JPS648326B2 - - Google Patents

Description

[Detailed description of the invention] (a) Field of the invention The present invention provides silver salt aqueous solutions and salts useful in the photographic field.
In the presence of a dispersion medium, the halide salt aqueous solution containing
At least 50 mol% relative to silver in contact with
tabular halogen with a halide content of chloride
Radiation (or radiation) sensitivity that produces silver oxide grains
This invention relates to a method for producing a reactive photographic emulsion. (b) Prior art Photographic emulsions containing radiation-sensitive silver chloride have special advantages.
It is known as something that brings points. for example,
Silver chloride is more specific than other silver halides useful in photography.
natural photosensitivity to the visible part of the vector.
Furthermore, silver chloride is more useful than other silver halides useful in photography.
high solubility and therefore shorter development and fixing times
can be achieved in time. In the field of photography, silver chloride is a {100} crystal.
Very strong tendency to form crystals with faces
is well recognized. The overwhelming majority of photographic emulsions
When silver chloride is present, silver chloride condensation occurs.
The crystals have the shape of cubic particles. some degree of difficulty
In order to change the crystal habit of silver chloride,
I can do it. Claes et al.
Modification of AgCl by Impurities
“Determining Solvation”The Journal of
Photographic Science, vol. 21, pp. 39-50, 1973
In 2007, {110} and
Explain the formation of silver chloride crystals with {111} and {111} planes.
There is. Wyrsch describes “Sulfur Sensitization of
Monosized Silver Chloride Emulsions with
{111}, {110}, and {100}Crystal Habit”,
International Congress of Photographic
Science, -13, pp. 122-124, 1978.
Presence of monium and small amounts of divalent cadmium ions
Triple jet precipitation process with silver chloride precipitated at the bottom
Disclosed. in the presence of cadmium ions
pAg (negative logarithm of silver ion concentration) and PH
{110}, {111}, and
Twelve diamond faces represented by particle planes located at {100}
octahedral, octahedral, and cubic crystal habits are produced. Tabular silver bromide grains have been extensively studied.
However, these are mostly macro-sized.
Therefore, it was not possible to use it in the field of photography. child
Here, tabular grains refer to any other single crystal grains.
two parallel or substantially larger planes
Refers to particles with parallel crystal planes. of tabular grains
Aspect ratio (i.e. the ratio of diameter to thickness)
is substantially greater than 1:1. high aspect ratio
Tabular silver bromide grain emulsions are deCugnac and Chateau.
“Evolution of the Morphology of Silver”
Bromide Crystals During Physical
Ripening”,Science et Industries
Photographiques, Volume 33, No. 2 (1962), 121-125
It is reported on page. From 1937 to the 1950s, Eastman Co.
Datsuku Co., Ltd. is Duplitized (registered).
(Registered Trademark) No-Scrip Radiographic Film Products
It was sold under the name X-ray code 5133. this
The product is placed on opposite major sides of the film support.
Contains a sulfur-sensitized silver bromide emulsion coating layer.
It was hot. This emulsion is intended for exposure to X-ray radiation.
Because it was hot, it was not spectrally sensitized. This flat plate
The particles have an average aspect ratio of about 5 to 7:1.
Ta. This particle accounts for more than 50% of its projected area.
tabular grains account for more than 25% of the projected area
The portion was dominated by nontabular grains. These emulsions
is the highest average aspect after several replications.
The emulsion has a mean tabular grain diameter of 2.5 μm;
Average tabular grain thickness 0.36μm and average aspect ratio
It showed 7:1. Other replication emulsions are thicker and better.
It is a tabular grain with a small diameter, and its average aperture is
The spectral ratio was small. Tabular silver iodobromide grain emulsions are well known in the photographic industry.
although it exhibits a high average aspect ratio.
Nothing is known. Tabular silver iodobromide grains are
Duffin'sPhotographic Emulsion Chemistry,
Focal Press, 1966, pp. 66-72 and Trivelli
and Smith's “The Effect of Silver Iodide”
Upon the Structure of Bromo−Iodide
Precipitation Series”The Photographic
Journal, Volume LXXX, July 1940, pp. 285-288.
explained. Trivalli & Smith Iodide
Both particle size and aspect ratio
We have observed a significant reduction. Gutoff “Nucleation”
and Growth Rates During the Precipitation
of Silver Halide Emulsions”,Photographic
Sciences and Engineering, Volume 14, No. 4, 1970
July-August, pages 248-257, continuous precipitation equipment
prepared by single-diet precipitation using
The preparation of silver bromide and silver iodobromide emulsions was reported.
ing. Recently, grains have become tabular (i.e., compared to their thickness).
silver halide (grains that spread in the plane direction)
No specific process for making emulsions has been published.
Ru. U.S. Patent No. 4,063,951 applies to {100} cubic surfaces.
Therefore, pAg is within the range of 5.0 to 7.0.
aspect by double jet precipitation method adjusted to
The ratio (here the ratio of edge length to thickness) is 1.5
Formation of tabular silver halide crystals with a ratio of ~7:1
I'm teaching you what to do. As shown in Figure 3 of this patent.
The silver halide grains produced are rectangular and
The rectangular main plane exhibits {100} crystal plane characteristics. English
National Patent No. 4067739 forms seed crystals and halogen
pre-treated by Ostwald ripening in the presence of silver oxide solvent.
increasing the size of the seed crystals and pBr (bromide).
Nuclear regeneration while controlling the negative logarithm of the ion concentration
Grain growth without formation or offtwald ripening
By completing the
Single-sized halogenated octahedral crystal
It teaches how to make silver emulsions. US Patent No.
No. 4150994, No. 4184877 and No. 4184878,
British Patent No. 1570581 and German Patent Publication No.
Nos. 2905655 and 2921077 cover at least 90 models.
By using seed crystals with % iodide,
octahedral silver halide grains with round twins
teaching the formation of Unless otherwise specified, halogen
All percentages of emulsions, grains, or
is based on the silver present in the grain region.
Ru. For example, silver chlorobromide containing 60 mol% chloride
The particles contain 40 mole percent bromide. E. Klein and E. Moisar,Berichte der Bun
sengesellschaft, volume 67 (issue 4), pages 349-355,
In 1963, purine bases such as adenine were
of silver chloride when added at various stages of emulsion precipitation.
reported a disturbing effect on particle growth. rice
National Patent No. 3519426, for example,
such as adenine, pentaazaindene, or adenine.
By precipitation in the presence of azaindene
Discloses the production of silver chloride emulsions with increased covering power.
Ru. Of course, other characteristics are comparable.
silver halide emulsions with finer grain size.
The covering power of silver halide with larger grain size
It has been observed that it is larger than that of emulsion. In the field of photography, various peptizers (peptizers)
Precipitation of silver halide grains in the presence of
It is known that this can be done. US Patent No.
No. 3415653 is a copolymer of vinylamine and acrylic acid.
By using Rimmer as a veptizer,
Silver iodobromide grains of various shapes including tabular shapes are precipitated using
Discloses that it is allowed to stagnate. US Patent No.
No. 3692753 is a peptizer that can coagulate and redisperse
-, one has one or more bonded alkyl carbons
contains an additional alkyl chain substituted with two sulfur atoms.
is acrylamide or acrylate,
Copolymer of at least three different monomers
(interpolymer) is used. US Patent No.
No. 3615624 uses amine or
is the alcohol condensation residue has two alkyl carbon atoms
an organic compound having at least one sulfur atom bonded to
maleic acid, acrylic acid or
is an amide or ester repeat of methacrylic acid
opened the use of linear copolymers with units
It shows. Similar to Example 5 of U.S. Pat. No. 3,615,624
A study of neutral silver iodobromide emulsions precipitated by
In this case, the emulsion contains less than 20% of the projected area of silver iodobromide.
Acknowledging that the amount was due to tabular grains,
There is. These tabular grains also have low aspect ratios.
However, the <211> connection located in the plane of the principal plane
It seems to have a peripheral edge parallel to the crystal vector.
I was disappointed. (c) Disclosure of the invention The object of the present invention is to provide an aqueous silver salt solution useful in the photographic field.
liquid and a chloride-containing halide salt aqueous solution as a dispersion medium.
at least 50% against silver when contacted in the presence of
Tabular with halide content where mol% is chloride
Radiation-sensitive photography that produces silver halide grains
The object of the present invention is to provide a method for producing an emulsion, and
Introduced into more multi-layered photographic elements to increase sharpness and improve
Sensitivity (speed) - particle size by chemical and spectral sensitization
Can improve relationships, and blue, green
and/or red sensitized and incorporated into the photographic element.
sensitivity to the spectral sensitization region of the spectrum when
Demonstrates increased separation in UV and UV sensitivity
Radiation-sensitive photographs capable of producing photographic elements
A true emulsion is provided. The purpose is to use aminoazaindene as well as
Add maleic acid, acrylic acid or meth to the polymer chain.
repeating unit of amide or ester of acrylic acid;
Therefore, the content of each amide and ester is
Each amine or alcohol condensation residue has two
at least one step bonding an alkyl carbon atom
Ruphid - contains an organic radical with a sulfur atom
and (2) at least one other ethylenically unsaturated moiety.
is a water-soluble linear copolymer containing nomeric units.
The silver salt aqueous solution and chloride in the presence of peptizer
By reacting an aqueous solution of a halide salt containing
The silver salt aqueous solution and chloride characterized by
containing halide salt aqueous solution in the presence of a dispersion medium.
At least 50 mol% salt based on silver
Tabular halogenation with halide content
Method for producing radiation-sensitive photographic emulsion that produces silver particles
achieved by. In the present invention, the halide is mainly a chloride.
High aspect ratio tabular silver halide grain emulsions
Regarding manufacturing methods. In one preferred form, this milk
The agent has a form previously unknown in the photographic field.
Contains tabular grains of . In another form, tabular
The particles are globally bound by {111} crystal faces.
and chloride and bromide halides.
A shape different from that previously obtained by combining
have In one form, there are multiple tabular grains
are located on different crystal planes providing different adsorption positions.
Including the end face (edge face) where the
It is possible to reduce competition for adsorption positions due to Book
"High aspect ratio" used in the specification
The term refers to thicknesses of less than 0.5 μm (preferably less than 0.3 μm).
chloride with a diameter of at least 0.6 μm
Contains as a halide and has an average aspect ratio of
greater than 8:1 and present in the emulsion
Less total projected area of chloride silver halide grains
Both are 50% based on tabular silver halide grains.
Refers to something like that. The level described below
The terms “average aspect ratio” and “projection area” are not specifically allowed.
Unless otherwise specified, the same definitions apply. Preferred high aspect ratio tabular halo of the present invention
The silver germide grain emulsion has a thickness of less than 0.5 μm (preferably
diameter of at least 0.3 μm) and at least 0.6 μm in diameter.
The halogenated particles are at least 12:1, preferably less.
with an average aspect ratio of at least 20:1
It is. Extremely high average aspect ratio (50:1,
100:1 or higher).
In a preferred form of the invention, these halogens
Silver halide grains have a smaller total projected area than silver halide grains.
make up at least 70%, optimally at least 90%.
Ru. Silver halide emulsions produced according to the present invention
The aforementioned particle properties can be determined by methods well known to those skilled in the art.
It can be easily verified. used in this specification.
The term “aspect ratio” used depends on the thickness of the particle.
means the ratio of the diameter of the particle to the diameter of the particle. Next, the particle
The term "diameter" refers to the diameter of an emulsion sample measured under a light microscope or
Projected area of particles when observed with an electron microscope, etc.
is defined as the diameter of a circle with a new area. emulsion
From the shadowed electron micrograph of the sample, each
The thickness and diameter of these particles can be measured,
and less than 0.5μm (or 0.3μm) in thickness and diameter
Tabular grains larger than 0.6 μm can be identified.
Ru. From this, calculate the aspect ratio of each tabular grain.
and based on said thickness and diameter
All applications of the tabular grains in the sample that meet the standard
Average aspect ratios to get their average aspect
You can get the ratio. By this definition, the average
Aspect ratio is the aspect ratio of individual tabular grains.
It will be clear that the average of actual
flat plate with a thickness of less than 0.3 μm and a diameter of 0.6 μm or more
Determine the average thickness and average diameter of the particles, and combine these two
Calculate the average aspect ratio as the ratio of the two average values.
It is generally easy to do so. Individual aspect ratio
Even if you calculate the average aspect ratio using the average value of
Or use the average thickness and diameter to
Determining the spectral ratio does not limit the tolerance range of possible particle measurements.
Within the range, the average aspect ratio obtained is essentially
There is no difference. The thickness and
Projection surface of silver halide grains that meet diameter standards
and the projected area of the remaining silver halide grains.
can be added separately, and these two
Particles that meet the criteria for thickness and diameter from the added value of
The total projection surface of silver halide grains given by
The percentage of the product can be calculated. In the above measurement, less than 0.5μm (or 0.3μm)
The reference (or reference) tabular grain thickness of
Poor quality thicker grains to unique thin tabular grains
It was selected to distinguish between Reference particle diameter 0.6μm
is smaller in diameter than that in the micrograph.
It is always important to distinguish between tabular and non-tabular grains.
This is because it is not always possible to do so. herein
“projected area” used in
is the “projection area” widely used in this industry.
(projection area or projective area)
These words have exactly the same meaning as, for example,
James & HigginsFundamentals of
Photographic Theory, Morgan and Morgan,
See New York, p. 15. Radiosensitivity of the present invention, as defined herein
Photographic emulsions are new in one preferred form
Contains tabular grains of. Typical particle shape is 1a
As schematically shown in FIG. 1 and FIG. 1b. grain
The child 100 has opposite parallel mains as shown in the figure.
It has main surfaces 102 and 104. Microscope photo
When looking at the plane, the main surfaces are the end surfaces 106a,
rules bounded by b, c, d, e, and f
It looks like a hexagon. Electron micrograph odor
When viewed from above, the end face appears planar. crystal study
According to
It was found that it was located on the surface. <211> crystal vector 108a shown in FIG. 1a,
108b, 110a, 110b, 112a, and
112b intersects the plane of the main surface 102 at an angle of 60°.
It's pointing. In particle 100, six end faces
each parallel to one of the <211> crystal vectors
shown as located. End surface 106a
and 106b are located parallel to vector 108,
The end faces 106c and 106d are parallel to the vector 110.
rows, and the end faces 106e and 106f are
Located parallel to vector 112. these
The end face is thought to be located on the {110} crystal plane, and if
may be located on a separately specified {220} crystal plane
It seems that it will. The unique characteristics of the tabular grains defined herein
For the crystal structure, see attached Figures 2a and 2b.
This can be further clarified by
There was a difference, but this too in a new way.
Controlled grain of typical tabular silver chloride produced by
The child is shown schematically. According to crystallographic research
For example, not only the main surfaces 202 and 204 but also the end surface 2
It is shown that 06 is also located on the {111} crystal plane.
be suggested. This end surface does not appear planar. sand
In other words, when it comes to the placement of faces and edges, the control
The tabular silver chloride grains obtained are composed of silver bromide and silver iodobromide.
Many published studies of tabular and sheet crystals
It looks similar to the one in . It's obvious on a plane
uni, these particles are regular hexagons.
unacceptable. Rather, these particles are typical
It is an irregular hexagon and is connected to a dart line.
As an equilateral triangle cut as shown in
can be observed. Seen from crystallographic studies
and the <211> crystal vector that intersects at an angle of 60 degrees.
208a, 208b, 210a, 210b, 21
Both 2a and 212b are against edge 206.
It looks like they are not parallel. In this way, the main
The end faces of tabular grains specified in the specifications are not controlled.
tabular grains and similar tabular silver bromide and iodine
30 relative to the crystal lattice compared to the end faces of silveride grains.
It can be seen as if it has been rotated by ℃. A flat plate that appears in a micrograph as a regular hexagon
particles can be produced according to the invention.
However, other peripheral shapes have also been manufactured and observed.
It was. For example, as particle 300 in FIG.
As shown schematically. These particles are 6
edges 306 instead of having 6 edges 306
a and six edges 306b appear alternately.
In other words, it appears to have a total of 12 edges.
When viewed in this way from a plan view, these particles are
It can be seen as a square. To the darts line
As shown, the six additional edges are
At the final stage of growth, hexagonal particles are
It is thought that this can be obtained by cutting. circles are regular
When the number of edges of a polygon reaches infinity,
Since it can be even larger than a hexagon
The dodecagon of the combination appears rounder in the micrograph.
especially at the intersection of those edges.
It's no surprise that the layers look round. In this specification
The tabular grains defined by
It has a very sharp regular hexagonal shape.
flat edges are not easily visually distinguishable.
Not nearly circular shapes, as well as intermediates between these
Can include shape. As defined herein
In one preferred form, the tabular grains are
<211 in the plane of one of its principal faces in each case
>At least one edge parallel to the crystal vector
can be characterized as having Chloride-containing tabular grains produced according to the invention
The emulsion, in its formed form, is part of the dispersion medium.
containing thioether bonds of the type described below.
Contains peptizer. This thioether bond
Approximately per total weight of peptizer in the emulsion
present at the end of precipitate formation at a concentration of 0.1-10% by weight.
Ru. This peptizer is a reaction volume in which particle precipitation occurs.
can exist completely in the vessel from the beginning, and
Identical along with silver and halide salts in reaction vessel
Or it can be included through another jet.
Wear. However, at least the minimum concentration is
reaction volume during formation and subsequent growth of tabular grains.
Must be present in the container. in the reaction vessel
The concentration of thioether bond-containing peptizer depends on the reaction
0.3 to 6% by weight based on the total weight of the container contents, maximum
It is preferably present in the range of 0.5 to 2.0% by weight.
Yes. During the precipitation, or preferably after the precipitation, said thio
Any common ether bond-containing peptizer
Approximately 10 weight per total weight when refilled with peptizer
The total peptizer concentration can be up to %
Ru. Few peptizers contain thioether bonds.
Both particles are partially adsorbed on the surface of tabular grains, and
Once the emulsion is formed in the presence of
Completely irreplaceable. However, the emulsion is completely
After being formed into
Reduces the concentration of the tizer in the final emulsion.
The original thioether bond-containing peptizer is
to leave a small amount (if any) in
I can do it. As a peptizer containing a thioether bond,
No. 3,615,624 and U.S. Pat. No. 3,615,624, cited above.
I can list what was disclosed in No. 3692753.
Ru. These peptizers are composed of (1) linear polymer chains;
of maleic acid, acrylic acid or methacrylic acid.
repeating unit of amide or ester, respectively
Each amine contained in these amides and esters
or alcohol condensation residue is at least one
Sulfide - two alkyl atoms bonded to sulfur atoms
Contains organic radicals with carbon atoms and (2) less
at least one other ethylenically unsaturated monomer
It is a water-soluble linear copolymer containing The latter cycle
The repeating unit is typically determined by the pH level at the time of precipitation.
at least one that can impart water solubility to the nomer.
Contains one group. For example, the unit may be sulfone
Acid or sulfonate substituted alkyl group is sulfide
- the two alkyl carbon atoms to which the sulfur atoms are bonded
The above except that the thioether group containing
It can be similar to repeating unit (1). child
A unit of the type is further disclosed in U.S. Pat. No. 3,615,624.
It is shown. Thioether bond-containing repeat unit
preferably about 2.5-35 moles of peptizer
%. The chloride-containing tabular grains defined herein are
In the absence of an ether bond-containing peptizer,
Not formed. Furthermore, the tabular grains contain thioether.
Even in the presence of a peptizer containing a ter bond,
Will not form unless a small amount of crystal modifier is present.
stomach. Emulsion 28 will be explained in detail below.
and, in some cases, high aspect ratio tabular grains.
Emulsions can also be obtained when iodide is used as a crystal modifier.
However, the preferred crystal modifier is aminoaza
It is inden. As defined herein,
Minoazaindene is an aminonitrogen as a ring substituent.
having an amino group attached to the ring at the elementary atom
Say azainden. It is generally understood
Uni, azaindene has the aromatic ring structure of indene.
A compound that has one or more of its ring carbon atoms
is replaced by more nitrogen atoms.
It is. Such compounds, especially 3 to 5
Compounds in which a carbon atom is replaced by a nitrogen atom
In photographic emulsions, grain growth modifiers,
It has been recognized that it is useful as a preventive agent and a stabilizer.
It is being Particularly suitable for use in practicing the invention
Preferred aminoazaindenes include, for example, adenine
In some cases, amino acids such as ion and guanine
Tetraazaindene ring charcoal, also called pudding
Those with a primary amino substituent bonded to an elementary atom
It is. Aminoazaindene has a particle growth modification amount and
and can be used in commonly used amounts.
Yes, but 10 per mole of silver^-3Very small amount on the order of moles
Effective at low concentrations. Useful concentrations are per mole of silver
The amount can range as high as 0.1 mole.
Ru. Generally preferred is silver halide precipitation.
In the process, about 0.5× per mole of silver in the reactor
Ten^-2~5×10^-2Maintain the molar amount of aminoazaindene.
It is to hold. Used as a stabilizer in photographic emulsions
Certain aminoazai are known to be useful.
U.S. Patent No. 2444605, U.S. Patent No. 2743181
and 2772146. Emulsion is one
Once formed, the aminoazaindene is no longer necessary.
Typically, at least some of the
It adsorbs and remains on the particle surface. silver halide grains
Compounds that exhibit strong affinity for surfaces, e.g. spectral sensitization
The dye can be replaced with aminoazaindene.
and thereby remove the azainden from the emulsion to the wash.
Therefore, it can be virtually completely removed. Contains aminoazaindene and thioether bonds
The peptizers work together to form the desired tabular grains.
It seems that it gives the properties of In some cases,
At the initial stage of grain formation, tabular grains are {111}
It can have not only major crystal planes but also {111} edges.
It was recognized that As precipitation progresses,
A transition to the main crystal face of the hedron was observed. lastly,
As precipitation progresses further, regular hexahedrons {111}
Ets located on major crystal planes and {110} crystal planes
A plane of one of the major surfaces that seems to show the
The surrounding area parallel to the <211> crystal vector located at
Tabular grains with edges can be produced.
Ru. The above-mentioned unique characteristics obtained by the method of the present invention
This book is based on the theory that tabular grains with characteristics are formed.
Although there is no particular intention to limit the invention, the inventors
is the aminoazaindene at each production step.
{111} Main salt to facilitate the generation of crystal planes
I think it affects the chemical particles. Then this
{111} crystal planes are those that conventionally form tabular grains.
form a double twin plane, which was regarded as
I think so. Peptizers containing thioether bonds
is then observed on top during the grain growth stage.
The dislocation that gives rise to the unique tabular grain edges was detected.
seems to be causing it. Consideration of this particle growth mechanism
The method is to observe the particles at various stages of their growth and to
By adjusting the level of minoaza indene
This has been confirmed. Concentration of aminoazaindene
Increasing the {111} crystal edge
Satisfactory particles can be obtained, but the above-mentioned unique
The generation of particle edges is delayed and in some cases
is excluded. The tabular grain emulsions defined herein are
Precipitated without the presence of halides other than the initial chloride.
In the case of stagnation, the central region of the particles produced is
Virtually free of both bromide and iodide;
one or more planes of the main surface
is located parallel to the further <211> crystal vector
The presence of one or more particle edges that
To distinguish the tabular grains defined here from other grains:
Provides additional structural differences that are convenient for use. At least in the tabular grains defined herein
The central region contains at least 50 mole percent chloride relative to silver.
However, substantial amounts of bromide and
It can contain at least one iodide. smell
When oxides and/or iodides are present, they are usually
Present at concentrations of at least about 0.5 mol%, but important
The photographic effect is achieved by bromide at a low concentration of about 0.05 mol%.
and/or iodides. The tabular grains may contain up to about 10 mole percent, preferably 6 mole percent.
Contains up to mol% iodide, optimally up to 2 mol% iodide
be able to. In addition to chlorides and iodides, halogens
When it contains a bromide, it can also contain a bromide.
In a preferred form of the invention, the tabular grains are silver
chloride in an amount greater than 75 mol%, optimally
Contains more than 90 mol% chloride. substantially chlorinated
Tabular grains consisting of silver are possible, and chloride
Especially suitable for applications where silver emulsions are commonly used.
suitable. Leveling out substantial amounts of bromide and/or iodide
assembled into tabular grains without adversely affecting the plate shape.
can be incorporated into various halogen
It is well suited for use in various photographic applications requiring chemical compounds.
It is possible to provide tabular grains that can be used for
It is a particular benefit of the present invention that it can be used. At the initial point of emulsion precipitation, the aforementioned peptizer
- and at least a portion of a dispersion medium containing a crystal modifier.
be present in the reaction vessel containing an effective stirring mechanism.
Ru. typically first introduced into the reaction vessel
The dispersion medium is the amount present in the emulsion at the end of grain precipitation.
At least about 10% by weight, preferably based on the total weight of the dispersion medium.
Preferably, it is 20 to 100% by weight. French patent no.
Belgian patent no. 886645 corresponding to no. 2471620
As taught, the dispersion medium is present during the precipitation of the particles.
Can be removed from the reaction vessel by ultrafiltration.
The dispersion medium initially present in the reaction vessel can be
The volume is the emulsion present in the reaction vessel at the end of grain precipitation.
or the volume of the emulsion.
It can even be more than the volume. Inside the reaction vessel
The first dispersion medium introduced into the
It is a dispersion liquid in which water is dispersed, and in some cases,
is a kind or
is a higher silver halide ripener and/or metal
Contains other ingredients such as doping agents and
You can. If the peptizer is initially present
is the total peptizer present at the end of the precipitation.
more preferably at least 10% of the amount of
Also preferably used at a concentration of 20%. additional minutes
The dispersion medium is added to the reaction vessel along with the silver and halide salts.
and introduced through another diet.
You can also After the introduction of the salt is completed, the dispersion medium is
Adjusting ratios, especially peptizer ratios
Increasing is a common method.
Ru. The pH inside the reaction vessel during precipitation is on the acidic side compared to neutral.
to hold. Optimal PH level was chosen for precipitation
Affected by growth modifier and temperature. 20〜
Within the temperature range of 90℃, the PH value is between 2 and 5.0.
is within the range of Precipitation has a PH value in the range of approximately 2.5 to 3.5
and is preferably carried out at a temperature range of 40 to 90°C.
Delicious. Chloride ions in the reaction vessel during precipitation
Concentration is also controlled. Generally useful, in reaction vessels
The chloride ion concentration is approximately 0.1 to 5.0 molar.
Ru. Preferred chloride ion concentration is approximately 0.5-3.0M
It is concentration. Other incorporated into tabular grains
The ratio of halides to other halides introduced
By adjusting the ratio of chloride to salt
can be controlled. Halogen in reaction vessel
The oxide ion concentration is monitored by measuring pAg.
can be viewed. Tabular grains in which the halide is primarily chloride
Once a child is formed according to the method of the invention, other
The halides can be prepared as described above by methods well known to those skilled in the art.
Can be incorporated into particles. Shape silver salt shell
The technology is based on U.S. Patent Nos. 3,367,778 and
No. 3206313, No. 3317322, No. 3917485 and
It is shown in the same No. 4150994. common shell
The oxidation method forms tabular grains with high aspect ratios.
It's not for Ciel's growth.
The average aspect ratio of the emulsion is therefore reduced. flat plate
The favorable conditions for the formation of shaped particles are during the formation of shells.
If present in the reaction vessel, shell growth will result in grain
Occurs preferentially on the outer edges of the child, and the aspect ratio
It is possible to prevent a decrease in flat plate
shaped grains are tabular grains used as core grains
Aspects of core-shell particles obtained compared to
shell without necessarily reducing the contrast ratio.
be able to. High aspect ratio core-shell flat
Platy grain emulsions can be used to produce direct reversal images.
It can be manufactured for use. After silver chloride tabular grains are formed, halogenation
By adding both grains and silver salts,
The particles remain intact, but with additional silver halide
Acts as a nucleus for attachment. Reacts with silver to form salt
It is possible to produce silver salts with lower solubility than silver oxide.
salts such as thiocyanates, bromides and/or
is mainly made of iodide salts without the addition of silver salts.
when added to emulsions containing tabular chloride grains.
These salts replace chloride in the crystal structure.
There will be. This replacement begins at the crystal surface.
and progresses into the interior of the particle. silver chloride crystal lattice
Replacement of chloride ion by bromide ion in
and in some cases small proportions of iodide ions.
The substitution by is well known. This way
Una emulsion is a halide conversion agent in the photographic industry.
It is called a silver halide emulsion. halo like this
Genide conversion emulsions and techniques for their use are covered by U.S. Patent No.
No. 2456953, No. 2592250, No. 2756148 and
It is shown in the same No. 3622318. In the present invention
contains less than 20 mol%, preferably less than 10 mol%
Logenides are introduced for substitution. Replacement is high
In the case of Bell, the tabular shape of the particle is resolved and the case
Sometimes it is destroyed. Thus, bromide and
and/or on or near the particle surface of iodide ions.
Although it is possible to replace chloride ions in
This is commonly done when producing latent image forming particles.
A large amount of halide conversion is performed here, as shown in
is not taken into account. In forming the tabular silver chloride grains specified herein,
However, the aqueous dispersion medium can be used in a general silver halide reaction vessel.
charged. The PH and pAg of the dispersion medium in the reaction vessel are
adjusted to satisfy the precipitation conditions according to the invention.
Ru. Can be used in carrying out the present invention
The range of pAg is the equilibrium point (silver and halide ions
halo of pAg) whose concentrations are stoichiometrically equal
Since it is on the genide side, first add the chloride salt aqueous solution.
Used to regulate pAg. Then, silver salt solution
Pour the liquid and chloride salt aqueous solution into the reaction vessel at the same time.
Ru. The pAg in the reaction vessel was measured using common measurement techniques.
and the relative flow rates of the silver and chloride salt solutions.
to keep it within the desired range. one
The pH of the reaction vessel was also monitored using common sensing techniques.
and the base while introducing the silver and chloride salts.
is maintained within a specified range by the addition of Halogen
Control equipment and matters for pAg and PH during silver oxide precipitation operation
In fact, U.S. Patent No. 3031304 and U.S. Patent No. 3821002
Claes and PeelaersPhotography
Disclosed in Korrespondenz, vol. 103, p. 161 (1967)
has been done. pAg, pBr and
The terms PH and PH refer to silver, bromine and hydrogen ions, respectively.
is defined as the negative logarithm (reciprocal of the logarithm) of the on concentration.
It is something that Individual silver and halide salts are described by Culhane et al.
U.S. Patent No. 3821002, Olver U.S. Patent No.
No. 3031304 and Claes et al.Photography
Korrespondenz, Band 102 Band, November 1967
10, page 162, gravity feed or
is the delivery rate and the PH and/or
Or by a delivery device to control pAg.
to the reaction vessel via the surface or inner surface supply pipe.
can be added. Rapidly transfer reactants into reaction vessels
No. 2,996,287,
Same No. 3342605, Same No. 3415650, Same No. 3785777,
4147551, 4171224, UK Patent Application No.
2022431A, German Patent Publication No. 2555364 and the same
No. 2556885, andResearch Disclosure, 166
Volume, February 1978, as shown in item 16662
Specially configured mixing equipment may be used to
can.Research Disclosureand its previous publication
thing,Product Licensing Indexis Industrial
Opportunities Ltd.; Homewell, Havant;
Publication of Hampshire, P09 1EF, UK. A particularly preferred method of precipitation produces silver and silver during the operation.
By increasing the rate of introduction of halide salts
This method shortens the precipitation time. silver and ha
The rate of introduction of the logenide salt depends on the dispersion medium and silver and
Increasing the rate of introduction of halide salts
It can be speeded up by
Increasing the concentration of silver and halide salts in the dispersion medium
It can also be made faster by silver and halogen
It is particularly preferred to increase the rate of introduction of the compound salt.
However, U.S. Patent No. 3650757, U.S. Patent No. 3672900 and
No. 4242445, German Publication No. 2107118, Europe
Patent Application No. 80102242 and Wey's “Growth”
Mechanism of AgBr Crystals in Gelatin
Solution”,Photographic Science and
Engineering, Volume 21, Issue 1, January/February 1977,
As taught from page 14 onwards, increase the speed of deployment.
Keep the temperature below the critical level where the generation of new particle nuclei is likely to occur.
The special feature is to maintain the
preferred. Emulsions with a coefficient of variation of less than about 30%
can prepare the process of the present invention. here
The term “coefficient of variation” used in
as 100 times the standard deviation divided by the average particle diameter
Define. At the precipitation growth stage, re-nucleation is considered.
By having it done graphically, you can substantially increase the
It is possible to produce polydisperse emulsions with high coefficients of variation.
It goes without saying that it can be done. As specifically mentioned above
Besides, the halide content is mainly chloride
There are various common methods for preparing tabular grain emulsions.
can take shape. Silver salt aqueous solution is similar to silver nitrate.
Soluble silver salts can be used, while halo
Genide salt aqueous solution contains one or more aqueous
ammonium, alkali metals (e.g. lithium)
aluminum, sodium or potassium) or alkali
Earth metals (e.g. magnesium or calcium)
halide salts of (m) can be used.
Silver and halide salt aqueous solutions have a wide range of concentrations.
for example 0.2 to 7.0 molar concentration or higher.
It can be used at higher concentrations. Charge silver and halide salt into reaction vessel
In addition, there are
Various compounds are known to be useful in the presence of
Ru. For example, copper, thallium, lead, bismuth, cadmium
Mium, zinc, intermediate chalcogens (i.e. sulfur)
yellow, selenium and tellurium), gold and group precious metals
Precipitation of silver halide emulsions with metal compounds such as
can be present at low concentrations during the process. child
This is described in U.S. Patent No. 1195432, U.S. Patent No. 1951933,
Same No. 2448060, Same No. 2628167, Same No. 2950972,
Same No. 3488709, Same No. 3737313, Same No. 3772031
and the same No. 4269927 andResearch Disclosure,
134, June 1975, item 13452.
Ru. In the silver chloride particles of these metal dopants,
distribution determines the location of the metal compound in the reaction vessel.
or by introducing silver and chloride salts.
control by adjusting the addition during the addition process.
can be done. Tabular grain emulsions are described by Moisar et al.
Journal of Photographic Science, Volume 25, 1977
of precipitation as shown in 1999, pp. 19-27.
In the process, reduction sensitization can be performed internally.
Wear. In producing a tabular silver chloride grain emulsion,
The dispersion medium is initially contained in the reaction vessel. Like
In a new form, the dispersion medium is an aqueous suspension of peptizer.
Consists of liquid. The peptizer concentration in the reaction vessel is
0.2 to about 10% by weight based on the total weight of emulsion components.
can be done. Before and after the formation of silver halide
In the reaction vessel, the concentration of peptizer is
Keep it below about 6% of the total weight, and
Added later to obtain coating properties
Emulsion vehicle concentration by adding vehicle
A common method is to adjust the degree to a high level. first
The emulsion formed is about 1 mole of silver halide.
~50g, preferably about 2.5-30g peptizer
including. The added vehicle is added later and the halo
Concentrations as high as 1000 g per mole of silver
You can do it at Preferably in the final emulsion
The vehicle concentration is 50 g per mole of silver halide.
It is huge. coating and drying during the manufacture of photographic elements.
The vehicle accounts for about 30 to 70% by weight of the emulsion layer.
It is preferable to of the peptizer containing the aforementioned thioether bond.
In addition, vehicles (binders and peptizers)
) are commonly used in the preparation of silver halide emulsions.
You can choose from what is available. preferable
Peptizers are hydrophilic colloids, and these
can be used alone or in combination with hydrophobic substances.
I can do it. Suitable hydrophilic vehicles include protein
white matter, protein derivatives, e.g. cellulose esters
Cellulose derivatives such as, e.g. alkaline treatment
Gelatin (cow bone or leather gelatin) or acid-treated gelatin
Gelatin, such as latin (pork skin gelatin), e.g.
For example, acetylated gelatin and phthalated gelatin.
Examples include substances such as gelatin derivatives. child
These and other vehicles are
Research Disclosure, Volume 176, December 1978, Section
Item 17643, listed in Chap. Especially hydrophilic
Vehicle substances containing roids and their use therewith
Useful hydrophobes are found only in the emulsion layers of photographic elements.
layers located below the overcoat layer, intermediate layer, and emulsion layer.
Can be used in other layers such as. Grain ripening may occur during the emulsion preparation process.
Ru. Silver chloride, due to its high level of solubility,
Due to the absence of agents, its shadow is lower than that of other silver halides.
There is little impact. Already used to promote ripening.
Known silver halide solvents are useful. For example, ripe
The ingredients are reacted before adding the silver and halide salts.
The entire amount can also be included in the dispersion medium in the container.
or one or more halides
It is a kind of reaction to adding salt, silver salt or peptizer.
It can also be introduced into a reaction vessel. Another variant
As a ripening agent, add halide salts and silver salts.
It can also be installed independently on each floor. The ripening agent is different.
Introduction following the introduction of silver and halide salts in steps
You can also. High aspect ratio flatness as defined herein.
The platelet grain emulsion is preferably washed to remove soluble salts.
remove. This soluble salt can be, for example,
Research Disclosure, Volume 176, December 1978, Section
No. 17643, decante as shown in Chap.
- filtration, and/or quenching and leaching.
It can be removed by known techniques such as.
In the present invention, after the completion of precipitation, the tabular grains are ripened.
Washing of tabular grains is carried out at the end of the formation process.
Increased thickness, reduced aspect ratio and/or diameter
It is particularly advantageous to avoid an excessive increase in . increase
Emulsions with or without sensitizers must be dry and ready for use.
Can be stored in advance. Follow the tabular silver halide grain preparation method described above.
For example, specify thickness and diameter criteria for aspect ratio.
Satisfied tabular grains are the sum of all silver halide grains.
High aspect ratio that occupies at least 50% of the projected area
Tabular grain emulsions with a ratio of
By increasing the proportion of such tabular grains,
It is recognized that further advantages are achieved when
Ru. Flat halogen that meets standards for thickness and diameter
The silver oxide grains make up at least 70% of the total projected area
preferably at least 90%).
Many photographic applications, even in the presence of small amounts of non-tabular grains
The advantages of tabular grains do not cause any problems in the field
is obtained completely, but increasing the proportion of tabular grains
can be done. Large tabular silver halide grains
may be performed using commonly used separation techniques such as centrifugation or
Small particles in the mixture using a hydrocyclone
Can be mechanically separated from non-tabular grains
Ru. Separation by hydrocyclone is a U.S. patent
No. 3,326,641. High aspect ratio tabular halves as defined herein.
Silver halide grain emulsions can be chemically sensitized.
Wear. That is, the emulsion isThe Theory of
the Photographic Process, 4th edition,
Macmillan, 1977, pp. 67-76.
Sea urchin can be chemically sensitized using activated gelatin.
Kirushi, againResearch Disclosure, 120 volumes,
April 1974, Item 12008,Research Disclosure,
Volume 134, June 1975, Item 13452, U.S. Pat.
No. 1623499, No. 1673522, No. 2399083, No. 1673522, No. 2399083, No.
No. 2642361, No. 3297447 and No. 3297446,
UK Patent No. 1315755, US Patent No. 3772031,
No. 3761267, No. 3857711, No. 3565633,
No. 3901714 and No. 3904415 and British patents
pAg5-10, PH as described in No. 1396696
5-8 and temperature 30-80℃, sulfur, selecium
tellurium, gold, platinum, palladium, iridium
osmium, rhodium, rhenium or phosphorus
Chemical sensitization using sensitizers or combinations of these
I can feel it. Chemical sensitization is sometimes
CHI as described in U.S. Patent No. 2,642,361
In the presence of oceanate compounds, also U.S. Pat.
No. 2521926, No. 3021215 and No. 4054457
carried out in the presence of sulfur-containing compounds of the type described.
be called. Chemical sensitization is finishing (chemical sensitization) modification
agents, namely azaindene, azapyridazine, azaindene, azapyridazine,
Zapyrimidine, benzothiazolium salt and
or sensitizers with more heterocyclic nuclei.
Sea urchin suppresses fog and improves sensitivity during the chemical sensitization process.
In the presence of compounds known to increase
It can be implemented. An example of a finish modifier is rice
National Patent No. 2131038, National Patent No. 3411914, National Patent No.
No. 3554757, No. 3565631 and No. 3901714,
Canadian Patent No. 778723 and Duffin
Photographic Emulsion Chemistry, Focal
Press (1966), New York, pp. 138-143.
has been done. In addition to or instead of chemical sensitization
As described in U.S. Patent Nos. 3,891,446 and 3,984,249,
For example, reduction sensitization using hydrogen, as described in
and also U.S. Patent No. 2983609,
Oftedahl et al.Research Disclosure, vol. 136,
August 1975, Item 13654, U.S. Patent No. 2,518,698;
Same No. 2739060, Same No. 2743182, Same No. 2743183,
As described in the same No. 3026203 and the same No. 3361564.
Sea urchin, stannous chloride, thiourea dioxide, polyamine
and with a reducing agent such as amine borane, or
Low pAg (e.g. less than 5) and/or high PH (e.g.
8) can be reduced sensitized by treatment.
Ru. Described in U.S. Patent Nos. 3,917,485 and 3,966,476.
surface chemical sensitization, including inner surface sensitization
I can do it. In addition to chemical sensitization, the high aspect ratio
Tabular silver chloride grain emulsions can be spectrally sensitized.
Wear. Blue and minus blue in the visible spectrum
A spectral sensitizing color that exhibits absorption maximum in the green and red) regions.
element can be used. In addition, special usage
In the field, spectral sensitizing dyes are used to detect the visible spectrum.
It is possible to improve the spectral response beyond . example
For example, it is possible to use infrared absorption spectral sensitizers. The emulsion of the present invention can be spectrally sensitized using various dyes.
can be done. The dyes used include cyani
merocyanine, complex cyanine and complex merocyanine
(i.e. tri-, tetra- and polynuclear mias)
nin and merocyanine), oxonol, hemio
Xonol, styryl, merostyril and stre
Contains polymethine dyes containing ptocyanin. Cyanine spectral sensitizing dyes include quinolinium, pin
Lysinium, Isoquinolinium, 3H-Indoli
Umu, Benz [e] Indolium, Oxazoliu
Mu, oxazolinium, thiazolium, thiazoli
ionium, selenazolium, selenazolinium, i
midazolium, imidazolinium, benzoxazo
linium, benzothiazolium, benzoselenazo
Benzimidazolium, Naphthoxazolium
um, naphthothiazolium, naphthoselenazoliu
dihydronaphthothiazolium, pyrylium and
and imidazopyrazinium quaternary salts.
Una, two bases linked by a methine bond
Contains sexual heterocyclic nuclei. For merocyanine spectral sensitizing dyes, barbiturates
acid, 2-thiobarbituric acid, rhodanine, folds
toin, 2-thiohydantoin, 4-thiohydantoin
Intoin, 2-pyrazolin-5-one, 2-iso
Xazolin-5-one, indan-1,3-dio
cyclohexane-1,3-dione, 1,3-
dioxane-4,6-dione, pyrazoline-3,
5-dione, pentane-2,4-dione, alkyl
rusulfonylacetonitrile, malononitrile,
Isoquinolin-4-one and chroman-2,4-
Acidic nuclei and cyanine staining as derived from diones
The basic heterocyclic nucleus of the compound type is bonded through a methine bond.
including those that have been One or more spectral sensitizing dyes may be used.
can. Maximum sensitivity to wavelengths across the visible spectrum
Spectral sensitivity songs with great variety and degree
Pigments having a linear shape are known. Dye selection
and the relative proportions of the spectrum for which sensitization is desired.
area and desired shape of the spectral response curve.
Depends on. Dyes with overlapping spectral sensitivity curves
are often at each wavelength in the overlapping region.
A combination whose sensitivity is approximately equal to the sum of the sensitivities of the individual dyes.
It shows a curve with a curved shape. Therefore, different maximum sensations
By using a combination of multiple pigments with different degrees of
Therefore, the maximum value is set between the maximum sensitivities of individual dyes.
It is possible to obtain a spectral sensitivity curve with It is possible to use a combination of multiple spectral sensitizing dyes.
and thereby supersensitize, i.e., certain spectral
region, one of those spectral sensitizing dyes is
greater than when used alone at any concentration.
and due to the additive effect of those spectrally sensitized dyes.
A greater spectral sensitization is achieved than the subsequent sensitization.
Supersensitization involves the use of spectral sensitizing dyes and other additives (e.g.
stabilizers and antifoggants, development accelerators or inhibitors;
agents, coating aids, fluorescent brighteners and antistatic agents
This is achieved by a selected combination of agents). Hyper
Some machines and compounds that can cause sensitization
Regarding both,Photographic Science
and Engineering, vol. 18, 1974, pp. 418-430.
Gilman’s “Review of the Mechanisms of
Supersensitization”. Spectral sensitizing dyes also affect emulsions in other ways.
I can do it. In addition, the spectral sensitizing dye is
As disclosed in No. 2131038 and No. 3930860
, halogen acceptor or electron acceptor, anti-fogging
Acts as an agent or stabilizer, development accelerator or inhibitor
do. Silver halide emulsions are useful for sensitizing spectral enhancement.
Some sensitizersResearch Disclosure, vol. 176,
December 1978, Item 177643, Chapter
There is. Non-tabular or low aspect ratio tabular halogens
Commonly used to spectrally sensitize emulsions containing silveride grains.
Any amount of dye can be used. Completeness of the invention
The optimal amount (i.e.,
Maximum photograph achievable from particles under possible exposure conditions
sufficient amount to achieve at least 60% of the sensitivity)
Spectral sensitizing dyes in high aspect ratio tabular grain emulsions
It is desirable that the particles be adsorbed onto the surface of the particles. use
The amount of dye used depends on the particular dye used or
The combination of dyes and particle size and ascent
It will vary based on the aspect ratio. Optimal spectroscopy
Sensitization is available for surface sensitized silver halide grains
Approximately 25% to 100% or more of the total surface area
using an organic dye at a monolayer coverage of
What is achieved in this case is well known in the photographic field.
It is being That is, this means that, for example,
“The Adsorption of Sensitizing” by West et al.
Dyes in Photographic Emulsions”Journal
of Phys.Chem. , vol. 56, p. 1065, 1952;
“Desensitization of Sensitizing” by Spence et al.
Dyes”,Journal of Physics and Colloids
Chemistry, Volume 56, Issue 6, June 1948, 1090~
page 1103; and as described in U.S. Patent No. 3,979,213.
There is. The optimal dye concentration level is Mees'Theory of
the Photographic Process, 1942,
Macmillan, pp. 1067-1069.
They may be selected by law. Spectral sensitization is conventionally known to be useful in milk.
It can be carried out at any stage of drug preparation.
Ru. Most commonly, spectral sensitization is the completion of chemical sensitization.
will be held subsequently. However, the U.S. patent
No. 3628960 and No. 4225666.
In addition, spectral sensitization can be performed simultaneously with chemical sensitization.
It can also be done completely prior to chemical sensitization.
and further prior to completion of precipitation of silver halide grains.
You can even start. US Patent No. 4225666
Some of the spectral sensitizing dyes, as taught in the issue
is present prior to chemical sensitization, and the remaining
Emulsions of spectral sensitizing dyes to be introduced after chemical sensitization
The introduction can be done separately. US patent
Unlike No. 4225666, 80% of silver halide
Adding a spectral sensitizing dye to the emulsion after precipitation has occurred.
I can do it. In the process of chemical and/or spectral sensitization,
Sensitization can be enhanced by pAg regulation including circulation.
can. A specific example of pAg regulation isResearch
Disclosure, Volume 181, May 1979, Item 18155.
has been done. In one preferred form, the spectral sensitizer is a chemical
may be incorporated into the emulsion of the invention prior to sensitization.
can. Also, in some cases, such as finish modifiers.
and other adsorbent substances in the emulsion prior to chemical sensitization.
Similar results were achieved by introducing
Ru. Apart from pre-introducing the adsorptive substance, the above
As taught in cited U.S. Pat. No. 2,642,361
As shown, in the process of chemical sensitization, approximately 2×10^-3
Using thiocyanate at a concentration of ~2 mol%
is preferred. Use of other ripening agents in the process of chemical sensitization
can do. Combined with one or both approaches mentioned above.
It can be carried out separately or separately.
In the third approach, direct chemical sensitization
Silver and/or halogen present before or during chemical sensitization
Preferably, the concentration of the chloride salt is adjusted. acetic acid
Soluble silver, such as silver trifluoroacetate and silver nitrate
silver salts, silver thiocyanate, silver phosphate, and silver carbonate.
With silver salts that can be precipitated on the particle surface like
Both can be introduced. On tabular grain surface
A fine grain that can be Ostwald-ripened to
Silver halide grains (i.e. silver bromide, silver iodide and
and/or silver chloride particles).
For example, Lipman emulsion is introduced during the chemical sensitization process.
can do. In addition, spectrally sensitized high asperity
Chemical sensitization of tabular grain emulsions with
Accomplished at a predetermined remote location of one or more of the children
can do. In one preferred form,
Spectroscopy on the crystal surfaces that form the major faces of tabular grains
By preferentially adsorbing the sensitizing dye, it becomes flat.
Chemical sensitization occurs on selected crystal surfaces of particles.
It becomes possible to not necessarily necessary to achieve all benefits
However, the emulsion according to the present invention is suitable for typical practical production.
Optimally chemically and spectrally sensitized according to the manufacturing method. vinegar
In other words, these sensitizations allow for possible uses and
those in the spectral region that are sensitized under processing conditions.
of the maximum log sensitivity achieved from particles of at least
A sensitivity equal to 60% is achieved. log feeling here
Degree means 100 (1-log E), and in this formula,
E is metric-key at a density of 0.3 above fog.
It is the exposure amount that can be expressed in Yandle-seconds. in emulsion layer
Once the silver halide grains of
The emulsion layer of the product is comparable to that of other manufacturers.
Optimally chemically and spectrally sensitized for
By further conducting product analysis and performance evaluation,
can be judged. The sharpness advantage of the present invention
To achieve this, silver halide emulsions must be chemically or
may be sensitized spectrally efficiently or inefficiently.
not important. As mentioned above, once high aspect ratio tabular grains
The emulsion is produced by a precipitation method and washed.
Once sensitized, add commonly used photographic additives.
Completing their preparation by blending
I can do it. And these are the images that should produce the silver image.
True application field, for example, ordinary black and white photography
be able to. A silver image is formed using the emulsion specified herein.
photographic elements that require additional hardening agents during processing.
The membrane can harden sufficiently to the point that it is not necessary to
Ru. Due to this hardening, it is also hardened and treated.
flat plate that is not flat or has a high aspect ratio
silver coverage compared to photographic elements using grain emulsions.
can be increased. Especially for black and white photographic elements.
High aspect ratio tabular grain emulsion layers and other parent
aqueous colloid layers, the degree of swelling of those layers is 200%
can be hardened to a sufficient degree to reduce
Wear. Here, the degree of swelling (%) is: (a) when the photographic element is heated to 38°C;
Incubate for 3 days at 50% relative humidity.
(b) measure the layer thickness, and (c) evaporate the photographic element at 21°C.
Immersed in distilled water for 3 minutes, then (d) Change in layer thickness
It can be found by measuring . form a silver image
It is necessary to incorporate a hardening agent into the processing solution to harden photographic elements.
It is especially desirable for the wound to harden to the extent that it is unnecessary.
However, the degree of hardening of the emulsion according to the present invention is
may be at any level that is Furthermore, in the processing liquid
It is also possible to add a hardening agent to the
especially with regard to the processing of radiographic materials.
However, for example, Research Disclosure, Volume 184,
Listed in August 1979, Item 18431, Section K. Typical useful compound hardeners (pre-hardeners) are:
Research Disclosure, Volume 176, December 1978, Item 17643, Chapter. Research
Disclosure, Volume 176, December 1978, Item
17643, chapter 17643, by incorporating stabilizers, antifoggants, antikinks, latent image stabilizers, and similar additives into the emulsion and adjacent layers prior to coating. Density (ie, fog) can be increased or minimum density increased or maximum density reduced in direct positive emulsion coatings freed from instabilities. C.
EKMees, The Theory of the Photographic
Process, 2nd edition, Macmillan, 1954, 677~
As described on page 680, many of the antifoggants effective in emulsions can also be incorporated into developers and can be classified under a few general headings. If aldehyde type hardeners are used, the emulsion layer can be protected with common antifoggants. In addition to sensitizers, hardeners, and antifoggants and stabilizers, various other commonly used photographic additives may be present. The specific selection of additives to be used depends on the characteristics of the photographic field of application and can be easily made by one skilled in the art. Various useful additives are described in Research Disclosure , Vol. 176,
Listed in December 1978, item 17643. Fluorescent brighteners may be incorporated as described in entry 17643, chapter 1 of the same document. Also, as described in the same literature section, absorbing and scattering materials can be used in separate layers of emulsions and photographic elements according to the invention. Coating aids may also be present, as described in Chapter XI, and plasticizers and lubricants, as described in Chapter XII. An antistatic layer can be present as described in Chap. Methods for adding additives are described in Chap. Matting agents can be incorporated as described in Chap. If desired, developers and development modifiers can be formulated as described in Sections and XI. When a photographic element containing an emulsion according to the invention is used in the radiographic field, the emulsion layer and other layers of the radiographic element may be
It can be in any form specifically described in Disclosure item 18431. Emulsions of this invention as well as other conventional silver halide emulsion layers, interlayers, overcoats, and subbing layers, if present in the photographic element, are research
Disclosure, Volume 176, December 1978, Item 17643,
Can be coated and dried as described in Chap. The high aspect ratio tabular grain emulsions of this invention can be blended with each other or with commonly used emulsions to achieve the properties desired in a particular emulsion layer, according to established practices in the art. can be satisfied. For example, by blending multiple emulsions, the characteristic curve of a photographic element can be tailored to meet a given objective. Blending increases or decreases the maximum density achieved by exposure and processing, reduces or increases the minimum density, and adjusts the shape of the characteristic curve between toe and shoulder. be able to. For this purpose, the emulsion according to the present invention was prepared in the above-mentioned Research Disclosure , Vol. 176,
It can be blended with conventional silver halide emulsions such as those described in December 1978, Item 17643, Chapter. In its simplest form, a photographic element comprises a single silver halide emulsion layer containing a high aspect ratio tabular grain emulsion according to the invention and a photographic support. Of course, 2
The above silver halide emulsion layers as well as overcoats, subbing layers and interlayers can be included.
Instead of blending the emulsions as described above, a similar effect can be achieved by coating the emulsions to be blended as separate layers. It is well known in the photographic art to coat emulsion layers separately to obtain exposure latitude;
Zelikman and Levi, Making and Coating;
Photographic Emulsions, Focal Press, 1964
, pp. 234-238, US Patent No. 3,663,228 and British Patent No. 923,045. Additionally, it is well known in the photographic art that photographic speed can be increased by coating fast and slow silver halide emulsions in separate layers rather than blending them. Usually, the high-speed emulsion layer is coated closer to the exposure source than the lower-speed emulsion layer. This approach can be applied to the preparation of three or more stacked emulsion layers. Such a layer configuration can also be used in implementing the present invention. The layers of photographic elements can be coated onto a variety of supports. Typical photographic supports include polymeric films, wood fibers (e.g. paper), metal sheets and foils, glass and ceramic support elements;
These supports may be coated with one or more primer coatings to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, friction properties, antihalation properties and/or other properties of their surfaces. It can have layers. These supports are well known in the art and are described, for example, in Research Disclosure , Vol. 176;
December 1978, Item 17643, Chap. The emulsion layer or layers are usually, but not necessarily, coated as a continuous layer on a support having opposing planar major surfaces. The emulsion layer can be coated as a plurality of laterally displaced layer segments onto a flat support surface. When segmenting one or more emulsion layers, it is desirable to use a microcellular support. Useful microporous supports are described in PCT Publication No.
W080/01641 (published August 7, 1980; corresponds to Belgian Patent No. 881513 of August 1, 1980) and US Pat. No. 4,307,165. The size of the micropores can be 1 to 200 μm in width and 1000 μm or less in depth. Generally, in the field of normal black and white photography, especially when enlarging photographic images, the size of the micropores is preferably at least 4 μm wide and less than 200 μm deep;
The best size is approximately 10 to 100μ for both width and depth.
It is m. Photographic elements employing emulsions of this invention can be imagewise exposed by any conventional method. Regarding this, see Research Disclosure above.
See item 17643, chapter. The present invention
It is particularly useful when imagewise exposure is carried out using electromagnetic radiation in the spectral region where the spectral sensitizer present exhibits maximum absorption. If blue, green, red or infrared exposures are to be recorded in the photographic element, a spectral sensitizer is present which absorbs in the blue, green, red or infrared portion of the spectrum. In the field of whiteners, it is desirable to orthochromatically or panchromatically sensitize photographic elements to extend sensitivity within the visible spectrum. The radiation used for exposure produced by a laser can be either incoherent (random phase) or coherent (in phase). Ambient, high or low temperatures and/or normal, high pressure, including high or low intensity exposures, intermittent or continuous exposures, relatively short exposure times of minutes to milliseconds to microseconds, and solarization exposures. or image exposure at low pressure, as described in TH James's The Theory of
the Photographic Process, 4th edition,
Macmillan, 1977, Nos. 4, 6, 17, 18 and 23
can be used within the useful sensitivity range as determined by commonly used sensitometric techniques, as described in Chap. The photosensitive silver halide contained in the photographic element is prepared in the conventional manner by combining the silver halide with an aqueous alkaline medium in the presence of an alkaline medium or developer contained in the photographic element following exposure to light. It can therefore be processed to form a visible image. Once the silver image has been formed in the photographic element, it is common practice to fix the undeveloped silver halide. The high aspect ratio tabular grain emulsion of the present invention is particularly advantageous in that fixing can be completed in a shorter time. This allows accelerated processing. The photographic elements and techniques described above for producing silver images can be readily applied to producing color images using dyes. In perhaps the simplest technique for obtaining a projectable color image, conventional dyes can be incorporated into the support of the photographic element and silver image formation can be carried out as described above. In the areas where the silver image is formed, the photographic element becomes substantially opaque to light, and in other areas, corresponding to the color of the support, it transmits light. Color images can be easily formed in this way. This same effect can also be achieved by using a separate dye filter layer or an element with a dye filter element and a transparent support element. Silver halide photographic elements can be used to form dye images by selective destruction or formation of dyes. The photographic elements for forming the silver image described above are described in Research Disclosure , Volume 176, December 1978,
It can be used to form dye images by using a developer containing a dye image forming agent such as a color coupler as described in Item 17643, Section D. In such a form,
The developer includes a color developer (eg, an aromatic primary amine) that is capable of reacting (coupling) with the coupler in its oxidized form to form a dye image. Dye-forming couplers can also be incorporated into photographic elements according to conventional methods. Dye-forming couplers can be incorporated in different amounts to achieve different photographic effects. For example, GB 923,045 and GB 3,843,369 teach limiting the concentration of coupler with respect to silver coverage to a level lower than that normally used in fast and intermediate speed emulsion layers. The dye-forming couplers that are incorporated are usually selected to form subtractive primary (ie, yellow, magenta and cyan) image dyes, and these couplers are non-diffusive colorless couplers. Dye-forming couplers with different reaction rates in single or multiple separate layers can be used to achieve the desired effect in a particular photographic application. A dye-forming coupler, by coupling,
Photographic agents such as development inhibitors or accelerators, bleach accelerators, developers, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competitive couplers, chemical or spectral sensitizers and desensitizers. release useful fragments. Development inhibitor releasing (DIR) couplers are well known in the photographic art. They are non-dye-forming compounds and dye-forming couplers that release a variety of photographically useful groups upon coupling. DIR compounds that do not form dyes when reacted with oxidized color developers can also be used. Silver halide emulsions with relatively poor photosensitivity, such as Lippmann emulsions, were utilized as interlayers and overcoat layers to prevent or suppress migration of development inhibitor fragments. The photographic element may incorporate colored dye-forming couplers and/or competing couplers, such as colored dye-forming couplers used to form layered masks for negative color images. The photographic element may further include conventional image dye stabilizers. All of these are Research
Disclosure, Volume 176, December 1978, Item 17643,
described in the chapter. Forming or amplifying a dye image by employing a method using an oxidizing agent in the form of an inert reduced metal ion complex and/or a peroxide oxidizing agent in combination with a dye image-forming reducing agent. can do. The dye elements are particularly suited for forming dye images by such methods. Dye images can be formed in photographic elements by selective destruction of dyes or dye precursors, such as silver-dye-bleach techniques. Removal of developed silver by bleaching is a common practice in forming dye images in silver halide photographic elements. Removal of such silver can be facilitated by incorporating bleach accelerators or precursors thereof into the processing solutions or into certain layers of the photographic element. In some cases, especially when amplifying dye images as described above, the amount of silver formed by development is small compared to the amount of dye produced. Silver bleaching is therefore omitted without substantially visible effects. In still other applications, a silver image is retained and a dye image is utilized to enhance or supplement the density provided by the silver image. When increasing the density of a silver image with dyes, it is usually desirable to use a single neutral dye or a combination of dyes that can produce an overall neutral image. The present invention can be used to produce multicolor photographic images. In general, conventional multicolor image elements containing at least one silver halide emulsion layer may be improved by simply adding or replacing the high aspect ratio tabular grain emulsions defined herein. I can do it. The present invention is fully applicable to both additive and subtractive polychromatic images. To demonstrate the application of the present invention to additive multicolor images, a filter array including intervening blue, green, and red filter elements is used in combination with a photographic element capable of producing a statue. I can do it. The high aspect ratio tabular grain emulsion defined herein, which is panchromatically sensitized and constitutes one layer of the photographic element, is imagewise exposed through an array of added primary color filters. After processing to produce a silver image, a multicolored image is seen when viewed through the filter array. This image is best viewed by projection. Thus, both the photographic element and the filter array have both or a common transparent support. Significant advantages are also obtained when the present invention is applied to multicolor photographic elements that produce multicolor images through combinations of subtractive mixed primary color image dyes. Such photographic elements consist of a support and typically at least triad laminated silver halide emulsion layers, i.e., blue;
It consists of layers that separately record green and red exposures as yellow, magenta and cyan dye images, respectively. As mentioned above, although only one high aspect ratio tabular silver chloride emulsion is required, multicolor photographic elements contain at least three separate emulsions, each recording blue, green, and red light. Emulsions other than the required high aspect ratio tabular grain green or red recording emulsions can be of any conventionally commonly used form. Various common emulsions are listed in Research Disclosure , Item 17643,
As shown in Chap. If more than one emulsion layer is intended to record in the blue, green and/or red portions of the spectrum, at least the more sensitive emulsion layer may contain a high aspect ratio tabular grain emulsion as described above. It is preferable to include. of course,
It will be appreciated that it is preferred that all of the blue, green and red recording emulsions of the photographic element, if desired, be tabular grain emulsions as defined herein. Multicolor photographic elements are often referred to as color-forming layer units. The most common multicolor photographic elements contain three stacked color-forming layer units.
Each of these layer units contains at least one silver halide emulsion layer capable of recording exposures in three different spectra and producing complementary subtractive mixed primary color dye images. That is, blue, green, and red recording color-forming layer units are used to produce yellow, magenta, and cyan dye images, respectively. The dye image-forming material need not be present in each color-forming layer unit, but can be supplied entirely from the processing solution. When dye image-forming materials are incorporated into the photographic element, they can be located in emulsion layers or can accept oxidized developer or electron transfer agents from adjacent emulsion layers of the same color-forming layer unit. It can be located in layers arranged as follows. It is common practice to use scavengers to prevent migration of oxidized developer or electron transfer agents between color-forming layer units with color separation. Scavenger is a U.S. patent no.
2,937,086, and/or as an intermediate layer between adjacent color-forming layer units, as shown in U.S. Pat. No. 2,336,327. I can do it. Although each color-forming layer unit can include a single emulsion layer, two, three, or more emulsion layers of different photographic speeds can often be incorporated into a single color-forming layer unit. If the desired layer order does not allow multiple emulsion layers of different sensitivities to be included in a single color-forming layer unit, multiple (usually 2 or 3) blue, green and/or
Alternatively, it is common practice to include color-forming layer units for red recording in a single photographic element. The multilayer photographic element can take any convenient form consistent with the requirements noted above.
Gorokhovskii's Spectral Studies of the
Any of the six possible layer arrangements of Table 27a on page 211 of Photographic Process, Focal Press, New York, may be used. To produce a specific simple example, one or more high aspect ratio tabular structures are sensitized to the negative blue portion of the spectrum and positioned to receive exposure radiation prior to the remaining emulsion layers. A grain emulsion layer can be added to a typical multicolor silver halide photographic element during its manufacture. However, in the most common case, one or more negative blue recording high aspect ratio tabular grain emulsion layers are combined with a conventional negative blue recording emulsion layer, possibly with a change in the layer sequence. Preferably, they are combined and replaced. Some layer arrangements will be made clearer by means of preferred exemplary embodiments shown below. [Table] [Table] [Table] (where D, G, and R represent any common type of blue, green, and red recording color-forming layer unit, respectively; and the color-forming layer unit B , G, or R indicates one or more emulsion layers comprising a high aspect ratio tabular silver chloride grain emulsion as described in detail above, and color forming layer unit D, G, or F located before R indicates a color-forming layer unit whose photographic speed is faster than that of at least one other color-forming layer unit recording light exposures in the same 1/3 of the spectrum in the same layer sequence; , S located before a color-forming layer unit B, G, or R is the photographic sensitivity of at least one other color-forming layer unit that records light exposure of the same 1/3 of the spectrum in the same layer sequence. and IL indicates an interlayer containing a scavenger and substantially free of yellow filter material. Each fast or slow speed color forming layer. The unit has different color-forming layer units that record light exposures in the same third of the spectrum and, as a result of its position in the layer sequence, its inherent sensitivity characteristics, or a combination of these, in terms of photographic speed. (It may be different.) In the above layer arrangement order ~, the arrangement of the support is not shown. In accordance with common practice, the support is often located furthest away from the exposure radiation source. That is, it is generally located at the bottom of the layer. If the support is colorless and specular, ie transparent, the support can be positioned between the exposure source and the layer shown in the figure. More generally, the support can be positioned between the exposure source and any color-forming layer unit in which light transmitted by the support is intended to be recorded. Photographic emulsions intended to form multicolor images consisting of a combination of subtractive primary dyes generally take the form of a plurality of stacked layers containing a combination of dye-forming substances such as dye-forming couplers. is never necessary. The three color-forming components, commonly called packets, include a silver halide emulsion that records light in one-third of the visible spectrum and a coupler that can form complementary subtractive primary dyes. They can be placed together in layers to produce multicolored images. Examples of mixed packet multicolor photographic elements are shown in U.S. Pat.
Disclosed in No. 2843489. The high aspect ratio tabular silver halide grains defined herein are advantageous because they can reduce high angle light scattering compared to non-tabular, low aspect ratio tabular grain emulsions. This can be shown quantitatively. As shown in Figure 4,
A sample of Emulsion 1 as defined herein is coated onto a transparent (specular) support 3 at a coverage of 1.08 g/m ² . Although not shown, the emulsion and support are preferably immersed in a liquid having an index of refraction that is substantially matched to minimize Fresnel reflections at the surfaces of the support and emulsion. The emulsion coating is exposed perpendicular to the support surface by a collimated light source 5. Light from the light source following the optical path indicated by dash line 7, forming the optical axis, strikes the emulsion coating at point A. The light passing through the support and emulsion can be detected at a semicircular sensing surface 9 at a fixed distance from the emulsion. At the intersection B of the first optical path extension and the sensing surface, the maximum intensity level of light is detected. Point C in FIG. 4 is an arbitrary point selected on the sensing surface. The dart line between A and C makes an angle φ with the emulsion coverage. By moving point C on the sensing surface, this angle φ can be varied in the range 0° to 90°. By measuring the intensity of the scattered light as a function of the angle φ, the cumulative light distribution can be determined as a function of the angle φ (due to the rotational symmetry of the light scattering about the optical axis 7). For a description of cumulative light distribution, see Depalma and Gasper, “Determining the Optical Properties of
Photographic Emulsions by the Monte Carlo
Method” ( Photographic Science and
Engineering, Volume 16, Issue 3, May-June 1971,
181-191). The cumulative light distribution is set at an angle φ of 0° to 90° with respect to emulsion 1.
After measuring as a function of , the same measurements are repeated for a typical emulsion with the same average grain volume coated with the same silver coverage on another part of the support 3.
Comparing the cumulative light distribution obtained as a function of the angle φ for the two emulsions up to φ 70° (up to 80° and above in some cases), it is found that the emulsion specified here has a lower amount of scattered light. I understand that. In FIG. 4, the angle θ is the supplementary angle of the angle φ. In this specification, the scattering angle will be explained in terms of angle θ.
That is, high aspect ratio tabular grain emulsions exhibit less high angle scattering. Since high angle scattering of light inversely reduces image sharpness, the high aspect ratio tabular grain emulsions defined herein will produce sharper images in any case. As defined herein, the term "collection angle" means that half of the light striking the sensing surface is within the area relative to the cone created by the rotation of line AC around the polar axis at angle θ. It refers to the value of the angle θ such that half of the light hitting the sensing surface hits the remaining part of the sensing surface. The theory for reducing the high angle scattering properties of high aspect ratio tabular grain emulsions as defined herein is
Although it is not intended to specifically limit the present invention to this theory,
The improvement in sharpness is believed to be due to the large flat major crystal faces provided by the high aspect ratio tabular grains as well as the arrangement of the grains in the coating. In particular, it has been observed that the tabular grains present in the silver halide emulsion coating are substantially parallel to the planar support surface on which they reside. That is, light perpendicular to the photographic element that falls on the emulsion layer is
They tend to impinge on tabular grains substantially perpendicular to one major crystal plane. Due to the thinness of the tabular grains and their placement during coating, high aspect ratio tabular grain emulsion layers can be substantially thinner than conventional emulsion layers, which also enhances sharpness. However, tabular grain emulsion layers exhibit high sharpness even when coated to the same thickness as conventional conventional emulsion layers. In particularly preferred forms of the invention, the high aspect ratio tabular grain emulsion layers are at least 1.0 μm thick;
Most preferably it exhibits a minimum average particle diameter of at least 2 μm. Both improved sensitivity and improved sharpness are obtained due to the increased average particle diameter. Although the maximum average grain diameter useful will vary depending on the grain size acceptable for the particular imaging application, the maximum average grain diameter for the high aspect ratio tabular grain emulsions specified herein is in all cases 30 μm. less than 15μm, preferably less than 10μm
m or less. Although single layer coatings of high aspect ratio tabular grain emulsions as defined herein can reduce high angle scattering, this phenomenon of high angle scattering does not necessarily need to be realized in polychromatic coatings. In some multicolor coating types, high sharpness can be achieved with the high aspect ratio tabular grain emulsions specified herein, while in other multicolor coating types, high sharpness can be achieved with the high aspect ratio tabular grain emulsions specified herein. Tabular grain emulsions can substantially reduce the sharpness of the emulsion layers stacked below them. Referring to the layer arrangement described above, the blue recording emulsion layer is located closest to the exposure radiation source, and the green recording emulsion layer below is the tabular grain emulsion as defined herein. This green recording emulsion layer then overlies the red recording emulsion layer. If the blue recording emulsion layer has average diameter grains in the range of 0.2 to 0.6 μm, as is typical in many non-tabular emulsions, the blue recording emulsion layer will cause light passing through it to have green and red recording properties. It will exhibit maximum scattering as it reaches the emulsion layer. Unfortunately, if the light has already been scattered before it reaches the green recording emulsion layer of a high aspect ratio tabular grain emulsion, the tabular grains will absorb the light passing through them into the typical conventional It scatters into the blue recording emulsion layer at a larger proportion than the blue emulsion.
Thus, by special selection of emulsions and arrangement of layers, the sharpness of the red recording emulsion layer can be improved to a greater extent than if the emulsions specified herein were not present in said layer sequence. significantly lower it. In order to fully realize the sharpness characteristics of the emulsion layer located below the high aspect ratio tabular silver chloride grain emulsion layer defined herein, the tabular grain emulsion layer must be able to absorb less scattered light. It is preferably positioned to receive (preferably substantially specularly transmitted) light. Stated differently, improving the sharpness of an emulsion layer located below a tabular grain emulsion layer is best achieved only when the tabular grain emulsion layer is not located below a turbid layer. I can do it. For example, if a high aspect ratio tabular grain green recording emulsion layer is located above a red recording emulsion layer and above a Lippmann emulsion layer and/or a high aspect ratio tabular grain blue recording emulsion layer, then The sharpness of the red recording emulsion layer may be improved by the presence of the overlying tabular grain emulsion layer(s). Quantitatively, sharpness of the red recording emulsion layer is improved if the collection angle of the layer or layers overlying the high aspect ratio tabular grain green recording emulsion layer is less than about 10°. can do. Of course, if the red recording emulsion layer itself is a high aspect ratio tabular grain emulsion layer as defined herein, there is no problem as far as the effect of the overlying layer on its sharpness is concerned. To obtain sharpness benefits in multicolor photographic elements containing laminated color-forming units,
Preferably, the emulsion layer located closest to the exposure radiation source is at least a high aspect ratio tabular grain emulsion. In a particularly preferred form, each emulsion layer located closer to the exposing radiation source than another image-recording emulsion layer is a high aspect ratio tabular grain emulsion layer. The above layer arrangement order...
and are examples of multicolor photographic element emulsion arrangements that can significantly increase the sharpness of underlying emulsion layers. The characteristic contribution of image sharpness in multicolor photographic elements of high aspect ratio tabular silver chloride grain emulsions has been specifically described for multicolor photographic elements, and this sharpness characteristic is due to the multilayer black-and-white structure that produces the silver image. It can also be embodied in photographic elements. It is common practice to separate emulsions forming black and white images into high-speed and low-speed layers. The use of high aspect ratio tabular grain emulsions as defined herein in the layer located closest to the exposure radiation source improves the sharpness of the underlying emulsion layer. EXAMPLES The present invention will be further explained according to the following examples.
In each example, the contents of the reaction vessel were vigorously stirred during the introduction of the silver and halide salts. Also,"%"
indicates weight percent unless otherwise indicated, "M" indicates molar concentration unless otherwise indicated, and all solutions are aqueous unless otherwise indicated. Emulsions 1-3 These emulsions demonstrate that the use of a thioether bond-containing peptizer is essential in order to obtain the high aspect ratio tabular grain emulsions defined herein. Emulsion 1 (Control) (AgCl, no peptizer) 0.4 of a 1.00 molar aqueous lithium chloride solution (solution A) containing ammonium nitrate (0.12 molar) and adenine (0.0135 molar) was prepared at 70°C and PH 3.0. An aqueous silver nitrate solution (7.0 molar concentration, solution C) was added to solution A maintained at the initial chloride ion concentration.
and an aqueous solution (solution B) of lithium chloride (9.0 molar), ammonium sulfate (0.25 molar) and adenine (0.027 molar) at a constant rate for 1 minute (consuming 1.1% of the total silver nitrate) by double jetting.
Added. While maintaining the initial chloride ion concentration, solutions B and C were run at an accelerated flow rate (20 times from start to finish, i.e., the flow rate at the end was 20 times faster than the flow rate at the start) by a double jet. Addition took 9 minutes (consumed 98.9% of total silver nitrate). A total of 0.67 moles of silver nitrate were consumed during precipitation. An aqueous lithium hydroxide solution (1.0 molar concentration, solution D) was used to maintain pH 3.0 at 70°C. Emulsion 2 (control) (AgCl99.8Br0.2 gelatin) An aqueous bone gelatin solution (1.5 molar) containing calcium chloride (0.50 molar), ammonium nitrate (0.25 molar), sodium bromide (0.0025 molar) and adenine (0.0185 molar). %gelatin,
Solution A) 0.4 was prepared at PH3.0 and 70°C. An aqueous solution of silver nitrate (7.0 molar, solution C) and an aqueous solution of calcium chloride (4.49 molar) containing ammonium nitrate (0.50 molar) (solution B) were added to solution A, maintained at the initial chloride ion concentration. Addition was made over 12 minutes at an accelerated flow rate (2x from start to finish) via a heavy jet. PH 3.0
Sodium hydroxide was used to maintain the temperature.
During precipitation formation, 0.50 mol of silver nitrate was consumed. Emulsion 3 [AgCl99.8Br0.2, gelatin-peptizer TA/APSA (2:1)] Poly(3-thiapentyl acrylate-co-3)
-acryloxypropane-1-sulfonic acid, sodium salt) [0.75% polymer of TA/APSA (1:6 molar ratio)], adenine (0.0185 molar concentration), ammonium nitrate (0.25 molar concentration), sodium bromide (0.0025 molar concentration) An aqueous bone gelatin solution (1.5% gelatin, solution A) containing 0.4 molar concentration) and calcium chloride (0.50 molar concentration) was prepared at pH 3.0 and 70°C.
Emulsion 3 was prepared by adding Solutions B, C and D identical to Emulsion 2 to Example 2 in the same manner. A 0.50 molar amount of silver nitrate was consumed during precipitation formation. Figures 5, 6 and 7 are micrographs of Emulsion 1 (control), Emulsion 2 (control) and Emulsion 3. The magnification of FIG. 5 is 1500 times, while the magnification of both FIGS. 6 and 7 is 600 times. Emulsion 3 contains tabular grains, whereas Emulsion 1 and Emulsion 2 only exhibit the formation of blurred non-tabular grains. If Emulsions 1, 2, and 3 are considered together, the importance of using a peptizer containing thioether linkages will be appreciated in order to obtain the high aspect ratio tabular grain emulsions defined herein. The grain characteristics of Emulsion 3 are shown in more detail in Table 1 below. Except as otherwise noted, in calculating the average tabular grain diameter and percent projected area of the emulsions in these and the following examples, the diameter
Although some tabular grains less than 0.6 μm were included,
The presence of insufficient small diameter particles did not significantly shift the reported numbers. Emulsion 4 (AgCl99.7Br0.3, Peptizer TA/
APSA, Single Jet) This example describes the preparation of the emulsion defined herein by a single jet precipitation process. An aqueous solution (1.25%) of TA/APSA (1:6 molar ratio) containing calcium chloride (1.62 molar), ammonium nitrate (0.25 molar), adenine (0.015 molar) and sodium bromide (0.005 molar).
Polymer, solution A) 0.4 was prepared at PH 3.0 and 70°C. Silver nitrate aqueous solution (7.0 molar concentration, solution B),
While maintaining the initial chloride ion concentration, solution A
at a constant speed for 1 minute (consuming 1.1% of total silver nitrate)
was added using a single jet. Solution B was then introduced at an accelerated flow rate (20 times from start to finish).
and solution B was added until consumed. An aqueous sodium hydroxide solution (1.0 molar concentration, solution C) was used to maintain pH 3.0. The amount of silver nitrate used to prepare this emulsion was 0.67 mole. The properties of the high aspect ratio tabular grain emulsion defined herein prepared with this emulsion are shown in Table 1. Emulsion 5 (AgCl99Br1, Peptizer TA/APSA,
Constant Flow Rate) This example describes the use of constant flow rate precipitation to prepare the high aspect ratio tabular grain emulsions defined herein. Aqueous solution of TA/APSA (1:6 molar ratio) containing calcium chloride dihydrate (0.50 molar), adenine (0.026 molar) and sodium bromide (0.013 molar) (0.625% polymer, solution A) 0.4
was prepared at PH2.6 and 55°C. Calcium chloride aqueous solution (3.0 molar concentration, solution B) and silver nitrate aqueous solution (2.0 molar concentration, solution C) were added at a constant rate to solution A, which maintained the initial chloride ion concentration, using a double jet over 1 minute. . Aqueous sodium hydroxide solution (0.2 molar,
Solution D) was used. The amount of silver nitrate used to prepare this emulsion was 0.50 moles. The grain characteristics of the obtained emulsion are shown in Table 1. Emulsion 6 (AgCl, Peptizer TA/APSA, LiCl
Salt) This example shows the results of using lithium chloride instead of calcium chloride. Lithium chloride (1.00 molar), adenine (0.0135 molar) and ammonium nitrate (0.12
TA/APSA (1:6 molar ratio)
Aqueous solution (1.32% polymer, solution A) 0.4 PH3.0
and prepared at 70°C. Solutions B, C and D, identical to those mentioned in Emulsion 1, were prepared and added as in Emulsion 1. The amount of silver chloride used to prepare this emulsion was 0.67 mole. The grain characteristics of the obtained emulsion are shown in Table 1. Emulsion 7 (AgCl99Br1, Peptizer TA/APSA) This example demonstrates the use of lower reactor temperatures and chloride concentrations to produce the high aspect ratio tabular grain emulsions defined herein. TA/APSA (1:6 molar ratio) aqueous solution (0.63% polymer, solution A) containing adenine (0.026 molar), calcium chloride (0.44 molar), ammonium nitrate (0.25 molar) and sodium bromide (0.013 molar) ) 0.4 was prepared at PH2.6 and 55°C. Solution A retaining the initial chloride ion concentration
, a calcium chloride aqueous solution (3.5 molar concentration, solution B) and a silver nitrate aqueous solution (2.0 molar concentration, solution C)
was added using a double jet at a constant flow rate for 1 minute (consuming 0.8% of the total silver nitrate). After the first minute, solutions B and C were added using a double jet at the same accelerated flow rate profile (4 times start to finish) over approximately 11 minutes (22.0% of the total silver nitrate consumed). However, the flow rate of solution B was half that of solution C. After an 11 minute accelerated flow rate addition period, solutions B and C
was added at a constant flow rate for 19 minutes. The flow rate of solution B was half that of solution C (77.2% of the total silver nitrate consumed). An aqueous sodium hydroxide solution (1.0 molar concentration, solution D) was used to maintain pH 2.6. The initial chloride ion concentration was maintained during precipitation. The amount of silver nitrate used to prepare this emulsion was 0.50
It was mole. Table 1 shows the grain characteristics of the emulsions produced. In addition, micrographs of the prepared emulsions (magnification
600x) is shown in Figure 8. Emulsion 8 (AgCl, peptizer TA/APSA, no NH ₄ ⁺ or Br ^- present in the reaction vessel) This example produces the high aspect ratio specified here without the inclusion of either ammonium or bromide ions in the reaction vessel. An example of preparing a tabular grain emulsion with a ratio of TA/APSA (1:6 molar ratio) aqueous solution (0.63% polymer, solution A) containing adenine (0.026 molar concentration) and calcium chloride (0.44 molar concentration) 0.4
was prepared at PH2.6 and 55°C. An aqueous solution of calcium chloride (3.0 molar concentration) containing sodium hydroxide (0.014 molar concentration) (solution B) and an aqueous solution of silver nitrate (4.0 molar concentration, solution C) were added to solution A, which maintained the initial chloride ion concentration. A heavy jet was used at a constant flow rate for 1 minute (consuming 1.6% of the total silver). After the first minute, solutions B and C were run at an accelerated flow rate (4x from start to finish) using a double jet for 11 minutes (44.0% of total silver nitrate) while maintaining the initial chloride ion concentration. % consumed) added. After this 11 minute accelerated flow period, solutions B and C
at a constant flow rate for 6.5 minutes (consuming 54.4% of total silver nitrate)
I added it. The amount of silver nitrate used to prepare this emulsion is
It was 0.50 mol. The grain characteristics of the prepared emulsions are shown in Table 1. Emulsion 9 (AgCl, Peptizer TA/APSA, 85°C) This example demonstrates the production of the high aspect ratio tabular grain emulsion described herein at a precipitation temperature of 85°C. TA/APSA (1:6 molar ratio) aqueous solution (1.25% polymer, solution A) containing calcium chloride (0.50 molar concentration), adenine (0.026 molar concentration) and ammonium nitrate (0.25 molar concentration) 0.4 at PH 3.0 and 85 °C Prepared with An aqueous solution of calcium chloride (4.5 molar concentration) containing ammonium nitrate (0.50 molar concentration) (solution B), an aqueous solution of silver nitrate (7.0 molar concentration,
Solution C) and an aqueous lithium hydroxide solution (1.0 molar, solution D) were prepared and added to solution A, maintaining the initial chloride ion concentration, in the same manner as in the preparation of emulsion 1. The amount of silver nitrate used to prepare this emulsion was 0.67 mole. The grain characteristics of the prepared emulsions are shown in Table 1. A micrograph (600x) of the prepared emulsion is shown in FIG. Emulsion 10 (AgCl99Br1, Peptizer TA/APSA) This example demonstrates the unique tabular crystal structure that can be produced by the practice of this invention. TA/APSA (1:6 molar ratio) aqueous solution (0.63% polymer, solution A) containing adenine (0.026 molar), calcium chloride (0.50 molar), ammonium nitrate (0.25 molar) and sodium bromide (0.013 molar) ) 2.0 was prepared at PH2.6 and 55°C. Solution A retaining the initial chloride ion concentration
, calcium chloride aqueous solution (3.0 molar concentration, solution B) and silver nitrate aqueous solution (4.0 molar concentration, solution C)
was added using a double jet at a constant flow rate for 1 minute (consuming 1.6% of the total silver nitrate). After the first minute of constant flow addition, solutions B and C were added at an accelerated flow rate (4x from start to finish) while maintaining the initial chloride ion concentration.
was added for 11 minutes (consuming 44.0% of the total silver nitrate). After this 11 minute accelerated flow rate addition period, solutions B and C were applied at a constant flow rate for approximately 9 minutes (consuming 54.4% of the total silver nitrate) while maintaining the initial chloride ion concentration.
I added it. Aqueous sodium hydroxide solution (1.0 molar, solution D) was used to maintain a pH of 2.6. The amount of silver nitrate used to prepare this emulsion was 2.5 moles. The grain characteristics of the emulsion prepared in this way were
Shown in the table. Further, a micrograph (600 times magnification) of the emulsion thus prepared is shown in FIG. 10a. 1st
Figures 0b and 10c show the sample of emulsion 10 directly above (0° inclination) and at an angle (inclination), respectively.
This is an electron micrograph taken at an angle of 60°. Chapter 10b
The magnification of the figures and Figure 10c is 10000x. To compare the crystal structure of the high aspect ratio tabular grains of Emulsion 10 with conventional conventional emulsions containing high aspect ratio tabular grains, grains from a high aspect ratio tabular silver bromide grain emulsion were Used as a control. It has been generally accepted that tabular silver bromide grains are completely surrounded by (111) crystal planes. Tabular silver bromide grains tested for comparison were cooled to the temperature of liquid nitrogen and placed in an electron microscope operating at 100 KV. The electron beam penetrating the tabular silver bromide grains was diffracted by the crystal planes. 10d
Six spots are clearly visible around the central ring in the figure, equidistant from the central beam position. These spots are reflections from the (220) crystal plane. (A second outer ring of the spot is also visible, but these are reflections from another crystal plane and are of no direct interest.) Relationship between the generated electron beam diffraction spot pattern and the crystal edge structure To illustrate, electron micrographs of the test particles are shown oriented at suitable angles on the electron beam diffraction pattern. (The proper angular configuration was confirmed by using an asymmetric crystal with known diffraction properties for calibration purposes.) From the materials making up Figure 10d, the 6 It can be seen that the innermost reflective spots lie in the line between the central electron beam and the apex of the hexagon defined by the tabular silver bromide grains. Figure 10e shows an emulsion instead of the grains in Figure 10d.
It was obtained in the same manner using the tabular grains obtained from No. 10. It is observed that the inner ring of six spots equidistant from the central electron beam position does not lie in a line between the central beam position and the apex of the hexagonal tabular grain. Looking at particle edges,
The diffraction pattern from the (220) crystal plane appears to be rotated by 30° compared to the diffraction pattern seen in Figure 10d. This is evidence of the unique crystal orientation of the tabular grains defined here. 10th
In figure e, <211> located on the plane of the main surface
The spectrum (not shown) is perpendicular to the intersection line connecting adjacent points of the six diffraction spots. In each case, the <211> spectrum extends from a central spot on the particle to the apex and is parallel to one of the crystal planes. In this way, the first
The six crystal faces of tabular grains as shown in the Oe diagram are <
211> parallel to the crystal vector. From this and other similarly tested emulsion samples, it appears that the tabular grains of Emulsions 4-9 all exhibit similar crystal structures. Emulsion 11 (AgCl99Bl, peptizer TPMA/AA/
MOES) This example shows how to prepare the emulsion specified herein by changing the thioether bond-containing peptizer. This example further demonstrates responsiveness to spectral sensitization. Poly(3-thiapentyl methacrylate co-
Acrylic acid-co-2-methacryloyloxy-ethyl-1-sulfonic acid, sodium salt)
(TPMA/AA/MOES, 1:2:7 molar ratio),
An aqueous solution (0.63% polymer, solution A) containing calcium chloride (0.50 molar), adenine (0.026 molar), and sodium bromide (0.013 molar) 2.0 was prepared at PH 2.6 and 55°C. Add calcium chloride aqueous solution (2.0 molar concentration, solution B) and silver nitrate aqueous solution (2.0 molar concentration, solution C) to solution A, which maintains the initial chloride ion concentration, at a constant flow rate for 1 minute (total silver nitrate concentration) using a double jet. (consumed 1.2% of the amount). After an initial 1 min constant flow period, solutions B and C were run for 53 min at an accelerated flow rate (2.3x from start to finish) using a double jet while maintaining the initial chloride ion concentration. Total silver nitrate 98.8
% consumed). Aqueous sodium hydroxide solution (0.2 molar, solution D) was used to maintain the pH at 2.6. The amount of silver nitrate used in preparing this emulsion was 2.5 moles. The resulting emulsion was separated from most of the soluble salts using a hydrocyclone washing method, after which gelatin was added. The grain characteristics of the obtained emulsion are shown in Table 1. Furthermore, a microscopic photograph (magnification: 600 times) of the emulsion is shown in FIG. An unsensitized sample of Emulsion 11 was coated on a cellulose triacetate support at a coverage of 1.07 g silver/m ² and 3.58 g gelatin/m ² . The coated element contained 1.07 g/ ^m2 of magenta coupler, 1-(6-chloro-2,4-
It contained dimethylphenyl)-3-[α-(m-pentadecylphenoxy)butyramide]-5-pyrazolone. The coating was exposed to a Horton® spectrograph for 4 seconds and processed in p-phenylenediamine color developer for 2 minutes at 33.4°C. Before coating, the emulsion was mixed with 0.25 mmol/mol Ag5−
(3-ethyl-2-benzothiazolinylidene)-3
-β-sulfoethylrhodanine and 0.5% KBr/
The second sample was coated in the same manner as the first, except that it was spectrally sensitized in the blue region with Mole Ag. Before coating, the emulsion was mixed with 0.25 mmol/mol Ag anhydro-5-chloro-9-ethyl-5'-phenyl-3,3'-diethyloxacarbocyanine hydroxide, p-toluenesulfonate and 0.5%
A third sample was coated similarly to the first except that it was spectrally sensitized in the green region with KBr/mol Ag. In Figure 11a, these three samples
The log sensitivity was plotted as a function of exposure irradiation wavelength. Curves 11a, 11b and 11c correspond to the first, second and third samples, respectively. These curves show the effect of expanding the sensitive wavelength range by spectral sensitization. Emulsion 12 (AgCl94Br6, Peptizer TA/APSA) This example illustrates the preparation of the emulsion defined herein using a higher proportion of bromine than in the previous examples. TA/APSA (1:6 molar ratio) aqueous solution (0.63%) containing calcium chloride (0.50 molar), adenine (0.026 molar), ammonium nitrate (0.25 molar) and sodium bromide (0.013 molar)
Polymer, solution A) 0.4 was prepared at PH 2.6 and 55°C. Solution B (3.00 molar calcium chloride, 0.18 molar sodium bromide) and solution C (4.0 molar silver nitrate) were added in the same manner as in Emulsion 8. Solution D to maintain pH at 2.6 at 55℃
(NaOH 1.0 molar concentration) was added. The concentration of silver nitrate used to prepare this emulsion was 0.50 molar. The grain characteristics of the prepared emulsions are shown in Table 1. Emulsion 13 (AgCl89Br11, Peptizer TPMA/
AA/MOES) This example illustrates the preparation of the emulsion defined herein using a higher proportion of bromine than in the previous example. TPMA/AA/MOES containing calcium chloride dihydrate (0.50 molar), adenine (0.026 molar) and sodium bromide (0.013 molar)
(1:1:7 molar ratio) aqueous solution (0.63% polymer,
Solution A) 0.4 was prepared at PH 2.6 and 55°C. An aqueous solution of calcium chloride (2.0 molar) containing potassium bromide (0.20 molar) (solution B) is added to solution A, which maintains the initial chloride ion concentration during total precipitation.
and an aqueous silver nitrate solution (2.0 molar concentration, solution C) were added using a double jet at a constant flow rate over 1 minute (consuming 1.6% of the total silver nitrate). After this first minute of constant flow rate addition, solutions B and C were added at an accelerated flow rate (from start to finish).
1.75 times) using a double jet in 49 minutes (consuming 98.4% of the total silver nitrate). Aqueous sodium hydroxide solution (0.20 molar, solution D) was used to maintain the pH at 2.6. The amount of silver nitrate used to prepare this emulsion was 0.50 mole. The grain characteristics of the prepared emulsions are shown in Table 1 below. A micrograph (magnification: 600 times) of this emulsion is shown in FIG. Individual tabular grains were analyzed for bromine using an energy dispersive X-ray analysis scanning transmission electron microscope along with appropriate standards. Analysis results showed that the tabular grains contained bromine at a concentration of 11 mole percent. Emulsions 14-17 These emulsions illustrate varying the ratio of thioether linkage-containing monomer units to sulfonic acid-containing monomer units to form the polymeric peptizer. Emulsion 14 [AgCl99Br1, peptizer TPMA/
MOES (1:9) poly(3-thiapentyl methacrylate co-co-containing adenine (0.026 molar), calcium chloride (0.50 molar), ammonium nitrate (0.25 molar) and sodium bromide (0.013 molar). 2-methacryloyloxyethyl-1-sulfonic acid, sodium salt) (TPMA/MOES, 1:9
molar ratio) aqueous solution (0.63% polymer, solution A) 0.4
was prepared at PH2.6 and 55°C. Aqueous solutions of calcium chloride (3.0 molar, solution B) and silver nitrate (4.0 molar, solution C) were added to solution A, maintaining the initial chloride ion concentration throughout the entire precipitation period, at a constant flow rate using a double jet. for 1 minute (consuming 1.6% of the total silver nitrate). After the first minute of constant flow addition, solutions B and C were added at an accelerated flow rate (4
times) for 11 minutes (consuming 44.0% of the total silver nitrate). After an 11 minute accelerated flow rate addition period, solutions B and C
at a constant flow rate for 9 minutes (consuming 54.4% of total silver nitrate)
I added it. Aqueous sodium hydroxide solution (1.06 molar, solution D) was used to maintain the pH at 2.6. Silver nitrate was used at 0.50 mole in preparing this emulsion. Emulsion 15 [AgCl99Br1, peptizer TPMA/
MOES (1:12)] The emulsion was prepared according to the precipitation method described for Emulsion 14, except that the monomer ratio TPMA/MOES was 1:12.
15 was prepared. Emulsion 16 [AgCl99Br1, peptizer TPMA/
MOES (1:15)] The emulsion was prepared according to the precipitation method described for Emulsion 14, except that the monomer ratio TPMA/MOES was 1:15.
16 was prepared. Emulsion 17 [AgCl99Br1, peptizer TPMA/
MOES (1:18)] The emulsion was prepared according to the precipitation method described for Emulsion 14, except that the monomer ratio TPMA/MOES was 1:18.
17 was prepared. The grain characteristics of Emulsions 14-17 are shown in Table 1 below. A micrograph (600x magnification) of Emulsion 15 is shown in FIG. Emulsions 18-20 These emulsions demonstrate variations in the use of polymers containing thioether linkages as peptizers in the preparation of the tabular grain emulsions defined herein. Emulsion 18 (AgCl, Peptizer TAA/APSA) Poly(N-3-thiapentylacrylamide-co-3-acryloyloxypropane) containing calcium chloride (0.50 molar), adenine (0.026 molar) and ammonium nitrate (0.25 molar) -1-sulfonic acid, sodium salt) (TAA/
APSA, 1:9 molar ratio) aqueous solution (1.25% polymer, solution A) 0.4 was prepared at PH 3.0 and 80°C.
While maintaining the initial chloride ion concentration, solution A
Aqueous solution B (calcium chloride 4.5 molar, ammonium nitrate 0.50 molar), aqueous solution C (silver nitrate 7.0 molar) and aqueous solution D (sodium hydroxide 1.0 molar) were added to the emulsion 1 in the same manner as described for emulsion 1. The amount of silver nitrate used to prepare this emulsion was 0.67 mole. Emulsion 18 was prepared following the precipitation method described for Emulsion 1, except that precipitation was carried out at 80°C. Emulsion 19 (AgCl, Peptizer TA/AA/APSA) Poly(3-thiapentyl acrylate-co-acrylic acid-co- 3-acryloyloxypropane-1-sulfonic acid, sodium salt)
(TA/AA/APSA, 1:2:11 molar ratio) aqueous solution (1.25% polymer, solution A) 0.4 at PH3.0 and 80℃
Prepared with Solution B (4.50 molar calcium chloride, 0.50 molar ammonium nitrate), solution C
(7.0 molar silver nitrate) and solution D (1.0 molar sodium hydroxide) were added to solution A in the same manner as described for emulsion 1, maintaining the initial chloride ion concentration throughout. The amount of silver nitrate used to prepare this solution was 0.67 mole. Emulsion 19 was prepared following the precipitation method described for Emulsion 1, except that precipitation was carried out at 80°C. Emulsion 20 (AgCl, peptizer TBAA/AA/
APSA) Poly(N-3-thiabutylacrylamide-co-acrylic acid-co-3-acryloyloxypropane-1-sulfonic acid, sodium salt) (molar ratio 1:2:7) in place of TA/AA/APSA Emulsion 20 was prepared according to the method described for Emulsion 19, except that Emulsion 19 was used in Example 1. The grain characteristics of Emulsions 18-20 are shown in Table 1. Micrographs (600x magnification) of Emulsions 18 and 20 are shown in Figures 14 and 15, respectively. Emulsion 21 (AgCl99Br1, peptizer TPMA/
AA/MOES) This example shows a relatively large tabular grain emulsion as defined herein with a high percentage of tabular grains. TPMA/AA/MOES with calcium chloride (0.50 molar) and adenine (0.026 molar)
(1:2:9 molar ratio) aqueous solution (0.63% polymer,
Solution A) 2.0 was prepared at PH 2.6 and 55°C. A calcium chloride aqueous solution (2.0 molar concentration,
Solution B) and an aqueous silver nitrate solution (2.0 molar, solution C) were added using a double jet at a constant flow rate over 1 minute (consuming 1.2% of the total silver nitrate). After the first minute of constant flow addition, solutions B and C were added at an accelerated flow rate (2.3
(Zengin's 98.8
% consumed). Aqueous sodium hydroxide solution (0.20 molar, solution D) was used to maintain a pH of 2.6. The amount of silver nitrate used to prepare this emulsion was 2.5 moles. The grain characteristics of Emulsion 21 are shown in Table 1.
A micrograph (magnification: 600 times) of this emulsion is shown in FIG. Emulsion 22 (blue spectral sensitization) This example shows the emulsion when sensitized with a blue spectral sensitizing dye.
The photographic sensitivity of the emulsion defined here is shown. TA/APSA (1:6 molar ratio) aqueous solution (0.63% polymer, solution A) containing calcium chloride (0.50 molar concentration), adenine (0.026 molar concentration) and sodium bromide (0.013 molar concentration) 0.4 at pH 2.6 and Prepared at 55°C. Add calcium chloride aqueous solution (3.0 mol, solution B) and silver nitrate aqueous solution (4.0 mol, solution C) to solution A, which maintains the initial chloride ion concentration, for 1 minute at a constant flow rate using a double jet (1.6 mol of total silver nitrate). % consumed). After an initial 1 minute constant flow rate addition, solutions B and C were added at an accelerated flow rate (4 times start to finish) using a double jet for 11 minutes (44.0% of total silver nitrate).
% consumed). After an accelerated flow period of 11 minutes, solutions B and C were flowed at a constant flow rate for approximately 10 minutes (consuming 54.4% of the total silver nitrate).
I added it. Aqueous sodium hydroxide solution (0.2 molar, solution D) was used to maintain the pH at 2.6 at 55°C.
The amount of silver nitrate used to prepare this emulsion is
It was 0.50 mol. The emulsion was cooled to 23°C, added to distilled water from step 5, allowed to stand, decanted, and then
Resuspended in 300 g of aqueous bone gelatin (3% gelatin). The emulsion was spectrally sensitized by the addition of 0.25 mmol 5-(3-ethyl-2-benzothiazolinylidene)-3-β-sulfoethylrhodanine/mol Ag and 0.5% KBr/mol Ag. Ta. This spectrally sensitized emulsion was deposited on a cellulose triacetate support at 1.07 g silver/m ² and 3.58 g gelatin/m ^{2 .}
It was coated with a coating amount of . This covering element is also 1.07
g/m ² magenta coupler, 1-(6-chloro-2,
Also contains 4-dimethyl-phenyl)-3-[α-(m-pentadecylphenoxy)butyramide]-5-pyrazolone, and based on the total gelatin content.
Cured with 1.1% by weight bis(vinylsulfonylmethyl)ether. Next, apply this coating to 0 to 4.0
600W and 2850 through the concentration step tablet
The sample was exposed to a tungsten light source for 2 seconds. p-
2 at 33.4°C in phenylenediamine color developer.
The following sensitometric values were obtained. Spectral sensitization contrast fog maximum density Dye + KBr 1.44 0.20 2.05 The grain characteristics of Emulsion 21 are shown in Table 1.
A micrograph (magnification: 600 times) of this emulsion is shown in FIG. Emulsion 23 (Coefficient of Variation) This example illustrates the production of a relatively monodisperse emulsion as defined herein with a coefficient of variation of approximately 20. TA/APSA (1:6 molar ratio) aqueous solution (0.63% polymer, solution A) containing calcium chloride (0.66 molar concentration), adenine (0.026 molar concentration) and sodium bromide (0.013 molar concentration) 0.4 at pH 2.6 and Prepared at 55°C. While keeping the initial chloride ion concentration constant throughout the period, aqueous calcium chloride solution (4.5 molar concentration, solution B) and aqueous silver nitrate solution (2.0 molar concentration, solution C) were constantly added to solution A using a double jet. flow rate for 1 minute (total silver nitrate
0.8% consumed). After an initial 1 min of constant flow rate addition, solutions B and C were added at an accelerated flow rate (4x from start to finish) using a double jet for 11 min (total silver nitrate concentration).
22.0% was consumed). The flow rate of solution B is the same as that of solution C.
The addition flow rate was half of that of . After an 11 minute accelerated flow rate period, solutions B and C were added at a constant flow rate for approximately 23 minutes (consuming 70.0% of the total silver nitrate). The flow rate of solution B was half that of solution C. An aqueous solution of sodium hydroxide (1.0 molar, solution D) was used to maintain a pH of 2.6 at 55°C.
The amount of silver nitrate used to precipitate this emulsion was
It was 0.50 mole. The grain characteristics of the obtained emulsion are shown in Table 1. A micrograph (magnification: 600 times) of this emulsion is shown in FIG. Emulsion 24 This example demonstrates the photographic sensitivity of the emulsion defined herein when sensitized with a blue spectral sensitizing dye and compares the performance with that obtained in the absence of the blue spectral sensitizing dye. This is an example of TPMA/AA/MOES (1:2:
7 molar ratio) aqueous solution (0.63% polymer, solution A)
4.0 was prepared at PH2.6 and 55°C. Solution A was added with an aqueous solution of calcium chloride (2.0 molar, solution B) and an aqueous solution of silver nitrate (2.0 molar, solution C), maintaining the initial chloride ion concentration throughout the period.
was added using a double jet at a constant flow rate for 1 minute (consuming 1.2% of the total silver nitrate). After an initial 1 minute constant flow period, solutions B and C were added at an accelerated flow rate (2.3 times from start to finish) using a double jet for 52 minutes (consuming 98.8% of the total silver nitrate). . Aqueous sodium hydroxide solution (0.2 molar, solution D) was used to maintain a pH of 2.6 at 55°C. By the end of this operation the PH gradually approached 2.8.
The amount of silver nitrate used to prepare this emulsion is
It was 5.0 mol. This emulsion was cooled to 23 °C and added to 30 °C of distilled water.
Let stand, decant and resuspend in approximately 1.4 Kg of 4.0% gelatin solution. This emulsion was mixed with 0.25 mmol of 5-(3-ethyl-
2-Benzothiazolinylidene)-3-β-sulfoethylrhodanine/mol Ag and 0.5% KBr/mol
Spectral sensitization was achieved by addition of Ag. 1.07 g of this spectrally sensitized emulsion was placed on a cellulose triacetate support.
It was coated with a coverage of silver/m ² and 3.58 g gelatin/m ² . The coated element also contains 1.07 g/m ² magenta coupler, 1-(6-chloro-2,4-dimethylphenyl)-3-[α(m-pentadecylphenoxy)butyramide]-5-pyrazolone. , and hardened with 1.1% bis(vinylsulfonylmethyl)ether based on total gelatin content. The coating was then exposed to 600 W and 2850 tungsten antigen for 2 seconds through a 0-4.0 density step tablet. Processing was carried out in p-phenylenediamine color developer at 33.4 DEG C. for 2 minutes. The obtained sensitometric values are as follows. Table: As evident from the table above, the blue spectrally sensitized tabular AgClBr (99:1) grain emulsion exhibited an increased photographic sensitivity of 0.76 logE. The grain characteristics of this emulsion are shown in Table 1 below. A micrograph (magnification: 600 times) of this emulsion is shown in FIG. 【table】
−
(1:1:7)

Table: The following emulsions exhibit a transition from {111} edges to {110} edges during the growth of tabular grains as defined herein. Additionally, these emulsions exhibit suppression of {110} edges due to the use of higher levels of adenine. Emulsion 25A [Tabular AgCl grains with {110} edges] TPMA/AA/MOES (1:2:
7 molar ratio) aqueous solution (0.63 polymer, solution A) 2.0
was prepared at PH2.6 and 55°C. Solution A maintained this initial chloride ion concentration throughout the period.
, calcium chloride aqueous solution (2.0 molar concentration, solution B) and silver nitrate aqueous solution (2.0 molar concentration, solution C)
was added using a double jet at a constant flow rate for 1 minute (consuming 0.75% of the total silver nitrate). After the first minute of constant flow rate addition, solutions B and C were added at an accelerated flow rate (start to end).
(2.3x) using a double jet for 15 minutes (consuming 18.8% of the total silver nitrate). After a 15 minute accelerated flow period, solutions B and C were added using a double jet at a constant flow rate over approximately 46 minutes (consuming 80.5% of the total silver nitrate). Aqueous sodium hydroxide solution (0.2 molar, solution D) was used to maintain a pH of 2.6 at 55°C. The amount of silver nitrate used to precipitate this emulsion was
It was 4.0 mol. After introducing 1.05 moles of Ag into the reaction vessel, the emulsion was tested and the grains were as shown in FIG. When a grain test was conducted to determine the grain edge as described above for emulsion 10, it was found that:
The tabular grain edges were found to be located in the {111} crystal plane. After introducing 1.68 moles of Ag into the reaction vessel, the emulsion was tested again. As a result, the particles were as shown in FIG. 20th
Both the figure and FIG. 21 have a magnification of 600 times. 22nd
The figure is a photograph at 15,500x magnification of a single grain from the emulsion shown in Figure 21. Note that there are 12 distinct edges on the particle.
Half of the edges are located in the {111} crystal plane, and the other half are located in the {110} crystal plane. After introducing 4.0 mol of Ag into the reaction vessel, the emulsion 10
The emulsions were tested as described above. This examination revealed that the tabular grains had edges located in the {110} crystal plane. A photograph of this emulsion at a magnification of 600 times is shown in FIG. This example can prove that a transition from {111} crystal plane edges to {110} crystal plane grain edges occurs during the growth process of tabular grains. Emulsion 25B (Tabular AgCl grains with {111} edges) Emulsion 25B was precipitated in the same manner as Emulsion 25A, except that additional adenine was added during the precipitation procedure. At 5 minute intervals starting 20 minutes after the start of the precipitation operation.
A quantity of 1.0 g of adenine suspended in 25 ml of 0.5 molar calcium chloride solution was added to solution A seven times.
Nitric acid was added with each addition of adenine to maintain pH 2.6 at 55°C. Emulsion 25A has an average thickness of 0.28 μm and an average grain size.
It contained tabular AgCl particles with a diameter of 6.2 μm, an aspect ratio of 21:1, and 80% of the particles being flat plates based on projected area. The presence of additional adenine during the precipitation process of emulsion 25B prevented the formation of {110} edges. Emulsion 25B containing tabular grains with {111} edges has an average thickness of 0.50μ
m, average particle size 5.8μm, aspect ratio 11.6:
1, and 85% of the grains were tabular, based on projected surface area. Emulsion 26A [Tabular AgCl grains with {110} edges] Aqueous solution 2.0 of 0.63% by weight of TA/APSA (1:6 molar ratio) containing calcium chloride (0.5 molar concentration) and adenine (0.013 molar concentration) at PH2.6 and prepared at 70°C. To this solution, which maintained the initial chloride ion concentration throughout the entire precipitation process, an aqueous calcium chloride solution (2.0 molar concentration) and an aqueous silver nitrate solution (2.0 molar concentration) were added at a constant flow rate for 1 minute (19 molar concentrations of total silver nitrate) using a double jet. % consumed). After the initial 1 minute constant flow rate addition, the halide and silver salt solutions were added at an accelerated flow rate (1.11 times start to finish) using double jets for 4 minutes. The consumption of silver nitrate is the total amount of silver nitrate.
It was 81%. Aqueous sodium hydroxide solution (0.2 molar concentration) was used to maintain pH 2.6 at 70°C. The amount of silver nitrate used to prepare this emulsion was 0.156 moles. The resulting AgCl emulsion contained tabular grains with hexagonal major faces and {110} edges. The tabular grains had an average diameter of 1.7 μm, an average thickness of 0.20 μm, an average aspect ratio of 8.5:1, and were approximately 60% of the total grain projected area. Emulsion 26B [Tabular AgCl grains with {110} and {111} edges] Poly[N-(3-thiabutyl)acrylamide-co-2-acrylamide containing calcium chloride (0.5 molar) and adenine (0.026 molar) -2-Methylpropanesulfonic acid, sodium salt] (1:4 molar ratio) 0.63% by weight aqueous solution 0.4
Prepared at PH2.6 and 55°C. The solution, which maintained this initial chloride ion concentration throughout the entire precipitation period,
Calcium chloride aqueous solution (2.27 molar concentration) and silver nitrate aqueous solution (4.0 molar concentration) using a double jet at constant flow rate for 1 minute (consuming 2.5% of total silver nitrate)
I added it. After this first minute of constant flow rate addition, the halide and silver salt aqueous solutions were added at an accelerated flow rate (4.0x from start to finish) using a double jet for 20 minutes (67.0% of the total silver nitrate used). consumed). The halide and silver salt aqueous solutions were then added using a double jet at a constant rate over 3 minutes (consuming 29.6% of the total silver nitrate used). Aqueous sodium hydroxide solution (0.2 molar) was used to maintain the pH at 2.6 at 55°C. The amount of silver nitrate used to prepare this emulsion was 0.324 moles. The resulting AgCl emulsion contained tabular grains with dodecagonal major faces and alternating six {110} and six {111} edges. The tabular grains had an average grain diameter of 1.7 μm, an average thickness of 0.19 μm, and an average aspect ratio of 8.7:1, and accounted for approximately 70% of the total grain projected area. The following examples illustrate emulsions with average aspect ratios slightly greater than 8:1. Emulsion 27 (AgCl79Br21, aspect ratio 8.2:1) 0.625 wt% TPMA/AA/MOES (1:1:
0.4 of an aqueous solution containing calcium chloride (0.5 molar), sodium bromide (0.0125 molar) and adenine (0.0259 molar) was placed in a precipitation vessel and stirred at pH 2.6 and 55°C. To this precipitation vessel, an aqueous calcium chloride solution (2.0 molar concentration) containing potassium bromide (0.10 molar concentration) and an aqueous silver nitrate solution (2.0 molar concentration) were added using a double jet at a constant flow rate for 1 minute (1.6 molar concentrations of total silver nitrate).
%). The halide salt and silver salt solutions were then added at an accelerated flow rate (1.75 times start to finish) over a period of 48.4 minutes (based on total silver nitrate used).
(consumed 98.4%). The initial chloride ion concentration was maintained in the precipitation vessel during the entire operation. pH 2.6
An aqueous sodium hydroxide solution (0.2 molar concentration) was used to maintain the temperature. The amount of silver nitrate used to prepare this emulsion was 0.5 mole. The resulting tabular silver bromochloride emulsion had an average tabular grain diameter of slightly greater than 2.0 μm (estimated at 2.05 μm), an average tabular grain thickness of 0.25 μm, and a mean tabular grain thickness of slightly greater than 8:1 (estimated at 8.2: 1) It had an average aspect ratio. Tabular grains accounted for more than 50% of the total grain projected area. The following emulsion is an example showing that iodine can be used in place of aminoazaindene to obtain the tabular grains defined herein. When using this grain preparation method, it is preferred to use iodine at a grain concentration of about 5 to 10 mole percent. Generally speaking, lower average aspect ratios are obtained when using aminoazaindenes according to the preferred method of production of this invention. Emulsion 28 (chemically and spectrally sensitized AgCl99Br1 emulsion) Solution 2.0 containing 0.63% TPMA/AA/MOES (1:2:7 molar ratio) and 0.026 molar concentration of adenine
was placed in the reaction vessel. This solution is further 0.5M
It contained calcium chloride and 0.0125M sodium bromide. The pH was adjusted to 2.6 at 55°C. Add 2.0M calcium chloride solution and
2.0M silver nitrate solution using double jet at constant rate for 1 minute (consuming 1.2% of total silver nitrate used) (2.33 times from start to finish) for 15 minutes, consuming 30.0% of total silver nitrate used did. During emulsion preparation, pCl was added in a measured amount 1 minute after the start of the addition. The addition of the solution was then maintained at the value in the reaction vessel at an accelerated flow rate. Next, the solution is further added at a constant flow rate.
It was added for 26 minutes, consuming 68.8% of the total silver nitrate used. During the first third of the precipitation, 0.2M sodium hydroxide solution was added gradually to maintain the pH at 2.6 at 55°C. A total of 2.6 moles of silver nitrate was consumed during precipitation.
The emulsion was cooled to 23°C and diluted with 0.001 molar nitric acid 15
, leave to stand, and finally add this solid to 3
% bone gelatin. The grains of this emulsion have an average diameter of 4.5 μm and an average thickness of
It had a diameter of 0.28 μm. Particles with a thickness of less than 0.5 μm and a diameter of at least 0.6 μm exhibited an average aspect ratio of 16:1 and occupied more than 80% of the total projected area. The tabular grains obtained were dodecahedral, suggesting the presence of {110} and {111} edges. The tabular AgCl grain emulsion was divided into four parts. Part A was not chemically or spectrally sensitized and was deposited at 1.07 g silver/m ² on a polyester film support.
and coated with a coverage of 4.3 g gelatin/m ² . Part B was sensitized as follows. Gold sulfide (1.0 mg/mol Hg) was added and the emulsion was heated to 65°C.
was held for 5 minutes. This emulsion was mixed with anhydro-5
-chloro-9-ethyl-5'-phenyl-3,3'-
It was spectrally sensitized with bis(3-sulfopropyl)oxacarbocyanine hydroxide, triethylamine salt (0.75 mmol/mol Ag) at 40°C for 10 minutes and then coated as in Part A. Chemical and spectral sensitization were optimal for the sensitizers used. Parts C and D are optimally sensitized.
Part C contains anhydro-5-chloro-9-ethyl-5'-phenyl-3, 0.75 mmol/mol Ag;
The triethylamine salt of 3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide was added and the emulsion was held at 40°C for 10 minutes. Next, 3.0 mole percent NaBr (based on total silver halide) was added and the emulsion was held at 40°C for 5 minutes.
Next, Na ₂ S ₂ O ₃ 5H ₂ Omg/mol Ag, NaSCN
(1600 mg/mol Ag) and KAuCl ₄ (5 mg/mol Ag)
was added and the emulsion was held at 65°C for 5 minutes before coating. Part D is 10 mg/mol Ag of Na ₂ S ₂ O ₃ .
It was sensitized in the same manner as Part C above except that 5H ₂ O was used. The coating was passed through a 0-4.0 concentration step tablet into a 600W and 5500〓 tungsten light source to 1/5
0 second exposure and processing for 10 minutes at 20°C in N-methyl-p-aminophenol sulfate (Elon®) ascorbic acid surface developer. The obtained sensitometric values are as shown below. [Table] * Under the conditions of this experiment, the maximum concentration did not reach the sensitivity limit level of 0.1 above fog. However, images were also obtained for portions A and B by varying the exposure and processing conditions. 365n
For m exposures, portions A and B were approximately 2 logE less sensitive than portions C and D. The results in Table 2 demonstrate the excellent sensitivity of the optimally sensitized emulsions. The following examples are examples of the tabular emulsions defined herein exhibiting higher covering power than comparable non-tabular emulsions of halide composition. Emulsion 29A (non-tabular AgCl98Br2 emulsion) A 2.0 molar solution of calcium chloride containing 0.04 molar sodium bromide and silver nitrate at PH 2.6 and 55°C in a 0.5 molar aqueous calcium chloride bone gelatin solution (1.0% gelatin by weight). A 2.0 molar solution of was added using a double jet at a constant rate over 1 minute (consuming 0.9% of the silver nitrate before use). next,
The halide and silver salt solutions were introduced at an accelerated flow rate (from start to finish) using a double jet.
3.6 times) for approximately 25.2 minutes. (50.5 of total silver nitrate
%). The halide and silver salt aqueous solution was then added at a constant rate for an additional 15.8 minutes, consuming 48.9% of the total silver nitrate used. Chloride ion concentration was held constant during the entire precipitation. The amount of silver salt used to prepare this emulsion was approximately 1.15 moles.
Following precipitation, the emulsion was dispersed in distilled water, allowed to stand, decanted, and then resuspended in approximately 0.5 aqueous bone gelatin solution (3.0% by weight). The grains of this emulsion were non-tabular and had an average diameter of 0.94 μm. Emulsion 29B (tabular AgCl98Br2 emulsion) 0.625% by weight TPMA/AA/MOES (1:2:
7 molar ratio) in an aqueous solution of 0.5 molar calcium chloride and 0.26 molar adenine at pH 2.0.
At 2.6 and 55°C, a 2.0 molar aqueous solution of calcium chloride containing 0.04 molar sodium bromide and
A 2.0 molar aqueous silver nitrate solution was added using a double jet at a constant rate over 1 minute (consuming 4.2% of the total silver nitrate used). The halide and silver salt solution was then added using a double jet at an accelerated flow rate (1.4 times start to finish) over about 19 minutes (consuming 95.8% of the total silver salt used). Chloride ion concentration was kept constant during the entire precipitation. Approximately 0.72 mole of silver salt was used to prepare this emulsion. Following precipitation, the emulsion was kept under stirring at 55° C. for 2.5 hours. The emulsion was then dispersed in distilled water, allowed to stand, decanted, and resuspended in approximately 0.25% aqueous bone gelatin solution (3.0% by weight). The emulsion contained tabular grains with an average thickness of 0.3 μm, an average diameter of 2.8 μm, and an average aspect ratio of 9.3:1. These tabular grains accounted for 85% of the projected area of all grains present. Emulsion 29A on polyester film support
Coated with 3.26g silver/m ² and 11.6g gelatin/m ² . Similarly, emulsion 29B was 3.07 g silver/m ² and 11.6 g
Coated with gelatin/ ^m2 . Both coatings were exposed to a mercury vapor lamp at 365 nm wavelength for 1 second through a 0-6.0 density step tablet (0.30 density steps) and developed with n-methyl-p-aminophenol sulfate (Elon®)-hydroquinone. The cells were treated in a solution at 20°C for 6 minutes. The sensitometric value is this tabular AgClBr
The (98:2) grain emulsion was shown to have higher covering power than the AgClBr (98:2) three-dimensional grain emulsion.
The coating of Emulsion 29A exhibited a Dmax density of 1.07 for 96.1% developed silver as determined by X-ray fluorescence analysis. However, the coverage of emulsion 29B is almost
It exhibited a Dmax density of 1.37 for 100% developed silver.
Nontabular emulsion grains have a lower average volume per grain than tabular grains (0.83 (μm) ³ vs. 1.85 (μm) ³ ) and more developed silver (3.13 g/m ² vs. 3.04
g/m ² ), and both of these differences act to increase the covering power of nontabular grains compared to tabular emulsions, but tabular grains have a higher Dmax than nontabular grains. and thus gave greater covering power than Emulsion 29B. The new radiation-sensitive photographic elements produced according to the method of this invention provide a variety of photographic properties. For example, the emulsions can enhance sharpness when incorporated into multi-photographic elements. The emulsions exhibit better sensitivity-grain size relationships when optimally chemically and spectrally sensitized. The emulsions are blue, green and/or red sensitized and when incorporated into photographic elements produce photographic elements with increased sensitivity separation to the spectral sensitized regions of the spectrum and high ultraviolet sensitivity. Furthermore, the emulsions exhibit properties that increase maximum density and covering power. Furthermore, additional features of the invention include, for example, increased sharpness, increased sensitivity separation in the natural and spectrally sensitized regions of the spectrum, improved speed-granularity correlation, and blue sensitization. It is possible to realize an increase in the sensitivity or the sensitivity granularity correlation when
Further, a feature of the present invention is that radiographic elements with relatively reduced crossover can be obtained;
Image transfer also provides a higher performance ratio of photographic speed to silver coverage (i.e., silver halide coverage per unit area), faster access to visible transferred images, and higher contrast or transferred images with less development time. A film unit can be provided.

[Brief explanation of drawings]

Figures 1a, 2a and 3 are plane views of individual silver halide grains, Figure 1b is a detailed cross-sectional view taken along line 1b-1b of Figure 1a, and Figure 2b is a detailed cross-sectional view taken along line 1b-1b of Figure 1a. FIG. 4 is a schematic diagram showing sharpness characteristics, and FIGS. 5, 6, 7, 8, 9, and 10 are end views of silver halide grains.
Figure a, Figure 11, Figure 12, Figure 13, Figure 14
Figures, Figure 15, Figure 16, Figure 17, Figure 18,
19, 20, 21, 22 and 23 are micrographs of emulsions according to the invention, and FIGS. 10b and 10c are electron micrographs of silver halide grains. , 10d and 1
Figure 0e is a top view of a silver halide grain showing the diffraction pattern, and Figure 11a is a graph of the correlation between relative log spectral sensitivity and wavelength. 100, 200, 300... tabular grains.

Claims (1)

[Scope of Claims] 1. A tabular halogen having a halide content of at least 50 mol % of chloride based on silver is obtained by contacting an aqueous silver salt solution and an aqueous solution of a chloride-containing halide salt in the presence of a dispersion medium. In the method for producing a radiation-sensitive photographic emulsion for producing silveride grains, aminoazaindene and (1) repeating units of amide or ester of maleic acid, acrylic acid or methacrylic acid are added to the linear polymer chain, and each amide and each amine or alcohol condensation residue contained in the ester has at least one sulfide linking two alkyl carbon atoms.
The aqueous silver salt solution and a chloride-containing halide salt in the presence of a peptizer which is a water-soluble linear copolymer containing an organic radical having a sulfur atom and (2) units of at least one other ethylenically unsaturated monomer. A method for producing a radiation-sensitive photographic emulsion, which is characterized by reacting an aqueous solution.