JPH04257847A - Photosensitive silver halide emulsion and silver halide photographic sensitive material using same - Google Patents

Abstract

PURPOSE:To enhance color sensitizing effect, to improve sensitivity/particles ratio and to raise contrast for a photosensitive silver halide emulsion. CONSTITUTION:A photosensitive silver halide emulsion is formed by providing an area having more silver iodide content inside of particles than at surface of the particles, allowing the surface of multilayers structured silver halide host particle which content of silver iodide in the surface is <5mol% and containing >=3mol% average silver iodide content over the whole particles to convert (halogen conversion) by fine silver iodide particles, or the emulsion can be obtained by adding at least two kinds of spectral sensitized dye after the above conversion and chemically sensitizing afterward.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention provides novel photosensitive halogen
Silver halide emulsion and silver halide photographic material using the same
particularly high sensitivity, excellent graininess, and high contrast.
Silver halide emulsion having
Regarding materials. [Prior Art] In recent years, silver halide emulsions for photography have
Demand for improved performance is becoming increasingly strict, and demands for high sensitivity and high control are becoming increasingly strict.
There is no high level requirement for last and excellent graininess.
It is. [0003] In response to such requirements, the silver iodide content inside the grains is
Technology to improve sensitivity/graininess ratio by increasing
JP-A No. 60-138538, No. 60-143331
No. 61-112142, No. 61-20944
It is described in No. 5, etc. However, regarding these techniques, sensitized color
The inherent desensitization caused by the material is large, and the sensitivity of the sensitive material under high temperature conditions is
Problems such as sensitizing dyes being easily desorbed when stored
It had a point. [0005] In order to solve these problems, Japanese Patent Application Laid-Open No. 63-1
06745 has a high silver iodide content in the outermost layer and
, due to silver halide grains with high silver iodide content inside the grains.
As a result, there is less inherent desensitization caused by sensitizing dyes, and color sensitization efficiency is improved.
No technology has been disclosed for providing the above silver halide emulsion.
Ru. However, the silver halide emulsion mentioned above has low contrast.
Also, there was a problem of poor storage stability under high humidity conditions. Problem to be Solved by the Invention The problem to be solved by the present invention is to
Excellent sensitivity, improved sensitivity/granularity ratio, and high control
A photosensitive silver halide emulsion having a luster and the emulsion
Our objective is to provide silver halide photographic materials containing
. [Means for solving the problem] The above problem is solved by the following photosensitive method.
silver halide emulsions and silver halide photographic materials.
It was found that this can be achieved. (1) Higher silver iodide content inside the grain than on the grain surface
The silver iodide content on the grain surface is 5 mol%.
and the average silver iodide content of the entire grain is 3 mol.
For multilayered silver halide host grains larger than %
The grain surface of the host grain is coated with fine silver iodide grains.
Formed by conversion (halogen conversion)
Characteristic photosensitive silver halide emulsion. (2) At least after performing the conversion
Add two types of spectral sensitizing dyes and then perform chemical sensitization
The photosensitive silver halide described in (1) above, characterized in that
emulsion. (3) The amount of fine silver iodide grains is greater than the total silver in the host grains.
It is characterized by being 0.05 to 1.0 mol% based on the amount
The photosensitive silver halide emulsion described in (2) above. (4) At least one layer of photosensitive halogen on the support
It has a silver halide emulsion layer, and the silver halide emulsion layer has the above (1)
) to (3) photosensitive silver halide milk according to any one of (3)
Silver halide photographic material characterized by containing an agent
fee. The present invention will be explained in detail below. The present invention
The host grains have higher iodide levels inside the grains than on the grain surfaces.
A region having a silver content (hereinafter also simply referred to as a "layer")
It is characterized by being a multilayer structure type silver halide grain having
shall be. Here, the "region" is the area near the apex of a particle, etc. that is mutually dissimilar.
It may be continuous, but preferably a continuous area.
It is preferable that the layer has a certain thickness.
. [0009] How to make such silver halide grains is as follows:
For example, JP-A-60-35726, JP-A-60-13853
No. 8, No. 60-143331, No. 61-1121
No. 42, No. 61-245151, No. 62-123
No. 445, No. 62-131247, No. 62-20
No. 9445, No. 63-106745, No. 63-1
No. 47156, No. 63-167347, No. 63-
No. 285534, No. 63-285535, etc.
It is listed. Multilayer means that there are at least two particles
layers, preferably from 3 to 8 layers.
say. The interior of the grain contains more silver iodide than the surface of the grain.
It is sufficient that there is at least one layer with a high amount of
In addition to the high silver iodide-containing layer described above, layers with various silver iodide contents
It is a so-called multilayer structure particle that contains several layers.
You can. In other words, for example, the inside of the grain contains high silver iodide.
The grain surface consists of a layer with a low silver iodide content.
It may be a so-called double structure type silver halide grain,
In order from the inside of the grain, a low silver iodide content layer, a high silver iodide content layer, and a low silver iodide content layer.
It is a triple-structured silver halide grain consisting of a silver iodide-containing layer.
Silver iodide may be added from the inside of the grain toward the surface of the grain.
The internal high silver iodide content gradually decreases.
It may also be a silver halide grain. Of these, the present invention
The silver halide grains include double structure silver halide grains and
Triple structure silver halide grains are preferred, but quadruple structure or more
The above silver halide grains can also be used. A high silver iodide content layer inside the grain and a low silver iodide content layer on the grain surface.
The presence of a silver iodide-containing layer is generally determined by X-ray diffraction
can. Here, the particle surface refers to 50 to 100 points from the particle surface.
This is the difference in the area near the particle surface with a thickness of angstroms.
Ru. [0012] Application of X-ray diffraction method to silver halide grains
An example is H. Hirsch's Journal of Photography
P. 129 of Fitz Science Vol. 10 (1962)
It is mentioned below. Lattice by halogen composition
Once the constant is determined, Bragg's condition (2dsinθ=nλ)
A diffraction peak occurs at a diffraction angle that satisfies . Regarding the measurement method of X-ray diffraction, please refer to basic analytical chemistry.
Lecture 24 “X-ray analysis” (Kyoritsu Shuppan) and “X-ray diffraction guide”
” (Rigaku Denki Co., Ltd.). The standard measurement method uses Cu as a target and
Using Kβ rays as a radiation source (tube voltage 40 kV, tube current 60 mA)
) Method for determining the diffraction curve of the (220) plane of silver halide
It is. In order to increase the resolution of the measuring machine, a slit (emission
width of the scattering slit, light receiving slit, etc.), the time constant of the device,
Select the scanning speed and recording speed of the goniometer appropriately.
It is necessary to check the measurement accuracy using a standard sample such as
be. [0014] Using Kβ rays of Cu, silver halide grains are
When we obtain the curve of diffraction intensity versus diffraction angle for the (220) plane,
, the diffraction peak corresponding to the internal high silver iodide content layer and the surface
The diffraction peak corresponding to the low silver iodide content layer is separated.
may be detected. This phenomenon is especially true for double-structured halos.
In the case of silver germide grains, this is often noticeable. Various diffraction peaks
The separation of peaks may be clear, but sometimes the peaks overlap each other.
Sometimes the relationship is not clear. However, if it is not clear
Two or more weak peaks may be observed even when the Silver halide grains with a quadruple structure or more as described above, and grains
The silver iodide content gradually decreases from the inside of the grain to the grain surface.
In the case of silver halide grains such as
There are no holes visible, and the shape is wide. The host particles used in the present invention have distinct peaks.
Or, X with a peak that can be identified even if it is unclear
Silver halide grains with a line diffraction pattern are preferred. Silver halide grains with clear peaks in X-ray diffraction pattern
For information on how to create children, see JP-A-60-14331, etc.
It is described in. Distribution amount of high silver iodide content layer inside grains
and its silver iodide content can be calculated from the grain forming recipe.
In addition, particle sections sliced with a microtome can be analyzed using an electrolyte.
By scanning with a microscope and mapping the results
You can ask for it. Silver iodide in the high silver iodide-containing layer inside the host grain
The content is clearly higher than the silver iodide content on the grain surface.
However, it is preferable that the silver iodide content on the grain surface be
5 mol% or more higher than the percentage, more preferably 7
It is preferable that it is higher by mol% or more. Actually inside the host particle
The silver iodide content of the high silver iodide content layer is from 5 mol%.
Between 40 mol% of the solid solubility limit, as a preferred range
is 7 mol% to 40 mol%. The silver iodide content on the surface of the host grain is 5 mol.
% (including zero), but preferably 3 mol% or less
, more preferably 0 to 2 mol% or less. Silver iodide content near the surface of silver halide grains
The measurement is performed using XPS (X-ray Photoele).
ctron Spectroscopy) surface area
This can be done by analytical method. Regarding the principle of XPS method
``Electron spectroscopy'' by Junichi Aihara et al. (Kyoritsu Library)
16, published by Kyoritsu Shuppansha, 1978).
However, 50 to 100 ohms from the silver halide grain surface
It is possible to measure the silver iodide content in a part of the order of
I can do that. [0019] The standard measurement method for XPS is to use excited X-rays.
Halogenation using Mg-Kα to obtain an appropriate sample form.
Photoelectrons of iodine (I) and silver (Ag) released from silver particles
(usually I-3d5/2, Ag-3d5/2) strength
This is a method of observing the degree of To find the iodine content,
Using several types of standard samples with known iodine content,
Intensification of photoelectrons of iodine (I) and silver (Ag) (intensity (I)
/ strength (Ag)) and calculate from this calibration curve.
You can In silver halide emulsions, halogenated
Gelatin adsorbed on the surface of silver particles is treated with proteolytic enzymes, etc.
After decomposition and removal, XPS measurement is performed. Determination of the silver iodide content on the grain surface by the XPS method
The measurement is performed from 50 to 50 m from the silver halide grain surface as described above.
Measure the silver iodide content in an area of about 100 angstroms.
Therefore, it is not always necessary to accurately determine the silver iodide content on the grain surface.
It cannot be measured exactly. That is, 1 from the particle surface
High silver iodide is placed inside about 0.00 angstroms.
If there is a layer with high silver iodide content or if there is a high silver iodide content layer inside the grain.
When silver iodide seeps from the containing layer near the grain surface
indicates a higher silver iodide content than the prescribed silver iodide content
Data may be available. Host particles in the present invention
The silver iodide content on the surface is determined by the calibration curve determined by the above XPS method.
This refers to the silver iodide content determined from The halogen composition of the host grains of the present invention is
Silver bromide or silver iodochlorobromide is preferred, with silver iodobromide being preferred. The average silver iodide content of the entire host grain is greater than 3 mol%
The effect of the present invention is noticeable when the particles are
It is preferable that the average silver iodide content is 5 mol% to 20 mol%.
and more preferably 5 mol% to 15 mol%.
. The average silver iodide content of the entire grain is determined by removing gelatin.
Sample with silver halide grains annealed at 350°C for 1 hour
can be measured using the aforementioned X-ray diffraction method. The size of the host particles of the present invention is particularly limited.
However, it is preferably 0.3 μm or more, and more preferably 0.6 μm.
It is preferable that it is m - 2.5 micrometers. The host particle type of the present invention is hexahedral, octahedral.
Regular crystal shapes (normal
It may also have spherical, potato
It may have an irregular crystal shape such as a shape or a plate shape. In the case of normal crystal grains, the (111) plane is 50%
Particularly preferred are particles having the above. For irregular crystal forms
However, particles having 50% or more (111) faces are particularly preferred.
stomach. The surface ratio of the (111) plane is the Kubelka-Munk dye absorption
This can be determined by the way it is worn. This is a (111) plane or (
100) preferentially adsorbs to one of the (111)
Association state of dyes on plane and association state of dyes on (100) plane
Select dyes whose states differ spectrally. This way
Spectral spectra of dye added to the emulsion
By examining the torque in detail, the surface ratio of the (111) plane can be determined.
You can decide. In the case of twin grains, tabular grains are preferred.
stomach. The average thickness is 0.5μm or less and the diameter is 0.6μm or more.
Particles with a spectral ratio of 2 or more, preferably 3 to 10, are in the same layer
At least the total projected area of silver halide grains present in
Particularly preferred is the case where it accounts for 50%. average aspect ratio
For the definition and measurement method of
Publication No. 58-113930, Japanese Patent Publication No. 113930/1983
Specifically described in Publication No. 58-113934 etc.
There is. The emulsion of the present invention has a broad grain size distribution.
However, emulsions with a narrow grain size distribution are preferable.
Delicious. Especially in the case of normal crystal grains, silver halide grains
accounts for 90% of the total of each emulsion in terms of weight or grain number
The particle size is within ±40% of the average particle size, and
Monodisperse emulsions within ±30% are preferred. The method for preparing the host particles of the present invention is described in Japanese Patent Application Laid-open No. 6
No. 0-35726, No. 60-138538, No. 60
-14331 No. 61-112142, No. 61-
No. 245151, No. 62-123445, No. 62
No.-131247, No. 62-209445, No. 6
No. 3-147156, No. 63-167347, No. 3-147156, No. 63-167347, No.
63-285534, 63-285535, etc.
Reference patents and the documents and patents cited in them
However, in order to lower the silver iodide content on the grain surface,
, when forming the outermost layer of silver halide grains, iodide
In a state where the presence of ions is as small as possible and inside the particles.
Precipitate to prevent silver iodide from seeping out onto the grain surface.
to form a surface layer by reducing the solubility as much as possible during
is preferred. [0028] The host particles of the present invention can be prepared during the particle formation process or
During the physical ripening process, cadmium salt, zinc salt, lead salt
, thallium salt, iridium salt, rhenium salt, or their complexes.
salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc.
You may leave it there. [0029] Conversion of the surface of host particles
The amount of silver iodide fine grains used for
0.05 mol% to 1.0 mol% of iodine based on the total silver content of the
Silveride content is preferred, more preferably 0.1 mol%
~1.0 mol%. [0030] Here, converting means
A well-known term for surface halo with relatively high solubility is
Relative solubility for silver halide grains with a composition of
Halides or fines that form silver halide grains with low
Adding fine silver halide grains increases the relative solubility.
High surface halogen composition, low solubility halogen composition
refers to the phenomenon of changes in the surface of Silver iodide fine particles for conversion
The particle size is determined by the particle size of the host particle and the halogen group.
Although it varies depending on the composition, the average equivalent sphere diameter is 0.3 μm or less
are used. More preferably 0.1 μm or less
It is something. The halogen composition of silver iodide fine grains is pure silver iodide.
It is preferable that components other than silver iodide be contained in an amount of 1 mol%.
The grains may be substantially pure iodine grains. Silver iodide grains used for conversion (
(hereinafter also referred to as silver iodide fine particles) is added to a predetermined number of moles.
Reaction of corresponding soluble iodide aqueous solution and soluble silver salt aqueous solution
Particles are formed in a mixer installed outside the container and immediately reacted.
Add it to the reaction container or prepare it in advance.
This is achieved by adding fine silver iodide particles.
be able to. [0033] Soluble iodide aqueous solution and soluble silver salt aqueous solution
Addition after particle formation in a mixer installed outside the reaction vessel
The method to do this is described in Japanese Patent Application No. 2-25037.
You can refer to the method. Also, prepared in advance
The method of adding silver iodide fine grains is described in JP-A-1-183.
No. 417, JP-A-2-156239, JP-A-2-20
It can be carried out using the apparatus described in No. 7240.
can. Conversion by silver iodide fine particles
This may be carried out immediately after the surface layer of the host particles is formed, or
After particle formation, the host particles are washed with water for desalination and then
You can also use the method of converting. Conversion using fine silver iodide particles
When coating, it is preferable to use a known silver halide solvent.
. Preferred silver halide solvents include thioetherified
compound, thiocyanate, tetrasubstituted thiourea, aqueous ammonia
Examples include solutions. Among them, thiocyanate is effective.
Yes, depending on host grain size, halogen composition, and iodine
Although it depends on the amount of silver oxide fine particles added, 1 mol of host particles
The amount used is preferably 0.1 g to 5 g. [0036] The temperature when performing the conversion is 30
It is carried out at any temperature between ℃~80℃, but 40℃~
Preferably, the temperature is between 70°C. Conversion
The aging time depends on the particle size and halogen composition of the host particles,
Addition amount of silver iodide fine particles, conversion temperature, halogen
Although it varies depending on the presence or absence of a silver iodide solvent, the amount of silver iodide added
It is preferable to carry out the process until the particles completely disappear. The silver halide grains of the present invention are usually chemically amplified.
It is felt. Chemical sensitization is converted using silver iodide fine particles.
Conversion is performed on silver halide grains that have been
After chemical sensitization, chemical sensitization can be carried out as is, or
After versioning, wash with water according to the usual method before chemical sensitization.
You may. As a method of washing with water, there is a wide range of research studies.
Closer No. 308119 (December 1989
The method described in Section II of the following can be used. Chemical sensitization is carried out by T. H. Jam
es) Author, The Theory of Photography
・Process, 4th edition, Macmillan Publishing, 1977, (
T. H. James The Theory
Photographic Process, 4t
h ed, Macmillan, 1977) 67-7
Do this using activated gelatin as described on page 6.
Research Disclosure 120
Volume, April 1974, 12008; Research Disc
Roger, Volume 34, June 1975, 13452, US
National Patent No. 2,642,361, National Patent No. 3,297,44
No. 6, No. 3,772,031, No. 3,857,7
No. 11, No. 3,901,714, No. 4,266,
No. 018, and No. 3,904,415, and
As described in British Patent No. 1,315,755
pAg 5-10, pH 5-8 and temperature 30-80°C
Sulfur, selenium, tellurium, gold, platinum, palladium
, using iridium or multiple combinations of these sensitizers.
It can be done by Chemical sensitization is optimally performed with gold compounds.
In the presence of a thiocyanate compound, also U.S. Pat.
No. 587,711, No. 4,266,018 and
Sulfur-containing compounds described in No. 4,054,457
Or hypo, thiourea compounds, rhodanine compounds
sulfur-containing compounds such as U.S. Pat. No. 3,297,446
Publication No. 3,297,447
Performed in the presence of a ren-containing compound. In the presence of chemical sensitization aids
It can also be chemically sensitized. Chemical sensitization aid used
include azaindene, azapyridazine, azapyrimidine
In the process of chemical sensitization, fog is suppressed and sensitivity is increased.
Compounds known to increase are used. chemistry
Examples of sensitizer modifiers include U.S. Pat. No. 2,131,038
No. 3,411,914, No. 3,554,74
No. 7, JP-A-58-126526 and the above-mentioned duff
It is described in "Photographic Emulsion Chemistry" by Lin, pp. 138-143.
ing. In addition to or in place of chemical sensitization, U.S. patents
No. 3,891,446 and No. 3,984,249
Reduction sensitization using e.g. hydrogen as described in
and U.S. Patent No. 2,518,698
No. 2,743,182 and No. 2,743,1
As described in No. 83, stannous chloride, thiol dioxide
With rare, polyamines and such reducing agents,
or low pAg (e.g. less than 5) and/or high pH
(e.g. greater than 8) can be reduced sensitized by treatment.
Wear. Also, U.S. Patent No. 3,917,485 and
Color enhancement using the chemical sensitization method described in No. 3,966,476
It can also improve sensitivity. Furthermore, the converted halo of the present invention
Silver genenide grains are produced by adding a spectral sensitizing dye before chemical sensitization.
Preferably, the film is then chemically sensitized. spectral sensitizing dye
A method of chemical sensitization in the presence of is described, for example, in U.S. Pat.
, No. 425,426, No. 4,442,201, Special
No. 59-9658, No. 61-103149,
It is described in No. 61-133941. use
The spectral sensitizing dye used is usually a silver halide photographic dye.
Any spectral sensitizing dye used in optical materials
However, cyanine dyes, merocyanine dyes, and
and composite merocyanine dyes are preferred, specifically those disclosed in Japanese Patent Application Publication No.
63-106745, pages 23 to 42.
Represented by general formula (I) and general formula (II)
Spectral sensitizing dyes are preferred. The spectral sensitizing dye added before chemical sensitization is
One type is fine, but from the point of view of increasing spectral sensitization efficiency, two
It is particularly preferable to use a mixture of more than one type of spectral sensitizing dye.
Delicious. [0041] Using a combination of two or more spectral sensitizing dyes
This improves the spectral sensitization efficiency. So-called strong
Color sensitization techniques are described, for example, in U.S. Patent No. 2,688,545.
No. 2,977,229, No. 3,397,06
No. 0, No. 3,522,052, No. 3,527,6
No. 41, No. 3,617,293, No. 3,628,
No. 964, No. 3,666,480, No. 3,672
, No. 898, No. 3,679,428, No. 3,70
No. 3,377, No. 3,769,301, No. 3,8
No. 14,609, No. 3,837,862, No. 4,
No. 026,707, Special Publication No. 43-4936, No. 5
No. 3-12375, JP-A-52-110618, same.
No. 52-109925, JP-A-2-127636, etc.
It is described in. Here, the above supersensitization technique and the above
Combined with chemical sensitization technology in the presence of spectral sensitizing dyes
When applied to the silver halide emulsion of the present invention, remarkable
effect, good color sensitization efficiency, excellent graininess,
A silver halide emulsion with high contrast can be obtained.
That's what I found out. The silver halide photographic emulsion of the present invention can be prepared by various
It can be applied to color and black and white photosensitive materials. Color negative film and slides for general use or motion pictures
Color reversal film for cards or television, color expansion
Scattered photosensitive materials, heat-developable color photosensitive materials, direct and indirect physicians
Medical X-ray film, negative black and white film for photography, and
Examples include silver salt diffusion transfer type photosensitive materials. The light-sensitive material of the present invention has a blue-sensitive material on a support.
layer, green-sensitive layer, and red-sensitive layer.
It is sufficient if at least one layer is provided, silver halide milk
There are no particular restrictions on the number or order of the agent layer and non-photosensitive layer.
stomach. Typically, a substantially color-sensitive
Multiple silver halide emulsions with the same but different sensitivities
halogenated with at least one photosensitive layer consisting of
It is a silver photographic light-sensitive material, and the photosensitive layer has blue light, green light,
and a unit photosensitive layer sensitive to either red light.
Yes, in multilayer silver halide color photographic materials.
Generally, the unit photosensitive layers are arranged in order of red sensitivity from the support side.
A chromatic layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order. deer
However, even if the above installation order is reversed depending on the purpose, the same
The installation order is such that different photosensitive layers are sandwiched between color-sensitive layers.
You can get it. Between and above the silver halide photosensitive layers,
Non-photosensitive layers such as various intermediate layers are provided on the top and bottom layers.
Good too. [0045] For the intermediate layer, Japanese Patent Application Laid-Open No. 61-43748
, No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038
Contains couplers, DIR compounds, etc. as described in the book.
It may also contain a color mixing inhibitor, as is commonly used.
You can stay there. A plurality of halogens constituting each unit photosensitive layer
The silver oxide emulsion layer is described in West German Patent No. 1,121,470.
or as described in British Patent No. 923,045.
A two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer is preferably used.
can be done. Typically, the photosensitivity is sequential towards the support.
It is preferable to arrange them so that each halogen
A non-photosensitive layer may be provided between the emulsion layers. Ma
JP-A-57-112751, JP-A No. 62-2003
No. 50, No. 62-206541, No. 62-2065
The side away from the support as described in No. 43, etc.
A low-sensitivity emulsion layer is installed on the side, and a high-sensitivity emulsion layer is installed on the side closer to the support.
You may. As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL
)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (R
L) or BH/BL/GL/GH/RH/RL
or BH/BL/GH/GL/RL/RH
etc. can be installed. [0048] Also described in Japanese Patent Publication No. 55-34932
Blue-sensitive from the side farthest from the support as shown
They can also be arranged in the order of layer/GH/RH/GL/RL.
Ru. [0049] Also described in Japanese Patent Publication No. 49-15495
The upper layer is made of silver halide, which is the most sensitive.
The emulsion layer and the middle layer are silver halide emulsions with lower sensitivity.
The agent layer and the lower layer are made of silver halide, which has lower photosensitivity than the middle layer.
The emulsion layers are arranged and the sensitivity gradually decreases toward the support.
An example of this is an array consisting of three layers with different photosensitivity.
Ru. When it is composed of three layers with different photosensitivity like this
However, it is stated in the specification of JP-A No. 59-202464.
As shown in the figure, the distance from the support in the same color sensitive layer is
Medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the side
They may be arranged in order. Other high-sensitivity emulsion layers/low-sensitivity emulsion layers/medium
High-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer
They may be arranged in the order of the sensitive emulsion layer, etc. Also, 4
Even in the case of more than one layer, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
, No. 666,271, No. 4,705,744,
No. 4,707,436, JP-A-62-16044
No. 8, BL described in the specification of No. 63-89850
, GL, RL, etc., which have different spectral sensitivity distribution from the main photosensitive layer.
Layer effect donor layer (CL) adjacent to or close to the main photosensitive layer
It is preferable that they be placed in contact with each other. As mentioned above, the purpose of each photosensitive material is
Various layer configurations and arrangements can be selected depending on the requirements. [0053] Photographic milk of photographic light-sensitive materials that can be used in combination with the present invention
The preferred amount of silver halide contained in the agent layer is about 30 mol%.
Silver iodobromide, silver iodochloride, including the following silver iodides:
Silver is iodochlorobromide. Particularly preferred is about 2 mol%.
Silver iodobromide containing up to about 10 mol% silver iodide
Silver is iodochlorobromide. Silver halide grains that can be used in photographic emulsion layers
represents regular crystals such as cubes, octahedrons, and dodecahedrons.
have an irregular crystal shape such as spherical or plate-like
crystal defects such as twin planes, or
A composite form of these may also be used. [0055] The grain size of silver halide is approximately 0.2 μm or less.
Even small particles with a projected area diameter of about 10 μm
Size particles may be used, and polydisperse emulsions or monodisperse emulsions may be used.
But that's fine. Silver halide photographic emulsion that can be used in the present invention
For example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
ion and types)”, and the same No.
18716 (November 1979), p. 648, No.
307105 (November 1989), 863-865
``Physics and Chemistry of Photography'' by Paul P. and Grafkide, Paul
Published by Montel Publishing (P. Glafkides, Chemi
e et Physique Photography
que, Paul Montel, 1967), Duff
“Photographic Emulsion Chemistry” by Yin, published by Focal Press (G.
F. Duffin, Photographic Em
ulsion Chemistry (Focal P
ress, 1966)), Zelikman et al.
"Manufacturing and Application", published by Focal Press (V.L.Z.
elikmanetal. , Making and
Coating Photographic Emul
sion, Focal Press, 1964) etc.
It can be prepared using the method described. [0057] US Patent No. 3,574,628, 3
, 655,394 and British Patent No. 1,413,74
Monodispersed emulsions described in No. 8 etc. are preferred for the present invention.
Can be used together. [0058] Also, the aspect ratio is about 3 or more.
Tabular grains can also be used in the present invention. Tabular grains are
Written by Toph, Photographic Science &amp;
Engineering (Gutoff, Photograp
hic Science and Engineering
ng), Vol. 14, pp. 248-257 (1970); US
National Patent No. 4,434,226, National Patent No. 4,414,31
No. 0, No. 4,433,048, No. 4,439,5
No. 20 and British Patent No. 2,112,157, etc.
It can be easily prepared by the method described in . The photosensitive material of the present invention includes photosensitive halogenated
Grain size, grain size distribution, halogen composition of silver emulsion,
Two types differing in at least one characteristic of particle shape and sensitivity
It is possible to mix different types of emulsions in the same layer.
Wear. [0060] Described in US Pat. No. 4,082,553
Silver halide grains coated with grain surfaces, U.S. Patent No.
No. 4,626,498, JP 59-214852
The silver halide grains and co
Lloyd's silver is deposited in a light-sensitive silver halide emulsion layer and/or as a material.
Can be preferably used in qualitatively non-photosensitive hydrophilic colloid layers.
Ru. Silver halide grains covered inside or on the surface
is uniformly applied to both unexposed and exposed areas of the photosensitive material.
Silver halide grains that can be developed (non-imagewise)
It means. Halogenation inside or on the surface of the particle
The method for preparing silver particles is described in U.S. Pat. No. 4,626,498.
, JP-A-59-214852. [0061] Core/shell type halves in which the inside of the particle is covered
The silver halide that forms the inner core of silver halide grains is
Even products with the same halogen composition can have different halogen compositions.
It can also be offal. particles inside or on the surface.
Silver chlorides include silver chloride, silver chlorobromide, silver iodobromide, and silver chloride.
Any silver iodobromide can be used. Are these?
There are special limitations on the grain size of suspended silver halide grains.
There is no fixed value, but the average particle size is 0.01 to 0.7
5 μm, especially 0.05 to 0.6 μm is preferred. Also,
There are no particular restrictions on the particle shape, even regular particles can be used.
Polydisperse emulsions may also be used, but monodisperse emulsions (halogen
At least 95% of the weight or number of silver oxide grains is on average
The particle size must be within ±40% of the particle size.
is preferable. In the present invention, non-photosensitive fine grain silver halide
It is preferable to use Non-photosensitive fine particle halogenation
Silver is a material that is not sensitive during imagewise exposure to obtain dye images.
Not exposed to light and virtually undeveloped in its development process
It is a silver halide fine grain and has not been fogged in advance.
It is preferable not to have it. [0063] The fine grain silver halide has a silver bromide content of
0 to 100 mol%, optionally containing silver chloride and/or
Alternatively, it may contain silver iodide. Preferably silver iodide is 0
．． It contains 5 to 10 mol%. [0064] The fine grain silver halide has an average grain size (projection surface
The average value of the equivalent circle diameter of the product is preferably 0.01 to 0.5 μm.
More preferably, the thickness is 0.02 to 0.2 μm. [0065] Fine grain silver halide is a conventional photosensitive halide.
It can be prepared in the same way as silver genenide. In this case, halogen
The surface of the silver oxide grains does not need to be optically sensitized;
Also, spectral sensitization is not required. However, if this is added to the coating solution,
Before adding triazole and azai,
benzothiazolium, or mercapto
Addition of known stabilizers such as compounds or zinc compounds
It is preferable to keep it. This fine silver halide grain containing
Colloidal silver can be preferably contained in the layer.
. The amount of coated silver in the photosensitive material of the present invention is 6.0 g.
/m2 or less is preferable, and 4.5g/m2 or less is most
preferable. Known photographic additives that can be used in the present invention
As stated in the three research disclosures above,
The relevant information is shown in the table below. Additive type RD 17643
RD 18716 RD
3071051. Chemical sensitizer 2
Page 3 648 Page right column
866 pages 2. Sensitivity enhancer
648 page right
Column 3. Spectral sensitizers, pages 23-24
648 page right column 8
Pages 66-868 Supersensitizer
~648
Right column of page 4. Brightener 2
Page 4 647 Page right column
868 pages 5. Anti-fogging
Pages 24-25 Page 649 Right column
Pages 868-870 Agents, stabilizers 6. Light absorber, pages 25-26
649 page right column 8
Page 73 Filter
~650 pages left column
Dyes, UV absorbers7. Stain page 25 right column
650 page left column 8
Page 72 Inhibitor
~Right column 8
．． Dye image 25 pages
650 page left column
Page 872 Stabilizers 9. Hardening agent page 26
651 page left column
874-875 pages 10. binder
26 pages 651 pages left
Column 873-874 Page 11. plasticizer,
27 pages
Page 650 Right column Page 876
Lubricant 12. Coating aids, pages 26-27
650 page right column 87
Pages 5-876 Surfactant 13. static page 27
650 page right column 876
~Page 877 Inhibitor 14. matting agent
　　　　　　　　　　　　　　　　　　　　　　　　　
Pages 878-879. [0069] In addition, photographic properties due to formaldehyde gas
In order to prevent deterioration of performance, U.S. Patent 4,411,98
7 and 4,435,503.
Compounds that can be immobilized by reacting with maldehyde are used as photosensitive materials.
It is preferable to add it to the ingredients. The photosensitive material of the present invention is disclosed in US Pat. No. 4,74
No. 0,456, No. 4,788,132, JP-A-Sho
Described in No. 62-18539 and JP-A No. 1-283551
It is preferable to contain a mercapto compound. [0071] The photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open No. 1-1060.
The amount of developed silver produced by the development process described in No. 52 and
Regardless of fogging agent, development accelerator, silver halide solvent
or contain compounds that release their precursors.
is preferable. [0072] The photosensitive material of the present invention is disclosed in International Publication WO88/
No. 04794, described in JP-A-1-502912
Dyes dispersed by the method or EP 317,308A
No., U.S. Patent No. 4,420,555, JP-A-1-25
Preferably, the dye described in No. 9358 is included. Various color couplers can be used in the present invention.
Specific examples can be found in the research disk mentioned above.
Roger No. 17643, VII-C~G, O
and same No. 307105, described in VII-C to G
described in the patent issued by Examples of yellow couplers include US special
Permit No. 3,933,501, No. 4,022,620
No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, Special Publication No. 1983
-10739, British Patent No. 1,425,020,
No. 1,476,760, U.S. Patent No. 3,973,
No. 968, No. 4,314,023, No. 4,5
No. 11,649, European Patent No. 249,473A, etc.
Those described in are preferred. 5-pyrazolone as magenta coupler
and pyrazoloazole compounds are preferred;
Permit No. 4,310,619, No. 4,351,897
No. 73,636, U.S. Patent No. 3,06
No. 1,432, No. 3,725,067, Reser
Chi Disclosure No. 24220 (1984
(June), Japanese Patent Publication No. 60-33552, Research D.
Closer No. 24230 (June 1984)
, JP-A-60-43659, JP-A-61-72238,
No. 60-35730, No. 55-118034, No. 55-118034, No. 55-118034, No.
No. 60-185951, U.S. Pat. No. 4,500,63
No. 0, No. 4,540,654, No. 4,556
, No. 630, International Publication No. WO88/04795, etc.
Particularly preferred are those listed below. As the cyan coupler, phenolic and
U.S. Patent No. 4,0
No. 52,212, No. 4,146,396, No. 4,146,396, No.
No. 4,228,233, No. 4,296,200
No. 2,369,929, No. 2,801,
No. 171, No. 2,772,162, No. 2,8
No. 95,826, No. 3,772,002, No. 3,772,002, No.
No. 3,758,308, No. 4,334,011
, No. 4,327,173, West German Patent Publication No. 3,3
No. 29,729, European Patent No. 121,365A,
No. 249,453A, U.S. Patent No. 3,446,622
No. 4,333,999, No. 4,775,
No. 616, No. 4,451,559, No. 4
, No. 427,767, No. 4,690,889,
Same No. 4,254,212, Same No. 4,296,199
No. 61-42658, etc. are preferred.
Delicious. Furthermore, JP-A-64-553, JP-A-64-55
Pyra described in No. 4, No. 64-555, No. 64-556
Zoroazole couplers and U.S. Patent No. 4,818,6
The imidazole couplers described in No. 72 may also be used.
I can do that. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. No. 3,451,820;
No. 80,211, No. 4,367,282, No. 80,211, No. 4,367,282, No.
No. 4,409,320, No. 4,576,910
, U.S. Patent No. 2,102,137, European Patent No. 341
, No. 188A, etc. A coupler in which the coloring dye has appropriate diffusivity
No. 4,366,237, U.S. Pat.
Patent No. 2,125,570, European Patent No. 96,570
Described in West German Patent (Publication) No. 3,234,533
Preferably. Color for correcting unnecessary absorption of coloring dye
The code coupler is Research Disclosure No.
．． Section VII-G of 17643, No. 3071
Section VII-G of 05, U.S. Patent No. 4,163,670
No., Special Publication No. 57-39413, U.S. Patent No. 4,00
No. 4,929, No. 4,138,258, U.S. Pat.
The one described in Japanese Patent No. 1,146,368 is preferred. Also, the cup described in U.S. Pat. No. 4,774,181
Fluorescent dye released during pulling eliminates the need for coloring dye
Couplers that correct for absorption and U.S. Pat. No. 4,777,1
Can react with the developing agent described in No. 20 to form a dye
Using a coupler with a dye precursor group as a leaving group
It is also preferable to be there. Photographically useful residues associated with coupling
Compounds that release can also be preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, Section VII-F and the same No. 3071
Patent listed in Section 05, VII-F, JP-A-57-
No. 151944, No. 57-154234, No. 60
-184248, 63-37346, 63-
37350, U.S. Pat. No. 4,248,962, U.S. Pat.
, 782,012 is preferred. [0081]R. D. No. 11449, 2424
1. Bleaching acceleration as described in JP-A No. 61-201247, etc.
Agent-releasing couplers shorten processing steps with bleaching capabilities.
In particular, the aforementioned tabular halogenated
When added to photosensitive materials using silver particles, the effect is
It's large. Nucleating agent or development accelerator added to the image during development
British Patent No. 2,097,
No. 140, No. 2,131,188, JP-A-59
-157638 and 59-170840
Preferably. Also, JP-A-60-107029
, No. 60-252340, JP-A-1-44940
No. 1-45687 and the oxidized form of the developing agent described in No. 1-45687.
The oxidation-reduction reaction of fogging agents, development accelerators, and halo
Also preferred are compounds that release silver germide solvents and the like. Other materials that can be used in the photosensitive material of the present invention
Compounds that can be used include U.S. Patent No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,3
No. 10,618, etc., multi-equivalent couplers described in JP-A No. 10,618, etc.
No. 0-185950, JP-A-62-24252, etc.
The DIR redox compound releasing couplers described,
Puller release coupler, DIR coupler release redox conversion
compound or DIR redox releasing redox compound,
European Patent No. 173,302A, European Patent No. 313,308A
R
．． D. No. 11449, 24241, JP-A-61
Bleach accelerator releasing coupler described in No.-201247 etc.
, U.S. Patent No. 4,555,477, etc.
A red-emitting coupler, disclosed in JP-A-63-75747
Ico dye-releasing couplers, U.S. Pat. No. 4,774,
Examples include couplers that emit fluorescent dyes as described in No. 181.
can be lost. The couplers used in the present invention include various known couplers.
It can be introduced into photosensitive materials by a dispersion method. Oil droplet dispersion method
Examples of high boiling point solvents used in
027, etc. Also as a co-solvent
has a boiling point of about 30°C or higher, preferably 50°C or higher and about 16
Organic solvents at temperatures below 0°C can be used; a typical example is vinegar.
Ethyl acid, butyl acetate, ethyl propionate, methyl ethyl
Chilketone, cyclohexanone, 2-ethoxyethyl acetate
Examples include acetate and dimethylformamide. [0084] Processes, effects and impregnation of latex dispersion method
Specific examples of latexes for use in
No. 63, West German Patent Application (OLS) No. 2,541,2
Described in No. 74 and No. 2,541,230, etc.
has been done. [0085] The color photosensitive material of the present invention contains phenethyl
alcohol and JP-A No. 63-257747, No. 62
-272248, and JP-A-1-80941
1,2-benzisothiazolin-3-one, n
-Butyl p-hydroxybenzoate, phenol, 4
-chloro-3,5-dimethylphenol, 2-phenokyl
Cyethanol, 2-(4-thiazolyl)benzimidazo
It is possible to add various preservatives or antifungal agents such as
preferable. The present invention is applicable to various color photosensitive materials.
be able to. Color negatives for general use or movies
color reversal film for slides or televisions
color paper, color positive film and color
A typical example is inverted paper. Suitable supports that can be used in the present invention include, for example
For example, the above-mentioned DR. No. 17643, page 28, same No.
．． 18716, page 647 right column to page 648 left column, etc.
Same No. 307105, page 879
. The light-sensitive material of the present invention has a side having an emulsion layer.
The total thickness of all hydrophilic colloid layers is 28 μm or less
preferably 23μm or less, more preferably 18μm or less
m or less is more preferable, and 16 μm or less is particularly preferable. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less;
More preferably, the time is 0 seconds or less. The film thickness is 25℃ relative humidity 55
% film thickness measured under humidity control (2 days), film swelling rate
T1/2 is determined according to methods known in the art.
can be measured. For example, A Green (A
．． Photographic Science by Green) et al.
S & Engineering (Photogr.S.
ci. Eng. ), Volume 19, No. 2, 124-129
Use a swellometer of the type described on page
T1/2 can be measured using a color developer at 30°C.
, the maximum swollen film thickness reached when treated for 3 minutes and 15 seconds, 90
% is the saturated film thickness, until it reaches 1/2 of the saturated film thickness.
defined as the time of [0089] The membrane swelling rate T1/2 is
Adding a hardener to the gelatin before application or
It can be adjusted by changing the aging conditions. Further, the swelling rate is preferably 150 to 400%. swelling rate and
is given by the formula: (
It can be calculated according to the maximum swelling film thickness - film thickness)/film thickness. The light-sensitive material of the present invention has a side having an emulsion layer.
On the other side, a hydrophilic film with a total dry film thickness of 2 μm to 20 μm
It is preferable to provide a colloid layer (referred to as a back layer)
. This back layer contains the aforementioned light absorbing agent and filter dye.
, UV absorber, anti-static agent, hardener, binder
-, plasticizers, lubricants, coating aids, surface active agents, etc.
It is preferable to include it. The swelling rate of this back layer is 1
50-500% is preferred. [0091] The color photographic material according to the present invention
The mentioned RD. No. 17643, pages 28-29, same No.
．． 651 left column to right column of 18716, and the same No.
Normal person listed on pages 880-881 of 307105
It can be developed by a method. Further, the silver halide photosensitive material of the present invention is
National Patent No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-23
No. 8056, European Patent No. 210,660A2, etc.
It can also be applied to the heat-developable photosensitive materials described above. [0093] The present invention will be further explained with reference to Examples below.
However, the present invention is not limited thereto. Examples Example 1 (1) Preparation of emulsion Preparation of AgI fine grain emulsion-I: 26 g of deionized gelatin
Dissolve 0.5 g of potassium iodide in 2 liters of distilled water.
Silver nitrate aqueous solution 80 containing 40g of silver nitrate in the aqueous solution
cc and 80 cc of an aqueous solution containing 39 g of potassium iodide
Additions were made simultaneously over 5 minutes with vigorous stirring at 5°C. child
When , the addition flow rate of silver nitrate aqueous solution and potassium iodide aqueous solution is
8 cc/min each at the start of addition, 80 cc in 5 minutes
The addition flow rate was linearly accelerated to complete the addition. addition
After finishing, remove by normal flocculation method at 35℃.
I salted it. Next, the temperature was raised to 40°C, and deionized gelatin was added.
Add 10.5g and 2.56g of phenoxyethanol.
The pH was adjusted to 6.8 to prepare Emulsion-I. obtained
The finished amount of Emulsion-I was 730g and the average diameter was 0.018μ.
They were monodisperse AgI fine particles of m. Preparation of host grain emulsion AY and emulsion A (
Host particles and comparative emulsion): 20 g of inert gelatin
, potassium bromide 3.2g, potassium iodide 0.98g
Stir the aqueous solution dissolved in 800 ml of distilled water at 62℃.
Then, instantly add 150 cc of an aqueous solution containing 5 g of silver nitrate.
In addition, excess potassium bromide and ammonia are added intermittently.
After adding the aqueous solution, the mixture was physically aged for 15 minutes. Ammonium
After neutralizing A, U.S. Pat.
According to the method described, 0.2 mol/liter, 0.67
mol/l, 2 mol/l silver nitrate and halide
Potassium chloride aqueous solution (based on 80 mol% potassium bromide)
(mixed with 20 mol% potassium iodide)
was added at a flow rate of 10 cc/min, and the silver iodide content was 20 molar.
% silver iodobromide grains were grown. normal floccule
The emulsion was washed with water for desalting by the ion method to prepare emulsion AX. emulsion
The completed amount of AX was 900g. Next, take 300 g of emulsion AX and add 850 g of distilled water.
cc and 30 cc of 10% potassium bromide aqueous solution, 75
An aqueous solution of 133 g of silver nitrate dissolved in a mixture heated to ℃ and stirred.
Aqueous solution 1 containing 950 cc of liquid and 99 g of potassium bromide
liters at the same time in 60 minutes, the particles of emulsion AX
It is grown to prevent re-nucleation, and the silver iodide content is 6.
7 mol% silver iodobromide host grains were prepared, and the host grain milk was
Agent AY. This host grain emulsion AY was processed into a normal flocculent.
Washed with water for desalination by ration method and prepared as emulsion A.
Ta. Emulsion A is twinned, and its (111) plane ratio is 82.
%Met. The grain size of emulsion A was 1.2 μm.
. When the X-ray diffraction pattern of emulsion A was measured, it was found that silver iodide
Diffraction angle corresponding to 0 mol% content (39.87°)
and the diffraction angle (39.35°) corresponding to 20 mol%.
A diffraction pattern with a peak at the center was obtained. Also emulsion A
When the surface silver iodide content was measured using the XPS method, the calibration curve
The value determined from this was 2.0 mol%. Preparation of emulsion B (comparative emulsion): Silver iodobromide
The grain emulsion AY was heated at a temperature of 75°C for 5 minutes.
The potassium iodide aqueous solution was added to the total silver content of the host grains.
, 0.3 mol% was added. Then, in the same way as emulsion A,
Emulsion B was obtained by washing with water. Preparation of emulsion C (invention): silver iodobromide host
In contrast to grain emulsion AY, the above-mentioned AgI fine grain emulsion-I
was added in an amount of 0.3 mol% based on the total amount of silver in the host grains.
The mixture was physically aged at 75°C for 5 minutes. After that, FloQ
Emulsion C was obtained by washing with water using the Lesion method. Preparation of emulsion D (invention): Same as emulsion A
The emulsion was added to the silver iodobromide host grains prepared by
Before washing, lower the temperature to 50°C and add potassium thiocyanate.
0.49g of particles and AgI fine particles-I were added to all of the host particles.
Added 0.3 mol% based on silver amount and physically aged for 5 minutes
did. Then, wash with water using the standard flocculation method.
, Emulsion D was obtained. Preparation of emulsion E (invention): silver iodobromide host
For grain emulsion AY, instead of AgI fine particles-I,
As shown in Figure 1 and Figure 2, a
AgI fine grain emulsion-II, which will be described later, is fed from mixer 7.
0.3 mol% of the total silver amount of the grains was added for 3 minutes.
After addition, physical ripening was performed for 2 minutes. Then wash with water
Emulsion E was obtained. [0103] AgI fine grain emulsion-II was prepared as follows.
It was prepared by In other words, the
Add a water solution containing 0.59 g of silver nitrate to a mixer for 3 minutes.
25cc of liquid and 0.58g of potassium iodide and average molecule
25 c of an aqueous solution containing 0.6 g of low molecular weight gelatin
c was added by double jet at a constant flow rate. mixer
The rotation speed of the stirring blade is 3000r. p. m and mixer
The residence time of the additive liquid in the tank was 30 seconds. Also, the temperature of the mixer
The temperature was maintained at 35°C. Obtained AgI fine particles-I
The average particle size of I was 0.025 μm. Preparation of emulsion F (comparative emulsion): Preparation of emulsion A
Emulsion AX was prepared in a manner similar to that described in . Next
Then, take 300g of emulsion AX, add 850cc of distilled water and 10%
Add 30 cc of potassium bromide aqueous solution and heat to 75°C.
710c of an aqueous solution of 100g of silver nitrate dissolved in a stirred solution
c and 750 cc of an aqueous solution containing 75 g of potassium bromide.
was simultaneously added over a period of 45 minutes, followed by dissolving 33 g of silver nitrate.
270 cc of clarified aqueous solution, 23.1 g of potassium bromide and iodine
290 cc of an aqueous solution containing 1.29 g of potassium
It was added over a period of 15 minutes. After the addition is complete, use the normal flocculent.
Emulsion F was obtained by washing with water using a ration method. Emulsion F is grain
The total silver iodide content is 7.3 mol%, and the prescription
The surface silver iodide content was 4 mol%, measured and inspected by the XPS method.
The surface silver iodide content obtained from the quantitative curve was 5.8 mol%.
It was. Preparation of emulsion G (invention): Same as emulsion F
However, the surface silver iodide content in the prescription is 1.0 mol%.
Host particles were prepared as follows. This host grain
The surface silver iodide content of the particles was determined by the XPS method and was 2.9.
It was mol%. Next, before washing with water, add the AgI fine particles mentioned above.
0.15 mol% of Co-I based on the total silver amount of the host grains
After physical ripening at 75°C for 5 minutes, it was washed with water to form emulsion G.
I got it. [0106] In addition to the seven types of emulsions (emulsions A to G) listed below,
Spectral sensitizing dyes SO-1, SO-2 and
2.3 x 10 and SO-3 per mole of silver, respectively.
-4 mol, 2.4 x 10-5, 6.5 x 10-5 mol added
After adding and holding at 62°C for 20 minutes, the pH was adjusted to 6.
Sodium thiosulfate, chloroauric acid and thiocyanic acid in 5
Emulsions A-1 to G were each optimally chemically sensitized using potassium.
-1 was obtained. Here, the optimal chemical sensitization means chemical sensitization.
After that, the sensitivity will be highest when exposed for 1/10 second.
chemical sensitization. (2) Preparation of samples Seven types of emulsions (emulsions A-1 to G) subjected to the above chemical sensitization
-1) Triacetyl cellulose with an undercoat layer
Emulsion layer and protection on the film support under the following coating conditions
Coat a layer to create color samples 1 to 7 as shown in Table 1.
Manufactured. Emulsion coating conditions: Emulsion layer Emulsion: A-1, B-1, C-1, D-1, E-1, F-
1,G-1 (Silver 2.2g/m2) Coupler: Magenta coupler (with the structure shown in chemical formula 2 below)
1.5×10-3 mole/m2) tricresilf
Phosphate (1.1g/m2) Gelatin (
2.3g/m2) Protective layer 2,4-dichloro-6-hydroxy-S-triazine
Thorium salt (0.08g/m2) Gelatin (1.8g/m2). (3) Evaluation These samples 1 to 7 were placed at 40°C and 70% relative humidity.
Color temperature conversion filter of 4800°K after being left for 14 hours
- and SC-50, which transmits light with wavelengths longer than 500 nm.
filter (yellow filter) and continuous wedge
exposed for 1/100 second through the
Image processing was performed. [0109] Process Processing time
Processing temperature Color development 2 minutes
00 seconds 40℃ bleach fixing
3 minutes 00 seconds 4
0℃ water washing (1) 20 seconds
Wash with water at 35℃ (2)
20 seconds 35 degrees Celsius
Fixed 20 seconds
Dry at 35℃
50 seconds 65℃. Next, the composition of the treatment liquid will be described. (color developer)
(Unit: g)
thylenetriamine pentaacetic acid
2.0 1-hydroxyethylidene
-3.
0 1,1-diphosphonic acid Sodium sulfite
4.0 Carbonic acid
Rium
30.0 Potassium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5mg hydroxyamine sulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
2.4 4-[N-ethyl-N-β-
4.5 Hydro
xyethylamino] -2-methylaniline sulfate Add water
1.0 liter
Tor pH
10
．． 05. (Bleach-fix solution)
(Unit: g)
Ferric diaminetetraacetate
90.0 Ammonium dihydrate ethylenediaminetetraacetic acid
5.0 Nina
Thorium salt Sodium sulfite
12.0 Thio
Ammonium sulfate aqueous solution (70%)
260.0ml acetic acid (98%)
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0ml Bleach accelerator (chemical shown in chemical formula 1 below)
compound) 0.01 mol
add water
1.0 liter
Tor pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0. (Washing liquid) Tap water is exchanged with H-type strong acid cation.
Replacement resin (Amberlite IR- manufactured by Rohm and Haas)
120B) and OH type anion exchange resin (Amberla
Water was passed through a mixed bed column packed with IR-400).
Calcium and magnesium ion concentration 3mg/li
of sodium isocyanurate dichloride.
Thorium 20mg/liter and sodium nitrate 1.5g
/liter was added. The pH of this solution is 6.5-7.5
within the range of (Stabilizing liquid)
(Unit: g)
Formalin (37%)
2.0ml polio
xyethylene-p-
0.3 Monononylphenyl
ether (average degree of polymerization 10) ethylenediamine tetra
Acetic acid disodium salt 0.
05 Add water
1
．． 0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0-8.0. [0114] The transmission density of the processed sample was measured using a green filter.
was measured to determine fog, sensitivity, and contrast. Feeling
The degree of exposure is the amount of exposure that gives a density of 0.2 above fog (looks).
expressed as a relative value of the reciprocal of contrast is turnip
From the logarithm of the exposure amount that gives a density of 1.2, the fog is 0.
．． The reciprocal of the value obtained by subtracting the logarithm of the exposure amount that gives a density of 2
Expressed as a relative value. [0115] In addition, the graininess of these samples was evaluated.
The RMS granularity was measured for this purpose. Measuring RMS granularity
For each sample, set the exposure amount to give a density of 0.3 above fog.
After uniform exposure and the color development process described above,
Published by Kumilansha “The Theory of the
Photographic Process” 4th edition
, described in “Image Structure” in Chapter 21.
Measured using the method described. Measure using the green filter
The measurement aperture used was 48 μm in diameter.
Ta. The RMS granularity is based on the RMS value of sample 1 as 100,
It is expressed as a relative value to this. [0116] Furthermore, before exposing samples 1 to 7, the relative humidity was
Samples stored for 3 days under 80% conditions (storability test sample)
sample) that was not subjected to such conditions.
(Resch sample) and color development processing.
Ta. Here, the exposure is at a color temperature of 4800°K as mentioned above.
Conversion filter and SC-50 Fuji filter and continuous
Color development by exposing to light for 1/100 seconds through a wedge
The treatment was carried out according to the treatment process described above. After processing, similar
The transmission density is measured using the method, and the range of change in fog for each sample is determined.
and the rate of change in sensitivity was determined. The change width of fog can be saved.
Difference between the fog of the fresh sample and the fog of the test sample
The rate of change in sensitivity is the same as that of the fresh sample.
Sensitivity ratio of storage test sample to
expressed. The results are shown in Table 1 below. Sample 1 is the invention
Compared to the samples using the emulsion (Samples 3, 4, 5, 7), the
The contrast is high to some extent, but the sensitivity is extremely low and grainy.
It turns out that the sex is extremely bad. In addition, sample 1 was tested for storage stability.
It can be seen that the rate of change due to Sensitivity of sample 1,
The performance of graininess and shelf life is comparable to that of the samples of the present invention.
The contrast is quite high and the contrast is quite poor.
However, the overall performance is inferior to that of the sample of the present invention. [0118] Samples 2 and 6 (comparative examples) are the milk of the present invention.
Sensitivity, granularity, and storage stability compared to samples using
Although the performance is quite similar to that of the sample using the emulsion of the present invention,
It can be seen that the contrast is low. From this
Increasing the silver iodide content on the grain surface increases sensitivity (color sensitization sensitivity)
increases, graininess improves, and storage stability improves.
I understand, but as a way to increase the silver iodide content on the grain surface.
can be carried out using the AgI fine particles of the present invention at a high cost.
It has been found to be superior in terms of obtaining a transparent emulsion.
Karu. Example 2 (1) Preparation of emulsion Emulsion H (invention): containing 0.04M potassium bromide
gelatin in 1 liter of 0.7% by weight gelatin solution.
2M silver nitrate aqueous solution containing gelatin and 2M silver nitrate solution containing gelatin.
of potassium bromide aqueous solution at 30°C with vigorous stirring.
25 cc of each were simultaneously mixed for minutes. After this, the temperature rose to 75℃.
It was heated and 300 cc of 10% by weight gelatin solution was added. Next, 30 cc of 1M silver nitrate aqueous solution was added over 5 minutes.
Then, 10cc of 25% by weight ammonia water was added.
, ripening was carried out at 75°C. Add ammonia after aging
After mixing, add 1M silver nitrate aqueous solution and 1M potassium bromide aqueous solution.
Accelerated flow rate while keeping the pBr at 2.3 (end)
The flow rate was 5 times that at the beginning).
The amount of acid silver aqueous solution was 600 cc). This emulsion
Wash with water using the standard flocculation method and add dispersed gelatin.
to obtain 800 g of hexagonal tabular silver halide emulsion.
(Seed emulsion-HX). This type of emulsion-HX has an aspect ratio of
Monodisperse tabular pure bromide with a ratio of 5.5 and a coefficient of variation of 11%
It was a silver particle. Next, 250 g of this seed emulsion-HX was taken,
800 cc of distilled water, 30 g of gelatin, and potassium bromide
Add 6.5g of 1M
of silver nitrate aqueous solution and 1M potassium halide aqueous solution (odor
Potassium iodide 10 mol% for 90 mol% potassium chloride
) was accelerated while keeping the pBr at 1.6.
mixed at the same flow rate (the flow rate at the end is 3 times that at the start).
(The amount of silver nitrate aqueous solution used was 600cc)
. Furthermore, 1M silver nitrate aqueous solution and 1M potassium bromide aqueous solution
at an accelerated flow rate while simultaneously maintaining pBr at 1.6.
(The flow rate at the end is 1.5 times that at the start) and continues simultaneous mixing.
(The amount of silver nitrate aqueous solution used was 200 cc). [0121] This emulsion was washed with water using the method described above to obtain dispersed gelatin.
host grain emulsion-HY was obtained. host grain
Child emulsion-HY has a hexagonal plate shape with 92% of the total projected area.
dominated by particles, with an average aspect ratio of 6.
Monodisperse tabular silver halide grains with a coefficient of variation of 16%.
It was. Coulter Count average particle size of host particles
The Theory of Photography
aphic Process 4th ed. P.
101), it was 1.05 μm. child
The host particle -HY contains 21% from the inside of the particle.
The first layer of pure silver bromide accounts for 59%, and the silver iodide content accounts for 59%.
10 mol% silver iodobromide second layer and 20% pure bromide
It is a particle with a triple structure consisting of a silver surface layer, and the entire particle is
The silver iodide content of the body is 5.9 mol%. Also, with the XPS method
The surface silver iodide content was determined to be 4.0 mol%.
Ta. Next, the above host grain emulsion-HY was heated to 64°C.
and AgI fine grain emulsion-I described in Example 1.
0.6 mol% based on the total silver content of the host grains and thiosi
Added 0.3 mol% potassium anate and physically aged for 7 minutes
did. Thereafter, the spectroscopy described in Example 1 was continued.
Sensitizing dyes SO-1, SO-2, SO-3 per mole of silver
and 3.22 x 10-4 mol and 3.43 x 10 mol, respectively.
-5 mol, 9.20 x 10-5 mol was added, and 2
After holding for 0 minutes, sodium thiosulfate, chloroauric acid and
Optimally chemically sensitized using potassium dithiocyanate.
Emulsion H was obtained. Emulsion I (comparative example): Seed in the same manner as Emulsion H.
Emulsion-HX was prepared. 250g of this seed emulsion-HX
800 cc of distilled water, 30 g of gelatin and potassium bromide
Add 6.5g of 1M
of silver nitrate aqueous solution and 1M potassium halide aqueous solution (odor
Potassium iodide 10 mol% for 90 mol% potassium chloride
) was accelerated while keeping the pBr at 1.6.
mixed at the same flow rate (the flow rate at the end is 3 times that at the start).
(The amount of silver nitrate aqueous solution used was 600cc)
. Furthermore, 1M silver nitrate aqueous solution and 1M potassium halide
Aqueous solution (potassium iodide to 95 mol% potassium bromide)
(mixed at 5 mol%) while maintaining pBr 1.6.
At accelerated flow velocity (flow velocity at the end is 1.5 times that at the beginning)
Simultaneous mixing was continued (the amount of silver nitrate aqueous solution used was 200 c
c). [0124] This emulsion was prepared in the same way as the host grains-HY described above.
host particles-I by adding dispersed gelatin and washing with water.
I got Y. The host particle-IY is 2 in order from the inside of the particle.
Pure silver bromide first layer accounts for 1% and silver iodide accounts for 59%
A second layer of silver iodobromide with a content of 10 mol% and a silver iodobromide content of 20 mol%
and a silver iodobromide surface layer with a silver iodide content of 5 mol%.
The silver iodide content of the entire grain is
, 6.9 mol%. In addition, surface iodization determined by the XPS method
The silver content was 7.2 mol%. [0125] Next, the host particles-IY were treated as described in Example 1.
The loaded AgI fine grain emulsion-I is added to the total silver content of the host grains.
0.1 mol% and 0.1 mol% of potassium thiocyanate.
3 mol% was added and physically aged at 64°C for 7 minutes. after that
, Add a spectral increase/decrease dye in exactly the same manner as Emulsion H, and
Emulsion I was obtained by sensitization. Emulsion J, Emulsion K, Emulsion L (comparison): Emulsion
Same as I, except that AgI fine grain emulsion-I is added.
0.2 mol each based on the total amount of silver in the host grains.
%, 0.4 mol%, 0.6 mol% and emulsions J and K
, L was obtained. (2) Preparation of samples Emulsions H to L were coated in the same manner as described in Example 1.
Color samples 8 to 12 were prepared. (3) Evaluation Samples 8 to 12 above were exposed and color developed in the same manner as in Example 1.
processed. The processed sample is passed through a green filter.
to determine fog, sensitivity, and contrast.
Ta. Sensitivity and contrast were determined in the same manner as in Example 1.
I asked for it. [0129] We also measured the RMS granularity of these samples.
Ta. RMS granularity was measured using the same method as in Example 1.
Relative to the RMS value of (the present invention) as 100
Expressed as a value. The results are shown in Table 2 below. From Table 2, XP
The present invention in which the surface silver iodide content determined by the S method is 4 mol%
Sample 8 using an emulsion with a high surface silver iodide content
High sensitivity and contrast compared to samples 9 and 10 using
I know it's expensive. Also, sample 11 and sample 12 have graininess.
is better than inventive sample 8, but the sensitivity and contrast are
The overall performance is significantly lower than that of the samples of the present invention.
I understand that. Example 3 (1) Preparation of emulsion Emulsion M (invention): Contains potassium bromide and was kept at 65°C.
Add ammonia equivalent to 1% by volume to the gelatin solution.
After that, add silver nitrate aqueous solution and potassium halide while stirring.
Aqueous solution (potassium iodide to 97 mol% potassium bromide)
(mixed at 3 mol %) with a pAg of 7.9.
It was added using a controlled double jet method. addition
continues until the amount of silver nitrate used reaches 5% of the total amount used.
Ta. Subsequently, add silver nitrate aqueous solution and halogenation while stirring.
Silver-potassium aqueous solution (90 mol% of potassium bromide
(mixed with 10 mol% potassium) and pAg 7
．． Add using controlled double jet method while maintaining the temperature at 7.
did. Addition should be made until the amount of silver nitrate used reaches 35% of the total silver amount.
I was able to continue. Furthermore, silver nitrate was added while stirring.
The aqueous solution and potassium bromide aqueous solution were maintained at pAg8.2.
However, it was added using the controlled double jet method. Addition continues until the amount of silver nitrate used reaches 60% of the total silver amount.
It was. Desalt this emulsion using the normal flocculation method.
A host grain emulsion-MY was obtained. The host particle-MY is
The average particle size is 0.90 μm, and from the inside of the particle
, a first layer of silver iodobromide with a silver iodide content of 3 mol%, which accounts for 5%.
and silver iodobromide with a silver iodide content of 10 mol%, which accounts for 35%.
It consists of a second layer and a pure silver bromide surface layer that accounts for 60%.
It is an octahedral particle with a triple structure. of the entire host particle.
The silver iodide content is 3.65 mol%. Also, with the XPS method
The determined surface silver iodide content was 1.1 mol%. Next, host grain emulsion-MY was kept at 64°C.
, AgI fine particles-I described in Example 1 were used as host particles.
0.8 mol% based on the total silver amount, and potassium thiocyanate
0.3 mol % of aluminum was added and physical ripening was performed for 7 minutes. Thereafter, the spectral sensitized color of the structural formula shown in chemical formula 3 below
element SP-1 and SP-2 per mole of silver.
3.54 x 10-4 mol, 1.06 x 10-5 mol, respectively
After adding and holding at 64°C for 20 minutes, the pH was adjusted to 5.8.
Sodium thiosulfate, N,N-dimethine selenourea
, optimized using chloroauric acid and potassium thiocyanate
Emulsion M was obtained by sensitization. Emulsion N (invention): In the same manner as Emulsion M,
However, the silver iodide content of the second layer of the host grains is 15 mol%.
Emulsion N was prepared by changing the silver iodobromide layer to . Emulsion N
The silver iodide content of the entire grain of ST grain-NY is 5.40 mole.
surface silver iodide of host grains determined by XPS method.
The content was 1.3 mol%. Emulsion O (invention): In emulsion N, converter
The amount of AgI fine grain emulsion-I used in the
Emulsion O was prepared in exactly the same manner except for changing the
Ta. Emulsion P (comparative example): Same as emulsion M,
However, the second layer of the host grains has a silver iodide content of 6 mol%.
Emulsion P was prepared by changing the silver iodobromide layer. Emulsion P
The silver iodide content of the entire grain of ST grain-PY is 2.25 molar.
surface silver iodide of host grains determined by XPS method.
The content was 0.9 mol%. Emulsion Q (comparative example): Same as emulsion M,
However, the silver iodide content of the second and third layers of the host grains is
Emulsion Q was prepared by changing the emulsion to a 4 mol % silver iodobromide layer. The silver iodide content of the entire host grains of emulsion Q-QY is
3.95 mol% of the host particles determined by the XPS method.
The surface silver iodide content was 3.9 mol%. (2) Preparation of sample Emulsion M-Q was coated in the same manner as described in Example 1.
Color samples 13 to 17 were prepared. (3) Evaluation Samples 13 to 17 above were exposed in the same manner as in Example 1 and color development was performed.
Image processing was performed. Transparent the treated sample through a green filter.
Measure overdensity, fog, sensitivity, and contrast
I asked for it. Sensitivity and contrast are the same as in Example 1.
required by law. [0139] We also measured the RMS granularity of these samples.
did. RMS granularity was measured using the same method as in Example 1.
The RMS value of 13 (this invention) is set as 100, and
Expressed as a relative value. [0140] The results are shown in Table 3 below. According to Table 3, the present invention
In the sample using the emulsion, the silver iodide content of the entire grain was 2.2.
Compared to sample 16 using 5 mol% emulsion P, it has higher sensitivity.
It can also be seen that the graininess is excellent. Also, inside the particle
Emulsion Q, which does not have a layer with a higher silver iodide content than the grain surface.
Compared to the sample 17 used, the sensitivity was high and the contrast was remarkable.
I understand that it is very expensive. Sample 17 is slightly superior in graininess.
However, there is a significant decrease in sensitivity and contrast.
It can be seen that the overall performance is inferior to that of the present invention.
. Example 4 (1) Preparation of emulsion Emulsion R (comparative example): Emulsion A of Example 1 was added to Emulsion A as described in Example 3.
Spectral sensitizing dyes SP-1, SP-2 and the following
When SP-3 having the structural formula shown in Chemical formula 4 is added to 1 mol of silver,
2.1 x 10-4 mol, 6.5 x 10-6 mol, 1.
After adding 0x10-4 mol and holding at 62°C for 20 minutes
pH was set to 5.8 at 62°C, sodium thiosulfate,
N,N-dimethylselenourea, chloroauric acid and thiothia
Optimally chemically sensitized using potassium phosphate to obtain emulsion R.
Ta. Emulsion S (comparative example): Emulsion B of Example 1
Agent R and the same amount of spectral sensitizing dyes SP-1, SP-2 and S
P-3 was added and chemically sensitized in the same manner as Emulsion R.
Emulsion S was obtained. Emulsion T (comparative example): Emulsion F of Example 1
Agent R and the same amount of spectral sensitizing dyes SP-1, SP-2 and S
P-3 was added and chemically sensitized in the same manner as Emulsion R.
Emulsion T was obtained. Emulsion U (invention): Emulsion C of Example 1
Agent R and the same amount of spectral sensitizing dyes SP-1, SP-2 and S
P-3 was added and chemically sensitized in the same manner as Emulsion R.
Emulsion U was obtained. Emulsion V (invention): Emulsion D of Example 1
Agent R and the same amount of spectral sensitizing dyes SP-1, SP-2 and S
P-3 was added and chemically sensitized in the same manner as Emulsion R.
Emulsion V was obtained. (2) Preparation of sample The following was prepared on the undercoated triacetylose support.
A multilayer color photosensitive material is created by coating each layer with the composition shown in multiple layers.
Sample 18, which is a sample, was prepared. (Photosensitive layer composition) The numbers corresponding to each component are in g/m2 unit.
For silver halides, the coating amount is expressed in degrees.
Shows the converted coating amount. However, the sensitizing dye is the same.
Indicates the coating amount in moles per mole of silver halide of the layer.
vinegar. (Sample 18) 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
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 EX-3
0.
020 EX-12
2.0×10
-3 U-1
0.0
60 U-2
0.0
80 U-3
0.1
0 HBS-1
0.10
HBS-2
0.020 Zera
Chin
1.04. Third layer (first red-sensitive emulsion layer) Emulsion I
silver 0.25
emulsion b
Silver 0.25 sensitized
Dye SP-1
3.1×10-4 Sensitizing dye SP
-2
1.8×10-5 Sensitizing dye SP-3
　　　　　　　　　　　　　　　　　　　　　　　　　
6.9×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 EX-14
0.
17 U-1
0.0
70 U-2
0.0
50 U-3
0.0
70 HBS-1
0.060
gelatin
0.87. Fourth layer (second red-sensitive emulsion layer) Emulsion C
Silver 1.00
Sensitizing dye SP-1
2.3×10-4 sensitizing dye
SP-2
1.4×10-5 Sensitizing dye WP-3
　　　　　　　　　　　　　　　　　　　　　　　　　
5.1×10-5 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015 EX-14
0
．． 20 EX-15
0.05
0 U-1
0.07
0 U-2
0.05
0 U-3
0.07
0 gelatin
1.30. Fifth layer (third red-sensitive emulsion layer) Emulsion R
Silver 1.60
Sensitizing dye SP-1
2.1×10-4 sensitizing dye
SP-2
6.5×10-6 Sensitizing dye SP-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.097 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010 EX-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.22 HBS-2
0.
10 Gelatin
1.63
. 6th layer (middle layer) EX-5
0.040
HBS-1
0.020 ze
latin
0.80. Seventh layer (first green-sensitive emulsion layer) Emulsion I
silver 0.15
emulsion b
Silver 0.15 sensitized
Dye SO-1
3.8×10-4 Sensitizing dye SO
-2
3.0×10-5 Sensitizing dye SO-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.021 EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.26 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 EX-8
0
．． 025 HBS-1
0.1
0 HBS-3
0.010
gelatin
0.63. 8th layer (second green-sensitive emulsion layer)
silver 0.45
Sensitizing dye SO-1
2.6×10-4 sensitizing dye
SO-2
2.1×10-5 Sensitizing dye SO-3
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-5 EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.094 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.026 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.018 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 HBS-3
8.0×
10-3 Gelatin
0.
50. Ninth layer (third green-sensitive emulsion layer) Emulsion A-1 (described in Example 1)
Silver 1.20 Sensitizing dye SO-1
　　　　　　　　　　　　　　　　　　　　　　　　　
2.3×10-4 Sensitizing dye SO-2
2.4×
10-5 Sensitizing dye SO-3
6.5×10-5
EX-1
0.013
EX-11
0.065E
X-13
0.019HBS
-1
0.25 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.54. 10th layer (yellow filter layer) Yellow colloid
De silver
Silver 0.050 EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.95. 11th layer (first blue-sensitive emulsion layer) Emulsion I
silver 0.080
emulsion b
silver 0.070
emulsion ho
Silver 0.070 increase
Sensitive dye SR-1
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)
silver 0.45
Sensitizing dye SR-1
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)
silver 0.77
Sensitizing dye SR-1
2.2×10-4 EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.69. 14th layer (first protective layer) Emulsion layer
silver 0.20
U-4
0.11U
-5
0.17 HB
S-1
5.0×10-2 gelati
hmm
1.00. 15th layer (second protective layer) H-1
0.40
BT-1 (diameter 1.7μm)
5.0×10-2 BT-2 (diameter
1.7μm)
0.10 BT-3
0.
10 S-1
0.2
0 gelatin
1.20. [0162] Furthermore, all layers have good storage stability, processability, pressure resistance,
To improve anti-mold, anti-bacterial properties, anti-static properties and applicability
, W-1, W-2, W-3, BT-4, BT-5, FT
-1, FT-2, FT-3, FT-4, FT-5, FT
-6, FT-7, FT-8, FT-9, FT-10, F
T-11, FT12-, FT-13 and iron salt, lead salt,
Contains gold salt, platinum salt, iridium salt, and rhodium salt.
There is. The contents of emulsion I to I used to create sample 18 are listed below.
Table 4 also shows the various compounds used to create sample 18.
The chemical structural formulas or names are shown in Chemical Formulas 5 to 13 below. [0163] In the same manner as Sample 18, the emulsion of the fifth layer was emulsified.
Emulsion B described in Example 1 was added to Emulsion S, and the emulsion of the ninth layer was added to Emulsion B described in Example 1.
-1 to sample 19, and the fifth layer emulsion to emulsion T.
, and the emulsion of the ninth layer to emulsion F-1 described in Example 1.
Sample 20 was created by replacing the sample. [0164] Furthermore, in the same manner as Sample 18, a fifth layer emulsion was prepared.
into emulsion U, and the emulsion in the ninth layer into emulsion C-1 (Example
1) and sample 21, and the milk of the fifth layer.
The emulsion of the ninth layer was changed to Emulsion V, and the emulsion of the ninth layer was changed to Emulsion D-1 (implemented).
Sample 22 was prepared by substituting the sample (described in Example 1). (3) Evaluation These samples 18 to 22 were subjected to conditions of 40°C and relative humidity of 70%.
After 14 hours under 4800°K color temperature exchange filter
1/100 second with white light through the tar and continuous wedge.
Expose it to light and process it using the method described below using an automatic processor.
Ta. [0166] Process Processing time
Processing Replenishment amount
tank
temperature
Capacity Color development
3 minutes 15 seconds 38℃
33ml 20 liter bleach
6 minutes 30 seconds 38℃
25ml 40 liters water washing
2 minutes 10 seconds 24℃
1200ml 20 liters fixed
4 minutes 20 seconds 38℃
25ml 30 liters
　　　　　　　　　　　　　　　　　　　　　　　　　
(2) to (1) Washing with water (1)
1 minute 05 seconds Toward 24℃
Flow 10 liters
　　　　　　　　　　　　　　　　　　　　　　　　　
Piping method Water washing (2) 1 minute 0
0 seconds 24℃ 1200ml
10 liters stable 1 minute 05 seconds
38℃ 25ml
10 liters drying 4 minutes 20 seconds
55℃ refill amount is 35ml per 1m length
Next, the composition of the treatment liquid will be described. (Color developer)
Mother liquor (g) Replenisher solution (
g) Diethylenetriaminepentaacetic acid
1.0 1.1 1-hi
Droxyethylidene 3.
0 3.2 -1,1-dipho
Sulfonic acid Sodium sulfite
4.0 4.4
potassium carbonate
30.0 37.0 Bromide
potassium
1.4 0.7 Yaw
Potassium
1.5mg - Hydroxy
Ruamine sulfate 2.4
2.8 4-[N-ethyl-N-
β-4.5
5.5 Hydroxyethylamino]-2-methylaniline sulfate Add water
1.0 liter 1.0 liter
Le pH
10.05 10
．． 10. (Bleach solution)
Mother liquor (g) Replenisher solution (
g) Ferric ethylenediaminetetraacetic acid
100.0 120.0 Ethylenedia
Minetetraacetic 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 Add water
hand
1.0 liter 1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 5.7. (Fixer)
Mother liquor (g) Replenisher solution (
g) Ethylenediaminetetraacetic acid
0.5 0.7
Disodium salt Sodium sulfite
7.0 8.0
sodium bisulfite
5.0 5.5 Thiosulfur
Ammonium acid aqueous solution (70%) 170.0ml 2
Add 00.0ml water
1.0 liter
1.0 liter pH
6.7
6.6. (Stabilizing liquid)
Mother liquor (g) replenishment
Liquid (g) Formalin (37%)
2.0ml 3.0ml
polyoxyethylene-p-
0.3 0.45 mo
Nononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.0
5 0.08 Add water
1.
0 liter 1.0 liter pH
5.
0-8.0 5.0-8.0. [0171] The treated sample was measured with a color transmission densitometer.
, the sensitivity is determined by measuring the concentration through a red filter.
(red sensitivity), fog and contrast, and green
Similarly, sensitivity (green) can be obtained by measuring the concentration through a
Sensitivity), fog, and contrast were determined. red sensitivity
and green sensitivity are the exposure values that give a density of 0.2 above fog, respectively.
Expressed as a relative value of the reciprocal of the amount of light. contrast is turnip
From the logarithm of the exposure amount that gives a density of 0.7 above fog,
．． Double the value obtained by subtracting the logarithm of the exposure amount that gives a density of 2.
The reciprocal of the value was calculated and expressed as a relative value. [0172] In addition, in order to evaluate the graininess of these samples,
For this purpose, cyan and magenta colors were prepared in the same manner as in Example 1.
RMS granularity was measured. Measurement of RMS granularity was performed for each sample.
The cyan and magenta color density of the material is 0.3 above fog.
Uniformly exposed each with an exposure amount that gives density, cyan color
The RMS of is the red filter, and the RMS of the magenta color is the green filter.
Each was measured using a filter. The measurements used
The char had a diameter of 48 μm as in Example 1.
. The RMS granularity is based on the RMS value of sample 18 as 100.
It is expressed as a relative value to that. [0173] A summary of the contents of samples 18 to 22 is shown below.
5, and the results are shown in Table 6. From Table 6, using the emulsion of the present invention
The sample has high sensitivity, excellent graininess, and contrast.
I know it's expensive. [0174] Notes on Tables 1 to 6 below are as follows:
It is. Table 1: *1 Shows the silver iodide content according to the manufacturing recipe. *2 Indicates the amount added to the total silver amount of host particles. *3 The reciprocal of the exposure amount that gives a density of 0.2 above fog.
Relative values are shown (sensitivity of sample 1 is set as 100). *4 Is it the logarithm of the exposure amount that gives a density of 1.2 above fog?
Subtract the logarithm of the exposure that gives a density of 0.2 above fog from
(The contrast of sample 1 is
1). *5 Indicates the relative value to the RMS value of sample 1 (sample
The RMS value of 1 was set as 100). *6 Fresh sample from fogging of storage test sample
Shows the value after subtracting the fog. *7 Preservability test for fresh sample sensitivity
The sensitivity ratio of the materials is expressed as a percentage. Table 2: *1 Because the host particle has a triple structure, the first layer inside the particle
The silver iodide content of the layer, second layer and surface layer is shown. *2 Shown as a relative value with the sensitivity of sample 8 as 100. *3 Shown as a relative value with the contrast of sample 8 as 1
. *4 Shown as a relative value with the RMS value of sample 8 as 100
. Table 3: *1 Because the host particle has a triple structure, the first layer inside the particle
The silver iodide content of the layer, second layer and surface layer is shown. *2 Shown as a relative value with the sensitivity of sample 13 set as 100. *3 Shown as a relative value with the contrast of sample 13 as 1.
vinegar. *4 Shown as a relative value with the RMS value of sample 13 as 100.
vinegar. Table 5: *The definition of each item in Table 5 is the same as Table 1. Table 6: *1 Shown as a relative value with the sensitivity of sample 18 as 100. *2 Is it the logarithm of the exposure amount that gives a density of 0.7 above fog?
Subtract the logarithm of the exposure that gives a density of 0.2 above fog from
The reciprocal of the value doubled is the contrast of sample 18.
It is expressed as a relative value with 1 as 1. *3 Shown as a relative value with the RMS value of sample 18 as 100.
vinegar. [0176] Effect of the invention: The present invention has a high silver iodide content inside the grains.
The grain has a thin region (layer) and a low silver iodide content on the grain surface.
The surface of the host grain is coated with silver iodide fine grains.
High iodine is uniformly distributed on the particle surface by conversion with
Introducing a layer with silver oxide content, high color sensitization sensitivity and low graininess.
It is possible to develop emulsions with superior quality and high contrast.
came. [Table 1] [Table 2] [0179] [Table 3] [0180] [Table 4] [Table 5] [0182] [Table 6] [0183] [Formula 1] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical 9] [Chemical 10] [0193] [Chemical 11] [Chemical 12] [0195] [Chemical 13] [Chemical 14]

[Brief explanation of the drawing]

FIG. 1 schematically represents a method that can be used to produce the emulsion of the present invention.

FIG. 2 is a diagram showing details of a mixer that can be used in the production of the emulsion of the present invention.

[Brief explanation of symbols]

1 Reaction container 2 Protective colloid aqueous solution 3 Propeller 4. Halogen salt aqueous solution addition system 5 Silver salt aqueous solution addition system 6 Protective colloid addition system 7 Mixer 8 Introduction system to reaction vessel 9 Stirring blade 10 Reaction chamber 11 Shaft

Claims (4)

[Claims] Claim 1: The interior of the grain has a region having a higher silver iodide content than the grain surface, and the silver iodide content on the grain surface is 5.
For multilayer structure type silver halide host grains in which the average silver iodide content of the entire grain is less than mol % and larger than 3 mol %, the grain surface of the host grain is converted by fine silver iodide grains ( A photosensitive silver halide emulsion characterized by being formed by subjecting the emulsion to halogen conversion. 2. The photosensitive silver halide emulsion according to claim 1, wherein at least two kinds of spectral sensitizing dyes are added after said conversion, and then chemical sensitization is performed. 3. The photosensitive silver halide emulsion according to claim 2, wherein the amount of fine silver iodide grains is 0.05 to 1.0 mol % based on the total silver amount of the host grains. . 4. A support having at least one photosensitive silver halide emulsion layer, the silver halide emulsion layer being the photosensitive silver halide emulsion according to any one of claims 1 to 3. A silver halide photographic material characterized by containing.