JPH0312645A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material which has high quality and is minimized in the deterioration of the photographic performance by specifying the total content of the potassium ions incorporated into the photosensitive material. CONSTITUTION:This photographic sensitive material contains the silver chloride particles in which a silver iodide phase of 20 to 40mol% silver iodide molar fraction exists, the silver iodide phase is coated with the silver chloride contg. the lower silver iodide and the surface of the particles include >=5mol% silver iodide in the particles of emulsion layers; in addition, the total content of the potassium ions incorporated into the photosensitive material is <=5X10<-3> by the weight of the silver to be applied. The images having the high sensitivity and high image quality are obtd. in this way and the deterioration of the green photosensitive material by natural radiations particularly the long-term aging thereof is lessened. The images which are less fogged and are not deteriorated in graininess are obtd.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material.
, related to highly sensitive photosensitive materials, photosensitive materials
Increase in capri and graininess when aged for a long time after manufacturing
This relates to technology to improve the deterioration of (Prior technology) In the field of silver halide photographic materials, various technological advances have been made.
In recent years, color sensitivity has exceeded 1000 in ISO display sensitivity.
Optical materials have now been released. Strobe in a darkroom etc.
When shooting without using a telephoto lens, or when using a telephoto lens for sports photography, etc.
Shooting with a high-speed shutter, long exposures such as astrophotography
It has even higher sensitivity for shooting that requires
There is a demand for photosensitive materials that can Many efforts have been made to improve the sensitivity of photosensitive materials.
It has been. Formation of silver halide grain shape, composition, etc.
Methods, chemical sensitization, spectral sensitization, additives, coupler structure, etc.
Many studies have been conducted on
It has been accomplished. Therefore, in order to achieve high sensitivity, the size of silver halide emulsion grains is
High sensitivity can be achieved by combining this method with other techniques to increase the
It is common practice in the industry to produce photosensitive materials. High-sensitivity, high-quality photosensitive materials made in this way
It has been found that there are some undesirable drawbacks such as:
. It is the process by which photosensitive materials are used after they are manufactured.
Deterioration of photographic properties such as increased graininess and deterioration of graininess may occur.
There is a problem. In particular, the increase in fog is large, which is a practical problem.
That's the issue. Turnip caused by aging photosensitive materials for a long period of time
In addition to the normal fog caused by heat and humidity, the increase in
Fog caused by gamma rays and cosmic rays, called boundary radiation, is a problem.
It has been reported that this will happen. However, in general, the sensitivity to visible light and the sensitivity to environmental radiation are
The sensitivity to visible light is closely related, so it is important to maintain visible light sensitivity.
It is extremely difficult to reduce environmental radiation sensitivity by
. Therefore, effective methods are extremely limited, and representative
Examples of means include: (1) T-particles
(tabular grains): This grain has a large specific surface area, so the unit
The amount of aggravating dye used per amount of silver can be increased. Silver halide is much more sensitive to environmental radiation than sensitizing dyes.
T-particles are not affected by environmental radiation because they absorb
Peg. (Nichishashi vol. 49, 499-504 (1986)
J, T, Kofron et al.) (2) Coated silver'M: Manufactured
The graininess immediately after production is improved in proportion to the amount of silver coated. deer
and to optimize the graininess at the point of use by the user.
It is necessary to select an appropriate amount of coated silver. (Unexamined Japanese Patent Publication No. 6
3-226650, JP-A-63-226651) (3)
Amount of applied gold: Reduces environmental radiation by reducing the amount of applied gold.
It is empirically known that it can be made less susceptible to the influence of
Ru. (JP-A-1-96642, JP-A-1-96651,
(Japanese Unexamined Patent Publication No. 1-96652) However, color negative film
Environmental radiation for high-sensitivity silver halide photosensitive materials
Reducing the effects of radiation remains highly desirable. (Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide photosensitive material with high image quality.
The second is to provide long-term aging of photosensitive materials.
Photographic properties such as increased fog and worsened graininess due to
Silver halide photographic materials with minimal deterioration in performance.
It is about providing. (Means for Solving the Problems) An object of the present invention is to provide at least one layer of halogen on a support.
In a silver halide photographic light-sensitive material having a silver emulsion layer
, the silver iodide mole fraction is 10 to 40 moles inside the emulsion layer grains.
% silver iodobromide phase is present, and this silver iodobromide phase is
coated with silver halide containing silver oxide, and the particles
is a silver halide whose surface contains 5 mol% or more of silver iodide.
contains silver halide grains that are contained in the light-sensitive material.
The total amount of potassium ions is the weight relative to the applied silver.
A halogen characterized by a quantitative ratio of 5X10-' or less
This was achieved using a silver-based photographic material. The structure of the present invention is as follows: (1) silver halide grains;
This will be explained in detail in terms of the total amount of lithium ions. The basic performance required of silver halide emulsions for photography is high sensitivity.
low fog (due to fine grain size and development activity)
is high. Silver halides include silver fluoride, silver chloride,
There are silver bromide and silver iodide, but silver fluoride is usually used because it is highly water-soluble.
, the remaining three types of silver halide are not used in photographic emulsions.
Efforts to improve the basic performance of emulsions by combining
has been done. Regarding light absorption, silver chloride, silver bromide, and iodine
The strength increases in the order of silver oxide, but the development activity increases in that order.
It is difficult to achieve both light absorption and development activity. Kula
Yin and Moiser are coated with different silver halide layers
A mixed silver halide emulsion consisting of a silver halide core
Physically, it is silver iodobromide with a core of silver bromide and 1 mol% of silver iodide.
(the first layer consisting of silver bromide and the outer layer consisting of silver bromide)
Disclosed that photosensitivity can be increased without impairing sex.
. (Japanese Patent Publication No. 43-13162) Koitabashi et al.
When attaching a thin shell of 0.01 to 0.1 μm,
Achieves photographically desirable properties such as improved burring power.
disclosed that it would be done. (Japanese Unexamined Patent Publication No. 57-154232) In these inventions, the silver iodide content in the core portion is low (and therefore the torrent content is low).
Useful when the silver iodide content of the metal is low, but
In order to achieve higher image quality, it is necessary to increase the iodine content of the emulsion.
ization was essential. High sensitivity and high image quality are achieved by increasing the iodine content of the core.
Publication No. 60-138538, Japanese Patent Publication No. 61-8825
Publication No. 3, JP-A-59-177535, JP-A-6
Publication No. 1-112142, Japanese Unexamined Patent Publication No. 143331/1986
Disclosed in official gazettes, etc. The technical idea common to these series of patents is the core
The iodine content in the shell should be as high as possible and the iodine content in the shell should be low.
It is possible to achieve both development activity and photosensitivity by increasing the amount of light. In response to this, the inventors of the present invention have made the following discovery as a result of intensive research.
went. That is, it is described in JP-A No. 63-106745.
The silver iodide mole fraction inside the 6 grains is 10 to 40 mol%.
silver iodobromide phase, and this silver iodobromide phase is lower than silver iodide phase.
The surface of the grain is coated with silver halide containing
surface, that is, X P S (X -ray Photo
electron 5pectroscopy) surface analysis
The silver iodide content in the area at a depth of approximately 50 mm analyzed by the method
Surprisingly, environmental radiation
The increase in capri due to lines and the deterioration of graininess can be reduced.
found. The mechanism of this phenomenon is still unclear
do not have. Used to analyze the iodine content near the surface of silver halide grains.
Regarding the principle of the XPS method, Atsushi Aihara et al.
Spectroscopy” (Imori Library 16, published by Imori Publishing, Akira
(2003) can be used as a reference. The standard measurement method for XPS is
from silver halide grains in an appropriate sample form using
Emitted iodine (1) and root (Ag) photoelectrons (usually
Observe the intensity of I-3dszt, Ag5dS/ri
It's a method. To determine the iodine content, the iodine content is known
Using several types of standard samples, iodine and silver (Ag) light
Calibration curve of electron intensity ratio (intensity (■) 7 intensity (Ag))
It can be determined from this calibration curve. halogen
In silver halide emulsions, gelatin adsorbed on the surface of silver halide grains
XPS measurement after decomposing and removing with proteolytic enzyme etc.
must be determined. The silver iodide content in the core and shell parts was determined by X-ray diffraction method.
It can be measured. Application of X-ray diffraction method to silver halide grains
An example of this is 1 (Hirunyu's Journal of Literature).
Graphic Science Volume 10 (1962) No. 1
It is stated on pages 29 onwards. Depending on the halogen composition
Once the lattice constant is determined, Bragg's condition (2dsinθ=
A diffraction peak occurs at a diffraction angle that satisfies nλ). Regarding the measurement method of X-ray diffraction, see Basic Analytical Chemistry Course 24 “X
``X-ray analysis'' (Kyoritsu Publishing) and ``Guide to X-ray diffraction'' (Rigaku)
Detailed information is provided in Denki Co., Ltd.). Standard
The measurement method uses Cu as a target and applies β rays to the Cu.
Halogen as a radiation source (tube voltage 40KV, tube current 60mA)
This is a method for determining the diffraction curve of the (220) plane of silver oxide. A slit (divergent slit) is used to increase the resolution of the measuring machine.
width of the light receiving slit, device time constant, goniometric
Select the scanning speed and recording speed of the data appropriately.
It is necessary to confirm the measurement accuracy using a standard sample. Using 79 wire on Cu, (220) plane of silver halide
When the curve of diffraction intensity vs. diffraction angle is obtained, 10 to 45 mo
The diffraction peak corresponding to the high iodine layer containing 1% silver bromide and
A state in which the diffraction peaks corresponding to the low iodine layer are clearly separated.
, and two distinct cases overlapped with each other.
It may not be resolved into peaks. Decompose a diffraction curve made up of two diffraction components
The method is well known, for example in Experimental Physics Course 11.
It is explained in books such as Lattice Defects (Kyoritsu Shuppan). Curves can be converted into Gaussian functions, Lorentzian functions, etc.
Assuming that it is a function, use Du Pont's curve analyzer
It is also useful to perform diffraction using a method such as -. The silver halide grains used in the present invention have the above-mentioned low iodine content.
The separation between the high iodine layer and the high iodine layer may or may not be clear. Different halogen compositions that do not have a clear layered structure
Even in the case of an emulsion in which two types of grains coexist, the X-ray diffraction
Two peaks appear. In such an emulsion, the excellent photographic performance obtained by the present invention is
cannot be shown. The silver halide emulsion is an emulsion according to the present invention or
Is it an emulsion in which two types of silver halide grains coexist?
In addition to the X-ray diffraction method, the EPMA method (E
Electron Probe Micro. This is possible by using the Analyzer method). This method allows the emulsion particles to be well dispersed so that they do not come into contact with each other.
A sample is prepared and irradiated with an electron beam. electron beam excitation
Elemental analysis of extremely small parts is performed using X-ray analysis based on
I can do it. By this method, the amount of silver and iodine emitted from each particle is
By determining the characteristic X-ray intensity, we can identify the halogen of each particle.
composition can be determined. At least 50 particles were halogenated by the EPMA method.
If the gene composition is f+1, the emulsion is considered to be the emulsion according to the present invention.
It is possible to determine whether it is a drug or not. The emulsion of the present invention has a more uniform iodine content between grains.
Preferably. The distribution of iodine content among particles was measured by EPMA method.
Sometimes the relative standard deviation is less than 50%, even less than 35%,
In particular, it is preferably 20% or less. Preferred halogen compositions of the silver halide grains of the present invention
is as follows. The core is high iodine silver halide with an average iodine content of
The amount is between 10 mol% and the solid solubility limit of 40 mol%. Preferably it is 15 to 40 mol%, more preferably
is 20 to 40 mol%. Depending on the method of preparation of the core particles, the core yolk content may be between 20 and 40 mol%.
If there is an optimum value of the code content, 30 mol to 40 mol
There may be cases where the optimum value is around %. In the core part, silver halide other than silver iodide is silver chlorobromide.
Either silver bromide or silver bromide may be used, but the one with a higher proportion of silver bromide
preferable. The average iodine content of the shell part is lower than that of the core part.
halogen containing silver iodide, preferably 10 mol% or less
silver iodide, more preferably 5 mol% or less silver iodide
It is a silver halide containing. The distribution of silver iodide in the shell portion may be uniform or non-uniform.
The grains of the present invention have silver iodide on the grain surface measured by the XPS method.
The average content of is 5 mol% or more, preferably 7 mol% or more
15 mol% or less, higher than the average silver iodide content of the shell portion
It's a good time. The distribution of silver iodide near the grain surface is uniform.
may also be non-uniform. Silver halides other than silver iodide on the surface include silver chloride.
, silver chlorobromide or silver bromide, but silver bromide
A higher ratio is desirable. Regarding the total halogen composition, the silver iodide content is 7 moles.
% or more, the effect of the present invention is significant. More preferably, the total silver iodide content is 9 mol% or more.
Yes, particularly preferably 12 mol% or more and 18 mol% or less
It is. Although there is no particular restriction on the size of the silver halide grains of the present invention,
, preferably 0.4 μm or more, more preferably 0.6 μm to 2.0 μm.
Preferably, the thickness is 5 μm. The shapes of the silver halide grains of the present invention are hexahedral, octahedral, and decahedral.
Regular crystal shapes such as dihedrons and tetradecahedrons (normal crystal particles)
), and may also be spherical, potato-shaped, or flat.
It may have an irregular crystal shape such as a plate shape. For normal crystal grains: Particles with 50% or more (111) planes
is particularly preferred. Even in the case of irregular crystal forms (111)
Particularly preferred are particles having 50% or more faces, (111)
The rate of hemostasis in the area is determined by the Kuchelka-Munk dye adsorption method.
can. This is a (111) plane or a (100) plane.
The association of dyes on the (111) plane
The association state of the dye on the (100) plane is determined by the spectroscopic spectrum.
Select pigments that are different in color. Emulsion of such dyes
The spectral spectrum for the amount of dye added can be precisely investigated.
The hemostasis rate of the (111) plane can be determined by In the case of twin grains, tabular grains are preferred. Thickness 0. Average asperity of 5 μm or less and 0.6 μm or more diameter
Particles with a spectral ratio of 2 or more, preferably 3 to 1O, are in the same layer.
at least 5 of the total projected area of silver halide grains present in
It is particularly preferable that it accounts for 0%. average aspect ratio
For definitions and measurement methods, see JP-A-58-113926.
Publication, JP-A-58-113930, JP-A-58-
It is specifically described in JP-A No. 113934 and the like. The emulsions of the present invention can also have a wide grain size distribution.
However, emulsions with a narrow grain size distribution are preferable, especially
In the case of normal crystal grains, the weight or grain of silver halide grains
The size of the grains that make up 90% of the total in each emulsion in terms of number
is within ±40% of the average particle size, further within ±30%
Monodisperse emulsions such as those in are preferred. The silver halide grains of the present invention can be produced by selecting from among various methods.
It can be prepared by combining. First, core particles are prepared using acidic method, neutral method, or ammonia method.
Methods such as Reaction of soluble silver salt and soluble halide salt
One-sided mixed method, simultaneous mixed method, and combinations of these methods are available.
You can choose from a combination. Silver halide production as a form of simultaneous mixing
A method of keeping OPAg in the liquid phase constant, that is, a control method.
A double-jet method can also be used. simultaneous mixing
Soluble silver halide of different compositions as different forms of legal
The triple jet method where each salt is added independently (e.g.
soluble silver salts, soluble bromine salts, and soluble iodide salts) may also be used.
I can do that. During core preparation, ammonia, rhodan salt, and
Halogenation of ureas, thioethers, amines, etc.
Particle size distribution of core particles that can be used in selected solvents
A narrow emulsion is desirable, especially the monodisperse core emulsion mentioned above.
Preferably, the halogen composition of each particle is uniform at the core stage.
Whether the
It can be determined based on The halogen composition of the core particle is
If the diffraction width is uniform, the diffraction width of X-ray diffraction will be narrow and the sharp peak will occur.
give a ku. In Japanese Patent Publication No. 49-21657, halogen is uniform between particles.
A method for preparing core particles with the composition is presented. One is
Using the double jet method, 5g of inert gelatin and 0.2g of
Make a solution by dissolving potassium bromide in 700 d of distilled water.
This was stirred at 50°C, and 52.7g of odor was released.
Aqueous solution of potassium iodide and 24.5g of potassium iodide
1N solution and 1N aqueous solution in which 100g of silver nitrate was dissolved.
Add honey to the previously stirred solution at a constant speed for about 80 minutes.
The silver iodide content was determined by adding distilled water and making the total amount 31.
25 mol % of silver iodobromide was obtained. X-ray diffraction shows that iodine has a relatively sharp iodine distribution.
It is known that they are silver bromide particles. Another method is
33g of inert bone gelatin, bromide by ash addition method
5.4 g of potassium and 4.9 g of potassium iodide in 50 g of distilled water
Stir the aqueous solution dissolved in 0Id at 70'C.
, add 125 d of an aqueous solution containing 12°5 g of silver nitrate.
By instantaneous addition, the silver iodide content is 40 mol%.
Relatively uniform silver iodobromide grains were obtained. JP-A-56-16124 has a halogen composition of 15 to 40.
A silver iodobromide emulsion containing mol% silver iodide and containing a protective colloid.
Uniform by maintaining the PAg of the liquid in the range of 1 to 8.
It is disclosed that silver iodobromide can be obtained. After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
Disclosed in Special Publication No. 4B-36890 by Irie and lead powder.
method of accelerating the addition rate over time, or
was disclosed by Saito in U.S. Pat. No. 4,242,445.
By increasing the additive concentration over time, the odor is reduced.
Uniform silver iodobromide can be produced depending on the method of growing the silver grains.
can get. These methods give particularly favorable results. Irie et al.
The method involves preparing an aqueous solution of two or more inorganic salts in the presence of a protective colloid.
The double decomposition reaction is carried out by simultaneously adding approximately equal amounts of
In the method for producing poorly soluble inorganic crystals for photography, the reaction
The inorganic salt aqueous solution is grown at a constant temperature acceleration or higher, and
Addition rate proportional to the total surface area of the poorly soluble inorganic salt crystals in
Add at the following addition rate Q, i.e. Q = r or more
and Q-α is added at a value less than or equal to
. On the other hand, Saito's method uses two or more types of non-binding agents in the presence of a protective colloid.
How to produce silver halide crystals by adding aqueous salt solution at the same time
In the crystal growth method, the concentration of the inorganic salt aqueous solution to be reacted is
increase to such an extent that almost no new crystal nuclei are generated during the period.
It is something that In addition, JP-A-60-138538, JP-A-61-
No. 88253, Japanese Unexamined Patent Publication No. 177535/1988,
JP-A-61-112142, JP-A-60-143
Prepared by applying the emulsion manufacturing method described in Publication No. 331 etc.
Can be manufactured. Introduction of silver iodide into the shell portion of the silver halide grains of the present invention
There are many laws. Aqueous solutions of water-soluble bromide salts and water-soluble
Iodization of the core part when adding silver salt aqueous solution using double jet method
Silver may be leached into the shell; in this case, during addition
By adjusting the pAg and using silver halide solvents,
It is possible to control the amount and distribution of silver iodide in the area. Water is also available
Aqueous solution containing a mixture of soluble bromide and water-soluble iodide and water-soluble
An aqueous silver salt solution can also be added using the double jet method.
water-soluble bromide solution, water-soluble iodide solution and
Water-soluble root salts can also be added using the triple jet method.
0 particle surface or 50 to 100 people from the particle surface
After grain formation, to introduce silver iodide into the water-soluble
Adding an aqueous solution containing iodide or adding 0. 1μ or less
Fine silver grains or fine silver halide grains with high silver iodide content
You can add children. In preparing the silver halide grains of the present invention, core grains
Although shelling may be performed directly after formation, core emulsion
It is preferable to add a shell after washing with water for desalination.
Yes. Shell attachment is also known in the field of silver halide photographic materials.
It can be prepared by various methods, but simultaneous mixing method is preferable.
, Irie et al.'s method and Saito's method described above have a clear layered structure.
Necessary shells preferred as a method for producing emulsions with
The thickness varies depending on the particle size, but 1. Larger than Oμ
Small size particles of 0.1 μm or more and 1.0 μm or less
The particles are covered with a shell thickness of 0.05 μm or more.
This is desirable. The silver content ratio between the core part and the shell part is in the range of 115 to 5.
is preferable, more preferably 115-3, and 1
A range of 15 to 2 is particularly preferred. In the present invention, in the process of silver halide grain formation or physical ripening,
In addition, cadmium salts, zinc salts, lead salts, thallium salts,
Rhodium salt or its complex salt, Rhodium salt or its complex salt, Iron
A salt or an iron complex salt may also be present. However, it generally contains grains with a large amount of iodide 5ift on the grain surface.
Silver halide, which is used in
have a problem. The emulsion is used to obtain desired photographic properties.
In some cases, it may be necessary to further increase the amount of silver coated. This is JP-A-63-226650, JP-A-63-226
651, the impact on environmental radiation
It was found that the effect of the emulsion was halved by increasing the effect of the emulsion.
I made it clear. As a result of further intensive research, the inventors were surprised to find that
Halo containing particles with a large amount of iodide 11I on the particle surface should be expected.
Optimum chemical sensitization of silver germide emulsions in the presence of spectral sensitizing dyes
When
It also has the advantage of being less susceptible to environmental radiation.
He found out. Performing chemical sensitization in the presence of a sensitizing dye is described in U.S. Pat.
, No. 735,766, No. 3,628゜960, No. 735,766, No. 3,628゜960, No.
No. 4,183,756, No. 4゜225.666, No. 4,183,756, No. 4,225.666, No.
No. 3,628,969, No. 4,435,501, No. 4,435,501, No.
No. 4,183,756, JP-A-58-113.928
, No. 60-196749, No. 61-103149,
No. 61-133941, No. 61-165751, No. 61-165751, No. 61-165751, No. 61-165751, No.
No. 59-9153, No. 5B-28738, No. 62-7
No. 040, Research Disclosure Magazine 19227.
It is described in Volume 192, Page 155 (1980), etc.
However, silver halide grains with a high silver iodide content on the grain surface are
This does not suggest any effect on silver halide emulsions containing
do not have. The following are examples of preferred sensitizing dyes for the present invention:
Ru. Pigments useful in the present invention include cyanine dyes and merocyanine dyes.
element, complex cyanine dye, complex merocyanine dye, holopo
cyanine dye, hemicyanine dye, styryl dye
and hemioxonol dyes. particularly useful
Pigments include cyanine dyes, merocyanine dyes, and complex
It is a pigment belonging to merocyanine pigments. These pigments
is usually used in cyanine pigments as a basic heterocyclic nucleus.
Any of the following nuclei can be used. i.e. pyridine
nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazoline nucleus
Sasol nucleus, thiazole nucleus, selenazole nucleus, imidazo
ole nucleus, tetrazole nucleus, pyridine nucleus, etc.; these nuclei
A nucleus in which an alicyclic hydrocarbon ring is fused to the
A nucleus in which aromatic hydrocarbon rings are fused, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxade
core nucleus, naphthoxazole nucleus, benzothiazole nucleus,
Naphthothiazole nucleus, benzoselenazole nucleus, benzene
Midazole nucleus, quinoline nucleus, etc. can be applied. these
The nucleus may be substituted on a carbon atom. Keto for merocyanine dyes or complex merocyanine dyes
Pyrazolin-5-one as a nucleus with methylene structure
nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, 4-dione nucleus, thiazolidine-2,4-dione nucleus,
- 5-6R variants such as danin nucleus and thiobarbic acid nucleus
A ring nucleus can be applied. These sensitizing dyes may be used alone, but a combination of them may be used.
Combinations of sensitizing dyes may be used, especially those with superchromic sensitizing dyes.
Often used for emotional purposes. A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397.060, No. 3,52
No. 2,052, No. 3.5'27.641, No. 3,61
No. 7,293, No. 3,628,964, No. 3,666
．． No. 480, No. 3.672898, No. 3,679,4
No. 28, No. 3,703.377, No. 3,769.30
No. 1, No. 3 814.609, No. 3,837,862
No. 4.026,707, British Patent No. 1,344,2
No. 81, No. 1,507,803, Special Publication No. 434936
No. 53-12,375, JP-A-52-110.6
No. 18, No. 52-109.925, etc.
. Along with sensitizing dyes, colors that do not themselves have spectral sensitizing effects
A substance that does not substantially absorb elementary or visible light,
A substance exhibiting supersensitization may also be included in the emulsion. In particular, the silver halide grains used in the present invention have the following general formula:
[! ] Or be spectrally sensitized with a sensitizing dye
These sensitizing dyes may be used alone, but
, combinations thereof may also be used.・In the χ-C formula, L and Zx may be different or the same 5.6
Represents a group of atoms forming a nitrogen-containing heterocycle. For example, thiazoline, thiazole, benzothiazole,
naphthothiazole, selenazoline, selenazole, ben
zoselenazole, naphthoselenazole, oxazole,
Benzoxazole, naphthoxazole, benzimide
dazole, naphthoimidazole, pyridine, quinoline,
Indolenine, imidazo(4,5-b)quinoxaline
Which heterocycles are mentioned, these heterocycle nuclei are substituted
Examples of substituents that may be substituted include lower alkyl
group (preferably carbon number 6 or less, hydroxy group, halogen
atom, phenyl group, substituted phenyl group, carboxy group,
Further substitution with alkoxycarbonyl group, alkoxy group, etc.
lower alkoxy group (preferably carbonaceous), lower alkoxy group (preferably carbon
a prime number of 6 or less), an acylamino group (preferably a carbon number of 8 or more),
lower), monocyclic aryl group, carboxy group, lower alkoxy
Carbonyl group (preferably carbon number 6 or less), hydroxy
group, a cyano group, a halogen atom, and the like. Q, represents a nitrogen ketomethylene ring-forming atom group in 5.6
For example, thiazolidin-4-one, selenazolidine-4-one,
4-one, oxazolidine-4one, imidazolidine-
Examples include 4-on. Rt, Rt, Rs and R4 are hydrogen atoms, lower alkali
Kill group (preferably carbon number 4 or less), optionally substituted
In addition to representing a phenyl group or an aralkyl group, 11 is 2 or
is different when represents 3, and when n represents 2 or 3.
R7 and Rt, Rt and Rx, R2 and R8 or R
4 and R4 are connected to form an oxygen atom, a sulfur atom, or a nitrogen atom.
It is also possible to form a 5- or 6-membered ring that may contain children.
represent. Rs and Rh contain oxygen atoms, sulfur atoms or nitrogen atoms in the carbon chain.
A substituted compound having a carbon number of 10 or less that may contain an elementary atom
represents an optionally alkyl group or an alkenyl group
, Examples of substituents include sulfo group, carboxy group, hydrogen
Roxy group, halogen atom, alkoxycarbonyl group, carbonyl group,
Rubamoyl group, phenyl group, substituted phenyl group, etc.
It will be done. In addition, the heterocycle represented by Z1 and Zt is benzimidazo
alcohol, naphthoimidazole, imidazo[4°5-b]ki
Containing another substitutable nitrogen atom such as noxaline
If the other nitrogen atom of those heterocycles is
Hydroxy group, alkoxy group, halogen having 6 or less carbon atoms
atom, phenyl group or alcoalkoxycarbonyl
an alkyl group which may be further substituted with a group,
It may be substituted with a kenyl group or the like. 1 and nl are 0 or positive integers less than or equal to 3, and L+11 is
3 or less, and 11 is 1.2 or 3.
When R3 and R1 are connected to form a 5.6-membered ring,
Good too. j+ -k+ and ml represent 0 or 1. Xl- represents an acid anion, n represents 0 or l
. At least one of R8, R& and R1 is a sulfo group
or a group containing a carboxy group is more preferable.
Yes. -a Among the sensitizing dyes contained in formula (1), preferred ones are
It is as follows. -1 03K Soen-2 So, K Oi! -3 OJa Oi -4 1-5 -6 SO, ni 05 -10 (CHI)3 (CHzh OJa O3 03Na OT 0i -7- (CHz) a (CHg)4 SO.Na Oi -9 -1 3 -14 So!K Oi (CHz)s ans Oi ■-16 SOJ-N (CJs) 3 SO1 ■ 7 ■-18 (CHg)s (CHz)s SO,Na Oi -21 JS ■-22 ans CI ICF 2 (C11 □). (CHg)s S(hK O5 ■-23 ans (CIri4 Or CJs !-19 C2115 (CHz)i Oi ■-20 -21 tHs Oi to SOl ■-24 2Hs ■-25 ■-26 ans (CHz) 3 Oi ■-27 ■-28 ■-29 ■-33 -34 ■-35 zHs zns ■-30 -31 ■-32 tNs r ■-36 General formula (It) C, II S In the formula, Zl+ represents a nitrogen-containing 5.6-membered heterocyclic ring-forming atom group.
WASU0 For example, thiazoline, thiazole, benzothiazo
ol, naphthothiazole, selenazoline, selenazole
, benzoselenazole, naphthoselenazole, oxazo
Benzoxazole, Naphthoxazole, Ben
zimidazole, naphthimidazole, pyridine, kino
Phosphorus, pyrrolidine, indolenine, imidazo(4,5-
b) Normal cyanine formation such as quinoxalinetetrazole
The heterocyclic nuclei used are listed, and these heterocyclic nuclei
may be substituted, examples of it substituents include lower
Alkyl group (preferably a hydroxy group with 10 or less carbon atoms)
, halogen atom, phenyl group, substituted phenyl group, carbo
Oxy group, alkoxycarbonyl group, alkoxy group, etc.
further substituted), lower alkoxy group (preferably
or carbon number 7 or less), acylamino group (preferably carbon number
(prime number 8 or less), monocyclic aryl group, monocyclic aryloxy group
, carboxy group, lower alkoxycarbonyl group (preferably
or 7 or less carbon atoms), hydroxy group, cyano group, or
Examples include halogen atoms. Q + + is a nitrogen-containing 5.6-membered ketomethylene ring-forming atomic group
For example, thiazolidin-4-one, selenazoli
Zin-4-oxazolidin-4-one, imidazolidine
Examples include atomic groups forming -4-one and the like. Q and □ represent nitrogen-containing 5.6-membered ketomethylene ring-forming atoms.
Was. For example, rhodanine, 2-thiohydantoin, 2
-Selenathiohydantoin, 2-thioxazolidine-
2,4-dione, 2-selenaoxapridine-2,4-
dione, 2-thioselenazolidine-2,4-dione, 2
-Selenthiazolidine-2,4-dione, 2-selenase
Regular merocyanine such as renazolidine-2,4-dione
List the atomic groups that form the heterocyclic nucleus that can form pigments.
It will be done. In the heterocycle represented by Zo, Q, and Q1□ above,
, two such as benzimidazole and thiohydantoin.
or more nitrogen atoms in the heterocycle-forming atoms.
Nitrogen atoms to which R13, RIS, and Ro are not connected, respectively
may be substituted, and the substituents include
carbon atoms are replaced by oxygen, sulfur or nitrogen atoms
carbon that may be substituted with or further have a substituent
Alkyl group of number 8 or less, alkenyl group or substituted
Examples include a monocyclic aryl group which may have a ring. R11 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.
I, R1□ is a hydrogen atom, an optionally substituted phenyl atom
(Examples of substituents include alkyl and alkyl groups having 4 or less carbon atoms.
Rukoxy group or halogen atom, carboxy group, hydro
(oxy group, etc.), or hydroxy group, carboxyl group, etc.
Substituted with boxy group, alkoxy group, halogen atom, etc.
0m3□ representing an alkyl group is 2 or 3.
, different R11 and R1□ are connected to form an oxygen source.
5.6-membered, which may contain a sulfur atom or a nitrogen atom
It may form a ring. RIff is an oxygen atom, a sulfur atom, or a nitrogen atom in the carbon chain.
Substituted carbon atoms containing 10 or less carbon atoms
represents an optional alkyl group or an alkenyl group,
Examples of substituents include sulfo group, carboxy group, and hydroxy group.
cy group, halogen atom, alkoxycarbonyl group, carba
Moyl group, phenyl group, substituted phenyl group or monocyclic saturation
Examples include heterocyclic groups. R14 and RIS have the same meaning as R1, and hydrogen
atoms or optionally substituted monocyclic aryl groups (substituted
Examples of groups include sulfo, carboxy, and hydroxy groups.
group, halogen atom, alkyl group having 5 or less carbon atoms,
(for example, a ruamino group or an alkoxy group)
also represents. m2. represents O or a positive integer less than or equal to 3, and 1 represents
O or l, R2, represents 0 or l. When m□ is a positive integer of 3 or less, Ro and R13
may be linked to form a 5- and 6-membered ring. At least one of RI3, R14 and Rts is
It is preferable that the group contains a sulfo group or a carboxy group.
More preferable. Among the sensitizing dyes included in the general formula (It),
Particularly preferred are the following compounds. ■-1 n-2 1-3 1-8 1-9 alls ■ ■ -5 -6- If-1 1 SO. K SO. K ans C t 11 5 CII□CIl; CI+□ Chemical sensitization that gives the highest sensitivity at various sensitizing dye amounts
Find the conditions first. Next, from this data, give the highest sensitivity
By determining the amount of sensitizing dye that coexists during chemical sensitization,
The optimum amount of sensitizing dye can be determined. During chemical sensitization
If the amount of sensitizing dye to be present is small, after chemical sensitization
Increase sensitivity by adding more sensitizing dye to
be able to. pHlPAg temperature except that no sulfur sensitizer is added
etc. for 30 minutes under the same conditions as chemical sensitization.
The preserved emulsion was transferred to a colorless triacetic acid cell to achieve Ig/nf.
Reflection spectrum of sample coated and dried in low space
The preferred amount of sensitizing dye can be determined from the peak value of . In other words, the amount of sensitizing dye corresponding to the maximum value of the reflection peak is
30% to 120%, preferably 50% to 110%, more
Chemical sensitization with preferably an amount of 70% to 100% of the enhancing dye
The purpose of the present invention can be achieved by coexisting at times.
. Exacerbating pigments are used before, during, and immediately after particle formation.
Add it at any time, such as before starting chemical sensitization or during chemical sensitization.
However, it may be added in the process before particle formation and before adding chemical sensitizer.
Preferably. Method of chemical sensitization of silver halide emulsion used in the present invention
Examples include sulfur sensitization method, selenium sensitization method, reduction sensitization method, gold sensitization method,
Known methods such as sensitization can be used;
Used alone or in combination. Among the precious metal sensitization methods, the gold sensitization method is the representative method.
Compounds, mainly gold complex salts, are used. Precious metals other than all, and
For example, it contains complex salts such as platinum, palladium, and iridium.
A specific example is U.S. Patent No. 2,448,06.
No. 0, British Patent No. 618.061, etc.
. As a sulfur sensitizer, 1. Sulfur compounds contained in gelatin
In addition to various sulfur compounds, such as thiosulfate,
Use of ureas, thiazoles, rhodanines, etc.
I can do it. Specific examples include U.S. Patent No. 1.574,944 and
No. 2,278,947, No. 2,410,689, No. 2
, No. 728,668, No. 3,501,313, No. 3,
No. 656,955. The combination of sulfur sensitization using thiosulfate and gold sensitization is an advantage of the present invention.
The effect can be effectively demonstrated. (Patent application No. 63-162145
) Reduction sensitizers include stannous salts, amines, and formamide.
Dinsulfinic acid, silane compounds, ascorbic acids, etc.
can be used. There are no particular restrictions on the conditions for chemical sensitization in the present invention.
However, the PAg is 6 to 11, preferably 7 to 10.
More preferably, it is 7 to 9.5, and the temperature is 40 to 9.5.
95°C, preferably 50 to 85°C. The amount of sulfur sensitizer and gold sensitizer is 11 mole halide.
from 10-6 to 10-' mole, preferably from 10-7 to
It is 10-4 mol. As the gold sensitizer, any known one such as chlorauric acid salt can be used.
I can be there. The silver halide grains used in the present invention contain sulfur-containing halides.
In the present invention, it is preferable that the present invention contains a silver germide solvent.
The sulfur-containing silver halide solvent used depends on the grain shape of the emulsion.
It may be added at any step from formation to application.
is particularly preferably present during chemical sensitization. Used in the present invention
The amount of sulfur-containing silver halide solvent added depends on the grain size.
For silver halide grains with a size of 0°5μ, the density is 5.0 per mole.
X101 mole to 5.0X10-” mole, particle size 1
．． 2.5X1 per mole of silver for 0μ silver halide grains
0-'mol to 2.5X10-'mol, particle size 2.
1.25X1 per mole of silver for 0μ silver halide grains
0-' mole to 1.25×10 13 mole is preferred. The sulfur-containing silver halide emulsion in the present invention refers to sulfur atoms.
is a halogenated 11 i9 agent that can coordinate to silver ions in
. Here, the halogenated ill agent is more specifically water
Or water/organic solvent mixed solvent (e.g. water/methanol-1
/1 etc.) at a concentration of 0.02 molar.
The weight of silver chloride that a halogenated solvent can dissolve at 60°C
Can dissolve more than twice the weight of silver chloride
It is something. Specifically, thiocyanates (Rhodankali, Rodanan)
monium, etc.), organic thioether compounds (e.g., U.S.
Patent No. 3574628, Patent No. 3021215, Patent No.
30577.24, 3038805, 42
No. 76374, No. 4297439, No. 37041
Compounds described in No. 30, JP-A-57-104926, etc.
), thione compounds (e.g., JP-A-53-82408)
, No. 55-77737, U.S. Pat. No. 4,221,863, etc.
Tetrasubstituted thiourea, thiourea, and thiourea described in
Acid salts and organic thioether compounds are particularly preferred. More specifically, as the organic thioether, -i formula (
Compounds represented by rV) are preferred. R,, (SR,.)-S Rat (rV) formula
In the formula, m represents O or an integer from 1 to 4. RI6 and Rlt may be the same or different.
Alkyl group (1 to 5 carbon atoms) or substituted alkyl group (total
carbon number 1 to 30). Here, examples of the substituent include -OHlC00M,
SO3M, NHRI9, N R+ q R1q(
However, Rlt may be the same or different), OR+*,
C0NHRI9, -COOR19, heterocycle, etc.
can be done. R1 is a hydrogen atom, a lower alkyl group, or
It may also be a substituted alkyl group substituted with . In addition, two or more substituents may be substituted, and
may be the same or different. R1 is an alkylene group (preferably having 1 to 12 carbon atoms)
represent. However, when m is 2 or more, m R18s may be the same or different.
You can leave it there. In addition, one or more OC0NH5 in the middle of the alkylene chain
It may contain a group such as OzNH-, or it may contain a group such as OzNH-, or
Substituents may be substituted. Also, by bonding R1^ and R1'l, a cyclic thioether
It is also possible to form a file. As a thione compound, a compound represented by the general formula (V)
Preferably. Represents 5R25. RZO1R21, Ro, R13, R14 and I'? zs
may be the same or different, and
Kenyl group, aralkyl group, aryl group or heterocyclic residue
and these may be substituted (preferably
, each having a total carbon number of 30 or less). Also, RED and R2+, Rlt and R23, or R2
゜ and Ro, R2゜ and R24, R2゜ and R25 are combined
may form a 5- or 6-membered heterocycle, in which
Substituents may be added. The synthesis of these compounds is described in the patent specifications mentioned above.
This can be done by the method described in the cited literature. Also
, some compounds are commercially available. Below, the sulfur-containing silver halide solvent used in the present invention
Examples of compounds are listed below. S S, S -(1) 5CN SSS-(2) NH,5CN SSS-(3) HO(CHI) 2S(C11ri zOH3SS-(a IO((:R2)4S(CIlri5S(C1h), 0H
3SS-(5) 110 (CHz) x-S-(C1h)! -S-(
CHz) z-011SSS-(6) IO-(CHz)! -S-(CHz) t-3-(C
1l□), -01lSSS-(7) HO(CHt) b-5-(CHz) t-5-(CL
) *-011SSS-(8) HO(CHt2) zS(CHz) zs(CHz)
1s(CL) zOH3SS-(9) 80(Clh) gs(Clb) zO(C1lz)
to(CHz) gs(CL) z011S S S
-00 S S 5-(18) tloOccHzs(CHz)zsc41zcOOHH
OCHzcHcHzS (CHz) zcONHcHz
NlIC0(CHz) zscHzctlcHzo)
ISSS -00 H H H2NCO(CH2)! 5(CI!2) zs(C1
h) zcONlhS S 5-(19) SSS-021 NaOsS (CHz) 33 (CHz) is (
Clh) zsOJas s s -a riS S S -(20) HO(CH2) zs (CI+ ri zcONHcH
JIICO (CH2) 25 (C8t) ZOH3SS
-04) S S S - (21) CI, 5CII□CHCOO11 SSS-Q NH2 HO (jlzcllcHzs(Ctlz) zsc)I
gCllCHzOH3S S -(22) H H C! H,5(CIl□) is (CHz) zNHc
O(Cll□)2CO'0IISSS-061 S S S - (23) H H 3SS-Q7) S S S - (24) NH. NH2 S S S - (25) S S S - (30) 0 ■ H S S 5- (31) 5S (27) S S S - (32) S S S - (28) S S 5- (33) S S S - (29) S S S - (34) S S S - (3B) S S S - (35) S S S - (39) S S S - (36) S S S - (40) S S S -(37) S S 5-(41) llt Also, when chemically sensitizing the emulsion of the present invention, together with the enhancing dye,
When silver halide adsorbing substances other than sensitizing dyes are present,
, which is preferable because it can increase the development speed. Other than sensitizing dyes
The silver halide adsorptive substance is used during grain formation and immediately after grain formation.
It can be added at any time, such as after ripening, before or after ripening.
stomach. Each addition time may be different, but chemical sensitizers (for example,
before the addition of gold or sulfur sensitizers, or
It is preferable to add it at the same time as the sensitizer, and at least
must also be present during the process of chemical sensitization.
Ru. As a condition for adding the silver halide adsorbent substance, the temperature is 30°C.
Any temperature between °C and 80 °C may be used, but
For the purpose of
, p, and Ag may be optional, but at the time of chemical sensitization,
pH 6-9, pAg 7-9, especially pAg 7.6-8.
It is preferable that it is 4. Silver halide adsorbent substances other than aggravating dyes as referred to in the present invention
means a type of photographic performance stabilizer. i.e. azoles (e.g. benzothiazolium salts,
Nzimidazolium salts, imidazoles, benzimidas
Sols, nitroindazoles, triazoles,
Zotriazoles, tetrazoles, triazines, etc.
) ; mercapto compounds (e.g. mercaptothiazo
Mercaptobenzothiazoles, Mercaptoys
Midazoles, Mercaptobenzothiazoles, Merca
Putobenzoxazoles, Mercaptothiadiazole
mercaptothiadiazoles, mercaptotetrazo
mercaptotriazoles, mercaptopyrimi
gins, mercaptotriazines, etc.);
Thioketo compounds niazaindenes like sadrinthione
(e.g. triazaindenes, tetraazaindenes)
(especially 4-hydroxy substituted (1,3,3a,?) tetra
azaindenes), pentaazaindenes, etc.);
Many known as antifoggants or stabilizers, such as
Compounds can be used as silver halide adsorbents.
Wear. Furthermore, purines or nucleic acids, or
No. 36213, JP-A No. 59-90844, especially those described in
High molecular compounds are also usable adsorbent substances. Especially azaindenes, purines, nucleic acids, and calcium.
Mercapto compounds with boxyl or sulfonic acid groups
is preferable and can be used in the present invention. These transformations
The amount of compound added is 0.05 to 5 per mole of silver halide.
．． 0 mmol, preferably 0.1 to 3.0 mmol.
Ru. Specific examples of compounds effective in the present invention are shown below. -1! -2 -3! -4 -5 -10 NA -6- NA NHCOCH! ■-14 C4H9 ■-17 tHs tHs NtlL+hi+s ■-29 ■-3O N+□N H H The color negative light-sensitive material of the present invention has a red-sensitive emulsion layer and a green-sensitive emulsion layer.
An emulsion with two or more layers, each having a different sensitivity, a blue-sensitive emulsion layer and a blue-sensitive emulsion layer.
It is generally composed of layers. In addition, to further improve graininess, each color-sensitive layer
It is also possible to have a three-layer structure. (Tokuko Showa 49-15.
No. 4.95) The emulsion of the present invention can be added to any of the above layers;
Preferably, the emulsion of the invention is added to a highly sensitive emulsion layer. mechanism
Although this has not been elucidated, the emulsion of the present invention may be used in the red-sensitive emulsion layer.
The effects of the present invention are most noticeable when . The next most remarkable effect is that the emulsion of the present invention is applied to the green-sensitive emulsion layer.
This is when the agent is included. However, our recent research shows that in addition to these, Capri
It has been discovered that there are factors that increase
As a result, the amount of potassium ions contained in the photosensitive material decreased.
I discovered that this was the cause. Based on this discovery, the above-mentioned emulsion of the present invention was incorporated into light-sensitive materials.
By combining a reduction in the amount of potassium ions in turnips
It was found that the increase in li was significantly suppressed. This potassium ion is released during the formation of silver halide emulsion grains.
KCffi, K used for emulsion OPAg adjustment, etc.
As Br, Kl, gelatin, dyes and various additives.
It is introduced into photosensitive materials as part of additives.
. Therefore, potassium, which is contained in large amounts in photosensitive materials,
To reduce the amount of potassium ions remaining, these potassium ions are
Consideration should be given to changing the material containing the compound. present invention
The purpose of is to reduce the total amount of potassium ions contained in the photosensitive material.
The amount is preferably 5XIO-' or less by weight relative to silver.
is 2XIO-” or less, more preferably l×10-” or less
, it is particularly preferable to set it to 5×10 −′ or less. most
The preferred range is 3XIO-' to 1x10-'
. Analyzing the amount of potassium ions contained in photosensitive materials
Several methods are known, such as atomic absorption
Analysis using methods is simple. In addition, in order to analyze the amount of silver contained in photosensitive materials, it is necessary to
Several methods are known, such as atomic absorption
Examples include elemental analysis using the method and fluorescent X-rays. Photosensitive materials are very complex systems. For example, one emulsion
To make it, silver nitrate, alkali halide, gelatin, acid,
Alkali, precipitant, chemical sensitizer, spectral enhancer, antifogging agent
More than 30 types of compounds such as inhibitors, stabilizers, thickeners, preservatives, etc.
Usually things are used. Also, color photosensitive materials
Color couplers, which are essential as pigment-forming substances, are added to the dye.
be done. These are emulsified using gelatin, oil, organic solvents, etc.
Generally, it is prepared and added as a substance, but one
More than 10 types of compounds are used to make emulsions.
is normal. Color photographic materials have about 15 hydrophilic layers.
It is made up of colloidal layers, and each layer has one type of colloid.
Or multiple emulsions, one or more emulsions, and various additions
Contains agents, hardeners, and coating aids. Therefore, one
A large number of compounds are used to make photosensitive materials. Many of these compounds contain potassium ions.
include. Therefore, in order to reduce the amount of potassium ions,
In order to
and replace it with compounds that do not contain potassium ions.
Steady work is required 0 For example, silver chloride, silver bromide, iodide
KCI, K as alkali halides used in making silver
Br. Kl is a compound that is inexpensive and easy to obtain with high purity.
It is the most commonly used compound. Also, adjust the emulsion OPAg, adjust the salt concentration,
p HG When adjusting the circle, KB r, KNO,, KOH
It is very common to use Also, in gelatin
It contains many 0 as impurities. Also thickener, min.
photosensitizing dyes, stabilizers, antifoggants, color couplers, etc.
Many counterions containing ゛ are used.
There is. These are inexpensive and highly pure products that do not contain 9-containing compounds.
Replaced with a compound, and then replaced with a compound that does not contain
Detailed efforts to adjust the performance changes that occur when
Necessary to achieve the present invention. Photosensitive materials that generally have high sensitivity to light and a large amount of coated silver
However, it is easily affected by natural radiation. Color negative film with wide exposure and attitude is
The amount of coated silver is large compared to other photosensitive materials, therefore the present invention
The effect is a color negative film with a specific photographic sensitivity of 320 or higher.
It is noticeable in the camera, and the specific photographic sensitivity is 800 or more.
This is even more noticeable in color negative films. Here, the specific photographic sensitivity is determined as follows. Sen
Wedge exposure according to the conventional method for measuring cytometry performance
After that, it is processed in the normal processing step (CN16). process
Sensitometric measurements were performed on the sample under blue, green, and red light.
and corresponds to a concentration 0.15 higher than each minimum concentration.
The exposure amount is expressed in lux and seconds, respectively, and is expressed as HBSH.
G. HR, and the larger value of HB and HR (lower sensitivity)
) is set as H3. At this time, a specific photographic feel and therefore a special
The larger the value of constant photographic sensitivity S, the higher the sensitivity of the sample.
show. By the way, in high-sensitivity color photosensitive materials, the above-mentioned
For example, JP-A No. 58-147゜744, etc.
As described in
Therefore, the content of silver halide emulsion grains should be set as high as possible.
It has been the industry's traditional practice to measure place
However, we are considering this common sense from the perspective of performance deterioration after storage.
After reviewing, if the silver content exceeds 9.0g/rtf,
Due to severe deterioration over time, photosensitive materials are not suitable for actual use.
It was found that there was a considerable difference compared to immediately after production. Surprisingly, when the silver content exceeds a certain level,
The effect of improving graininess, which was the original objective, was small; for example,
In terms of performance after storage for half a year, the one with lower silver content
However, because the deterioration of graininess during storage is small, the
Reverse development was discovered with good graininess.
It was. The content of silver contained in the color photosensitive material of the present invention is 3.
0g/a or more9. Og/rrf or less is preferable. good
The desired silver content range depends on the layer structure of the photosensitive material and its use.
It varies depending on the type of coupler used, etc., and cannot be determined unconditionally.
No, but 9.0 for photosensitive materials with a specific photographic sensitivity of 320 or higher.
g/rt? If the silver content is higher than that, it will last for about 6 months to 2 years.
Sensitivity to the extent that it becomes a practical problem due to exposure to natural radiation
This will cause a decrease in grain quality and grainy deterioration. Also, 3. Og/
Silver content below rrf is required for color photosensitive materials.
It is not possible to store the maximum concentration. Photo sensitivity 320
For the above sensitive materials, preferably 3.0 g/nT or more, 8.5 g,
/rrf or less, more preferably 3. Og/rrf or more 8
．． It is 0g/po or less. The color negative film according to the invention is provided on a support with
Blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer
It has layers. The order of these layers can be chosen arbitrarily depending on your needs.
Bell. Yellow coupler in blue-sensitive emulsion layer, green-sensitive emulsion
Magenta coupler in the layer and cyan coupler in the red-sensitive emulsion layer
Usually, each group contains a different set of
You can also take a combination. Also, any same color sensitive milk
Achieved by constructing the emulsion layer from two or more emulsion layers with different sensitivities.
It is preferable to use the method of improving the devil, three-layer structure
It is more preferable to use a method to further improve graininess.
Yes. In order to achieve both high sensitivity and high image quality, the order of the layer arrangement is
Various inventions related to this have been made. These techniques may also be used. Notes on the order of layer arrangement
U.S. Pat. No. 4,184,876, No. 4.129.
No. 446, No. 4,186,016, British Patent No. 1,
No. 560,965, U.S. Patent No. 4°186.011;
No. 4,267.264, No. 4.173.479, No.
No. 4,157,917, No. 4,165,236, United Kingdom
Patent No. 2.138962, Japanese Unexamined Patent Publication No. 177.55/1986
No. 2, British Patent No. 2,137,372, Japanese Unexamined Patent Publication No. 1983-
Described in No. 180.556, No. 59-204,038, etc.
has been done. Layer of photosensitive emulsion layer in the color negative photosensitive material of the present invention
Specific examples of the arrangement order are listed below, but are not limited to these.
Note that the non-photosensitive layer can be omitted here.
However, it may be located at a location well known to the person concerned. (1) Support, low-sensitivity red-sensitive emulsion layer (hereinafter referred to as RL), low-sensitivity
High-sensitivity green-sensitive emulsion layer (hereinafter referred to as GL), low-sensitivity blue-sensitive emulsion layer (GL)
BL), high-sensitivity red-sensitive emulsion layer (RH), high-sensitivity green-sensitivity
high-sensitivity blue-sensitive emulsion layer (BH). (2) Support, RL, CL, BL, 0H1RH. BH (3) Support, RL, GL, BL, RH, medium green sensitivity
Emulsion layer (hereinafter referred to as GM), OH, BH (4) support, RL
, GL, GM, BL, R) (, GH, BH (5) Support, RL, medium red-sensitive emulsion layer (hereinafter referred to as RM)
, CL, GM, BL, intermediate blue-sensitive emulsion layer (hereinafter referred to as BM)
, RHSGH, BH (6) Support, RL, GL, BL, RM, RHIC
M, GHSBM, , BH (7) Support, RL, GL, RHLGH, BL. BH (8) Support, GLSRL, RH,, GH,, BL. BH (9) Support, RL, GL, RHSGM, GH. BL, BH (10) Support, RL, GL, Gl(, R1(, BL,
BH (11) Support, RL, RH, GL, GH, BL. BH (12) Support, RL, RM, RH, GL, GM, O
HS BL, BH (13) Support, RL, RM, RH, GL, GM. Gl (% B, BM, BH
There may be layers. There is fine grain silver halide under the high-speed layer, especially the high-speed blue-sensitive layer.
This technology allows any reflective layer to be provided to improve sensitivity.
It is described in Japanese Patent Laid-open No. 160,135/1983. Also, U.S. Patent No. 3,497,350 or JP
The texture of the emulsion layer as described in No. 9-214853.
This layer is supported by appropriate combinations of chromatic and color image-forming couplers.
You can also use a method such as installing it at the farthest position from the holding body.
can. The color photographic material of the present invention usually has a yellow filter.
Contains layers. The yellow filter layer contains colloidal silver.
Rui is the item described in Japanese Patent Application No. 183945/1983.
Preferably, yellow filter dyes are used. Various couplers can be used in the photosensitive material of the present invention.
can. Cyan dye-forming coupler in red-sensitive emulsion layer, green color
Magenta dye-forming coupler in the sensitive emulsion layer, and dye-forming coupler in the blue-sensitive emulsion layer.
Each usually contains a yellow dye-forming coupler.
may be used in different combinations depending on the case, or a near-infrared sensitive layer may be used.
It can also be a combination with As a yellow coloring coupler, a well-known open chain ketomethylene type coupler is used.
Couplers can be used. Among these, benzoylacetanilide and pivalo
Compounds based on ylacetanilide are preferred. Available yellow
Specific examples of color-forming couplers are given in U.S. Patent No. 2,875,057.
No. 3,265,506, No. 3,408,194
, No. 3,551.155, No. 3,582,322,
3.725072, 3,891,445, West Germany
Patent I. No. 547.868, West German Application No. 2,219,917
, No. 2,261,361, No. 2,414゜006,
British Patent No. 1,425,020, Special Publication No. 1978-1078
No. 3, JP-A-47-26133, JP-A No. 48-73147
No. 51-102636, No. 50-6341, No. 50-6341, No. 51-102636, No. 50-6341, No.
No. 50-123342, No. 50-130.442, No. 50-130.442, No.
No. 51-21827, No. 50'-87650, No. 52
- Described in No. 82424, No. 52-115219, etc.
It is something that was given. Magenta coloring couplers include pyrazolone compounds,
Uses indacylon compounds, cyanoacetyl compounds, etc.
In particular, pyracicone compounds are advantageous.
. Specific examples of magenta color-forming couplers that can be used include the U.S. patent
No. 2,600,788, No. 2,983,608, No. 3
, No. 062,653, No. 3,127,269, No. 3,
311゜476, 3,419,391, 3,5
No. 19.429, No. 3,558,319, No. 3゜58
No. 2.322, No. 3,615,506, No. 3.834
, No. 908, No. 3,891,445, West German Patent No. 1,8
No. 10,464, West German Patent Application (OLS) 2,408,
No. 665, No. 2,417゜945, No. 2,418,9
No. 59, No. 2,424.467, Special Publication No. 1973-1960'
No. 31, JP-A-51-20826, JP-A No. 52-5892
No. 2, No. 49-129538, No. 49-74027
, No. 50-159336, No. 52-42121, No. 52-42121, No. 52-42121, No. 52-42121, No.
No. 49-74028, No. 50-60233, No. 51-
Those described in No. 26541, No. 53-55122, etc.
It is. Cyan coloring couplers include phenolic compounds and sodium chloride.
Phthol compounds and the like can be used. The specifics
Examples are U.S. Pat. Nos. 2,369,929 and 2,434,2
No. 72, No. 2,474,293, No. 2,521,90
No. 8, No. 2.895826, No. 3,034,892
, 3,311.476, 3.458 315,
3476.563, 3,583,971, 3
．． No. 591,383, No. 3,767.411, No. 4,
No. 004,929, West German Patent Application (OLS) 2.414
, No. 830, No. 2,454,329, Japanese Unexamined Patent Publication No. 1973-5
No. 9838, No. 51-26034, No. 48-5055
No. 51-146828, No. 52-69624,
It is described in No. 52-90932. As a cyan coupler, JP-A No. 57-204545,
No. 56-65134, No. 5B-33252, No. 58
Couplers having ureido groups as described in No.-33249 etc.
can be preferably used. For the coupler, 4 moles of silver halide produces 1 mole of color.
1 mole color created with 4 equivalent coupler and 2 moles of silver halide
There are 2-equivalent couplers that do this. 2-equivalent coupler is more silver
It is highly efficient and preferable. However, 2-equivalent couplers also have a high fog amplification rate.
I have a problem. 2-equivalence in the photosensitive material of the present invention with reduced fog
The characteristics of the coupler can be fully demonstrated. Special
At least 50 mol% of the total amount of coupler is 2-equivalent coupler.
It is preferable to include the emulsion of the present invention in the high-sensitivity layer which is a puller.
Delicious. In particular, silver halide milk with an average silver iodide content of 7 mol% or more
In the development agent, a two-equivalent coupler is used to
It is better to use oxidants more effectively in terms of photographic performance.
. This 2-equivalent coupler used in the present invention has the following general formula:
It is represented by (Cp-1) to (Cp-9). General formula (Cp-1) 0 111 R8I-C-CH-C-NO-R8! Z. General formula (Cp General formula (Cp General formula (Cp 2) 0 111 Rsa-NH-CH-C-NH-RszZyu3) 1ss 4) ■ 5) General formula (Cp 6) ■ General formula ( Cp 9) General formula (Cp=7) 0 ■ 1 General formula (Cp 8) Next, R51= of the above general formulas (Cp-1) to (Cp-9)
R59, l, m and p will be explained. In the formula, Rfil is an aliphatic group, aromatic group, alkoxy group or
or a heterocyclic group, and R32 and Rs3 are each an aromatic group.
Or represents a heterocyclic group. In the formula, the aliphatic group represented by R5I preferably has a carbon number of
1 to 22, substituted or unsubstituted, linear or cyclic,
Preferred substituents for alkyl groups, which may be any
is an alkoxy group, an aryloxy group, an amino group, an acyl group
These themselves are further substituted with amino groups, halogen atoms, etc.
Aliphatic groups useful as eR8l which may have groups
A specific example is as follows. : Isopropyl
group, isobutyl group, terL-butyl group, isoamyl group
, tert-amyl group, 1,1-dimethylbutyl group, 1
．． 1-dimethylhexyl i,l,l-diethylhexyl
group, dodecyl group, hexadecyl group, octadecyl group,
Chlorhexyl group, 2-methoxyisopropyl group, 2-phenyl group
phenoxyisoprobil'J% 2p jerk-
Butylphenoxyisopropyl group, α-aminoisopropyl group
Pyl group, α-(diethylamino)isopropyl group, α-
(succinimide) isopropyl group, α-(phthalimide)
d)isopropyl group, α-(benzenesulfonamide)
Examples include isopropyl group. RSt, Rsz or R1 is an aromatic group (especially a phenyl group)
), the aromatic group may be substituted. Aromatic groups such as phenyl groups are alkyl groups having 32 or less carbon atoms.
group, alkenyl group, alkoxy group, alkoxycarbonyl group
group, alkoxycarbonylamino group, aliphatic amino group
, alkylsulfamoyl group, alkylsulfonamide
group, alkylureido group, alkyl-substituted succinimide
In this case, the alkyl group is substituted with
An aromatic group such as phenylene may also be present. phenyl group
Also aryloxy group, aryloxycarbonyl group
, arylcarbamoyl group, arylamide group,
Rusulfamoyl group, arylsulfonamide group, aryl
May be substituted with ureido group, etc., and these substitutions
The aryl group of the group further has a total number of carbon atoms of 1 to 22.
may be substituted with one or more alkyl groups. Rsl%R%! , or be hailed with R53
The phenyl group is further a lower alkyl group having 1 to 6 carbon atoms.
Amino groups, including substituted ones, hydroxy groups, carbo
Oxy group, sulfo group, nitro group, cyano group, thiocyano group
Alternatively, it may be substituted with a halogen atom. In addition, RSt, RS2v or R53 has a phenyl group other than
Substituents with fused rings, such as naphthyl group, quinolyl group
, isoquinolyl group, chromanyl group, chromanyl group, tet
These substitutions may represent a lahydronaphthyl group, etc.
The radicals may themselves have further substituents. When RSt has an alkoxy group, the alkyl part
1 to 32 carbon atoms, preferably 1 to 22 straight chain carbon atoms.
Branched chain alkyl group, alkenyl group, cyclic alkyl group
represents a group or a cyclic alkenyl group, and these represent a halogen group or a cyclic alkenyl group.
Substituted with carbon atoms, aryl groups, alkoxy groups, etc.
It's okay. Also, if Rsl, RSt or R52 is a heterocyclic group,
, each heterocyclic group contains one of the carbon atoms forming the ring.
Acyl in alpha acylacetamide through one
The carbon atom of the carbonyl group or the nitrogen atom of the amide group
Join. Examples of such heterocycles include thiophene and fluoride.
N, biran, pyrrole, pyrazole, pyridine, pyrazi
pyrimidine, pyridazino, indolizine, imidazo
ole, thiazole, oxazole, triazine, thiazizole
Examples include azine and oxazine. These are further
may have a substituent on the ring. In the general formula (Cp-3), Rss has 1 to 3 carbon atoms.
2, preferably 1 to 22 linear or branched alkyl
group (e.g. methyl, isopropyl, lert-butyl)
, hexyl, dodecyl, etc.), alkenyl groups (e.g.
allyl group), cyclic alkyl group (e.g. cyclopentyl group), cyclic alkyl group (e.g. cyclopentyl group),
group, cyclohexyl group, norbornyl group, etc.),
alkyl group (e.g. benzyl, β-phenylethyl group, etc.)
), cyclic alkenyl groups (e.g. cyclopentenyl, cyclo
halogen group, etc.), and these represent halogen i atoms.
, nitro group, cyano group, aryol group, alkoxy group, a
Ryloxy group, carboxy group, alkylthiocarbony group
group, arylthiocarbonyl group, alkoxycarbonyl group
group, aryloxycarbonyl group, sulfo group, sulfo group
Amoyl group, carbamoyl group, acylamino group, diacylamino group
Ruamino group, ureido group, urethane group, thiourethane group
, sulfonamide group, heterocyclic group, arylsulfonyl group
, alkylsulfonyl group, arylthio group, alkylthi
o group, alkylamino group, dialkylamino group, aniline group
group, N-arylanilino group, N-alkylanilino group
group, N-acylanilino group, hydroxyl group, mercap
It may be substituted with a group, etc. Furthermore, Rss can be an aryol group (e.g., phenyl group, α-, etc.).
or β-naphthyl group). Allie
The group may have one or more substituents, and as a substituent
For example, an alkyl group, an alkenyl group, a cyclic alkyl group
, aralkyl group, cyclic alkenyl group, halogen atom,
Toro group, cyano group, aryl group, alkoxy group, aryl group
ruoxy group, carboxyl group, alkoxycarbonyl group
, aryloxycarbonyl group, sulfo group, sulfamo
yl group, carbamoyl group, acylamino group, diacyl group
mino group, ureido group, urethane group, sulfonamide group,
Heterocyclic group, arylsulfonyl group, alkylsulfonyl group
group, arylthio group, alkylthio group, alkylamino
group, dialkylamino group, anilino group, N-alkyl group
Nilino group, N-arylanilino group, N-acylanilino group
It may have a radical, a hydroxyl group, etc. Furthermore, R8 is a heterocyclic group (for example, a nitrogen atom as a heteroatom).
a 5- or 6-membered ring complex containing atoms, oxygen atoms, and sulfur atoms.
Also includes bare rings and fused heterocycles, including pyridyl groups, quinolyl groups, and free rings.
group, benzothiazolyl group, oxacylyl group, imidazo group
(lyl group, naphthoxacylyl group, etc.), the above-mentioned aryl
Heterocyclic radicals substituted with the substituents listed for the radicals
, aliphatic or aromatic acyl group, alkylsulfonyl group
, arylsulfonyl group, alkylcarbamoyl group, alkylcarbamoyl group,
Rylcarbamoyl group, alkylthiocarbamoyl group or
Alternatively, it may represent an arylthiocarbamoyl group. In the formula, RS4 is a hydrogen atom, having 1 to 32 carbon atoms, preferably
1 to 22 straight or branched alkyl or alkeni
cyclic alkyl, aralkyl, cyclic alkenyl group (this
These groups have the substituents listed for Rss above.
), aryl groups and heterocyclic groups (these are the above R
may have one substituent listed for ss), alco
Oxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group)
Oxycarbonyl group, stearyloxycarbonyl group, etc.
), aryloxycarbonyl groups (e.g. phenoxycarbonyl
carbonyl group, naphthoxycarbonyl group, etc.), aralkyl group,
benzyloxycarbonyl group (e.g. benzyloxycarbonyl group)
), alkoxy groups (such as methoxy, ethoxy, etc.),
cy group, heptadecyloxy group, etc.), aryloxy group
(e.g. phenoxy group, tolyloxy group, etc.), alkyl
Ruthio group (e.g. ethylthio group, dodecylthio group, etc.)
, arylthio group (e.g. phenylthio group, α-naphthio group)
ruthio group), carboxy group, acylamino group (e.g.
acetylamino group, 3-((2,4-tert-
amylphenoxy)acetamide]benzamide group, etc.)
, diacylamino group, N-alkylacylamino group (e.g.
For example, N-methylpropionamide group, etc.), N-ary
lyacylamino group (e.g. N-phenylacetamide)
etc.), ureido groups (e.g. ureido, N-arylure
), urethane group, nitrogen group, N-alkylureido group, etc.
urethane group, arylamino group (e.g. phenylamine group)
-, N-methylanilino group, diacylamino group N-methy
luanilino group, diphenylamino group, N-acetylani
Lino group, 2-chloro-5=tetradecanamide anilino
group), alkylamino group (e.g. n-butylamino group), alkylamino group (e.g. n-butylamino group),
group, methylamine group, cyclohexylamino group, etc.),
Cycloamino group (e.g. piperidino group, pyrrolidino group)
etc.), heterocyclic amino groups (e.g. 4-pyridylamino group,
(2-benzoxasilylamino group, etc.), alkylcar
Bonyl group (e.g. mail carbonyl group, etc.), aryl
Carbonyl group (e.g. phenylcarbonyl group), carbonyl group
sulfonamide group (e.g. alkylsulfonamide group,
lylsulfonamide group), carbamoyl group (e.g.
ethylcarbamoyl group, dimethylcarbamoyl group, N
-Methyl-phenylcarbamoyl, N-phenylcarba
moyl, etc.), sulfamoyl group (e.g. N-alkyl
Sulfamoyl, N,N-dialkylsulfamoyl
, N-arylsulfamoyl group, N-alkyl-N-
Arylsulfamoyl group, N,N-diarylsulf
amoyl group, etc.), cyano group, hydroxy group, and
Represents any of the ruho groups. In the formula, R1 is a hydrogen atom or has 1 to 32 carbon atoms, preferably
or 1 to 22 straight or branched alkyl groups,
alkenyl group, cyclic alkyl group, aralkyl group or ring
represents an alkenyl group, and these represent the above R85
It may have the listed substituents. Furthermore, R11& represents an aryl group or a heterocyclic group;
These may also include the substituents listed for Rss above.
May have. R1 is a cyano group, an alkoxy group, an aryloxy
group, halogen atom, carboxy group, alkoxycarbonyl
ru group, ryo-ruoxy carbonyl group, acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acyl
Amino group, diacylamino group, ureido group, urethane group
, sulfonamide group, arylsulfonyl group, alkyl
Sulfonyl group, alkylthio group, alkylthio group, alkylthio group,
Kylamino group, dialkylamino group, anilino group, N-
Arylanilino group, N-alkylanilino group, N-a
It may also represent a cylanilino group or a hydroxyl group. R1, R51 and Ra9 are each a normal 4-equivalent type phenol.
used in alcohol or α-naphthol couplers.
Specifically, I'? 5? At the end is a hydrogen atom,
Halogen atom, alkoxycarbonylamino group, aliphatic
Hydrocarbon residue, N-Rori-roureido group, azilamino
group, ORig or S”'-Rhz (however, R&□
is an aliphatic hydrocarbon residue), with two residues in the same molecule.
If more than one R1 exists, two or more R8? is different
The aliphatic hydrocarbon residue may have a substituent.
Including those who do. In addition, when these substituents contain an aryl group, the aryl
The group may have substituents listed above for R5S.
. RS and R59 are aliphatic hydrocarbon residues,
enumerate groups selected from ring groups and heterocyclic residues;
or one of these may be a hydrogen atom.
In addition, these groups include those having substituents. In addition, Rse and R99 jointly form a nitrogen-containing heterocyclic nucleus.
You may. And as aliphatic hydrocarbon residues, saturated and unsaturated
It can be any of the following, and can be straight chain or branched.
, or a ring shape. and preferably al
Kill groups (e.g. methyl, ethyl, propyl, isopropyl)
butyl, t-butyl, isobutyl, dodecyl, octyl
groups such as tadecyl, cyclobutyl, cyclohexyl),
Alkenyl groups (e.g. allyl, octenyl, etc.)
be. Aryl groups include phenyl groups, naphthyl groups, etc.
In addition, heterocyclic residues include pyridinyl, kyl/IJyl,
Typical groups include thienyl, piperidyl, imidazolyl, etc.
It is. These aliphatic hydrocarbon residues, aryl groups and
Halogen atoms are introduced as substituents into heterocyclic residues.
, nitro, hydroxy, carboxyl, amino, substituted a
mino, sulfo, alkyl, alkenyl, aryl, hetero
ring, alkoxy, aryloxy, arylthio, a
lylazo, acylamino, carbamoyl, ester,
Acyl, acyloxy, sulfonamide, sulfamoy
Examples include groups such as ru, sulfonyl, and morpholino. l is an integer of 1 to 4, m is an integer of 1 to 3, p is an integer of 1 to 5
represents a number. Among the above coupler residues, yellow coupler residues
In formula -a (Cp-1), Rst is L-butyl.
or a substituted or unsubstituted aryl group, Rsz is
When representing a substituted or unsubstituted aryl group, and
In general formula (Cp-2), Rsz and Rsj are
It is preferable to represent a substituted or unsubstituted oryl group.
. Preferred magenta coupler residues are of the general formula (Cp
-3) in which R54 is an acylamino group, a ureido group, or
and arylamino group, R5% represents a substituted aryl group
When R54 in -a formula (Cp-4) is acyl
Amino group, ureido group and arylamino group, R
When representing a hydrogen atom, and the general formula (Cp-5) or
and (Cp-6), RS4 and R5& are linear
or branched alkyl groups, alkenyl groups, cyclic alkyl groups,
When representing a group, an aralkyl group, or a cyclic alkenyl group,
be. Preferred cyan coupler residues have the general formula (Cp
-7) if R5'l is an acylamino group at the 2-position.
is a ureido group, and the 5th position is an acylamino group or an alkyl group.
group, and the 6th position represents a hydrogen atom or a chlorine atom
and -N9 formula (Cp9) where R5'l is at the 5th position
Hydrogen atom, acylamino group, sulfonamide group, alcohol
In the xycarbonyl group, Rs++ is a hydrogen atom, and R
%9 is phenyl group, alkyl group, alkenyl group, cyclic atom
alkyl, aralkyl, and cyclic alkenyl groups.
This is the case. Zl is a halogen atom, a sulfo group, an acyloxy group, an alkyl
koxy group, ryoroxy group, heterocyclic oxy group, alkyl group
represents a ruthio group, an arylthio group or a heterocyclic thio group.
, these groups can further be aryl groups (e.g. phenyl group)
, nitro group, hydroxyl group, cyano group, sulfo group, alkoxy
groups (e.g. methoxy group), aryloxy groups (e.g.
phenoxy group), acyloxy group (e.g. acetoxy group)
, acylamino group (e.g. acetylamino group), sulfonate
amide group (e.g. methanesulfonamide group), sulfonamide group (e.g. methanesulfonamide group),
amoyl group (e.g. methylsulfamoyl group), halogen
(e.g. fluorine, chlorine, bromine, etc.), carboxy
group, carbamoyl group (e.g. methylcarbamoyl group),
Alkoxycarbonyl group (e.g. methoxycarbonyl group)
), sulfonyl groups (e.g. methylsulfonyl group),
It may be substituted with any substituent. Z2 and Y are oxygen atoms, nitrogen atoms or sulfur atoms
Represents a leaving group attached to the coupling position, Z2 and
and Y is cupped by an oxygen atom, nitrogen atom or sulfur atom
When bonded in the ring position, these atoms
Kyl group, aryl group, alkylsulfonyl group, aryl
Sulfonyl group, alkylcarbonyl group, arylcarbo
It is bonded to a nitrogen group or a heterocyclic group, and further contains a nitrogen atom.
In some cases, a 5- or 6-membered ring containing the nitrogen atom is formed.
It also means a group that can serve as a leaving group (for example, imidazolyte).
group, pyrazolyl group, triazolyl group, tetrazolyl group
Such). The above alkyl groups, aryl groups, and heterocyclic groups have substituents.
Specifically, an alkoxy group (e.g.
methyl group, ethyl group), alkoxy group (e.g. meth)
xy group, ethoxy group, etc.), aryloxy group (e.g.
phenyloxy group, etc.), alkoxycarbonyl group (e.g.
(e.g. methoxycarbonyl group), acylamino group (e.g.
(e.g. acetylamino group), carbamoyl group, alkyl group
Rubamoyl group (e.g. methyl carbamoyl group, ethyl carbamoyl group)
rubamoyl group), dialkylcarbamoyl group (e.g.
dimethylcarbamoyl group), arylcarbamoyl group
(e.g. phenylcarbamoyl group), alkylsulfony
group (e.g. methylsulfonyl group),
group (e.g. phenylsulfonyl group), alkylsulfonyl group
amide group (e.g. methanesulfonamide group), aryl
sulfonamide group (e.g. phenylsulfonamide group)
), sulfamoyl group, alkylsulfamoyl group (e.g.
(e.g. ethylsulfamoyl group), dialkylsulfamoyl group)
yl group (e.g. dimethylsulfamoyl group), alkyl group
Thio group (e.g. methylthio group), arylthio group (e.g.
phenylthio group), cyano group, nitro group, halogen source
(e.g. fluorine, chlorine, bromine, etc.)
When there are two or more substituents, they may be the same or different. Particularly preferred substituents include halogen atoms and alkyl groups.
, alkoxy group, alkoxycarbonyl group, cyano group
Can be mentioned. A preferable group for Z2 is a nitrogen atom or a sulfur group.
The group that binds to the coupling site as a child is mentioned, and the preferable group of Y is
Preferred groups include chlorine atom, oxygen atom, and nitrogen atom.
Or a group that binds to the coupling site with a sulfur atom.
be. Z is a hydrogen atom or the following general formula (R-1) (R-[
3 (R-111) or (R-rV)
be. 0Ras (RI) R1 represents an optionally substituted aryl group or heterocyclic group
. represents an atom. In general formula (R-IV), preferably [R-V] ~ [
R-■]. (R-I[) (R-III)Rh4,
R6S is a hydrogen atom, a halogen atom, a carboxylic acid ester, respectively.
Tel group, amine group, alkyl group, alkylthio group, alkyl group
Koxy group, alkylsulfonyl group, alkylsulfini
group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted
It represents a substituted phenyl group or a heterocycle, and these groups are the same.
They may be the same or different. In the nonmetallic formula required to form a membered ring or a 6-membered ring,
R66% Rh is a hydrogen atom, an alkyl group, an aryl group, respectively.
group, alkoxy group, aryloxy group or citrooxy group
R61, R1? and R1° are a hydrogen atom and an atom, respectively.
Alkyl group, aryl group, aralkyl group, or acyl group
, Wz represents an oxygen or sulfur atom. The coupler for use in the present invention is represented by the following general formula (CI)
Derived from a coupler monomer and represented by the general formula (Cl)
Polymers with repeating units or aromatic-grade amino acids
It does not have the ability to oxidatively couple with the developer.
A type of non-chromic monomer containing one ethylene group
It may also be a copolymer with the above. Here, the amount of coupler is
Two or more types of bodies may be polymerized simultaneously. General formula (CI) R' CIb=C→ni 2 sho-→nishicho-→ni+h b general formula (C
m) R' (CHz-C) 1 + K z h-1 → K s 辷r-published K l) y 0 formula
where R' is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms;
, or represents a chlorine atom, K is -CONR'--N
R"C0NR"NR"coo--coo--so□-〇〇-1NR' CO--sow NR'NR' S
Ox 0CO-0CONR'NR'--5-Also
represents -〇-, R2 is -CONR"- or -CO
O-, Rh represents a hydrogen atom, an aliphatic group, or an aliphatic group.
- If there are two or more Rh in the molecule,
, may be the same or different. K is unsubstituted or substituted alkylene having 1 to 10 carbon atoms.
group, aralkylene group, or unsubstituted or substituted arylene group
Represents a lene group, and an alkylene group can be a straight chain or a branched chain.
stomach. (Examples of alkylene groups include methylene and methylmethylene.
dimethylmethylene, dimethylene, trimethylene,
Tramethylene, pentamethylene, hexamethylene, decyl
Examples of lumethylene and aralkylene groups include benzylidene.
Examples of arylene groups include phenylene and naphthylene.
etc.) where the alkylene group represented by 3, aral
Aryl as a substituent for kylene group or arylene group
groups (e.g. phenyl group), nitro group, hydroxyl group, cyan group
, sulfo group, alkoxy group (e.g. methoxy group), ali
yloxy group (e.g. phenoxy group), acyloxy group
(e.g. acetoxy group), acylamino group (e.g. acetoxy group), acylamino group (e.g. acetoxy group), acylamino group (e.g. acetoxy group),
thylamino group), sulfonamide group (e.g. methanesulfonate group),
phonamide group), sulfamoyl group (e.g. methyl sulf
famoyl group), halogen atoms (e.g. fluorine, chlorine,
bromine, etc.), carboxyl groups, carbamoyl groups (e.g.
methylcarbamoyl group), alkoxycarbonyl group (e.g.
For example, methoxycarbonyl group, etc.), sulfonyl group (for example,
methylsulfonyl group). Two of these substituents
If there are more than one, they may be the same or different. i, j and k represent 0 or l. Q is R5I of the general formulas (Cp-1) to (Cp-9)
In any part of R8I, Zl""Zx and Y, one
When combined with a moiety other than Q in general formula (CI) or (Cn)
Ru. Next, the oxidation product of the aromatic-grade amine developing reagent and the cup
As a non-chromic ethylene-like monomer that does not ring, acrylic
lylic acid, α-=chloro'J acrylic acid, α-alkylaque
lylic acid (e.g. acrylic acid, methacrylic acid), and
Esters or amines derived from these acrylic acids
(e.g. acrylamide, methacrylamide, t
-butylacrylamide, methyl acrylate, methyl
Methacrylate, ethyl acrylate, n-propyla
acrylate, 1so-propyl acrylate, n-butyl
Acrylate, t-butyl acrylate, n-butyl
methacrylate, 2-ethylhexyl acrylate, n
-hexyl acrylate, n-octyl acrylate,
Laryl acrylate, and methylene bisacrylate
vinyl esters (e.g. vinyl acetate, vinyl esters), vinyl esters (e.g. vinyl acetate, vinyl
nylpropionate, and vinyl laurate), acrylic
Rylonitrile, methacrylonitrile, aromatic vinylation
compounds (e.g. styrene and its derivatives, vinyl
ene, divinylbenzene, vinylacetophenone), vinyl
Nylidene chloride, vinyl alkyl ether (e.g.
(vinyl ethyl ether), maleic acid ester,
Nyl-2-pyrrolidone, N-vinylpyridine, and 2
- and 4-vinylpyridine. especially acrylic acid
Esters, methacrylic esters, maleic esters
Preferred are the following. There are two types of non-color-forming ethylenically unsaturated monomers used here.
The above can also be used together. For example, n-butyl
Acrylate and divinylbenzene, styrene and methacrylate
lylic acid, n-butyl acrylate and methacrylic acid, etc.
Can be used. The polymer coupler used in the present invention is a water-soluble one.
However, water-insoluble materials may also be used, especially polyesters.
Marker coupler latex is preferred. Polymer coupler latex is the polymerization of coupler monomers
I took out the hydrophilic polymer coupler made with
Later, it was dissolved in an organic solvent and made into latex.
It can also be dispersed with a hydrophilic polymer obtained by polymerization.
The solution of the puller may be dispersed directly in latex form,
Or polymer coupler latex made with emulsion type compounding.
Furthermore, layered polymer coupler latex can be directly synthesized.
It may also be added to latin silver halide emulsions. In the silver halide photographic material of the present invention, these
Among 2-equivalent couplers, preferably 2-equivalent magenta couplers
or 2-equivalent cyan coupler, more preferably
is a 2-equivalent magenta coupler. 2-equivalent yellow coupler Y-1 -2 Uυ■ -5 -6 C4Hq(n) -3 -4 -7- tt C 2I+ . 9 -13 -11 -12 -15 -17 CI+. Cz It s Y-18 Y-19 -22 -23 し■N! Co-20 -21 2-equivalent magenta coupler-2 3 -4 -5 -6- 0 M-11 M-12 -15 r ρ -13 -14 -17 -18 M-19 M 0 -23 4 -21 -22 5 6 n-CJH Shizuku-27 all 7(t) C1(. 10 C-11 -12 -16 -17 -18 H 0 ■ 11 il -13 -19 0 -21 H H i1 0 (1 C-22 C-23 -24 Sushi 113 5 -26 -30 -31 -32 H 0OII H C-33 C-34 Colored couplers include, for example, U.S. Pat.
No. 6.560, No. 2,521.908, No. 3,034
, No. 892, Special Publication No. 44-2016, No. 38-223
No. 35, No. 42-11304, No. 44-32461
, JP-A-51-26034, JP-A-52-4212
Specification No. 1, West German patent application (OLS) 2,418,95
Those described in No. 9 can be used. As a DIR coupler, for example, US Pat. No. 3,227.
No. 554, No. 3,617.291, No. 3.701,7
No. 83, No. 3.790.384, No. 3,632,34
No. 5, West German Patent Application (OLS) No. 2.414.006,
No. 2,454,301, No. 2,454,329, English
National Patent No. 953,454, Japanese Patent Application Publication No. 52-69624,
No. 49-122335, Special Publication No. 51-16141
You can use what is listed. In addition to the DIR coupler, a development inhibitor is added during development.
A releasing compound may be included in the photosensitive material, e.g.
U.S. Patent No. 3,297,445, U.S. Patent No. 3,379,529
No., West German Patent Application (OLS) No. 2.417,914, Patent Application No.
Kaisho 52-. Described in No. 15271 and No. 53-9116
can be used. Also, for development as described in JP-A No. 57-150845,
A coupler that releases a development accelerator or fogging agent along with the
- can be particularly preferably used. Also, as described in British Patent No. 2,083,640,
Nondiffusive couplers that form slightly diffusive dyes are also preferred.
It can be used in many ways. These couplers have −a per mole of silver in the emulsion layer.
2×10−” mol to 5×1 O−′ mol, preferably
is added to the photosensitive material of the present invention during the manufacturing process, during storage, or during development.
Prevent fog during processing or stabilize photographic performance
For the purpose of silver halide adsorption in the chemical sensitization process of the present invention,
It is possible to further contain an antifoggant in addition to the chemical substance.
can. i.e. azoles, e.g. benzothiazoliu
salts, nitroimidazoles, nitrobenzimidazole
compounds, chlorobenzimidazoles, promohenzimid
dazoles, mercaptothiazoles, mercaptothia
Diazoles, mercaptohenzimidazoles, mer
captothiadiazoles, aminotriazoles, ben
zotria, soles, nitrobenzotriazoles, meth
Lucaptotetrazoles (especially l-phenyl-5-mer
captotetrazole); mercaptopyrimidines;
Mercaptotriazines; e.g. oxadorinthione
thioketo compounds such as; azaindenes, e.g.
Riazaindenes, tetraazaindenes (especially 4-hyperazaindene)
Droxy-substituted (1,3,3a,?)tetraazaindene
), pentaazaindene, etc.; benzenethiosulfur
fonic acid, henzenesulfonic acid, benzenesulfonic acid
Known as antifoggants or stabilizers such as amides, etc.
Many compounds can be added. For example, rice
National Patent No. 3,954,474, 3. 982. 94
No. 7, as described in Special Publication No. 52-28,660.
Can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention has increased sensitivity and contrast.
For the purpose of increasing trust or promoting development, for example,
Alkylene oxide or its ether, ester, a
Derivatives such as amines, thioether compounds, thiomorphs
Phosphorus, quaternary ammonium salt compounds, urethane derivatives,
Urea derivatives, imidazole derivatives, 3-pyrazolidones
etc. may also be included. For example, U.S. Patent 2,400,53
No. 2, No. 2,423,549, No. 2,716,062
No. 3,617,280, No. 3.772021,
No. 3,808,003, British Patent No. 1゜488.991
You can use those listed in the No. The photosensitive material made using the present invention contains hydrophilic colloids.
layer as a filter dye or irradiation silin
May contain water-soluble dyes for prevention and other purposes.
stomach. Such dyes include oxonol dyes, hemioxonol dyes,
Sonol dye, styryl dye, merocyanine dye, shea
Included are nin dyes and azo dyes. Among them, Oxono
hemioxonol dyes and merocyanine dyes
is useful. In the light-sensitive material produced using the present invention, the photographic emulsion layer
Other hydrophilic colloid layers include stilbene-based, thoria
Increased amounts of gin, oxazole, or coumarin
May contain whitening agents, these may be water-soluble;
A water-insoluble brightener may also be used in the form of a dispersion. When carrying out the present invention, the following known anti-fading agents may be used.
The color image stabilizer that can be used in combination and is also used in the present invention
can be used alone or in combination of two or more. known retirement
Color inhibitors include, for example, U.S. Pat.
No. 90, No. 2,418゜613, No. 2,675,31
No. 4, No. 2,701.197, No. 2,704,713
No. 2728.659, No. 2,732,300,
2.735.765, 2,710,801, 2.735.765, 2.710,801,
No. 2,816.028, British Patent 1. 363°921
Hydroquinone derivatives described in US Pat. No. 3, etc.
Described in No. 457,079, No. 3.069262, etc.
gallic acid derivatives, U.S. Pat. No. 2,735.765,
No. 3,698,909, Special Publication No. 49-20977, same
p-alkoxyphenol described in No. 52-6623
U.S. Pat. No. 3,432.300, U.S. Pat. No. 3.5730
No. 50, No. 3,574,627, No. 3,764.33
No. 7, JP-A-52-35633, JP-A No. 52-14743
No. 4, p-oxy described in No. 52-152225
Phenol derivatives, US patent 3. TOo, No. 455
There are bisphenols listed above. The photosensitive material produced using the present invention contains a color antifoggant and
Hydroquinone derivatives, aminophenol derivatives
Contains gallic acid derivatives, ascorbic acid derivatives, etc.
It's okay. The photographic light-sensitive materials of the present invention include black-and-white light-sensitive materials, multilayer multicolor
Of all photosensitive materials, especially those used for high-sensitivity imaging,
- Preferably used as a photosensitive material. The photosensitive material produced using the present invention includes hydrophilic colloids.
The layer may contain an ultraviolet absorber. For example, an aryl group
hensitriazole compounds substituted with
No. 3,533,794), 4-thiazoli
Don compounds (e.g., U.S. Pat. No. 3,314,794;
3.352681), benzophenonation
compounds (e.g. those described in JP-A No. 46-2784),
Cinnamate ester compounds (e.g., U.S. Pat. No. 3,705.
No. 805, No. 3,707,375),
tagene compounds (e.g., U.S. Pat. No. 4,045,229)
), or hendioxazole compounds (
For example, as described in U.S. Pat. No. 3,700.455)
Can be used. Additionally, U.S. Patent No. 3,499,76
No. 2, and those described in JP-A No. 54-48535 are also used.
be able to. UV-absorbing couplers (e.g. α-Na)
Phthol-based cyan dye-forming couplers) and ultraviolet absorption
These UV-absorbing polymers may also be used.
The agent may be mordanted into the characteristic layer. Any known method can be used for photographic processing of the light-sensitive material of the present invention.
can also be used, and known treatment liquids can be used.
can be done. In addition, the processing temperature is usually from 18°C to 50°C.
selected between ℃ but below 18℃ or 50℃
Depending on the purpose, temperatures can exceed
Development processing (black and white photographic processing) or formation of a dye image
Any of the color photographic processing consisting of the development processing to be applied
can be used. In particular, the photosensitive material of the present invention can be used for so-called color development.
Parallel development is extremely favorable in terms of sensitivity and graininess.
Color developers that give good results are generally alkaline solutions containing a color developing agent.
The zero color developing agent consisting of aqueous solution is a well-known general aromatic alkali.
developer such as phenylenediamine II (e.g. 4
=amino-N, N-diethylaniline, 3-methyl-4
-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4amino-N-ethyl-N-β-hydroxye
Thylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, 4-ami
Nor-3-methyl-N-ethyl-N-βmethoxyethyl a
Nilin, etc.) can be used. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process or separately.
Examples of bleaching agents that may be used include iron (■),
Polyvalents such as cobalt (■), chromium (■), copper (II), etc.
Metal compounds, peracids, quinones, nitroso compounds, etc.
For example, ferricyanide, dichromate
, iron(III) or cobal) (III) organic complex salts
, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Amino acids such as 1.3-diamino-2-propatoltetraacetic acid
Nopolycarboxylic acids or citric acid, tartaric acid, apple
Complex salts of organic acids such as acids; persulfates, permanganates;
Trosophenol and the like can be used. these
Of these, potassium ferricyanide, iron ethylenediaminetetraacetate (
Sodium I[[] and iron ethyleneaminetetraacetate ([
[I) Ammonium is particularly useful. Ethylenediami
Iron tetraacetate (Ill) complex salt is also present in a stand-alone bleaching solution.
-Also useful in bath bleach-fix solutions. The present invention will be further explained with reference to Examples below.
is not limited to this. The present invention will be explained in more detail by examples below.
The present invention is not limited to these. Example 1 (Preparation of emulsion) Iodobromation by the method described in JP-A-62-209445
Silver emulsions I to (2) were prepared. Distill 30g of inert gelatin and 5.2g of sodium bromide.
Water 1! Stir the aqueous solution dissolved in at 60℃ and bring it here.
35 cc of an aqueous solution containing 5.0 g of silver nitrate and sodium bromide
2.8g of lium and 0.88g of sodium iodide were dissolved.
35 cc of aqueous solution to 70 cc each at a flow rate of 1 min.
After adding for 0 seconds, increase PAg to 10 and mature for 30 minutes.
A seed emulsion was prepared. Collect 2 quantities of this seed emulsion and distill 15g of inert gelatin.
Add to an aqueous solution dissolved in 500 cc of water and keep at 60°C.
It was. Next, add aqueous solution 11 containing 147.5 g of silver nitrate.
Specified amounts of sodium bromide and sodium iodide
An equimolar amount of an aqueous solution of a mixture with a ratio of
Co., Ltd. was added at a constant PAg and at a rate close to the critical growth rate.
The emulsion was prepared. Further, the remaining silver nitrate aqueous solution and core emulsion preparation
Sodium bromide and sodium iodide have a different composition than when manufactured.
An aqueous solution of a mixture of
It coats the core and forms a core/shell type iodine.
Silver bromide emulsions ① to ② were prepared. After that, it is washed with water and desalted using the conventional flocculation method.
The pH was adjusted to 6.3pAg to 8.6. PAg adjustment was done with sodium bromide. Table 1 shows the size and iodine content composition of emulsions ■～■.
show. xps was measured using Shimadzu's ESCA-750.
I did it. α (acceleration voltage
8KV electric fJt 30mA), 1-
3d5/2 and A g -3d5/2
The peak area of the silver halide is determined from the intensity ratio.
The average silver iodide content of the surface portion of the grains was determined. silver iodobromide
emulsion

Eight types of emulsions were prepared by chemically sensitizing [~■] by the following method so as to exhibit optimum sensitivity at 1/I G O' exposure. Method: Sodium thiosulfate, potassium chloroaurate, Add sodium thiocyanate and heat at 60°C. (In this case, add the specified sensitizing dye to perform spectral sensitization when preparing the coating solution.) Method 2: Add sensitizing dye D-10- at 60°C.
[1. After adding D-m and heating for 15 minutes, add sodium thiosulfate, potassium chloroaurate, and sodium thiocyanate and further heat at 60°C Method 3: Add exacerbation dye D-5D-6D7 at 60°C After heating for 15 minutes, sodium thiosulfate, potassium chloroaurate, and sodium thiocyanate were added and further heated at 60°C. (In the case of Method 2 and Method 3, there is no need to further add a sensitizing dye when preparing the coating solution.) Table 2 shows the amount added per mole of silver. -1 U-2 -3 HB S -1 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-2 X-10 Gelatin No. 4 layers (second red-sensitive emulsion layer) Emulsion C Sensitizing dye! Sensitizing dye ■ Sensitizing dye m Sensitizing dye m On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrf units, and for silver halide, it indicates the coating amount in terms of silver.However, for the sensitizing dye, the same 78 halogen The coating amount per mole of silveride is shown in moles. (Sample A) First layer (antihalation layer) Black colloid 11 Silver 0.18 Gelatin 0.40 Second layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0,18EX-10
,07 EX-30,02 EX-120,002 0,25 0,25 9X10-' 8 X 1 0-'lXl0-' 0.335 0.020 0,87 1.0 1 X 10-'4XIO-'3xto-' X-2 X-3 X-10 Gelatin 5th Ji (3rd red emulsion N) Emulsion! -1 Sensitizing dye! Sensitizing dye ■ Sensitizing dye ■ X-3 X-4 X-2 5B-1 5B-2 Gelatin 6th layer (intermediate layer) X-5 B5-1 Gelatin 00 50 15 0 1, 60 0 X1O-5 IXIO-' 0.010 0.080 0.097 0, 22 0, 10 1, 63 0.040 0, 20 0, 80 7th layer (first green emulsion N) Emulsion A Emulsion B Sensitization Dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 EX-8 HB S -1 B5-3 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 0° 15 0, l 5 0XIO-' OX IF'8XIO-' 0.260 0.021 0.030 0.025 0.100 0.010 0,63 0 , 45 IXIO-'0XIO-'6X10-' 0.094 o, oia EX-1 BS-1 HB S-3 Gelatin 9th layer (third green-sensitive emulsion N) Emulsion 1-1 Silver sensitizing dye V 4° Sensitizing dye Vl
1゜sensitizing dye■
3゜EX-13 EX-1 B5-1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloid! ! Daughter 95 11th layer (first blue-sensitive emulsion layer) Emulsion emulsion B Emulsion F Enhanced dye ■ EX-9 EX-8 B5-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ EX- 9 EX-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ EX-9 0, 08 0, 07 0, 07 5X10-' 0.721 Q, 042 0, 28 1 , 10 tIO, 45 2, lX10-' 0.154 0, 00? 0,05 0,78 Silver 0.77 2.2XIO-' 0,20) [B5-1 0.
．． 07 Gelatin 1.69 1st
4N (first protective layer) Emulsion 1 iIo, 5U-40
,11 U-50,17 HBS-10,05 Gelatin 1,00 15th layer (
2nd adhesive layer) Polymethyl acrylate particles (diameter approx. 1.5 μm) 0.543-1
0.20 gelatin
1.20 In addition to the above ingredients, each layer contains:
Gelatin hardener H-1 and a surfactant were added. In addition to the above components, B-1 is contained as a thickener, and the total amount of B-1 applied is 0.165 g/rd. EX-4 EX CJ+5(n) EX-1 EX-2 EX-3 υ-ω しEX 1 zHs zlls CzHsOS(h X-9 X-10 -1 -2 11 CH. 4 V-5 B5-1 Tri Cresyl phosphate B5-2 Di-n-butyl phthalate B5-3 (t)CsH++ CO,H Sensitizing dye -1 -1 CHt=CI-SOx-CHx CONII-C1b CHx CH-SOz-C)lx CONII- CHz Sensitizing dye■ Sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ -1 Emulsion of sample 101 in the 5th layer and emulsion E in the 91'# in the 3rd layer
102 to 106 were created by changing them as shown in the table. However, when using I-2, 1-3, ■-2, and ■-3, no sensitizing dye was added. Table 3 Sample Emulsion of 5th layer Emulsion of 9th layer (present invention) 102 1-2 1-3 (present invention) 103 n-1■-1 (present invention) 104 11-2 1l-3
(Present invention) 105 I[1-1111-1 (comparison) 106 ■-11V-1 (comparison) Next, potassium bromide was substituted for sodium bromide, potassium iodide was substituted for sodium iodide, and thiocyanide was used. Emulsion VI-I by changing potassium thiocyanate instead of sodium thiocyanate
V-2V-3Vl-1Vl-2Vl-3■-1■-1
It was created. The same changes as above were also made to emulsions A-C1 and emulsions F-G. Next, sample 107 was prepared by changing the counter ion of compound B-1 from sodium ion to potassium ion.
~112 was created. Table 4 shows the contents of the sample. Table 4 Sample contents (comparison) are the same as sample 101 except that the content of potassium ions is higher (comparison).
109 Same as sample 102 (comparison) Same as sample 103 except for high potassium ion content (comparison) 110 Same as sample 103 except for high potassium ion content (comparison)
(Comparison) is the same as sample 104 (111) Same as sample 105 (comparison) except that the content of potassium ions is high (112) Potassium ions of samples 101 to 112 are the same as sample 106 (comparison) except that the content of potassium ions is high (comparison) A sample to be subjected to zero analysis, in which the content was analyzed by atomic absorption spectrometry, was prepared by the method described below. Each film 2cmX 5CI1
1 (Cut out 10cd>, H,5O45+d and HNO
After wet ashing with 33,5-H! 0 was added to make it 10-. In addition, Hz SOa and HNO, without adding a sample,
A solution for a calibration curve was prepared by adding a known amount of potassium ion to 5 samples prepared using a chisel and a known amount of potassium ions. The measurements were performed using a Hitachi Zeeman atomic absorption spectrometer in flame light mode. The measurement results are shown in Table 6. After storing these 12 types of samples under the storage conditions (A) and (B) shown in Table 5, they were exposed to wedge light according to the usual method for measuring sensitometric performance (sensitivity/fog) and graininess. It was processed in the treatment step (CN-16). The treated samples were subjected to sensitometric and granularity measurements using blue, green, and red light. Table 2 (Storage conditions) Table 6 shows the measurement results for 12 types of samples. Regarding fog, R, M, and S, data obtained for red light are shown, but similar results were obtained when measured using blue light and green light. The RoM and S values are shown as relative values with the value of (A) of sample 101 as 100. Specific photographic sensitivity: The exposure amount corresponding to a density 0.15 higher than the minimum density of each of blue, green, and red is expressed in lux seconds as HB, HG, and HR, respectively. The specific photographic sensitivity S characterized by the larger value (lower sensitivity) is calculated using the following formula. The larger the value of specific photographic sensitivity S, the higher the sensitivity. Fog: This is the minimum density of the so-called characteristic curve obtained by sensitometry, and the larger the value, the higher the fog is, and it is preferable. Granular layer (R, M, S)... Dye image density is minimum density +
This is the standard deviation of density value variations that occur when a 0.1 dye image is scanned with a micro-density needle having a circular scanning aperture of 48 μm; the larger the value, the coarser the graininess, which is undesirable. The following matters became clear from Table 6. 101vsl 03vsl O5, 107vs As the surface iodine content increases, there is less deterioration of photographic properties due to long-term storage.
This is clear from the comparison of l 09 vs l 11. Furthermore, even if the total iodine content increases, there is little deterioration in photographic properties due to long-term storage (103 vs. 106.109 vs.
This is clear from the comparison of 112. 101 vs 102.107 vs 108.10 shows that the effect of increasing photographic sensitivity by coexisting a sensitizing dye during chemical sensitization is more pronounced as the surface iodine content increases.
This is clear from the comparison of 3vs104.109vsllO. Furthermore, it has been found that the degree of improvement in photographic properties upon long-term storage when potassium ions are reduced in a light-sensitive material is more pronounced as the surface iodine content increases and as the total iodine content increases.
s107.102vs10B, 103vs109.10
This is clear from the comparison of 4vsllO1105vsl11.106vsl12. Furthermore, the higher the surface iodine content and the higher the total iodine content, the higher the sensitivity and the better the graininess.
03.107vs109.102vslO4,108v
s110.101vs105.107vs111.10
This is clear from the comparison of 3vs106.109vsl12. Combining these results, the photosensitive materials of the present invention 101-
It can be concluded that 104 has extremely excellent properties. Example 2 Sample 113 was prepared in exactly the same manner as Sample 102 of Example 1, except that the amounts of silver halide emulsions in the fourth and ninth layers were increased by 1.6 times. The test results are shown in Table 8. Table 12 13 7.2g/n? 496 475 0.05 0
．． 08 988.9g/n? 511 456
0.0? 0.12 91 From this result, coating s
It has been found that reducing it reduces the deterioration of photographic properties due to long-term storage. Considering the cost, it can be concluded that Sample 112 is preferable to Sample 113 since the user will not actually use it until quite some time after manufacture. (Effects of the Invention) According to the structure of the present invention, a silver halide photosensitive material capable of producing high-sensitivity and high-quality images can be obtained. In addition, since the raw photosensitive material does not deteriorate over a long period of time, especially due to natural radiation, it is possible to obtain a silver halide photosensitive material that produces images with little fog (and no deterioration of graininess).The color negative film of the present invention , the effects of the present invention become even more remarkable when items corresponding to the following items (a)03 12 to (g) are included, and even more remarkable when a plurality of items are included. (a) At least red sensitivity The emulsion of the present invention is contained in the highly sensitive layer. (B) The emulsion of the present invention is contained in at least the red sensitive layer and the green sensitive layer. (C) The emulsion of the present invention is contained in at least the red sensitive layer and the green sensitive layer. The emulsion of the present invention is contained in the layer and the blue-sensitive highly sensitive layer. (d) The emulsion particles of the present invention are chemically sensitized in the presence of a spectral sensitizing dye. (e) The specific photographic sensitivity is 320 or higher. (f) The total amount of silver halide contained in all emulsion layers is 3.
It is 0 to 9.0 g/rd. (g) At least 50 mol % or more of the total amount of couplers in the highly sensitive emulsion layer is a 2-equivalent coupler. Procedural amendment 1゜2゜3゜

Claims (1)

[Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, in which the emulsion layer has a silver iodobromide phase with a silver iodide mole fraction of 10 to 40 mol % inside the grains. and silver halide grains in which the silver iodobromide phase is coated with silver halide containing lower silver iodide, and the surface of the grain is silver halide containing 5 mol% or more of silver iodide. and the total amount of potassium ions contained in the photosensitive material is 5 x 10 in weight ratio to the coated silver.
A silver halide photographic light-sensitive material characterized in that it has a molecular weight of ^-^3 or less.