160-177 (1988)
physical ripening and/or halo as described above.
Selective introduction of rearrangement by conversion by gene
I don't see any intention. In addition, the surface iodine content is 10 mol.
% or more of silver iodobromide, no site indicator is used.
Even if silver chloride or silver chlorobromide epitaxy occurs at the top of the grain and/or
Or attach to the ridge. The silver halide emulsion of the present invention has halogenated
Select from various methods known in the field of silver photographic materials.
It can be prepared by combining The base grains may be normal crystal grains, and may be cubic grains.
body, octahedral, dodecahedral particles, and other polyhedral particles, etc.
is used. Cubic, octahedral, and tetradecahedral particles are
``Theory of Photographic Process'' by H. James, 4th edition Makumi
Run Inc. (T.H. James “The Theory”
of the Photographic Proc
ess”4th ed. Macmillan) No. 3
Referring to the descriptions in chapters (pp. 88-104) etc.
Can be easily prepared. Regarding other polyhedral particles,
J. E. Maskasky. J. Img. Sc
i 30 247-254 (1986) etc.
It can be prepared by referring to the reported method. [0042] In the formation of base particles, protective colloid water
Silver salt aqueous solution and halide aqueous solution are placed in the reaction vessel that holds the solution.
Instead of adding silver halide fine particles, positive
Formation of ordinary crystal particles may also be carried out. About this method
, JP-A-1-183645 and U.S. Patent No. 48
The technology is disclosed in the specification of No. 79208. When the base particle is a tetradecahedron, the (111) plane
The surface ratio is determined by the carbon replica method of silver halide emulsion grains.
can be observed directly from electron micrographs taken by
. More precisely, Journal of the Chemical Society of Japan 1984, No. 6, 9
The method described on page 42 can be used. Sunawa
The dye (anhydro-3,3'-bis-(sulfur)
Rufobutyl)-9-methylthiacarbodianine hydroxide
Reflection of a thick liquid emulsion layer with addition of cydopyridinium salts
The spectrum was measured and the dye was observed on the (100) plane and on the (1
11) Focus on giving significantly different spectra on the surface
By treating it with Kubelker-Munk's equation, (1
The ratio between the 00) plane and the (111) plane can be determined. [0044] The particle size of the base particles is 0.1 μm to 3 μm.
Preferably it is μm. The size distribution of the base particles can be narrow or wide.
However, one preferred base particle has a narrow (variable) size distribution.
The emulsion is a monodispersed emulsion (dynamic coefficient of 20% or less). In the present invention, in the process of forming base particles,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium
salt or its complex salt, rhodium salt or its complex salt, iron salt or
Iron complex salts and the like may also be present. The halogen composition of the base particles of the present invention is as follows:
, silver bromide, silver iodobromide (iodine content 40 mol% or less)
be. Based on silver chloride or silver chlorobromide epitaxy
When selectively forming in the plane of the particle, the base particle
The smaller the silver iodide content near the surface, the better. near the surface
Silver iodide content is 20 mol% or less, preferably 15 mol%
% or less, more preferably 10 mol% or less. The silver iodide content near the surface was measured by ESCA.
can be determined. Increased total silver iodide content of base grains
If it is not possible, use double-structure or multi-structure particles.
It is possible to reduce the silver iodide content near the surface
. [0050] Regarding double structure particles, Japanese Patent Application Laid-Open No. 1986-1
It is disclosed in Japanese Patent No. 43331. Also, multi-structure particles
As for the
ing. Depositing epitaxy on the top and/or ridge
When using a site-indicating agent, silver iodide near the surface can be
The content is arbitrary. If no site indicator is used, the top and
/ or to deposit epitaxy on the ridges, base grains
The higher the silver iodide content near the surface of the grain, the better. Near the surface
The silver iodide content is 5 mol% or more, preferably 7 mol% or more.
More preferably, it is 10 mol% or more. [0052] Using these as base particles, silver chloride or salt odor
Adding silver oxide to the surface of the base grain or on the top and/or edge of the base grain
Deposit a number of minute epitaxies. Silver chloride or silver chlorobromide epitaxy of the present invention
After forming the particles that will become the base particles in the preparation of
Epitaxy preparations can be performed. Also, the foundation
Prepare epitaxy after washing particles with water for desalination
You can also. The halogen composition of the epitaxy of the present invention is:
The halogen composition near the surface of the base particle is different from that of chloride.
silver or silver chlorobromide, preferably with a silver chloride content of 30
silver chloride bromide, particularly preferably silver chloride.
be. Iodine during epitaxy has photographic properties (especially
If the amount is so small that it does not substantially affect image quality)
May be included. When depositing epitaxy, the substrate particles
and epitaxy to avoid mixing with each other.
Preferably, it is deposited. An exemplary method of deposition is silver halide
Water-soluble silver salts and water-soluble halogens compatible with epitaxy compositions
It is preferable to add salt. Water solubility at this time
It is preferable to add the silver salt as fast as possible without causing re-nucleation.
Delicious. For depositing silver halide epitaxy
For this reason, the silver potential during deposition is generally adjusted to a high silver potential.
is often desirable. However, the epitaxy
halogen composition, temperature or additives coexisting during preparation, etc.
It depends. Silver potential (the reference electrode is a saturated calomel electrode)
) is +30mV to +300mV, preferably +50
mV to +250 mV. Also in preparation for epitaxy
It is preferable that the temperature is lower. The temperature of the reaction vessel is 70℃ ~
30°C, preferably 60°C to 35°C, more preferably 5°C
It is 0°C to 35°C. Added silver salt (mainly silver nitrate) and
The amount of halide is preferably 0.1 to 30 mol% of the base particles.
Preferably 0.5 to 20 mol%, more preferably 1 to 1
It is 0 mol%. The size of the generated epitaxy and
The number depends on the epitaxy formation conditions and the halogen composition of the base particles.
Depends on. The size of epitaxy can be determined using a replica electron microscope.
Epitaxy can be confirmed by microscopic photography.
The average projected area diameter is 0.5 μm or less, and the number of pieces is 1
~100,000 particles/μm2 exist in the plane of the base particle.
Ru. If epitaxy is deposited on the top and/or ridge
, 1-10 pieces/μm at the top, 1-100 pieces/μm at the ridge
exists. Next, there is epitaxy in the plane of the base grain.
Physical ripening of top and/or edge epitaxy and/or
performs halogen conversion. Physical maturity
If this is done, the microepitaxy will collapse and form a larger hill.
becoming. It is thought that dislocation lines are introduced at this time.
ing. [0060] The temperature for physical ripening is 40°C to 90°C;
Preferably 50°C to 90°C, more preferably 60°C to 8°C
It is 0°C. After physical ripening, it is subsequently exposed to halogen.
You may also perform a conversion, but before that,
The eggs may be washed with water to desalinate them. [0061] Halogen conversion refers to halogenation
Different halogens are used to form silver crystals.
halogen present as a crystal
silver halide, which has a smaller solubility product than silver halide.
It is caused by adding halogen, and halogen
The conversion from the greater solubility of silver oxide is
will be started. Therefore, perform halogen conversion
Halogen is grown epitaxially for halogen
silver halide, which has a lower solubility than silver halide.
Any halogen can be used as long as it has the following composition. The amount of halogen added depends on epitaxial growth.
Preferably 50 to 500 mol% based on the amount of silver added
, more preferably 100 to 400 mol%. [0063] The halogen used is iodide, iodide and
In combination with bromide or as a bromide and its aqueous solution
Added. In addition, as a method of adding these halogens, iodine is used.
It may also be added as fine particles of silver oxide, silver iodobromide, and silver bromide.
stomach. The size of the fine particles is 0.1 μm or less, preferably 0.1 μm or less.
06 μm or less. These fine particles are made of fine particles in advance.
It is also possible to prepare baby emulsions, but U.S. Pat.
Mixing according to the method disclosed in No. 79208
It is preferable to supply these fine silver halide particles from a container.
Delicious. [0064] Further, dislocation growth is performed by shell formation.
You can. In the plane or on the top and/or edge of the base particle
Physical ripening of generated micro epitaxy and/or halogen
Dislocations are introduced by conversion, and then
Then add silver salt aqueous solution and halide aqueous solution to form a shell.
When this happens, dislocations grow as shells form. The halogen composition of the shell is arbitrary, and chloride
Silver, silver bromide, silver iodobromide, silver chloride iodobromide, silver chlorobromide
It's okay if it's off. [0066] Also, in forming the shell, protective colloid
Silver salt aqueous solution and halide aqueous solution are added to the reaction vessel holding the aqueous solution.
Instead of adding liquid, silver halide fine particles are added.
Formation of a shell may also be performed. For this method,
The technology is disclosed in U.S. Patent No. 4,879,208.
It is. In addition, when forming a silver iodobromide shell, iodine
As a method of supplying elementary ions, fine particles of AgI (
Particle size: 0.1 μm or less, preferably 0.06 μm or less) Milk
Aqueous solution of alkali halide may be used.
It may be used in combination with the method. At this time, the supply of AgI fine particles
As disclosed in U.S. Pat. No. 4,879,208,
It is preferable to use a manufacturing method that has been described. Added shell silver salt (mainly silver nitrate) and
There is no particular limit to the amount of halide, but the amount of halide is
After depositing silver chloride or silver chlorobromide epitaxy on
Grains subjected to physical ripening and/or halogen conversion
1 to 300 mol%, preferably 5 to 200 mol% of
It is. Introducing dislocations into silver halide grains
This increases sensitivity, improves reciprocity law failure, and improves spectral sensitization sensitivity.
A rise is brought about. Furthermore, it originally darkens due to pressure.
The pressure properties of particles that tend to be significantly modified by the introduction of dislocations
It will be good. Maximize the effects of these favorable dislocations.
In order to make this happen, the location (topography) of dislocation introduction and
It is essential to freely control the density.
However, the present invention makes it completely possible.
It's groundbreaking. Size of silver halide grains in the present invention
There is no particular restriction on the average particle diameter of 0.3 μm to 4 μm
m, preferably 0.6 μm to 3 μm. The emulsions of the present invention are usually spectrally sensitized. The spectral sensitizing dye used in the present invention is
Methine dyes are usually used, but cyanine dyes
, merocyanine pigment, composite cyanine pigment, composite merocyanine
Nin pigment, holopolar cyanine pigment, hemicyanine color
Includes dyes, styryl dyes, and hemioxonol dyes.
It will be done. These pigments contain a sialic ring as a basic heterocyclic nucleus.
Any of the nuclei commonly used for pigment pigments can be applied.
. i.e. pyrroline nucleus, oxazoline nucleus, thiazoline
nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, sele
Nazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine
Nuclei, etc.; Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei.
; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, immediately
Chi, indolenine nucleus, benzindolenine nucleus, indo
le nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Benzothiazole nucleus, naphthothiazole nucleus, benzocele
Nazole nucleus, benzimidazole nucleus, quinoline nucleus, etc.
Applicable. These nuclei are substituted on carbon atoms
Good too. Merocyanine dye or complex merocyanine
The dye contains pyrazoli as a core with a ketomethylene structure.
ion-5-one nucleus, thiohydantoin nucleus, 2-thioxa
Zolidine-2,4-dione nucleus, thiazolidine-2,4-
dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, etc.
A 5- to 6-membered heteroartic ring nucleus can be applied. [0074] The sensitizing dye is used after chemical ripening or before chemical ripening.
added to. For the silver halide grains of the present invention,
Also preferably, the sensitizing dye is used during or before chemical ripening (
(for example, during particle formation, physical ripening). Silver halide emulsions are usually chemically sensitized.
Ru. That is, it can react with activated gelatin and silver.
Compounds containing sulfur (e.g. thiosulfates, thioureas,
Sulfur sensitization using mercapto compounds, rhodanines)
method: Reducing substances (e.g. stannous salts, amines, hydrogen
Radin derivatives, formamidine sulfinic acid, silanization
reduction sensitization method using noble metal compounds (e.g.
In addition to gold complex salts, periodic table VII of Pt, Ir, Pd, etc.
Noble metal sensitization method using group I metal complex salts) alone or
can be used in combination. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the manufacturing process, storage, or photo processing of materials.
For the purpose of stopping or stabilizing photographic performance, various
Compounds may be included. i.e. azole
For example, benzothiazolium salts, nitroindazoles
triazoles, benzotriazoles, benzene
Midazoles (especially nitro- or halogen-substituted);
Telocyclic mercapto compounds, such as mercaptothiazole
mercaptobenzothiazoles, mercaptoben
Zimidazoles, Mercaptothiadiazoles, Mel
captotetrazoles (especially 1-phenyl-5-merca)
(puttetrazole), mercaptopyrimidines; carbo
The above-mentioned hexafluoride having a water-soluble group such as a xyl group or a sulfone group
Terocyclic mercapto compounds; thioketo compounds, e.g.
Xazolinthione; azaindenes, e.g. tetraaza
Indenes (especially 4-hydroxy substituted (1,3,3a,
7) Tetraazaindenes); Benzenethiosulfonic acid
Antifoggants such as benzenesulfinic acid; etc.
or by adding a number of compounds known as stabilizers.
Can be done. When adding these antifoggants or stabilizers
The period is usually carried out after chemical sensitization, but it is more
Preferably during chemical ripening or before the start of chemical ripening
You can choose from among the periods. The emulsion of the present invention has one or more emulsion layers.
Can be used in photographic materials with any layer structure regardless of the above.
can. Silver halide multilayer film using the emulsion of the present invention
Color photosensitive materials separately emit blue, green, and red light.
Contains binder and silver halide grains for recording
It has a multilayer structure with overlapping emulsion layers, and each emulsion layer has a small
It consists of at least two layers: a high-sensitivity layer and a low-sensitivity layer. The silver halide emulsion of the present invention is a color photosensitive material.
It can be applied to single and multilayer emulsion layers.
Other photosensitive materials, such as X-ray photosensitive materials
materials, photosensitive materials for black and white photography, photosensitive materials for plate making, photographic paper, etc.
can also be applied in the same way. Various additives for the silver halide emulsion of the present invention
, such as binders, chemical sensitizers, spectral sensitizers, and stabilizers.
fixing agent, gelatin hardening agent, surfactant, antistatic agent, polyester
Maratex, matting agent, color coupler, ultraviolet absorber
Photosensitivity using absorbents, antifading agents, dyes, and emulsions of these
For material supports, coating methods, exposure methods, development processing methods, etc.
There are no particular restrictions on this, for example, research discs.
Roger Volume 176, Item 17643 (RD-17
643), Volume 187, Item 18716 (RD-1
8716) and volume 225, item 22534 (RD
-22534) can be referred to. [0083] These research disclosure notes
The details are shown below. ────────────────────────
──────────── Additive type
RD17643 RD18716
RD22534──────────────────
────────────────────1 Chemical sensitization
agent page 23 6
Page 48 right column Page 24 2 Sensitivity enhancer
64
Page 8 right column 3 Spectral sensitizer, pages 23-24
Page 648 right column - pages 24-28
supersensitizer
Page 649, right column 4 Brightening agent
Page 24 5 Antifogging agent
Pages 24-25 Page 649 Right column ~ 24
Pages, page 31 and stabilizers 6 light absorbers, pages 25-26
Page 649 right column~
filter dye
Page 650 left column Ultraviolet absorption
Collection agent 7 Stain inhibitor Page 25 right column
650 pages left to right column
8 Dye image stabilizer page 25
32
Page 9 Hardener Page 26
Page 651 left column Page 28 1
0 binder 26 pages
Page 651 left column 11 Plasticizer, lubricant
27 pages 650 pages right column 12 coats
Auxiliary agents, pages 26-27 65
0 page right column
Surfactant 13 Static inhibitor page 27
Page 650 Right column 14 Color coupler 25
Page 649
Page 31────────────────────
──────────────── [0085] The present invention
Do the color couplers used in
Or it should be diffusion resistant due to polymerization.
is preferred. The coupling active site is four equivalents of hydrogen atom.
Two-equivalent capacitors substituted with coupling-off groups than pullers
A puller is preferable because the amount of coated silver can be reduced. difference
In addition, couplers whose coloring dyes have appropriate diffusivity,
Colorless couplers or development inhibitors associated with coupling reactions.
A DIR coupler that releases a drug or a development accelerator.
Couplers that release can also be used. Yellow coupler that can be used in the present invention
oil-protected acylacetamide caps.
A typical example is Ra. [0087] Oxygen atom separation type yellow coupler or
A representative example of this is a nitrogen atom dissociative yellow coupler.
can be mentioned. α-pivaloylacetanilide couplers
- has excellent color fastness, especially light fastness, and is one of the
α-Benzoylacetanilide couplers have high color development.
concentration is obtained. Magenta coupler that can be used in the present invention
For oil protection type, indazolone type or
Cyanoacetyl, preferably 5-pyrazolone and
Pyrazoloazole caps such as pyrazolotriazoles
Ra is an example. 5-pyrazolone couplers are at the 3-position
is substituted with an arylamino group or an amylamino group
These couplers are preferred from the viewpoint of the hue and color density of the coloring dye.
Yes. [0089] Low yellow sub-absorption of the coloring dye and
In terms of light fastness, it is described in US Pat. No. 4,500,630.
The imidazo[1,2-b]pyrazoles listed above are preferred,
Pyrazolo [
1,5-b][1,2,4]triazole is particularly preferred.
stomach. As a cyan coupler that can be used in the present invention
is an oil-protected naphthol and phenol
There is a type coupler. US Patent No. 2,474,293
A naphthol coupler as described in the specifications, preferably a US patent
Permit No. 4052212, No. 4146396, No. 4
In each specification of No. 228233 and No. 4296200
Described two-equivalent naphthol coupler with oxygen atom separation type
- is given as a representative example. [0091] JP-A-60-237448, JP-A No. 61-1
53640 and 61-145557.
A sulfonamide group, an amino group at the 5-position of the naphthol
Cyan couplers substituted with do groups, etc. also improve the stability of colored images.
It has excellent durability and can be preferably used in the present invention. [0092] Couplers whose coloring dyes have moderate diffusivity
can be used in combination to improve graininess. like this
The coupler is described in U.S. Pat. No. 4,366,237 and
Magenta coupler in British Patent No. 2125570
Specific examples are also found in EP 96570 and
In West German Application No. 3234533, yellow
, specific examples of magenta and cyan couplers are described.
There is. [0093] In the present invention, a development inhibitor is added during development.
Even if it contains emitting couplers, so-called DIR couplers,
good. Combination with the present invention in DIR couplers
A more preferable example is JP-A No. 57-151944.
Developer deactivated type represented by couplers described in publications;
Specification No. 4248962 and Japanese Unexamined Patent Publication No. 154-1988
Timing type typified by the coupler described in Publication No. 234
; instead of the coupler described in JP-A No. 60-184248
There are reaction types etc. Particularly preferably,
Kaisho 57-151944, Kaisho 58-217932,
No. 60-218644, No. 60-225156,
and the developer described in each publication No. 60-233650
Deactivated DIR coupler and JP-A-60-184248
List the reactive DIR couplers described in the publication
Can be done. [0095] The photosensitive material of the present invention has an image-like structure during development.
Nucleating agents or development accelerators or their precursors (hereinafter referred to as
, a compound that releases a "development accelerator, etc.")
can do. A typical example of such a compound is
Patent No. 2097140 and Patent No. 2131188
Description of aromatic primary amine developer
Development accelerators etc. can be produced by coupling reaction with oxidants.
emitting couplers, or DAR couplers. High boiling point used to disperse color couplers
Specific examples of organic solvents include phthalate esters (di
Butyl phthalate, dicyclohexyl phthalate, di-
2-ethylhexyl phthalate, decyl phthalate, etc.
), esters of phosphoric or phosphonic acids (triphenyl
phosphate, tricresyl phosphate, 2-ethyl phosphate
hexyl diphenyl phosphate, tricyclohexy
tri-2-ethylhexyl phosphate, tri-2-ethylhexyl phosphate
tridodecyl phosphate, tolbutoxyethyl phosphate
Sphate, trichloropropyl phosphate, di-2
-ethylhexylphenylphosphonate, etc.), benzoin
Acid esters (2-ethylhexylbenzoate, dode
Sylbenzoate, 2-ethylhexyl-p-hydroxy
cybenzoate, etc.), amides (diethyldodecane, etc.)
(mido, N-tetradecylpyrrolidone, etc.), alcohols
or phenols (isostearyl alcohol, 2,
4-di-tert-amylphenol, etc.), aliphatic carbon
Rubonic acid esters (dioctyl azelate, glycero
tributyrate, isostearyl lactate, tri-
octyl citrate, etc.), aniline derivatives (N,N-
Dibutyl-2-butoxy-5-tert-octylani
phosphorus, etc.), hydrocarbons (paraffin, dodecylbenze,
diisopropylnaphthalene, diisopropylnaphthalene, etc.)
. In addition, as an auxiliary solvent, those having a boiling point of about 30°C or higher are preferable.
Do not use organic solvents at temperatures above 50°C and below approximately 160°C.
Typical examples include ethyl acetate, butyl acetate, and propioacetate.
ethyl phosphate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide
Examples include. Examples of gelatin hardening agents include active halogen
Gen compound (2,4-dichloro-6-hydroxy-1,
3,5-triazine and its sodium salt, etc.) and
Active vinyl compound (1,3-bisvinylsulfonyl-2
-propanol, 1,2-bis(vinylsulfonylacetate)
toamido)ethane or vinylsulfonyl group in the side chain
hydrophilic polymers such as gelatin), hydrophilic polymers such as gelatin
It is preferable because it hardens the colloid quickly and gives stable photographic properties.
Delicious. N-carbamoylpyridinium salts (1-mol
phorinocarbonyl-3-pyridinio) methanesulfoner
etc.) and haloamidinium salts (1-(1-chloro-
pyridinomethylene) pyrrolidinium-2-naphthalene
Ruphonate, etc.) also have a fast curing speed. Photography using the silver halide photographic emulsion of the present invention
Color photosensitive materials are developed, bleach-fixed or fixed.
This is usually followed by washing with water or stabilization. [0099] In the water washing process, two or more tanks are used as countercurrent water washing,
It is common to conserve water. Water washing as stabilization treatment
Instead of the process, as described in Japanese Patent Application Laid-Open No. 57-8543
A typical example is multi-stage countercurrent stabilization treatment. [0100] Coloring used in the development process of the photosensitive material of the present invention
The developer is preferably an aromatic primary amine color developer.
It is an alkaline aqueous solution containing medicine as its main ingredient. This color development
Aminophenol compounds are also useful as image agents.
However, p-phenylenediamine compounds are preferably used.
A typical example is 3-methyl-4-amino-N
, N-diethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methane
Thyl-4-amino-N-ethyl-N-β-methanesulfo
amidoethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methoxyethylaniline and these
sulfate, hydrochloride or p-toluenesulfonate of
Can be mentioned. Two or more of these compounds may be used in combination depending on the purpose.
can do. [0101] Also, when performing inversion processing, it is usually black and white.
After imaging, color development is performed. This black and white developer has
Dihydroxybenzenes such as hydroquinone, 1-phenyl
3-pyrazolidones such as phenyl-3-pyrazolidone
or aminophenol such as N-methyl-p-aminophenol.
Known black and white developing agents such as phenols may be used alone or in combination.
Can be used together. [0102] The pH of these color developing solutions and black and white developing solutions
is generally from 9 to 12. Also, these current
The amount of image solution replenishment depends on the color photographic material being processed.
However, it is generally less than 3 liters per square meter of photosensitive material.
, to reduce the bromide ion concentration in the replenisher.
The volume can also be reduced to 500 ml or less. The photographic emulsion layer after color development is usually bleached.
It will be done. The bleaching process may be carried out simultaneously with the fixing process.
(Bleach-fixing treatment) may be carried out separately. further processing
In order to speed up the process, bleach-fixing treatment is applied after bleaching.
It may be a method. In addition, iron aminopolycarboxylate (III
) Complex salts are particularly important in both bleach and bleach-fix solutions.
Useful. These aminopolycarboxylic acid iron (III
) The pH of the bleach or bleach-fix solution using complex salts is usually 5.
5-8, but for faster processing, lower p
It can also be treated with H. Bleach solution, bleach-fix solution and their prebaths
, a bleach accelerator can be used if necessary. Useful bleach accelerators include mercapto or disulfide groups.
Compounds with a fido group are preferred because they have a large promoting effect.
particularly in U.S. Pat. No. 3,893,858,
Specification No. 1290812 and Japanese Patent Application Laid-Open No. 53-9563
The compounds described in Publication No. 0 are preferred. Additionally, U.S. Patent No.
Also preferred are the compounds described in No. 4,552,834. child
These bleach accelerators may be added to the photosensitive material. Silver halide color photographic material of the present invention
After desilvering, it is easier to go through a water washing and/or stabilization process.
Common. The amount of water used in the washing process is determined by the characteristics of the photosensitive material.
(for example, depending on the material used, such as couplers), the purpose, and even the water
Replenishment of washing water temperature, number of washing tanks (number of stages), countercurrent flow, forward flow, etc.
It can be set in a wide range depending on the method and various other conditions. Of these, the number of washing tanks and water volume in the multi-stage countercurrent method
The relationship is Journal of the Society
of Motion Picture and Tel
evision Engineers Volume 64, 24
The method described on pages 8 to 253 (May 1955 issue)
You can [0106] The present invention will be further explained with reference to Examples below.
do. [Example 1] "Emulsion 1-A Octahedral silver bromide based grains" Potassium bromide was added to water.
Add and dissolve gelatin, gelatin and ammonia, and boil for 60 minutes.
Add the silver nitrate solution and potassium bromide with stirring into the solution kept at ℃.
A silver potential of −40 mV was obtained using a double jet method.
vsSCE and added. After the addition is complete, the temperature drops to 35℃.
After heating and removing soluble salts by sedimentation method,
℃, add gelatin to dissolve and adjust the pH to 6.3.
Ta. The obtained base particles are monodisperse with a projected area diameter of 0.7 μm.
It was an octahedral particle (coefficient of variation 12%). Emulsion 1-B Octahedral bromide with dislocation
"Silver particles (present invention)" Emulsion 1-A 625 g (in terms of silver nitrate)
Add 1110ml of water to 76g (equivalent to 76g) and heat to 50℃.
and held at a potential of +190 mV (vs. saturated calomel electrode).
While adding 160 ml of 0.34 M (mol) silver nitrate solution
and 0.84M sodium chloride aqueous solution in 8 minutes.
It was added by the Troll double jet method. Come here
As shown in Figure 1, minute silver chloride epitaxy
Many were generated on the faceplate base. FIG. 1 shows that on the surface of silver bromide octahedral base grains,
Showing the structure of a crystal formed by minute silver chloride epitaxy
This is a replica electron micrograph. [0110] Next, the temperature was raised to 75°C and physical ripening was performed for 12 minutes.
After that, 195cc of 0.84M KBr aqueous solution was added.
The conversion was completed in 15 minutes. Temperature drops to 50℃
Then, 340 ml of 0.51M silver nitrate aqueous solution and 0.51M
・KBr aqueous solution at a potential of -50 mV (vs. saturated calomel voltage)
Control jet method for 17 minutes while maintaining
It was added by After that, the emulsion was cooled to 35°C, and the conventional method was applied.
Washed with flocculation method and added 23g of bone gelatin.
and adjusted the pH to 6.3 and pAg to 8.5 at 40°C.
Afterwards, it was stored in a cool dark place. The obtained particles have a projected area diameter
It was a monodisperse octahedron of 0.83 μm (coefficient of variation 12%).
Ta. Emulsion 1-C Decahedral silver bromide base grains
”0.02 weight containing 0.004M potassium bromide
% gelatin solution at 60°C and do not stir it.
0.50M silver nitrate solution and 0.5M silver nitrate solution using the double jet method.
Add 40cc of 50M potassium bromide solution to each
Ta. After the addition is complete, 50% ammonium nitrate 15c
c and 6.4 cc of 25% aqueous ammonia were added. Then 1 liter of 1.2M silver nitrate solution was added over 50 minutes.
. 1.3 to keep the pAg at 8.1 during this addition.
A potassium bromide solution of M was added at the same time. [0113] After this, the emulsion was cooled to 35°C and the conventional method was applied.
Washed by flocculation method and adjusted to pH 6 at 40°C.
．． 3. Adjusted pAg to 8.7. The resulting particles are monodisperse
consisting of dodecahedral particles (coefficient of variation 13%), and the average
The projected area diameter is 0.7 μm, and the Kubelker-Munk equation
The {111} surface ratio calculated from the above was 63%. "Emulsion 1-D with dislocations on the {111} plane"
Decahedral Silver Bromide Grains (Present Invention) Emulsion 1-C625
g (equivalent to 76 g in terms of silver nitrate) and 1110 ml of water
and a potential of +190 mV at 50°C (versus saturation calories).
0.34M silver nitrate solution was added to the
60ml and 0.84M sodium chloride aqueous solution for 8 minutes
It was added by a controlled double jet method between child
In this, minute silver chloride epitaxy forms a dodecahedral grain.
It was deposited only on the {111} plane. After this, the temperature is 75℃.
After raising the temperature and physically aging for 12 minutes, 0.84M KBr
Add 195cc of aqueous solution and convert in 15 minutes
complete. [0115] The temperature was lowered to 50°C, and 0.51M silver nitrate aqueous solution was added.
340 ml of liquid and 0.51 KBr aqueous solution were charged at +10 mV.
(vs. saturated calomel electrode) for 17 minutes.
It was added by the Troll double jet method. After that, the emulsion was cooled to 35°C and the conventional method was applied.
Washed with flocculation method and added 23g of bone gelatin.
and adjusted the pH to 6.3 and pAg to 8.5 at 40°C.
After that, it was stored in a cool dark place. The obtained particles have a projected area diameter of 0
．． 83 μm monodispersed tetradecahedral particles (coefficient of variation 12%)
there were. Emulsion 1-E with dislocations at the edges and apex
octahedral silver bromide grains (invention)” +19 at 50°C
Add silver nitrate and sodium chloride aqueous solution at a potential of 0 mV.
1.5mM of Compound I per mole of silver was added before
except that it was adsorbed by stirring at 40°C for 30 minutes.
, in exactly the same manner as Emulsion 1-B. Here silver chloride
A large number of epikitasis were generated at the tops and edges of the base grains.
. (Compound I) [0118] The obtained particles have a projected area of 0.83 μm.
The particles were dispersed octahedral particles (coefficient of variation 12%). Emulsion 1-F Silver bromide 8 without dislocation
"Hedron particle (comparative example)" +190mV electric potential at 50℃
160ml of 0.34M silver nitrate solution and 0.34M silver nitrate solution.
Emulsion except that 84M KBr aqueous solution was added for 8 minutes.
It was carried out in exactly the same manner as 1-B. The obtained particles have a projected area of 0
．． 83μm monodisperse octahedral particles (coefficient of variation 12%)
It was. Emulsion 1-G Silver bromide without dislocation
Tetrahedral particles (comparative example)” +190 mV at 50°C
160 ml of 0.34 M silver nitrate solution and 0
．． Milk except that 84M KBr aqueous solution was added for 8 minutes.
The reaction was carried out in exactly the same manner as in Agent 1-D. The obtained particle has a projected area
0.83 μm monodispersed tetradecahedral particles (coefficient of variation 12%)
Met. 0121 “Confirmation of dislocations introduced into normal crystal grains” Milk
Regarding agents 1-B, 1-D, 1-E, 1-F and 1-G
Then, use the method described above to check for the presence of dislocation lines.
Ta. (Direct observation using a transmission electron microscope) Above
Grain made into a thin plate by wet etching
Direct observation of dislocations using a transmission electron microscope
went. The electron microscope is JEM2000 manufactured by JEOL Ltd.
Using FXII, acceleration voltage 200kV, temperature -120℃
Observed at. An example of a transmission electron micrograph is shown in 1-B.
2 and 1-F are shown in FIG. 3, respectively. Emulsion 1-B has dislocations on the entire surface.
I understand that. Also, for 1-D, on the {111} plane
1-E, there are many near the ridges and tops.
The presence of dislocations was confirmed. On the other hand, 1-F
No dislocation was found in 1-G and 1-G. Next, 1-B, 1-D, 1-E, 1-F,
Add the following spectral sensitized colors to the emulsion of 1-G at a temperature of 60°C.
The total amount of elements A and B is halogen at a weight ratio of 200:1.
Added as 800 mg per mole of silveride, and after 10 minutes
Added 0.6g of copolymer of styrene and maleic anhydride.
, after another 2 minutes add 1 mol of silver ammonium thiocyanate.
1.9 x 10-3 mol per chloroauric acid, and the appropriate amount of chloroauric acid.
and Hypo were added to start chemical ripening. 4-Hydroxy
C-6-methyl-1,3,3a,7-tetrazaindene
After adding 3 x 10-2 mol, the temperature was lowered after 1 minute.
After finishing the sensitization, a photographic emulsion coating solution was prepared. [0125] The photographic emulsion layer has a silver equivalent value of one piece of the support.
1.8g/m2 per side, gelatin amount 2.0g/m2
The amount of gelatin applied to the protective layer is 1.0g so that
/m2, two slide hopper type cords
polyethylene terephthalate at a speed of 60 m/min.
Coat both sides simultaneously on a sheet film base in 2 minutes and 20 seconds.
It was dried and a sample was obtained. The spectral sensitizing dyes used for sample preparation are as follows:
It is. Spectral sensitizing dye A [Chemical 2] Spectral sensitizing dye B [Chemical 3] Also, emulsion liquid (silver halide photographic emulsion coating
The additives used in the liquid) are as follows. The amount added is halogen
The amount is expressed per mole of silver oxide. 1,1-dimethylol-1-prom-1-nitromethane
70
mg [Chemical formula 4] 150mg t-butyl-catechol
400
mg polyvinylpyrrolidone (molecular weight 10,000)
1.0g styrene
-maleic anhydride copolymer
2.5g Trimethylo
Lupropane
10g Jie
tyrene glycol
　　　　　　　　　　　　　　　　　　　　　　　　　
5g nitrophenyl-triphenylphosphonium
Lorido 50mg1,3-
Ammonium hydroxybenzene-4-sulfonate
4g2-Mercaptobenzimidazole
Sodium L-5-sulfonate 1.5g [Chemical formula 5
] 70mg [Chemical formula 6] 1g [0128] Also, the additives used in the protective layer solution are as follows.
It is. The amount added is expressed per liter of coating solution. Lime-treated inert gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
68g acid-treated gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2g [Chemical 7] (Coating aid) 1g Po
Limethyl methacrylate (macro with an area average particle size of 3.5 μm)
1.1g silicon dioxide particles (area average particle size
1.2μm matting agent) 0.5g
Ludox AM (DuPont colloidal silica)
3.0g2,4-diku
Rolo-6-hydroxy-1,3,5-triazinna
2% aqueous solution of thorium salt (hardener)
10ml formalin 35% (hardener)
　　　　　　　　　　　　　　　　　　　　　　　　　
2ml glyoxal aqueous solution
40% (hardener)
1.5ml [Formula 8] 1.0g [Formula 9] 0.4g [Formula 10] 0.3g [Formula 11] (n is a mixture of 2 to 5) 2.5g [Formula 12]
] 0.5g [Chemical formula 13] 3mg C4 F9 SO3 K
　　　　　　　　　　　　　　　　　　　　　　　　　
2mgC10H21CONH(CH
2CH2O)6H
3g 0129 In addition, apply
In addition to the above additives, the liquid contains the following compounds (1) and (2):
Add the following amount per mole of silver halide.
Ta. (1) [Chemical formula 14] 200mg (2) Tricresyl phosphate
0.6g [
That is, compound (1) was prepared in JP-A-61-28
Method described in Example 1 (3) in Publication No. 5445
Dissolved in oil consisting of compound (2) according to
Dispersed in the aqueous colloid solution, the amount added above is
was added in an amount equal to [0131] "Automatic processing machine processing" The developing solution and fixing solution are as follows.
I used the one from (Developer) Potassium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
70g Hydroxyethylethylenediami
trisodium triacetate
8g 1,4-dihydroxybenzene
　　　　　　　　　　　　　　　　　　　　　　　　　
28g boric acid
　　　　　　　　　　　　　　　　　　　　　　　　　
10g5-methy
Rubenzotriazole
0.04g 1
-phenyl-5-mercaptotetrazole
0.01g metabisulfite
sodium
5
g Acetic acid (90%)
　　　　　　　　　　　　　　　　　　　　　　　　　
13g triethylene glycol
　　　　　　　　　　　　　　　　　　　　　　　　　
15g1-phenyl-3
-pyrazolidone
1.2g 5-nitroin
Dazol
0.2g
15] 0.001g glutaraldehyde
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0g Disodium ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0g5-nitrobenzoy
midazole
1.0g1L aqueous solution
Then, the solution was made into a solution having a pH of 10.50 with potassium hydroxide. (Fixer) Sodium thiosulfate-pentahydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
45g ethylenediaminetetraacetic acid disodium
0
．． 5g ammonium thiosulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
150g anhydrous sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
8g potassium acetate
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
16g Aluminum sulfate 10-18 hydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
27g sulfuric acid (50wt%)
　　　　　　　　　　　　　　　　　　　　　　　　　
6g citric acid
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1g boric acid
　　　　　　　　　　　　　　　　　　　　　　　　　
7g glacial acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Add glacial acetic acid to make 5g1l aqueous solution.
It was made into a liquid with a pH of 4.0. [0133] Place the above developer concentrate in a polyethylene container.
Each part was filled. This container is part A, B, C.
Each container is connected together. [0134] The fixer concentrate mentioned above is also made of polyethylene.
Filled the container. [0135] These developing solutions and fixing solutions were mixed in the following proportions.
In the developing tank and fixing tank of the automatic processor,
It was filled using a metering pump installed in the. Developer IA agent
　　　　　　　　　　　　　　　　　　　　　　　　　
55ml B agent
　　　　　　　　　　　　　　　　　　　　　　　　　
10ml C agent
　　　　　　　　　　　　　　　　　　　　　　　　　
10ml
water
　　　　　　　　　　　　　　　　　　　　　　　　　
125ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
10.50 [0137] Fixer Concentrate
　　　　　　　　　　　　　　　　　　　　　　　　　
80ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
120ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
4.65
[0138] Fill the washing tank with tap water and drain the bottom of the tank.
A solution consisting of Na2O/B2O5/SiO2
Silver sustained release agent 50 containing 1.0 wt% Ag2O in synthetic glass
4 bags wrapped in non-woven fabric were submerged. 0139 “Configuration of automatic processor” Use an automatic processor with the following configuration.
used. ──────────────────────────
────────────
Tank Processing temperature Processing path length
Processing process
Liquid amount
time
────────────────
────────────────────── Current
Image 15l 35℃
466mm 10.1 seconds
(Liquid surface area and tank capacity ratio = 35cm2
/l) Fixation 15l
32℃ 328mm 7.
Wash with water for 1 second 13l 17
°C flowing water 268mm 5.0 seconds
squeeze
　　　　　　　　　　　　　　　　　　　　　　　　　
Dry for 5.0 seconds
58℃ 29
9mm 6.5 seconds total
　　　　　　　　　　　　　　　　　　　　　　　　　
33.7 seconds────
──────────────────────────
──────── [0140] Obtained “photographic evaluation”
The sample was transferred to a fluorescent intensifying screen KO-250 (sold by Konica Corporation).
sandwiched between, tube voltage 130KVP, 20mA, 0.0
After irradiating X-rays for 5 seconds,
Exposure through a mini-staircase (sold by Konica Medical Co., Ltd.)
After that, the above treatment was performed. [0141] The sensitivity is 1-F in Table 4, fog +1
．． Relative to 100, which is the reciprocal of the X-ray dose that gives a degree of darkening of 0.
Shown as sensitivity. The gradations are Fog+0.25 and Fog+2.
It is expressed by the slope of a straight line connecting the 0 concentration points. The results are shown in Table 1.
I stopped it. [0142] “Method for evaluating stress characteristics of the above sample” Obtained graph
The film-coated sample was conditioned to a relative humidity of 40% at 25°C.
bend under certain conditions. This bending is done using a piece of iron with a diameter of 6mm.
It was bent 180° along the rod. Immediately after this operation 10
Wedge exposure was given at −2 sec. Place the exposed sample in front of
Developed using the processing solution and automatic developing machine described above, fixed, washed with water,
Dry. [0143] Thus, after processing, the
Darkening due to bending is relative to the maximum density of fog change.
It was expressed as the ratio ΔFog/Dm. The results are shown in Table 1. [Table 1] As shown in Table 1, the emulsion of the present invention has a
The temperature is high, the gradation is high, and the pressure build-up is significantly improved.
Ru. [Example 2] "Emulsion 2-A Octahedral silver iodobromide base grains" 0.00
0.02% by weight gelatin containing 4M potassium bromide
Keep 1 liter of carbon solution at 60°C and add carbon bromide while stirring.
Apply a solution containing potassium iodide and silver nitrate solution.
Addition using the double jet method while maintaining a suitable silver potential
did. [0146] After the addition was completed, the temperature was lowered to 35°C and the sedimentation method was performed.
After removing soluble salts, heat the gelatin at 40℃ again.
Add 50g and dissolve, adjust the pH to 6.8 and prepare the base grains.
I made baby emulsion. The obtained base grains are monodisperse octahedral grains.
(coefficient of variation 14%), and its average projected area diameter is 0.9
It was 5 μm. In addition, the AgI content near the surface is
According to the measurement of A, it was 8 mol%. Emulsion 2-B Silver iodobromide with transition
"Octahedral grains (present invention)" Emulsion 1-A 625 g (silver nitrate conversion)
(equivalent to 76g) and 1110ml of water at 50°C.
to a potential of +190 mV (vs. saturated calomel electrode) at
While maintaining, add 160 ml of 0.34 M silver nitrate solution,
Control 0.84M sodium chloride aqueous solution in 8 minutes
It was added by double jet method. Here, silver chloride
Epitaxy was generated in some planes on the octahedral base.
. After heating to 75℃ and physical aging for 12 minutes, 0.84
Add 195cc of M・KBr aqueous solution and convert in 15 minutes.
Completed version. The temperature was lowered to 50℃, and 0.51M
340ml of silver nitrate aqueous solution, 0.51M KBr and 0.0
A solution in which 4M KI was mixed and dissolved was heated to a potential of -50mV.
Using the controlled jet method for 17 minutes while maintaining
Added. [0148] After this, the emulsion was cooled to 35°C and
Washed with flocculation method and added 23g of bone gelatin.
and adjusted the pH to 6.3 and pAg to 8.5 at 40°C.
Afterwards, it was stored in a cool dark place. The obtained particles have a projected area diameter
1.12 μm monodispersed octahedral particles (coefficient of variation 14%)
there were. Emulsion 2-C Decahedral silver iodobromide base
0.02 particles containing 0.004M potassium bromide
Keep 1 liter of gelatin solution at 60℃ and stir it.
While preparing a solution containing potassium bromide and potassium iodide,
Double jet silver nitrate solution while maintaining appropriate silver potential
Added by method. [0150] After the addition, the temperature was lowered to 35°C and the precipitation method was carried out.
After removing more soluble salts, the gelatin was heated to 40°C again.
Add 50g of Chin to dissolve, adjust the pH to 6.8, and add the base.
A disk grain emulsion was made. The obtained base particles were monodisperse
Hedron grains (coefficient of variation 14%), whose average projected area diameter is
0.95 μm, calculated from Kubelker-Munk's formula
The {111} surface ratio is 58%, and the Ag near the surface
The I content was 8 mol% as determined by ESCA. "Emulsion 2-D has dislocations on the {111} plane"
Decahedral Silver Iodobromide Grains (Invention)” Emulsion 2-C625
g (equivalent to 76 g in terms of silver nitrate) and 1110 ml of water
and a potential of +190 mV (versus saturation voltage) at 50°C.
0.34M silver nitrate solution while keeping it at a Romel electrode).
160 ml and 0.84 M sodium chloride aqueous solution
It was added by controlled double jet method for 1 minute. Here, silver chloride epitaxy is caused by {
111} surface only. After this, the temperature was raised to 75℃
After physical aging for 12 minutes, 0.84M KBr aqueous solution
Add 195cc of liquid and complete the conversion in 15 minutes.
Completed. [0152] The temperature was lowered to 50°C, and 0.51M silver nitrate aqueous solution was added.
340 ml of liquid, 0.51 KBr and 0.04 M K
Keep the solution containing I mixed and dissolved at a potential of +10 mV.
Added using controlled double jet method in 17 minutes.
added. [0153] After this, the emulsion was cooled to 35°C and
Washed with flocculation method and added 23g of bone gelatin.
and adjusted the pH to 6.3 and pAg to 8.5 at 40°C.
After that, it was stored in a cool dark place. The obtained particles have a projected area diameter of 1
．． With 12 μm monodispersed tetradecahedral particles (coefficient of variation 14%)
there were. Emulsion 2-E with dislocations at the edges and apex
"octahedral silver iodobromide particles (invention)" at 50°C
Silver nitrate and sodium chloride aqueous solution were added at a potential of 190 mV.
1.5 mM of Compound I per mole of silver before addition.
After adding it and stirring it for 30 minutes at 40℃, it was adsorbed.
The rest was carried out in exactly the same manner as Emulsion 2-B. salt here
Silver compound epikitacy occurs in large numbers at the tops and edges of the base grains.
was. The obtained particles are monodisperse with a projected area of 1.12 μm.
It was an octahedral particle (coefficient of variation 14%). Emulsion 2-F Iodobromide without rearrangement
Silver octahedral particles (invention)” +190 mV at 50°C
160 ml of 0.34 M silver nitrate solution at a potential of
By mixing 0.84M KBr and 0.04M KI
Emulsion 2-B except that the dissolved solution was added for 8 minutes.
I did exactly the same thing. The obtained particles have a projected area of 1.12μ
m monodisperse octahedral particles (coefficient of variation 12%). Emulsion 2-G Iodobromide without rearrangement
Silver dodecahedral particles (comparative example) +190 m at 50°C
160 ml of 0.34 M silver nitrate solution at a potential of V
by mixing with 0.84M KBr and 0.04M KI.
Emulsion 2-D except that the dissolved solution was added for 8 minutes.
I did exactly the same thing. The obtained particles have a projected area of 0.83μ
m monodispersed tetradecahedral particles (coefficient of variation 12%). (Confirmation of dislocations introduced into normal crystal grains) Milk
Regarding agents 2-B, 2-D, 2-E, 2-F, and 2-G,
The presence or absence of dislocation lines was confirmed using the method described in Example 1.
. For observation using a direct transmission electron microscope, see Example 1.
Similarly, emulsions 2-B, 2-D, and 2-E are silver chloride epitaxy.
It was confirmed that a dislocation line exists in the area where the sea was formed.
did it. No dislocation was observed for emulsions 2-F and 2-G.
It wasn't served. From the above, the emulsion of the present invention contains silver chloride.
A dislocation line was introduced at the site where epitaxy was formed.
is clear. Next, emulsions 2-B, 2-D, 2-E, 2-
F, 2-G with sodium thiosulfate at a temperature of 60 °C
Optimal chemical amplification with potassium thiocyanate and chloroauric acid
I felt it. Cellulose triacetate film with primer coating
Coat each layer of the composition shown below on the support in multiple layers.
, Emulsion 2 of this example was applied to the first green-sensitive layer of the multilayer color light-sensitive material.
-B, 2-D, 2-E, 2-F, 2-G (optimally gold-sulfur
Samples 201 to 205 containing sensitized samples were prepared. (Photosensitive layer composition) The numbers corresponding to each component are as follows:
Indicates the coating weight in g/m2, and is applied to silver halide.
In this case, the coating amount is shown in terms of silver. However, regarding sensitizing dyes
Then, the coating amount per mole of silver halide in the same layer is
Expressed in moles. (Sample 101) First layer (antihalation layer) Black colloidal silver
Silver 0.
18 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.40 Second layer (middle layer) 2,5-di-t-pentadecylhydroquinone
0.18 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070EX
-3
0.
020 EX-12
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-3 U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.060 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
080 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 Zera
Chin
1.
04 [0164] Third layer (first red-sensitive emulsion layer) Emulsion A
Silver
0.25 Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.25 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
6.9×10-5 sensitization
Dye II
1.8×
10-5 Sensitizing dye III
　　　　　　　　　　　　　　　　　　　　　　　　　
3.1×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.34 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020
U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070H
BS-1
0.
060 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.87 [0165] Fourth layer (second red-sensitive emulsion layer) Emulsion G
Silver
1.00 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.1×10-5 Sensitizing dye II
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4×10-5
Sensitizing dye III
2.3
×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015
U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.30 [0166] Fifth layer (third red-sensitive emulsion layer) Emulsion D
Silver
1.60 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.4×10-5 Sensitizing dye II
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4×10-5
Sensitizing dye III
2.4
×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.097 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010 EX-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08
0 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.22 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.63 0167 6th layer (middle layer) EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.040 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80 7th layer (first green-sensitive emulsion layer) Emulsion 2-B, 2-D, 2-E, 2-F or 2-G
Silver 0.15 Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.15 Sensitizing dye IV
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-5
Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 Sensitizing dye VI
　　　　　　　　　　　　　　　　　　　　　　　　　
3.8×10-4 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.021
EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.26 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.025 HBS-
1
0.10
HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.63 [0169] 8th layer (second green-sensitive emulsion layer) Emulsion C
Silver
0.45 Sensitizing dye IV
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-5 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-5
Sensitizing dye VI
2.
6×10-4 EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.094 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.026 EX-
8
0.0
18 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-3 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50
9th layer (third green-sensitive emulsion layer) Emulsion E
Silver
1.20 Sensitizing dye IV
　　　　　　　　　　　　　　　　　　　　　　　　　
3.5×10-5 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-5
Sensitizing dye VI
3.
0x10-4 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.025 EX-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 EX-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015
HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.54 0
171] 10th layer (yellow filter layer) yellow colloidal silver
Silver 0.
050 EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.95 01
72] Eleventh layer (first blue-sensitive emulsion layer) Emulsion A
Silver
0.015 Emulsion F
　　　　　　　　　　　　　　　　　　　　　　　　　
silver 0.070
Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
3.5×10-4 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.042
EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.72 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.28
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 12th layer (second blue-sensitive emulsion layer) Emulsion G
Silver
0.45 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-4
EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-3
HBS-1
0
．． 050 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.78 [
13th layer (third blue-sensitive emulsion layer) Emulsion H
Silver
0.77 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.2×10-4
EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.69 14th layer (first protective layer) Emulsion I
Silver
0.20 U-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11
U-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 HBS-
1
5.0×1
0-2 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 15th layer (second protective layer) H-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 B-1 (diameter 1.
7μm)
5.0×10-2 B-2(
diameter 1.7μm)
0.10
B-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.20 0177
In addition, all layers are preservable, processable, pressure resistant, and anti-mold/bacterial.
In order to improve the properties, antistatic properties, and coating properties.
, W-1, W-2, W-3, B-4, B-5, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F
-8, F-9, F-10, F-11, F-12, F-1
3 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains dium salts. 0178] ──────────────────────────
──────────── Average AgI
Average particle size Diameter related to particle size/
Silver content ratio
Rate (%) (μm) Coefficient of variation (%) Thickness
Ratio (AgI content%) ────────
──────────────────────────
────Emulsion A 4.0 0.45
27 1 Core/Shell=
1/3 (13/1),
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion B
8.9 0.70 14
1 core/shell = 3/7 (25/2),
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion C 10 0.7
5 30 2 ko
A/shell = 1/2 (24/3),
　　　　　　　　　　　　　　　　　　　　　　　　　
double structure particles
Emulsion D 16 1.05 35
2 Core/Shell = 4/6
(40/0),
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion E 10
1.05 35
3 Core/shell = 1/2 (24/3),
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion F 4.0 0.25
28 1 Core/Si
Well = 1/3 (13/1),
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion G
14.0 0.75 25
2 Core/shell = 1/2 (42/0
),
　　　　　　　　　　　　　　　　　　　　　　　　　
Double structure grain emulsion H 14.5 1.3
0 25 3
A/shell = 37/63 (34/3),
　　　　　　　　　　　　　　　　　　　　　　　　　
double structure
Grain emulsion I 1 0.07
15 1 Uniform particles────
──────────────────────────
──────── [0179]EX-1 [Formula 16] [Formula 16] [Formula 16] [Formula 17] [Formula 17] [Formula 17] [Formula 18] [Formula 18] [Formula 18] ]EX-5 [Chemical formula 20] [Chemical formula 21] n=50, m=25, m'=
25, mol. wt. Approximately 20000 0185 EX-
7 [Chemical 22] EX-8 [Chemical 23] EX-9 [Chemical 24] [Chemical 24] EX-10 [Chemical 25] 12 [Chemical 27] EX-13 [Chemical 28] [Chemical 29] U-1 [Chemical 29] [Chemical 29] [Chemical 30] 4 [Chemical 32] x:y=70:30 (wt%) [0196] U-5 [Chemical 33] [0197] HBS-1
Tricresyl phosphate HBS-2
Ji
-n-Butyl phthalate HBS-3 [Chemical 34] Sensitizing dye I [Chemical 35] Sensitizing dye II [Chemical 36] [0200] Sensitizing dye III [Chemical 37] [0201] Sensitizing Dye IV [Chemical 38] [Chemical 38] Sensitizing Dye V [Chemical 39] [Chemical 40] Sensitizing Dye VI [Chemical 40] [Chemical 41] [Chemical 41] [Chemical 41] [Chemical 42] [Chemical 42] H-1 [Chemical 43] B-1 [Chemical 44] x/y=10/90 [0208] B-2 [Chemical 45] x/y=40/60 0209] B-3 [ Formula 46] B-4 [Chemical 47] B-5 [Chemical 48] x/y=70/30 [Chemical 49] [Chemical 49] n=2-4 W-3 [Chemical 51] F-1 [Chemical 52] F-2 [Chemical 53] F-3 [Chemical 54] [0218] F- 4 [Chemical 55] F-5 [Chemical 56] F-6 [Chemical 57] [Chemical 57] F-7 [Chemical 58] F-8 [Chemical 59] [0223] F- 9 [Formula 60] F-10 [Formula 61] [Formula 61] [Formula 62] [Formula 62] [Formula 63] [Formula 63] [Formula 64] [Formula 64] [Formula 64] Samples 201-20 obtained by
SC-52, which transmits light with a wavelength longer than 520nm.
Automatically develops by exposing to light in 1/10 seconds through a professional filter.
Using the processing method described below (cumulative replenishment amount of bleach solution)
(until the volume was three times the volume of its mother liquor tank). 0229] ──────────────────────────
──────────── Process
Processing time Processing temperature Replenishment fee*
Tank capacity ────────────
──────────────────────────
Color development 3 minutes 15 seconds 38℃
33ml 20l floating
White 6 minutes 30 seconds 38℃
25ml 40l water wash
2 minutes 10 seconds 24℃ 120
0ml 20l Fixation
4 minutes 20 seconds 38℃ 25ml
30l water washing (1) 1 minute 05 seconds
24℃ (2) to (1)
10l
Countercurrent piping method
Washing with water (2) 1 minute 00 seconds 24℃
1200ml 10l stable
1 minute 05 seconds 38℃
25ml 10l dry
4 minutes 20 seconds 55℃────────────
──────────────────────────
*Replenishment amount per 35 mm width and 1 m length Next, the composition of the treatment liquid will be described. (color developer)
Mother liquor (g)
Replenisher (g) diethylenetriaminepentaacetic acid
1.0
1.11-hydroxyethylidene-
3.0
3.2 Sodium 1,1-diphosphonate sulfite
4.0 4
．． 4 potassium carbonate
30.0
37.0 Potassium Bromide
1.4
0.7 potassium iodide
1.5
mg - hydroxylamine sulfate
2.4
2.84-(N-ethyl-N-β-hydroxy
ethylamino)-2-methylaniline sulfate (water
plus 1 liter) 4.5 5.
5pH
10.05
10.10 (Bleach solution)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
2nd iron
sodium trihydrate
100.0 120.0 Ethylenediaminetetravinegar
acid
　　　　　　　　　　　　　　　　　　　　　　　　　
disodium salt
10.0 11
．． 0 ammonium bromide
140.0 160.0
ammonium nitrate
30.0 35.0
Ammonia water (27%)
6.5ml 4.0ml water
plus
1.0l
1.0lpH
6.
0 5.7 0232 (Fixer)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
Ninato
lium salt
0.5 0.7 sulfur
acid sodium
7.0 8.0
sodium bisulfite
5.0 5.
5Ammonium thiosulfate aqueous solution (70%) 17
0. ml 200.0ml add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0lpH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.7
6.6 (Stabilizer)
Mother liquor (g)
Replenisher (g) Formalin (37%)
2.0ml
3.0ml polyoxyethylene-p-monononi
phenyl ether (average degree of polymerization 10)
0.3 0.45 ethylenedia
Minetetraacetic acid disodium salt 0.0
5 Add 0.08 water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0lpH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0~8.0 5.0~8.0 02
34] The sample treated in this way is passed through a green filter.
The concentration was measured. The photographic performance results obtained are shown in Table 2 below.
vinegar. [0235] Further, pressure was applied in the same manner as shown in Example 1.
The force characteristics were evaluated. The sample that was bent is shown above.
The same process was performed as described. The obtained results are also shown in Table 2.
show. [Table 2] As can be seen from the results in Table 2, the emulsion of the present invention
Coated samples 201 to 203 are samples coated with comparative emulsion.
Higher sensitivity and less pressure build-up than materials 204 and 205
.

[Brief explanation of drawings]

FIG. 1 is a representative replica electron micrograph showing the structure of a crystal in which minute silver chloride epitaxy is formed on the surface of silver bromide octahedral base grains.

2 is a transmission electron micrograph showing a typical silver halide crystal structure of Emulsion 1-B prepared in Example 1. FIG.

FIG. 3 shows emulsion 1-1 prepared in Example 1, respectively.
This is a transmission electron micrograph showing a typical silver halide crystal structure of F.

Claims (2)

[Claims] 1. A photographic light-sensitive material having a silver halide emulsion layer on a support, wherein the emulsion layer contains normal crystal silver halide grains, and at least 30% of the normal crystal silver halide grains. A silver halide photographic material characterized in that the above grains have dislocation lines inside the grains. [Claim 2] A silver halide emulsion containing normal silver halide crystals having dislocation lines inside the grains is prepared by the following three processes, and then the obtained silver halide emulsion is coated on a support. A method for producing a silver halide photographic material characterized by: ■Preparation of normal crystal grains as a base;■
Formation of fine epitaxy of silver chloride or silver chlorobromide on the underlying normal crystal grains; and (2) physical ripening of the fine epitaxy of normal crystal grains and/or conversion by halogen.