Silver halide photographic emulsion, method for producing thereof, and light-sensitive material using the same

A method for producing a silver halide photographic emulsion, a method for producing thereof, and a light-sensitive material using the same, the method comprising the steps of: (a) producing a host emulsion comprising silver bromide or silver iodobromide tabular grains having an average silver iodide content (I.sub.1 mol %) of the entire silver halide grains of 5 mol % or less, in which 60% or more of the projected area of the entire silver halide grains accounting for tabular grains having an aspect ratio of 3.0 or more; (b) dissolving a periphery of the tabular grains completely with an iodide ion being added to the host emulsion; and then (c) producing final tabular grains by reclaiming a periphery containing silver iodobromide from the region containing the periphery having been completely dissolved.

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic emulsion, a 
method for producing thereof and a light-sensitive material using the same 
and, specifically, relates to a silver halide grain emulsion which is high 
sensitive and less in fluctuations in photographic properties due to 
mechanical stress, a method for producing thereof and a light-sensitive 
material using the same. 
BACKGROUND OF THE INVENTION 
Various mechanical stresses are put on a photographic material coated with 
a silver halide emulsion, in general. For example, a negative film for 
general photographing is rolled up into a magazine, folded when loading in 
a camera, or pulled for frame sliding. Further, an emulsion face is 
pressed in a swollen state, in some cases, depending on processors when an 
exposed negative film is development processed. 
As described above, when various stresses are put on a photographic 
material, stresses are put on silver halide grains through gelatin, which 
is a binder of silver halide grains, and a plastic film support. It is 
known that if stress is put on silver halide, photographic properties of a 
photographic material are fluctuated. Examples thereof are disclosed in 
detail, for example, in K. B. Mother, J. Opt. Soc. Am., 38 (1948), p. 
1054, P. Faelens and P. de Smet, Sci. et Ind. Phot., 25, No. 5 (1954), p. 
178, and P. Faelens, J. Phot. Sci., 2 (1954), p. 103. 
With respect to tabular silver halide grains, production methods and 
techniques for using thereof have been disclosed in U.S. Pat. Nos. 
4,433,048 and 4,434,226, etc. It has been known in this field of industry 
that the shape of tabular grains has various advantages which contribute 
to the improvement of sensitivity/graininess relationship, the improvement 
of sharpness due to the peculiar optical nature of tabular grains and the 
improvement of covering power, and tabular grains have supported the rapid 
progress of silver halide photographic materials in recent years. 
Because of their peculiar "tabular shape", on the other hand, the 
performance degradation of photographic properties by stress 
(pressureability) of tabular grains is large, and therefore, various means 
have been contrived to cope with this drawback. 
For example, U.S. Pat. No. 4,806,461, JP-A-63-220238 and JP-A-3-189642 (the 
term "JP-A" as used herein means an "unexamined published Japanese patent 
application") disclose techniques for improving sensitivity/graininess 
relationship, dependency on illumination intensity of exposure, 
pressureability and storage stability by introducing dislocation lines 
into tabular silver halide grains while controlling. 
The technique of improving sensitivity/graininess ratio by forming tabular 
silver iodobromide grains having iodide nonuniformly dispersed in the 
grains is disclosed in U.S. Pat. No. 4,414,310. Further, JP-A-3-136032, 
JP-A-3-136033 and U.S. Pat. No. 5,061,616 disclose techniques of improving 
the desensitization due to pressure by forming a silver bromoiodide thin 
layer shell which comprise adding iodide to a tabular host emulsion and 
then prescribing the pAg and the temperature. However, the techniques 
disclosed therein only refer to the improvement of the desensitization due 
to pressure among the degradations of photographic properties caused by 
various stresses. Therefore, the effects of these techniques have been 
insufficient concerning very important and annoying performance 
degradations of photographic properties due to other stresses in 
photographic materials, that is, stress marks by folding and stress marks 
in a swollen state of a coated film. 
While, in recent years, demands for tabular silver halide emulsions have 
become increasingly strict, in particular, the development of high 
sensitivity emulsions which are improved in performance degradation of 
photographic properties due to various stresses has been desired. 
SUMMARY OF THE INVENTION 
Accordingly, an object of the present invention is to resolve the 
above-described problems of the prior art and provide a method for 
producing a silver halide emulsion which is high sensitive and less in 
fluctuation in photographic properties due to stresses. 
Another object of the present invention is to provide a silver halide 
emulsion produced by the above method and a silver halide photographic 
material using the emulsion. 
As a result of eager studies, the above objects of the present invention 
have been attained by the following means. 
(1) A method for producing a silver halide photographic emulsion comprising 
the steps of: 
(a) producing a host emulsion comprising silver bromide or silver 
iodobromide tabular grains having an average silver iodide content 
(I.sub.1 mol %) of the entire silver halide grains of 5 mol % or less, in 
which 60% or more of the projected area of said entire silver halide 
grains accounting for tabular grains having an aspect ratio of 3.0 or 
more; 
(b) dissolving a periphery of said tabular grains completely with an iodide 
ion being added to said host emulsion; and then 
(c) producing final tabular grains by reclaiming a periphery containing 
silver iodobromide from the region containing said periphery having been 
completely dissolved. 
(2) A method for producing a silver halide photographic emulsion as 
described in (1), wherein (I.sub.2 -I.sub.1) is from 0 to 8, where 12 mol 
% represents the ratio of said iodide ion added in step (b) to the total 
amount of silver contained in said host emulsion. 
(3) A method for producing a silver halide photographic emulsion as 
described in (1) or (2), wherein the temperature T.degree. C. and the pAg 
of said host emulsion, when an iodide ion is added to said host emulsion, 
are within the region A in FIG. 3. 
(4) A method for producing a silver halide photographic emulsion as 
described in any one of (1) to (3), wherein said tabular grains in said 
host emulsion have two or more interior regions substantially different in 
silver iodide contents and the silver iodide content of the outermost 
layer of said tabular grains in said host emulsion is substantially zero. 
(5) A method for producing a silver halide photographic emulsion as 
described in any one of (1) to (4), wherein said periphery reclaimed in 
step (c) of said final tabular grains has dislocation lines. 
(6) A silver halide photographic emulsion produced by the method described 
in any one of (1) to (5). 
(7) A silver halide photographic material comprising a support having 
provided thereon a photographic emulsion layer containing a silver halide 
photographic emulsion produced by the method described in any one of (1) 
to (5).

DETAILED DESCRIPTION OF THE INVENTION 
The present invention will be described in detail below. 
Silver halide grains of the present invention are basically produced 
according to three steps of a host grain forming step (step (a)), a 
dissolution step by the addition of an iodide ion (step (b)), and a silver 
iodobromide thin layer forming step (step (c)). Each step is described in 
detail below. 
A host grain forming step (step (a)) according to the present invention 
comprises at least a nucleation process, a ripening process and a growing 
process. These processes are disclosed in detail in U.S. Pat. No. 
4,945,037. A ripening process and a growing process may be carried out 
repeatedly in arbitrary orders. A growing process is a process of adding 
an aqueous solution of silver salt and an aqueous solution of halide to a 
mixer according to a double jet method. Mixers to be used are preferably 
mixers capable of adding each aqueous solution within a liquid, e.g., 
those disclosed in U.S. Pat. No. 3,785,777 and West German Patent 
2,556,888. 
A method in which the pAg in the liquid phase in which the silver halide is 
formed is kept constant, that is, a controlled double jet method, can also 
be used as one type of the double jet method. A silver halide emulsion 
having a regular crystal form and almost uniform grain size can be 
obtained according to this method. 
The host grain according to the present invention is a tabular silver 
halide grain having one twin plane or two or more twin planes parallel to 
each other. In this case, when ions at all the lattice points at both 
sides of (111) plane are in enantiomer relationship, the twin plane means 
this (111) plane. 
An aspect ratio in tabular silver halide grains (tabular grains) means the 
ratio of the diameter to the thickness of the tabular grains, that is, an 
aspect ratio is defined as the value obtained by dividing the diameter by 
the thickness of each silver halide grain. Herein, the diameter means the 
diameter of the circle of the area corresponding to the projected area of 
the grain when silver halide grains are observed with a microscope or an 
electron microscope. Accordingly, aspect ratio of 3 or more means the 
diameter of the circle is 3 times or more as larger than the thickness of 
the grain. 
One example of a measuring method of an aspect ratio is a method in which 
the circle-corresponding diameter and the thickness of each grain are 
measured from a transmission type electron microphotograph by a replica 
method. In this case, the thickness is calculated from the length of the 
shadow of the replica. 
In the host emulsion for use in the present invention, 60% or more of the 
projected area of the entire silver halide host grains account for tabular 
grains having an aspect ratio of 3.0 or more, preferably 5.0 or more, and 
more preferably 7.0 or more. If an aspect ratio is too large, the 
variation coefficient of the grain size distribution becomes large, 
accordingly, in general, an aspect ratio is preferably 20 or less. 
When the grains in the host emulsion (host grains) for use in the present 
invention are silver iodobromide, the variation coefficient of the grain 
size distribution is preferably 25% or less, more preferably 20% or less. 
The diameter of the above-described host grain is preferably from about 0.2 
to 5.0 .mu.m, more preferably from 0.3 to 4.0 .mu.m, and still more 
preferably from 0.4 to 3.0 .mu.m. Further, the thickness of the host grain 
is preferably less than about 0.5 .mu.m, more preferably from 0.05 to 0.5 
.mu.m, and still more preferably from 0.08 to 0.4 .mu.m. 
The host grains for use in the present invention are preferably silver 
bromide or silver iodobromide. When the host grains are silver 
iodobromide, the average silver iodide content I.sub.1 of the grains is 5 
mol % or less. If it exceeds 5 mol %, complete dissolution of the 
periphery of the host grain in the process of conversion by an iodide ion 
(step (b)), which will be described later, becomes difficult. As a result, 
the aspect ratio of the final grains reduces and the variation coefficient 
of the grain size distribution becomes large. Therefore, I.sub.1 is 
necessary to be set 5 mol % or less. 
I.sub.1 is more preferably 4 mol % or less. Further, the host grains may 
contain silver chloride and the preferred content of silver chloride is 
preferably 8 mol % or less, more preferably 3 mol % or less, and most 
preferably 0 mol %. 
The host grain for use in the present invention may have at least two or 
more interior regions having substantially different halide compositions 
in the grain, as far as I.sub.1 is 5 mol % or less. The host grain may 
have a uniform halide composition, but the structure preferably comprises 
two or more halide compositions. The boundary between different halide 
compositions of the grain may be distinct or may be made of a continuous 
change in composition. 
When the host grain having two or more structures having different halide 
compositions is used, the halide composition of the outermost layer 
preferably comprises silver bromide substantially not containing silver 
iodide. 
The silver iodide content of the grain surface can be measured by an XPS 
method (X-ray Photoelectron Spectroscopy). 
The principle of an XPS method is described in detail, for example, in 
Jun-ichi Aihara et al., Denshi no Bunko (Spectroscopy of Electron), 
Kyoritsu Library 16, Kyoritsu Shuppan, 1978. 
A standard measuring method of XPS is a method of measuring the strengths 
of the photoelectrons of iodine (I) and silver (Ag) released from the 
silver halide grain of an appropriate form of a sample using Mg--K.alpha. 
as an exciting X-ray. The content of iodine can be obtained from the 
calibration curve of the strength ratio of the photoelectrons of I and Ag 
(strength (I)/strength (Ag)) prepared using several kinds of standard 
samples the contents of iodine of which are known. In the case of silver 
halide emulsion, the gelatin adsorbed onto the surface of a silver halide 
grain must be decomposed and removed with proteolytic enzyme or the like 
before XPS measurement. 
The average silver iodide content can be measured by analyzing the 
composition of the grain one by one with an X-ray microanalyzer. The 
"average silver iodide content" means the arithmetical mean value obtained 
by measuring the silver iodide content of at least 100 emulsion grains 
with an X-ray microanalyzer. The method of measuring the silver iodide 
content of individual emulsion grain is disclosed, for example, in 
EP-A-147868. 
The silver amount of the host emulsion for use in the present invention is 
preferably from 3% to 97%, more preferably from 30% to 90%, and most 
preferably from 50% to 90%, based on the total silver amount of the entire 
emulsion. 
The host emulsion for use in the present invention may be reduction 
sensitized. Reduction sensitization is conducted by ordinary methods known 
in the field of the industry such as the addition of reducing agents and 
the like or the reduction by high pH. 
The host emulsion grains for use in the present invention may be prepared 
by previously forming grains and through washing and precipitation process 
and being added as a seed emulsion or may be prepared by growing a seed 
emulsion. 
The halogen conversion step by an iodide ion (step (b)) is described in 
detail below. 
The term "dissolution" used in the present invention means that the 
periphery of the tabular grain having a hexagonal or triangular shape is 
dissolved and becomes rounded in shape by the addition of an iodide ion to 
the tabular silver halide host grains which is hardly soluble. The term 
"periphery" used herein means the region outside of the circle inscribed 
by at least three sides of the hexagonal or triangular tabular grain 
within the major (111) faces. In the present invention, the periphery of 
the tabular host grain is "completely dissolved" and not incompletely 
dissolved. That is, the entire periphery is dissolved. This terminology 
"completely dissolved" includes that the dissolution reaches concentric 
circles having smaller radii than the above inscribed circle. Accordingly, 
the dissolution of the present invention is definitely distinguished from 
the dissolution of a vertex in the prior art, which is possible to occur 
at the time when silver iodide which is more hardly soluble salt than the 
silver halide host grain or high silver iodobromide of solid solubility 
limit region is formed. In one embodiment of the present invention, it can 
be observed from the electron microphotograph in FIG. 1 that the periphery 
of the tabular grain having been subjected to the dissolution process is 
completely dissolved. 
JP-A-63-220238, JP-A-3-136032, JP-A-3-136033 and JP-A-4-149541 can be cited 
as close to the embodiment of the present invention. The techniques of 
these patents fundamentally comprise three processes of (1) preparation of 
a substrate grain, (2) provision of a high iodide layer, and (3) covering 
with a silver iodobromide layer having "a lower silver iodide content than 
that of (2)". 
With respect to the provision of a high iodide layer (2), JP-A-63-220238 
discloses that it is important for iodide rather to be present locally on 
a substrate tabular grain than adsorbed onto a grain uniformly. The 
present invention is characterized in that the host grain is dissolved by 
an iodide ion and is apparently different from the epitaxial formation of 
localized silver iodobromide. 
In the disclosure of JP-A-4-149541, dislocation lines are concentrated only 
in the vicinity of the vertex of a tabular grain, which is fundamentally 
different from the conception of the present invention. As one embodiment 
thereof, there is a method of dissolving only the vicinity of a vertex 
with an iodide ion, but the technique of the present invention is 
characterized in that not only the periphery of a vertex but the entire 
periphery including a vertex is completely dissolved. Another embodiment 
thereof is to substantially dissolve only the vicinity of a vertex with a 
silver halide solvent, which is also different from the present invention. 
Still another embodiment thereof is a method via halogen conversion in 
which potassium iodide is added to host grains as an orientating compound, 
subsequently silver chloride is epitaxially grown only at the vertex part 
of a host grain limitedly (accordingly, silver chloride is not grown in 
the site where iodide is present), and then the silver chloride epitaxis 
is selectively halogen-converted with potassium iodide, which is also 
different that of the present invention. 
Emulsion B-3 disclosed in JP-A-4-149541, which may be the closest to the 
present invention, is dissolved outside of the preferred temperature-pAg 
range of the present invention. 
In JP-A-3-136032, iodide as a silver salt is adhered on the periphery of a 
host tabular grain, further, the iodide as a silver salt is rapidly 
introduced into the system at that time (added as silver iodide Lippmann 
emulsion in the working examples). This mode of the above patent is 
different from the addition method of an iodide ion to the system of the 
present invention. Further, the pAg at that time of the present invention 
is far higher than that of the above patent. 
The embodiment of JP-A-3-136033 is characterized in that silver iodobromide 
thin layers having a silver iodide content higher than that of the host 
grains are formed on the major faces of tabular grains, and at that time, 
the aqueous solution containing a bromide ion and an iodide ion in 
admixture is added with an aqueous solution of a silver salt and silver 
iodobromide thin layers of from 5 mol % to 40 mol % are formed on the host 
grains so as not to cause phase separation. According to the embodiment of 
the present invention, only an aqueous solution containing an iodide ion 
is added to the host grains and the pAg at that time of the present 
invention is far higher than that of the above patent. Therefore, the 
embodiment of the present invention is apparently different from that of 
the above patent. 
The technique of the present invention is to completely dissolve the 
periphery of the host tabular grains by the addition of only the aqueous 
solution containing an iodide ion on the host tabular grains containing 
the prescribed amount of silver iodide. As a result, the production of a 
high sensitive emulsion can be realized without deteriorating photographic 
sensitivity against various stresses. In particular, the above effect is 
further conspicuously exhibited by regulating the total amount of the 
iodide ion to be added and the iodide composition of the host grains, or 
regulating the temperature and the pAg at the time of the addition of the 
iodide ion. 
The dissolution process by the addition of an iodide ion (step (b)) of the 
present invention can be attained by the addition of a halide solution 
containing an iodide ion. When an iodide ion is added, the addition of an 
aqueous solution of silver salt such as silver nitrate is substantially 
not conducted. 
For achieving the effective dissolution according to the present invention, 
the total amount of the iodide ion to be added is preferably such a value 
that (I.sub.2 -I.sub.1) is from 0 to 8, in which the silver iodide content 
in the host grains as I.sub.1 (mol %), and the value obtained by dividing 
the total mol number of the iodide ion amount by the total mol number of 
the silver amount of the host grains and multiplying by 100 as I.sub.2 
(mol %). 
When this value becomes negative values, effective dissolution is difficult 
to be generated and accompanied by lowering in sensitivity. When this 
value is greater than 8, host grains are liable to be dissolved 
excessively and the silver iodide content per one grain becomes extremely 
large, as a result, lowering in sensitivity soft gradation and pressure 
desensitization are brought about. 
The value of (I.sub.2 -I.sub.1) is more preferably from 0 to 4. 
The concentration of the iodide ion to be added in the present invention is 
preferably lower, specifically, 0.2 mol/liter or less, most preferably 0.1 
mol/liter or less. 
The time required for the addition of the iodide ion in the present 
invention is preferably 5 minutes or more, more preferably 10 minutes or 
more. 
An iodide ion may be directly added to a reaction vessel using a nozzle 
which is usually used for adding an aqueous solution of a silver salt or 
an aqueous solution of halide to a reaction vessel, or may be added at the 
position above the liquid surface of the reaction solution, but is 
preferably added using a nozzle used for adding an aqueous solution of a 
silver salt or an aqueous solution of halide. 
When an iodide ion is added in the present invention, it is preferably 
added on the conditions of the host emulsion within region A shown in FIG. 
3 which is a diagram plotting pAg to temperatures (.degree.C.) (on the 
lines or within the region surrounded by four lines connecting in order 
four points represented by (temperature, pAg) (55, 9.66), (55, 10.74), 
(80, 8.87) and (80, 9.85)). Herein, pAg is the logarithm of the reciprocal 
of the ion concentration of Ag.sup.+ of the reaction system. Further, 
within region A, the region of higher temperature and higher pAg is more 
preferred. That is, the effect of the present invention is more 
effectively manifested in the region where the solubility of hardly 
soluble silver halide host grain in the reaction solution is extremely 
high. 
As the function of temperature, when the temperature of the reaction 
solution is less than 55.degree. C., effective dissolution according to 
the present invention is difficult to occur. Further, even when it is 
55.degree. C. or more, if the pAg in the reaction solution system is in 
the lower region than region A, effective dissolution is difficult to 
occur. In such cases, the local epitaxial formation of silver iodide orthe 
deposition and lamination of silver iodobromide on the grain are often 
observed. 
In the present invention, host grains having a prescribed silver iodide 
content can be converted to the substrate grains of the shape unlimitedly 
approaching to a cylinder by the complete dissolution of the periphery of 
hexagonal or triangular grains by the addition of an iodide ion, but it is 
more preferred to conduct the above conversion within a predetermined 
temperature-pAg range to exhibit the above-described effect of the present 
invention. This is very important process to form dislocation lines in 
silver halide grains and will be described later. 
The silver iodobromide thin layer forming step (step c)) is described in 
detail below. 
It is presumed that the iodide ion added in Process b is present as the 
iodide ion in the reaction solution or precipitated as silver iodide or 
silver iodobromide containing 40 mol % silver iodide of almost solid 
solubility limit on the host grain. These are present in an equilibrium 
condition. 
This equilibrium condition is controlled by the relationship of the 
temperature of the reaction solution and the concentration of the halide 
ion present. 
In the present invention, the iodide ion is recrystallized and deposited on 
the host tabular grain as silver iodobromide, making supply source of this 
iodide ion or silver iodide or silver iodobromide on the host grain in the 
equilibrium condition, with the aid of an aqueous solution of a silver 
salt added from the outside of the reaction system. 
The formation of silver iodobromide thin layer in the present invention is 
preferably conducted within region B shown in FIG. 3 which is a diagram 
shown by the functions of temperatures and pAg (on the lines or within the 
region surrounded by four lines connecting in order four points 
represented by (temperature, pAg) (55, 8.74), (55, 10.74), (80, 8.00) and 
(80, 9.85)). When a silver iodobromide thin layer is formed within this 
preferred temperature-pAg range, it is preferred to add a bromide ion with 
the addition of an aqueous solution of a silver salt in a corresponding 
degree. This preferred embodiment of the present invention is outside of 
the temperature-pAg range disclosed in the above JP-A-3-136032 and 
JP-A-3-136033. 
There are cases where silver halide tabular grains prepared according to 
steps (a), (b) and (c) of the present invention have dislocation lines. 
Tabular grains accounting for 60% or more of the entire silver halide 
grains prepared according to the present invention preferably have 
dislocation lines within the region from the outer circumference of the 
silver halide grain the periphery of which is completely dissolved in Step 
(b) to the position where a silver iodobromide thin layer is formed in 
step (c) as shown in FIG. 1. 
Dislocation lines may be formed, other than the above position, over the 
region inclusive of the center part of two major faces parallel to each 
other of a tabular grain. When dislocation lines are formed over the 
entire region of the major faces, when viewed from the vertical direction 
to the major face of the grain, the directions of these dislocation lines 
are sometimes about the (211) directions crystallographically, but there 
are other cases such as in which the directions of dislocation lines are 
(110) directions or formed at random. Further, the length of each 
dislocation line is also variously different and there are a case where 
dislocation lines are observed on the major face as short lines, and a 
case where dislocation lines are observed as long lines arriving to the 
side (outer circumference). Dislocation lines are sometimes straight lines 
and sometimes snaking. Further, in many cases, they are mingling with each 
other and forming network-like dislocation lines. 
The dislocation lines of tabular grains can be observed directly with the 
transmission type electron microscope at low temperature as disclosed, for 
example, in J. F. Hamilton, Phot. Sci. Eng., vol. 11, p. 57 (1967) and T. 
Shiozawa, J. Soc. Phot. Sci. Japan, vol. 35, p. 213 (1972). That is, the 
silver halide grains taken out from the emulsion with a care so as not to 
apply such a pressure as generates dislocation lines on the grains are put 
on a mesh for observation by an electron microscope, and observation is 
conducted by a transmission method with the sample being in a frozen state 
so as to prevent the injury by an electron beam (e.g., printout). At this 
time, the thicker the thickness of the grain, the more difficult is the 
electron beam to be transmitted. Accordingly, it is preferred to use a 
high voltage electron microscope (200 kV or more with the grains of the 
thickness of 0.25 .mu.m) for observing clearly. When viewed from the 
vertical direction to the major face of the grain by the photograph of the 
grains obtained as described above, the place of dislocation lines in each 
grain can be obtained. 
Further, since the dislocation lines can be seen or cannot be seen 
according to the inclination angle of the sample to the electron beam, it 
is necessary to detect the existing positions of dislocation lines by 
observing the photographs of the same grain taken at different angles as 
many as possible to make a thorough observation of dislocation lines. In 
the present invention, the existing posotions and the number of 
dislocation lines were pursued by photographing five kinds of photographs 
of the grain with respect to the same grain with changing the inclination 
angle at 5.degree. step using a high voltage electron microscope. 
FIG. 1 is a high voltage electron microphotograph of a grain produced 
according to the present invention, and FIG. 2 is a drawing of the grain 
of the photograph in FIG. 1. 
In the present invention, host grains can be converted to the substrate 
grains of a shape unlimitedly approaching to a cylinder by the complete 
dissolution of the periphery of hexagonal (or triangular) grains by the 
addition of an iodide ion. In FIG. 1, the remaining prototype of the 
substrate grain of a cylindrical shape having a boundary line on the 
circle can be observed. Thereafter, the reclaimed hexagonal shape by 
recrystallization in the silver iodo-bromide thin layer forming step can 
be observed. That is, the host grain the lateral sides of which were 
completely dissolved in step (b) and the silver iodobromide thin layer 
formed in step (c) are present with a clear boundary. 
Further, dislocation lines are formed in step (c) and, as shown in FIG. 2, 
high density dislocation lines are present in the region reclaimed in step 
(c). The lengths of these dislocation lines increase gradually from the 
center region of each side between vertexes of the hexagon toward the 
vertexes. 
Dislocation lines are considered to be generated by the disagreement of the 
lattice constant of silver bromide containing silver iodide of the host 
grain which is dissolved to a cylindrical shape with the lattice constant 
of silver bromide containing high silver iodide in the hexagonal region 
(region of oblique lines in FIG. 2) which is reclaimed by 
recrystallization. 
The tabular grains according to the present invention have such a 
characteristic as the lengths of dislocation lines in the region in the 
vicinity of the vertex are longer than those in the region on each side of 
a hexagon or triangle. This is because the highly active part of tabular 
grains, i.e., the highly soluble vertex region of tabular grains, are 
dissolved best. The tabular grains of the present invention are also 
characterized in that dislocation lines are present very densely. 
The dislocation lines of the tabular grains of the present invention are 
apparently different in aspects from the dislocation lines shown in FIGS. 
2 and 3 of JP-A-63-220238. 
The dislocation lines shown in FIG. 1 of JP-A-3175440 are present only in 
the vicinity of the vertex of tabular grains, therefore, apparently differ 
in aspects from the dislocation lines of the tabular grains of the present 
invention. 
While as for JP-A-3-136032 and JP-A-3-136033, there are no disclosures 
about dislocation lines. 
This distribution conditions of the dislocation lines in grains are 
considered to effectively inhibit deterioration of degradation of 
photographic properties due to various stresses, but the details thereof 
have not been elucidated yet. 
Gelatin is preferably used as a protective colloid at the time of 
preparation of the emulsion of the present invention and as a binder for 
other hydrophilic colloid layers, but other hydrophilic colloids can also 
be used. 
Examples thereof include proteins such as gelatin derivatives, graft 
polymers of gelatin and other high polymers, albumin and casein; sugar 
derivatives such as cellulose derivatives such as hydroxyethyl cellulose, 
carboxymethyl cellulose, and cellulose sulfate, sodium alginate, and 
starch derivatives; and various kinds of synthetic hydrophilic high 
polymers of homopolymers or copolymers such as polyvinyl alcohol, 
partially acetalated polyvinyl alcohol, poly-N-vinylpyrrolidone, 
polyacrylic acid, polymethacrylic acid, polyacrylamide, 
polyvinylimidazole, and polyvinylpyrazole. 
Acid-processed gelatin and enzyme-processed gelatin disclosed in Bull. Soc. 
Sci. Photo. Japan, No. 16, p. 30 (1966) can be used as well as 
lime-processed gelatin, and hydrolyzed product and enzyme decomposed 
product of gelatin can also be used. 
The emulsion of the present invention is preferably washed with water for 
the purpose of desalting and dispersed in a newly prepared protective 
colloid. The washing temperature can be selected according to the purpose 
but is preferably from 5 to 50.degree. C. The pH at washing time can also 
be selected according to the purpose but is preferably from 2 to 10, more 
preferably from 3 to 8. The pAg at washing time can also be selected 
according to the purpose but is preferably from 5 to 10. The washing 
method can be selected from among a noodle washing method, a dialysis 
method using a semi-permeable membrane, a centrifugal separation method, a 
coagulation precipitation method, and an ion exchange method. In the case 
of a coagulation precipitation method, a washing method can be selected 
from among a method using sulfate, a method using an organic solvent, a 
method using a water-soluble polymer, a method using a gelatin derivative, 
etc. 
Metal ion salts are preferably contained, according to purposes, in the 
emulsion of the present invention during emulsion preparation, e.g., at 
the time of grain formation, during desalting process, during chemical 
sensitization or before coating. When grains are doped with, the addition 
is preferably conducted during grain formation, and when ornamenting the 
surfaces of grains or using as a chemical sensitizer, it is preferably 
added after grain formation and before completion of chemical 
sensitization. A method of doping can be selected such that a grain is 
entirely doped or only a silver iodobromide thin layer part is doped. 
Examples of the metals which can be used include Mg, Ca, Sr, Ba, Al, Sc, 
Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, 
Hg, Tl, In, Sn, Pb, Bi, etc. These metals can be added if in the form of a 
salt, such as ammonium salt, acetate, nitrate, sulfate, phosphate, 
hydroxide, or a complex salt having six ligands or a complex salt having 
four ligands, which can be dissolved at the time of grain formation, for 
example, CdBr.sub.2, CdCl.sub.2, Cd(NO.sub.3).sub.2, Pb(NO.sub.3).sub.2, 
Pb(CH.sub.3 COO).sub.2, K.sub.3 [Fe(CN).sub.6 ], (NH.sub.4).sub.4 
[Fe(CN.sub.6 ], K.sub.3 IrCl.sub.6, (NH.sub.4).sub.3 RhCl.sub.6, K.sub.4 
Ru(CN).sub.6, etc. A ligand of a coordination compound can be selected 
from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo 
and carbonyl. They may comprise only one kind of a metal compound or may 
comprise two, three or more metal compounds in combination. 
Metal compounds are preferably dissolved in water or an appropriate solvent 
such as methanol or acetone. For stabilizing the solution, a method of 
adding an aqueous solution of halogenated hydrogen (e.g., HCl, HBr) or an 
aqueous solution of alkali halide (e.g., KCl, NaCl, KBr, NaBr) to the 
solution can be used. Acid or alkali may be added, if desired. Metal 
compounds can be added to a reaction vessel before grain formation or may 
be added during grain formation. They also can be added to aqueous 
solutions of a water-soluble silver salt (e.g., AgNO.sub.3) or an alkali 
halide (e.g., NaCl, KBr, KI) and added to a reaction solution continuously 
during silver halide grain formation. Further, they may be added as a 
separate solution independently from a water-soluble silver salt or an 
aqueous solution of alkali halide and added continuously at a proper time 
during grain formation. It is also preferred to use various addition 
methods in combination. 
There are cases where a method in which the chalcogenide compounds as 
disclosed in U.S. Pat. No. 3,772,031 are added during the emulsion 
formation is useful. Cyanide, thiocyanide, selenocyanic acid, carbonate, 
phosphate and acetate can be present in addition to S, Se and Te. 
The silver halide grains of the present invention can be subjected to at 
least one of sulfur sensitization, selenium sensitization, gold 
sensitization, palladium sensitization, noble metal sensitization and 
reduction sensitization during an optional stage of the production process 
of the silver halide emulsion. A combined use of two or more sensitizing 
methods is preferred. Various types of emulsions can be prepared depending 
upon the stages when the chemical sensitization is carried out. There are 
a type in which a chemically sensitized nucleus is buried in the internal 
part of a grain, a type in which a chemically sensitized nucleus is buried 
in the shallow part from the surface of a grain, or a type in which a 
chemically sensitized nucleus is formed on the surface of a grain. The 
emulsion of the present invention can select the position of a chemically 
sensitized nucleus according to the purpose, but it is generally preferred 
to have at least one chemically sensitized nucleus in the vicinity of the 
surface of a grain. 
Chemical sensitizing methods which can be preferably conducted in the 
present invention include chalcogenide sensitization alone, noble metal 
sensitization alone and the combinations thereof, and these sensitizing 
methods can be carried out using active gelatin as disclosed in T. H. 
James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, 
pp. 67 to 76, and also sensitization can be conducted using sulfur, 
selenium, tellurium, gold, platinum, palladium, or iridium, or two or more 
of these sensitizers in combination at pAg of from 5 to 10, pH of from 5 
to 8, and temperature of from 30 to 80.degree. C. as disclosed in Research 
Disclosure, Vol. 120, April, 1974, 12008, idib., Vol. 34, June, 1975, 
13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 
3,901,714, 4,266,018 and 3,904,415 and British Patent 1,315,755. In noble 
metal sensitization, a noble metal salt such as gold, platinum, palladium 
and iridium can be used, and particularly preferred are gold 
sensitization, palladium sensitization, and the combined use of them. 
In gold sensitization, known compounds such as chloroauric acid, potassium 
chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide 
can be used. 
The palladium compound means 2-equivalent or 4-equivalent salt of 
palladium. Preferred palladium compound is represented by R.sub.2 
PdX.sub.6 or R.sub.2 PdX.sub.4, wherein R represents a hydrogen atom, an 
alkali metal atom or an ammonium group; and X represents a halogen atom, 
e.g., chlorine, bromine or iodine. Specifically, K.sub.2 PdCl.sub.4, 
(NH.sub.4).sub.2 PdCl.sub.6, Na.sub.2 PdCl.sub.4, (NH.sub.4).sub.2 
PdCl.sub.4, Li.sub.2 PdCl.sub.4, Na.sub.2 PdCl.sub.6 or K.sub.2 PdBr.sub.4 
is preferred. A gold compound and a palladium compound are preferably used 
in combination with thiocyanate or selenocyanate. 
Hypo, thiourea based compounds, rhodanine based compounds, and the 
sulfur-containing compounds disclosed in U.S. Pat. Nos. 3,857,711, 
4,266,018 and 4,054,457 can be used as a sulfur sensitizer. 
Chemical sensitization can be conducted in the presence of a so-called 
auxiliary chemical sensitizer. The compounds known to inhibit fogging 
during chemical sensitization and to increase sensitivity, such as 
azaindene, azapyridazine, azapyrimidine, are used as a useful auxiliary 
chemical sensitizer. Examples of auxiliary chemical sensitizer reformer 
are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,751, 
3,554,757, JP-A-58-126526 and G. F. Duffin, Photographic Emulsion 
Chemistry, pp. 138 to 143. 
The emulsion of the present invention is preferably subjected to gold 
sensitization in combination. The amount of a gold sensitizer for use in 
the present invention is preferably from 1.times.10.sup.-4 to 
1.times.10.sup.-7 mol, more preferably from 1.times.10.sup.-5 to 
5.times.10.sup.-7 mol, per mol of the silver halide. The amount of a 
palladium compound for use in the present invention is preferably from 
1.times.10.sup.-3 to 5.times.10.sup.-7 mol per mol of the silver halide. 
The amount of a thiocyanide compound or a selenocyanide compound is 
preferably from 5.times.10.sup.-2 to 1.times.10.sup.-6 mol per mol of the 
silver halide. 
The amount of the sulfur sensitizer for use in the silver halide grains of 
the present invention is preferably from 1.times.10.sup.-4 to 
1.times.10.sup.-7 mol, more preferably from 1.times.10.sup.-5 to 
5.times.10.sup.-7 mol, per mol of the silver halide. 
The emulsion of the present invention are preferably sensitized by a 
selenium sensitizing method. Known unstable selenium compounds are used in 
selenium sensitization, and specific examples thereof include selenium 
compounds such as colloidal metal selenium, selenoureas (e.g., 
N,N-dimethylselenourea, N,N-diethylselenourea), seleno ketones and 
selenoamides. There are cases where selenium sensitization is rather 
preferably conducted in combination with sulfur sensitization or noble 
metal sensitization or with both of them. 
The silver halide emulsion of the present invention is preferably reduction 
sensitized during grain formation, or after grain formation and before 
chemical sensitization or during chemical sensitization, or after chemical 
sensitization. 
The method of the reduction sensitization can be selected from a method in 
which a reduction sensitizer is added to a silver halide emulsion, a 
method in which grains are grown or ripened in the atmosphere of low pAg 
of from 1 to 7 which is called silver ripening, or a method in which 
grains are grown or ripened in the atmosphere of high pH of from 8 to 11 
which is called high pH ripening. Further, two or more of these methods 
can be used in combination. 
A method of adding a reduction sensitizer is preferred from the point of 
capable of delicately controlling the level of the reduction 
sensitization. 
Stannous salt, ascorbic acid and derivatives thereof, amines and 
polyamines, hydrazine derivatives, formamidine-sulfinic acid, silane 
compounds and borane compounds are well known as a reduction sensitizer. 
These known reduction sensitizers can be selected and used in the present 
invention, and two or more of these compounds can also be used in 
combination. Stannous chloride, thiourea dioxide, dimethylamineborane, 
ascorbic acid and derivatives thereof are preferred compounds as a 
reduction sensitizer. As the addition amount of the reduction sensitizer 
depends upon the production conditions of the emulsion, the addition 
amount needs to be selected, but 10.sup.-7 to 10.sup.-3 mol per mol of the 
silver halide is preferred. 
The reduction sensitizers are dissolved in water or a solvent such as 
alcohols, glycols, ketones, esters or amides and added during grain 
growth. The reduction sensitizers may be previously added to a reaction 
vessel, but the addition at proper time during grain growth is more 
preferred. Further, the reduction sensitizers have been previously added 
to an aqueous solution of water-soluble silver salt or an aqueous solution 
of water-soluble alkali halide and silver halide grains can be 
precipitated using these aqueous solutions. In addition, the solution of 
the reduction sensitizers may be divided to several parts and added in 
several times or may be added continuously over a long period of time with 
the degree of the grain growth. 
It is preferred to use an oxidant for silver during the production process 
of the emulsion of the present invention. An oxidant for silver is a 
compound having a function of acting on metal silver and converting it to 
a silver ion. In particular, a compound which can convert superminute 
silver grains by-produced in the course of the formation of silver halide 
grains and chemical sensitization to a silver ion is effective. The silver 
ion converted may form hardly water-soluble silver salt such as silver 
halide, silver sulfide or silver selenide, or may form easily 
water-soluble silver salt such as silver nitrate. An oxidant for silver 
may be inorganic or organic. Examples of inorganic oxidants include 
oxyacid salt, such as ozone, hydrogen peroxide and addition products 
thereof (e.g., NaBO.sub.2.H.sub.2 O.sub.2.3H.sub.2 O, 2NaCO.sub.3.3H.sub.2 
O.sub.2, Na.sub.4 P.sub.2 O.sub.7.2H.sub.2 O.sub.2, 2Na.sub.2 
SO.sub.4.H.sub.2 O.sub.2.2H.sub.2 O), peroxyacid salt (e.g., K.sub.2 
S.sub.2 O.sub.8, K.sub.2 C.sub.2 O.sub.6, K.sub.2 P.sub.2 O.sub.8), peroxy 
complex compound (e.g., K.sub.2 [Ti(O.sub.2)C.sub.2 O.sub.4 ].3H.sub.2 O, 
4K.sub.2 SO.sub.4.Ti(O.sub.2)OH.SO.sub.4.2H.sub.2 O, Na.sub.3 [VO(O.sub.2) 
(C.sub.2 H.sub.4).sub.2 ]. 6H.sub.2 O), permanganate (e.g., KMnO.sub.4), 
and chromate (e.g., K.sub.2 Cr.sub.2 O.sub.7), halogen element such as 
iodine and bromine, perhalogen acid salt (e.g., potassium periodate), salt 
of metal of high valency (e.g., potassium hexacyanoferrate-(III)), and 
thiosulfonate. 
Further, examples of organic oxidants include quinones such as p-quinone, 
organic peroxide such as peracetic acid and perbenzoic acid, a compound 
which releases active halogen (e.g., N-bromosuccinimide, chloramine T, 
chloramine B). 
The oxidants which are preferably used in the present invention are 
inorganic oxidants such as ozone, hydrogen peroxide and addition products 
thereof, halogen element, thiosulfonate, and organic oxidants such as 
quinones. It is preferred to use the above described reduction 
sensitization in combination with an oxidant for silver. The method of 
usage can be selected from a method in which an oxidant is used and then 
reduction sensitization is carried out, an inverse method thereof, or a 
method in which both are concurred with. These methods can be selectively 
used in a grain forming process and a chemical sensitization process. 
The photographic emulsion for use in the present invention can contain 
various compounds for preventing fogging during manufacture of the 
photographic material, during storage, or during photographic processing, 
or for stabilizing photographic capabilities. That is, many compounds 
known as antifoggants and stabilizers can be incorporated into the 
emulsion, for example, thiazoles, e.g., benzothiazolium salt, 
nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, 
bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, 
mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, 
benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, 
1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; 
thioketo compounds, e.g., oxazolinethione; and azaindenes, e.g., 
triazaindenes, tetraazaindenes (in particular, 
4-hydroxy-substituted(1,3,3a,7)tetraazaindenes), and pentaazaindenes. For 
example, the compounds disclosed in U.S. Pat. Nos. 3,954,474, 3,982,947, 
JP-B-52-28660 (the term "JP-B" as used herein means an "examined Japanese 
patent publication") can be used. One preferred compound is the compound 
disclosed in JP-A-63-212932. Antifoggants and stabilizers can be added to 
the emulsion according to the purpose at any time before grain formation, 
during grain formation, after grain formation, during washing process, at 
the time of dispersion after washing, before chemical sensitization, 
during chemical sensitization, after chemical sensitization, and before 
coating. They are added during emulsion preparation for various purposes 
of, in addition to their original functions of prevention of fogging and 
stabilization of photographic capabilities, controlling crystal habit of 
grains, decreasing the grain size, reducing the solubility of grains, 
controlling chemical sensitization, or controlling arrangement of dyes. 
The photographic emulsion for use in the present invention is preferably 
spectrally sensitized with methine dyes and the like to exhibit the 
effects of the present invention. The dyes which are used include a 
cyanine dye, a merocyanine dye, a complex cyanine dye, a complex 
merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, 
and a hemioxonol dye. Particularly useful dyes are dyes belonging to a 
cyanine dye, a merocyanine dye and a complex merocyanine dye. Nuclei which 
are usually utilized as basic heterocyclic nuclei in cyanine dyes can be 
applied to these dyes. For example, a pyrroline nucleus, an oxazoline 
nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a 
thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole 
nucleus, a pyridine nucleus; the above nuclei to which alicyclic 
hydrocarbon rings are fused; the above nuclei to which aromatic 
hydrocarbon rings are fused, that is, an indolenine nucleus, a 
benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a 
naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, 
a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline 
nucleus can be applied. These heterocyclic nuclei may be substituted on 
the carbon atoms. 
As a nucleus having a ketomethylene structure, a 5- or 6-membered 
heterocyclic nucleus such as a pyrazolin-5-one nucleus, a thiohydantoin 
nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione 
nucleus, a rhodanine nucleus, or a thiobarbituric acid nucleus can be 
applied to a merocyanine dye or a complex merocyanine dye. 
These sensitizing dyes may be used alone or in combination. A combination 
of sensitizing dyes is often used for the purpose of supersensitization. 
Examples thereof are disclosed in U.S. Pat. Nos. 2,688,545, 2,977,229, 
3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 
3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 
4,026,707, British Patents 1,344,281, 1,507,803, JP-B-43-4936, 
JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925. 
Further, dyes which themselves do not have a spectral sensitizing function 
or substances which substantially do not absorb visible light but show 
supersensitization can be incorporated into the emulsion with sensitizing 
dyes. 
Sensitizing dyes may be added to the emulsion at any stage of the 
preparation of the emulsion hitherto known to be useful. In general, it is 
conducted during the period after the completion of chemical sensitization 
and before coating, however, a method in which sensitizing dyes are added 
at the same time with the addition of chemical sensitizers and spectral 
sensitization is carried out simultaneously with chemical sensitization 
can be employable as disclosed in U.S. Pat. Nos. 3,628,969 and 4,225,666, 
further, as disclosed in JP-A-58-113928, spectral sensitization can be 
conducted prior to chemical sensitization, or sensitizing dyes can be 
added and spectral sensitization can be started before completion of the 
precipitation formation of the silver halide grains. Still further, as 
disclosed in U.S. Pat. No. 4,225,666, sensitizing dyes can be divided and 
added separately, that is, a part of them is added prior. to chemical 
sensitization and the remaining is added after chemical sensitization, 
therefore, any time during silver halide grain formation is feasible, as 
well as the method disclosed in U.S. Pat. No. 4,183,756. 
A sensitizing dye can be added in an amount of from 4.times.10.sup.-6 to 
8.times.10.sup.-3 mol per mol of the silver halide, but in the case of 
more preferred silver halide grain size of from 0.2 to 1.2 .mu.m, the 
amount of from 5.times.10.sup.-5 to 2.times.10.sup.-3 mol per mol of the 
silver halide is more preferred. 
The above-described various additives are used in photographic materials 
according to the present invention but various other additives can be used 
according to the purpose. 
These additives are disclosed in detail in Research Disclosure, Item 17643 
(December, 1978), ibid., Item 18716 (November, 1979) and ibid., Item 
308119 (December, 1989). The locations corresponding thereto are indicated 
in the table below. 
__________________________________________________________________________ 
Type of Additives 
RD 17643 
RD 18716 RD 308119 
__________________________________________________________________________ 
Chemical Sensitizers 
page 23 
page 648, right column 
page 996 
Sensitivity Increasing 
-- page 648, right column 
-- 
Agents 
Spectral Sensitizers 
pages 23-24 
page 648, right column 
page 996, 
and Supersensitizers 
to page 649, right 
right column 
column to page 998 
right column 
Brightening Agents 
page 24 
page 647, right column 
page 998, 
right column 
Antifoggants and 
pages 24-25 
page 649, right column 
page 998, 
Stabilizers right column 
to page 1000, 
right column 
__________________________________________________________________________ 
Type of Additives 
RD 17643 
RD 18716 RD 307105 
__________________________________________________________________________ 
Light Absorbers, Filter 
pages 25-26 
page 649, right column 
page 1003, left 
Dyes, and Ultraviolet 
to page 650, left 
column to page 
Absorbers column 1003, right 
column 
Antistaining Agents 
page 25, 
page 650, left to 
page 1002, 
right column 
right columns 
right column 
Dye image Stabilizers 
page 25 
-- page 1002, 
right column 
Hardening Agents 
page 26 
page 651, left column 
page 1004, 
right column to 
page 1005, left 
column 
10. 
Binders page 26 
page 651, left column 
page 1003, left 
column to page 
1004, right 
column 
Plasticizers and 
page 27 
page 650, right column 
page 1006, left 
Lubricants column to page 
1006 right 
column 
Coating Aids and 
pages 26-27 
page 650, right column 
page 1005, left 
Surfactants column to page 
1006, left 
column 
Antistatic Agents 
page 27 
page 650, right column 
page 1006, 
right column to 
page 1007, left 
column 
Matting Agents 
-- -- page 1008, left 
column to page 
1009, left 
column 
__________________________________________________________________________ 
The emulsion of the present invention, and techniques such as layer 
arrangement, silver halide emulsion, functional couplers such as 
dye-forming couplers and DIR couplers, various additives and the like and 
development processing which can be used in the photographic material 
using the emulsion of the present invention are disclosed in EP-A-565096 
(published on Oct. 13, 1993) and the patents cited therein. Each item and 
corresponding locations are listed below. 
______________________________________ 
1. Layer Structures 
lines 23 to 35, page 61, line 41, 
page 61 to line 14, page 62 
2. Interlayers lines 36 to 40, page 61 
3. Interlayer Effect 
lines 15 to 18, page 62 
Donating Layers 
4. Halide Composi- 
lines 21 to 25, page 62 
tions of Silver 
Halide 
5. Crystal Habits of 
lines 26 to 30, page 62 
Silver Halide 
Grains 
6. Grain Sizes of 
lines 31 to 34, page 62 
Silver Halide 
Grains 
7. Producing lines 35 to 40, page 62 
Methods of 
Emulsions 
8. Grain Size lines 41-42, page 62 
Distributions of 
Silver Halide 
Grains 
9. Tabular Grains 
lines 43 to 46, page 62 
10. Structures of lines 47 to 53, page 62 
Interiors of 
Grains 
11. Latent Image line 54, page 62 to line 5, page 63 
Forming Types of 
Emulsions 
12. Physical Ripening 
lines 6 to 9, page 63 
and Chemical 
Ripening of 
Emulsions 
13. Mixed Usage of 
lines 10 to 13, page 63 
Emulsions 
14. Fogged Emulsions 
lines 14 to 31, page 63 
15. Light-Insensitive 
lines 32 to 43, page 63 
Emulsions 
16. Coating Amount of 
lines 49 and 50, page 63 
Silver 
17. Photographic disclosed in Research Disclosure, 
Additives Item 17643 (Dec., 1978), ibid., Item 
18716 (Nov., 1979) and ibid., Item 
307105 (Nov., 1989) and the locations 
related thereto are indicated below 
______________________________________ 
__________________________________________________________________________ 
Type of Additives 
RD 17643 
RD 18716 RD 307105 
__________________________________________________________________________ 
1) 
Chemical Sensitizers 
page 23 
page 648, right column 
page 866 
2) 
Sensitivity Increasing 
-- page 648, right column 
-- 
Agents 
3) 
Spectral Sensitizers 
pages 23-24 
page 648, right column 
pages 866-868 
and Supersensitizers 
to page 649, right 
column 
4) 
Brightening Agents 
page 24 
page 647, right column 
page 868 
5) 
Antifoggants and 
pages 24-25 
page 649, right column 
pages 868-870 
Stabilizers 
6) 
Light Absorbers, Filter 
pages 25-26 
page 649, right column 
page 873 
Dyes, and Ultraviolet 
to page 650, left 
Absorbers column 
7) 
Antistaining Agents 
page 25, 
page 650, left to 
page 872 
right column 
right columns 
8) 
Dye image Stabilizers 
page 25 
page 650, left column 
page 872 
9) 
Hardening Agents 
page 26 
page 651, left column 
pages 874-875 
10) 
Binders page 26 
page 651, left column 
pages 873-874 
11) 
Plasticizers and 
page 27 
page 650, right column 
page 876 
Lubricants 
12) 
Coating Aids and 
pages 26-27 
page 650, right column 
pages 875-876 
Surfactants 
13) 
Antistatic Agents 
page 27 
page 650, right column 
pages 876-877 
14) 
Matting Agents 
-- -- pages 878-879 
__________________________________________________________________________ 
______________________________________ 
18. Formaldehyde lines 54 to 57, page 64 
Scavengers 
19. Mercapto-Based 
lines 1 and 2, page 65 
Antifoggants 
20. Releasing Agents 
lines 3 to 7, page 65 
of Antifoggants 
and the like 
21. Dyes lines 7 to 10, page 65 
22. Color Couplers 
lines 11 to 13, page 65 
in General 
23. Yellow, Magenta 
lines 14 to 25, page 65 
and Cyan Couplers 
24. Polymer Couplers 
lines 26 to 28, paqe 65 
25. Diffusible Dye- 
lines 29 to 31, page 65 
Forming Couplers 
26. Colored Couplers 
lines 32 to 38, page 65 
27. Functional lines 39 to 44, page 65 
Couplers in 
General 
28. Bleaching lines 45 to 48, page 65 
Accelerator- 
Releasing Couplers 
29. Development lines 49 to 53, page 65 
Accelerator- 
Releasing Couplers 
30. Other DIR line 54, page 65 to line 4, page 66 
Couplers 
31. Methods of lines 5 to 28, page 66 
Coupler 
Dispersion 
32. Preservatives, 
lines 29 to 33, page 66 
Antibacterial 
Agents 
33. Kinds of lines 34 to 36, page 66 
Photographic 
Materials 
34. Film Thickness of 
line 40, page 66 to line 1, page 67 
Light-Sensitive 
Layer and Film 
Swelling Rate 
35. Backing Layers 
lines 3 to 8, page 67 
36. Development lines 9 to 11, page 67 
Processing in 
General 
37. Developing lines 12 to 30, page 67 
Solutions and 
Developing Agents 
38. Additives for lines 31 to 44, page 67 
Developing 
Solution 
39. Reversal Process 
lines 45 to 56, page 67 
40. Open Factor of 
line 57, page 67 to line 12, page 68 
Processing 
Solutions 
41. Developing Time 
lines 13 to 15, page 68 
42. Bleach-Fixing, 
line 16, page 68 to line 31, page 69 
Bleaching and 
Fixing 
43. Automatic lines 32 to 40, page 69 
Processors 
44. Washing, Rinsing 
line 41, page 69 to line 18, page 70 
and Stabilization 
45. Replenishment of 
lines 19 to 23, page 70 
Processing 
Solutions and 
Reuse 
46. Incorporation of 
lines 24 to 33, page 70 
Developing Agent 
in Photographic 
Material 
47. Temperature of 
lines 34 to 38, page 70 
Development 
Processing 
48. Use in Film lines 39 to 41, page 70 
Equipped with 
Lens 
______________________________________ 
In addition, bleaching solutions containing ferric salt and persulfate such 
as 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid with ferric 
nitrate as disclosed in European Patent 602600 can also be preferably 
used. When using these bleaching solutions, it is preferred to use a 
stopping process and a washing process between a color developing process 
and a bleaching process, and an organic acid such as acetic acid, succinic 
acid, or maleic acid is preferably used in a stopping solution. In 
addition, it is preferred for such bleaching solutions to contain an 
organic acid such as acetic acid, succinic acid, maleic acid, glutaric 
acid, or adipic acid in an amount of from 0.1 to 2 mol/liter for the 
purpose of pH adjustment and bleaching fog. 
The present invention will be illustrated in more detail with reference to 
examples below, but the present invention is not construed as being 
limited thereto. 
EXAMPLE 1 
Preparation of Emulsion 
Preparation of Tabular Seed Crystal A 
An aqueous solution (1,600 ml) containing 4.5 g of KBr and 7.9 g of gelatin 
having an average molecular weight of 15,000 was stirred while maintaining 
the temperature at 40.degree. C. To the aqueous solution, an aqueous 
solution containing 8.9 g of silver nitrate and an aqueous solution of KBr 
(6.2 g) containing 18.9 wt% of KI were added by a double jet method for 40 
seconds. After 38 g of gelatin was added thereto, the temperature was 
raised to 58.degree. C. An aqueous solution containing 1.9 g of silver 
nitrate was added thereto, then 0.05 mol of ammonia was added, and 15 
minutes after, pH was adjusted to 5.0 with acetic acid. Subsequently, an 
aqueous solution containing 219 g of silver nitrate and an aqueous 
solution containing KBr were added by a double jet method for 40 minutes 
with increasing the feed rate and maintaining the pAg in the solution at 
8.2. After the completion of the addition, the temperature was lowered to 
40.degree. C., and the reaction mixture was washed with water and 
desalted, then 50 g of gelatin was added and pH was adjusted to 5.8 and 
pAg to 8.8 at 40.degree. C. 
This seed crystal emulsion contained tabular grains containing 0.5 mol % of 
silver iodide, 1.2 mol per kg of the emulsion of Ag, 60 g of gelatin, and 
having average diameter corresponding to circle of 0.35 .mu.m, variation 
coefficient corresponding to circle of 16%, average thickness of 0.09 
.mu.m and average aspect ratio of 3.9. 
Preparation of Tabular Seed Crystal B 
Seed crystal B was prepared in the same manner as the preparation of seed 
crystal A except that pAg in the solution was maintained at 9.1 at the 
time of addition by a double jet method by accelerated feed rate. 
This seed crystal emulsion contained tabular grains containing 0.5 mol % of 
silver iodide, 1.2 mol per kg of the emulsion of Ag, 60 g of gelatin, and 
having average diameter corresponding to circle of 0.40 .mu.m, variation 
coefficient corresponding to circle of 20%, average thickness of 0.06 
.mu.m and average aspect ratio of 6.7. 
Preparation of Emulsion Em-1 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
75.degree. C. After 34 g of silver bromide tabular seed crystal A was 
added, an aqueous solution containing 142.3 g of silver nitrate and 566 ml 
of an aqueous solution of halide containing 103 g of potassium bromide and 
9.5 g of potassium iodide were added by a double jet method for 45 minutes 
with increasing the feed rate and maintaining the pAg in the solution at 
8.0. After the completion of addition, the temperature was lowered to 
55.degree. C., the pAg in the solution at this time was 8.90. After 100 ml 
of an aqueous solution containing 10 g of silver nitrate and 540 ml of an 
aqueous solution containing 9.0 g of potassium iodide were added by a 
double jet method for 5 minutes with maintaining the feed rate constant, 
pAg was adjusted to 9.3. Further, an aqueous solution containing 63 g of 
silver nitrate and an aqueous solution containing 43 g of potassium 
bromide were added by a double jet method and the reaction solution was 
cooled. After washing the solution with water, gelatin was added at 
40.degree. C. and pH was adjusted to 5.8 and pAg to 8.8. 
This emulsion contained tabular silver iodobromide grains having average 
diameter corresponding to circle of 1.2 .mu.m, variation coefficient 
corresponding to circle of 22%, average thickness of 0.28 .mu.m, average 
aspect ratio of 4.3 and total silver iodide content of 8.8 mol %. 
Preparation of Emulsion Em-2 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
75.degree. C. After 34 g of silver bromide tabular seed crystal A was 
added, an aqueous solution containing 142.3 g of silver nitrate and 566 ml 
of an aqueous solution of halide containing 107 g of potassium bromide and 
4.2 g of potassium iodide were added by a double jet method for 60 minutes 
with increasing the feed rate and maintaining the pAg in the solution at 
7.7. 
The temperature of the above emulsion was lowered to 55.degree. C., and pAg 
was adjusted to 8.75 with an aqueous solution containing 30 wt% of 
potassium bromide. Then, 540 ml of an aqueous solution containing 9.0 g of 
potassium iodide was added for 5 minutes with maintaining the feed rate 
constant, and stirring was continued for further 2 minutes. pAg at this 
time was 9.4. 
Further, 250 ml of an aqueous solution containing 73 g of silver nitrate 
and 180 ml of an aqueous solution containing 43 g of potassium bromide 
were added to the above emulsion by a double jet method and the reaction 
mixture was cooled. After washing the mixture with water, gelatin was 
added at 40.degree. C. and pH was adjusted to 5.8 and pAg to 8.8. 
This emulsion contained tabular silver iodobromide grains having average 
diameter corresponding to circle of 1.00 .mu.m, variation coefficient 
corresponding to circle of 16%, average thickness of 0.33 .mu.m, average 
aspect ratio of 3.0 and total silver iodide content of 5.9 mol %. 
Preparation of Emulsion Em-3 
a) Preparation of Host Tabular Grains 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
75.degree. C. After 34 g of silver bromide tabular seed crystal B was 
added, 670 ml of an aqueous solution containing 142.3 g of silver nitrate 
and 566 ml of an aqueous solution of halide containing 107 g of potassium 
bromide and 4.2 g of potassium iodide were added by a double jet method 
for 45 minutes with increasing the feed rate and maintaining the pAg in 
the solution at 8.0. 
b) Dissolution by Addition of Iodide Ion 
The temperature of the above emulsion was lowered to 55.degree. C., pAg at 
this time was 8.9. Then, 540 ml of an aqueous solution containing 9.0 g of 
potassium iodide was added for 5 minutes with maintaining the feed rate 
constant, and stirring was continued for further 2 minutes. pAg was 
adjusted to 8.9 at this time with an aqueous solution containing 1.0 wt% 
of silver nitrate. 
c) Formation of Silver Iodobromide Thin Layer 
Further, 250 ml of an aqueous solution containing 73 g of silver nitrate 
and 180 ml of an aqueous solution containing 43 g of potassium bromide 
were added to the above emulsion by a double jet method while maintaining 
pAg at 8.9 and the reaction mixture was cooled. After washing the mixture 
with water, gelatin was added at 40.degree. C. and pH was adjusted to 5.8 
and pAg to 8.8. 
Preparation of Emulsion Em-4 
a) Preparation of Host Tabular Grains 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
65.degree. C. After 34 g of silver bromide tabular seed crystal B was 
added, 670 ml of an aqueous solution containing 142.3 g of silver nitrate 
and 566 ml of an aqueous solution of halide containing 107 g of potassium 
bromide and 4.2 g of potassium iodide were added by a double jet method 
for 45 minutes with increasing the feed rate and maintaining the pAg in 
the solution at 8.0. 
b) Dissolution by Addition of Iodide Ion 
An aqueous solution containing 30 wt % of potassium bromide was added to 
the above emulsion and pAg was adjusted to 9.78. Then, 840 ml of an 
aqueous solution containing 9.0 g of potassium iodide was added for 20 
minutes with maintaining the feed rate constant, and stirring was 
continued for further 2 minutes. pAg at this time was 9.58. 
c) Formation of Silver Iodobromide Thin Layer 
Further, 250 ml of an aqueous solution containing 73 g of silver nitrate 
was added to the above emulsion with maintaining the feed rate constant 
and the reaction mixture was cooled. After washing the mixture with water, 
gelatin was added at 40.degree. C. and pH was adjusted to 5.8 and pAg to 
8.8. 
Preparation of Emulsion Em-5 
a) Preparation of Host Tabular Grains 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
75.degree. C. After 34 g of silver bromide tabular seed crystal B was 
added, 670 ml of an aqueous solution containing 142.3 g of silver nitrate 
and 566 ml of an aqueous solution of halide containing 107 g of potassium 
bromide and 4.2 g of potassium iodide were added by a double jet method 
for 45 minutes with increasing the feed rate and maintaining the pAg in 
the solution at 8.0. 
b) Dissolution by Addition of Iodide Ion 
An aqueous solution containing 30 wt % of potassium bromide was added to 
the above emulsion and pAg was adjusted to 9.2. Then, 840 ml of an aqueous 
solution containing 9.0 g of potassium iodide was added for 20 minutes 
with maintaining the feed rate constant, and stirring was continued for 
further 2 minutes. pAg at this time was 9.38. 
c) Formation of Silver Iodobromide Thin Layer 
Further, 250 ml of an aqueous solution containing 73 g of silver nitrate 
was added to the above emulsion with maintaining the feed rate constant 
and the reaction mixture was cooled. After washing the mixture with water, 
gelatin was added at 40.degree. C. and pH was adjusted to 5.8 and pAg to 
8.8. 
Preparation of Emulsion Em-6 
a) Preparation of Host Tabular Grains 
1,200 ml of an aqueous solution containing 1.2 g of potassium bromide and 
33 g of gelatin was stirred while maintaining the temperature at 
75.degree. C. After 34 g of silver bromide tabular seed crystal B was 
added, 440 ml of an aqueous solution containing 94.3 g of silver nitrate 
and 480 ml of an aqueous solution of halide containing 72 g of potassium 
bromide and 2.72 g of potassium iodide were added by a double jet method 
for 40 minutes with increasing the feed rate and maintaining the pAg in 
the solution at 8.0. 
Then, 300 ml of an aqueous solution containing 48 g of silver nitrate and 
155 ml of an aqueous solution containing 38 g of potassium bromide were 
added by a double jet method for 10 minutes while maintaining the pAg in 
the solution at 8.0 and maintaining the feed rate constant. 
b) Dissolution by Addition of Iodide Ion 
An aqueous solution containing 30 wt % of potassium bromide was added to 
the above emulsion and pAg was adjusted to 9.2. Then, 840 ml of an aqueous 
solution containing 14.6 g of potassium iodide was added for 20 minutes 
with maintaining the feed rate constant, and stirring was continued for 
further 2 minutes. pAg at this time was 9.42. 
c) Formation of Silver Iodobromide Thin Layer 
Further, 250 ml of an aqueous solution containing 73 g of silver nitrate 
was added to the above emulsion with maintaining the feed rate constant 
and the reaction mixture was cooled. After washing the mixture with water, 
gelatin was added at 40.degree. C. and pH was adjusted to 5.8 and pAg to 
8.8. 
Preparation of Emulsion Em-7 
Em-7 was prepared in the same manner as the preparation of Em-6 except that 
dissolution by the addition of iodide ion b) was changed as follows. 
Dissolution by Addition of Iodide Ion 
An aqueous solution containing 30 wt % of potassium bromide was added to 
the above host emulsion and pAg was adjusted to 9.2. Then, 840 ml of an 
aqueous solution containing 5.0 g of potassium iodide was added for 20 
minutes with maintaining the feed rate constant, and stirring was 
continued for further 2 minutes. pAg at this time was 9.35. 
Emulsions Em-3 to Em-7 were tabular silver iodobromide grains having 
average diameter corresponding to circle of 1.38 .mu.m, variation 
coefficient corresponding to circle of 25%, average thickness of 0.23 
.mu.m, average aspect ratio of 6.0 and total silver iodide content of 5.9 
mol %. 
The temperature of each of the above-obtained tabular silver halide 
emulsions Em-1 to Em-7 was raised to 59.degree. C., dipotassium 
hexachloroiridate, sensitizing dyes ExS-4, ExS-7 and ExS-8 shown below, 
sodium thiosulfate, chloroauric acid, potassium thiocyanate and 
N,N'-dimethylselenourea were added and chemical sensitization was carried 
out optimally. The term "optimally" as used herein means the condition by 
which the highest sensitivity is obtained by 1/100 seconds exposure. 
Photographic properties of the thus-obtained emulsions Em-1 to Em-7 are 
summarized in Table 1 below. 
TABLE 1 
__________________________________________________________________________ 
Host Emulsion 
Silver 
Condition od Process b 
Iodide Amount 
Final Grain Content in Added 
Condition of 
Diameter Content Silver 
Outermost When 
of Iodide 
Process c 
Corresponding 
of Silver 
Iodide 
Nuclear 
Temper- 
Iodide 
to Host pAg from 
Emulsion 
to Circle 
Iodide 
Aspect 
Content I.sub.1 
Layer 
ature 
Was Grain I.sub.2 
Temperature 
Start to 
No. (.mu.m) 
(mol %) 
Ratio 
(mol %) 
(mol %) 
(.degree. C.) 
Added 
(mol %) 
(.degree. C.) 
Completion 
Remarks 
__________________________________________________________________________ 
Em-1 1.20 8.8 4.3 9.4 -- 55 8.90 
6.5 55 9.3-9.0 
Comparison 
Em-2 1.00 5.9 3.0 3.0 -- 55 8.75 
6.5 55 9.4-8.4 
" 
Em-3 1.38 5.9 6.0 3.4 -- 55 8.90 
6.5 55 8.9-8.9 
" 
Em-4 1.38 5.9 6.0 3.4 -- 65 9.78 
6.5 65 9.6-8.4 
Invention 
Em-5 1.38 5.9 6.0 6.4 -- 75 9.20 
6.5 75 9.4-8.4 
" 
Em-6 1.38 8.0 6.0 2.2 0.0 75 9.20 
10.5 75 9.4-8.4 
Comparison 
Em-7 1.38 5.6 6.0 2.0 0.0 75 9.20 
3.6 75 9.4-8.4 
Invention 
__________________________________________________________________________ 
*Em-1, 2 and 3: Dissolution of the periphery of host grains hardly 
occurred. 
*Em6: Only the vertex part of the host grain was dissolved. 
*Em4, 7, and 7: Formation of dislocation lines as shown in FIG. 2 was 
confirmed. 
Preparation of Coated Sample and Development 
On a triacetate film support having an undercoat layer, the above-prepared 
chemically sensitized emulsions Em-1 to Em-7 were coated with a protective 
layer according to the coating conditions shown in Table 2 below and 
Sample Nos. 101 to 107 were prepared. 
TABLE 2 
______________________________________ 
(1) Emulsion Layer 
.cndot. Emulsion Em-1 to Em-7 
Ag 1.2 g/m.sup.2 
.cndot. Coupler (compound shown below) 
1.5 .times. 10.sup.-3 mol/m.sup.2 
1 #STR1## 
.cndot. Tricresyl phosphate 
1.10 g/m.sup.2 
.cndot. Gelatin 2.30 g/m.sup.2 
(2) Protective Layer 
.cndot. Sodium 2,4-Dichloro-6-hydroxy-s-triazine 
0.08 g/m.sup.2 
.cndot. Gelatin 1.80 g/m.sup.2 
.cndot. Antifoggant (compound shown below) 
8.4 .times. 10.sup.-5 mol/m.sup.2 
2 #STR2## 
______________________________________ 
These samples were allowed to stand at 40.degree. C., 70% RH for 14 hours. 
Then, each sample was exposed for 1/100 sec. through gelatin filter SC-50, 
a product of Fuji Photo Film Co., Ltd., and continuous wedge. 
Samples were processed according to the following step using Nega Processor 
FP-350 manufactured by Fuji Photo Film Co., Ltd. until the accumulated 
replenishment amount of the processing solution reached 3 time of the 
capacity of the mother liquid tank. 
______________________________________ 
Processing Step 
Processing 
Replenishment* 
Processing 
Temperature 
Amount 
Step Time (.degree. C.) 
(ml) 
______________________________________ 
Color Development 
2 min 45 sec 
38 45 
Bleaching 1 min 00 sec 
38 20 
The overflow 
from the 
bleaching tank 
was all 
introduced into 
the bleach- 
fixing tank. 
Bleach-Fixing 
3 min 15 sec 
38 30 
Washing (1) 40 sec 35 countercurrent 
system from 
(2) to (1) 
Washing (2) 1 min 00 sec 
35 30 
Stabilization 
40 sec 38 20 
Drying Step 1 min 15 sec 
55 
______________________________________ 
*Replenishment rate: per 1.1 meter of a 35 mm wide photographic material 
(corresponding to a 24 ex. film) 
The composition of each processing solution is described below. 
______________________________________ 
Tank 
Solution Replenisher 
Color Developing Solution 
(g) (g) 
______________________________________ 
Diethylenetriaminepentaacetic 
1.0 1.1 
Acid 
1-Hydroxyethylidene-1,1- 
2.0 2.0 
diphosphonic Acid 
Sodium Sulfite 4.0 4.4 
Potassium Carbonate 30.0 37.0 
Potassiuin Bromide 1.4 0.7 
Potassium Iodide 1.5 mg -- 
Hydroxylamine Sulfate 
2.4 2.8 
4-[N-Ethyl-N-(.beta.-hydroxyethyl)- 
4.5 5.5 
amino]-2-methylaniline Sulfate 
Water to make 1.0 l 1.0 l 
pH (adjusted with potassium 
10.05 10.10 
hydroxide and sulfuric acid) 
______________________________________ 
Replenisher and 
tank solution 
Bleaching Solution (unit: g) 
______________________________________ 
Ammonium Ethylenediaminetetraacetato 
120.0 
Ferrate Dihydrate 
Disodium Ethylenediaminetetraacetate 
10.0 
Ammonium Bromide 100.0 
Ammonium Nitrate 10.0 
Bleach Accelerator 0.005 mol 
(CH.sub.3).sub.2 N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2 
--N(CH.sub.3).sub.2.2HCl 
Aqueous Ammonia (27%) 
15.0 ml 
Water to make 1.0 l 
pH (adjusted with aqueous ammonia 
6.3 
and nitric acid) 
______________________________________ 
Tank 
Solution Replenisher 
Bleach-Fixing Solution 
(g) (g) 
______________________________________ 
Ammonium Ethylenediaminetetra- 
50.0 -- 
acetato Ferrate Dihydrate 
Disodium Ethylenediaminetetra- 
5.0 2.0 
acetate 
Sodium Sulfite 12.0 20.0 
Aqueous Solution of Ammonium 
240.0 ml 400.0 
ml 
Thiosulfate (700 g/liter) 
Aqueous Ammonia (27%) 
6.0 ml -- 
Water to make 1.0 l 1.0 l 
pH (adjusted with aqueous ammonia 
7.2 7.3 
and acetic acid) 
______________________________________ 
Washing Water (replenisher and tank solution) 
City water was passed through a mixed bed column packed with an H-type 
strongly acidic cation exchange resin (Amberlite IR-120B of Rohm & Haas) 
and an OH-type anion exchange resin (Amberlite IR-400 of Rohm & Haas) and 
treated so as to reduce the calcium ion and magnesium ion concentrations 
to 3 mg/liter or less, subsequently 20 mg/liter of sodium isocyanurate 
dichloride and 0.15 g/liter of sodium sulfate were added thereto. The pH 
of this washing water was in the range of from 6.5 to 7.5. 
______________________________________ 
Stabilizing Solution (replenisher and tank solution) 
(unit: g) 
______________________________________ 
Sodium p-Toluenesulfinate 0.03 
Polyoxyethylene-p-monononylphenyl 
0.2 
Ether (average polymerization degree: 
Disodium Ethylenediaminetetraacetate 
0.05 
1,2,4-Triazole 1.3 
1,4-Bis(1,2,4-triazol-1-ylmethyl)- 
0.75 
piperazine 
Water to make 1.0 l 
pH 8.5 
______________________________________ 
Density of each processed sample was measured using a green filter. 
Sensitivity is represented by relative value of the reciprocal of an 
exposure amount giving the density of fog density +0.2. 
For the evaluation of pressureability of each coated sample, the following 
three kinds of test were conducted. 
(1) Pressure resistance by folding 
Sample was humidity conditioned at 25.degree. C., 55%, folded with a tester 
at an angle of 156.degree. with the emulsion face being inside and 
subjected to exposure and development processing described above. The fog 
generated at the folded part of the obtained sample was measured with a 
microdensitometer. 
(2) Pressure resistance by scratching with a fine needle 
Sample was humidity conditioned at 25.degree. C., 55%, and after the 
emulsion face of the sample was scratched in a certain direction with a 
fine needle of a diameter of 50 .mu.m loaded by 4 g, the sample was 
subjected to exposure and development processing described above. Density 
reduction of the scratched part of each sample was measured. 
(3) Pressure resistance by scratching with a fine needle in a swollen state 
After each sample subjected to exposure in the same manner as above was 
immersed in hot water maintained at 35.degree. C. for 30 sec., the 
emulsion face of the sample was scratched in a certain direction with a 
fine needle of a diameter of 50 .mu.m loaded by 4 g, and subjected to 
development process. The fog generated at the scratched part of each 
sample was measured with a micro-densitometer. 
Sensitivity of each coated sample shown in Table 3 and the results of the 
above pressure resistance test of each coated sample are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Pressure Desensiti- 
.DELTA.Pressure Fog in a 
zation due to Fine 
.DELTA.Fog due to Folding 
Swollen State 
Needle (Dmax after 
(fog after application 
(fog after application 
pressure applica- 
Sample Emulsion 
Relative 
of pressure) - (fog before 
of pressure) - (fog before 
tion) - (Dmax before 
Sample No. 
No. Sensitivity 
application of pressure) 
application of pressure) 
pressure application) 
__________________________________________________________________________ 
101 Em-1 100 +0.20 +0.30 -0.10 
(Comparison) 
102 Em-2 90 +0.30 +0.80 -1.50 
(Comparison) 
103 Em-3 110 +0.50 +0.50 -1.00 
(Invention) 
104 Em-4 135 +0.20 +0.40 -0.05 
(Invention) 
105 Em-5 158 +0.15 +0.15 -0.05 
(Invention) 
106 Em-6 115 +0.30 +0.30 -1.10 
(Comparison) 
107 Em-7 185 +0.10 +0.10 -0.05 
(Invention) 
__________________________________________________________________________ 
As is apparent from Table 3, emulsion Em-4 of the present invention is 
higher in aspect ratio and sensitivity than comparative emulsions Em-1 and 
Em-2, and reduction of image density due to scratching by a fine needle is 
extremely small compared with Em-3 which is rapid in supplying speed of 
iodide ion at the time of dissolution. From these results, it is apparent 
that sample of the present invention is high sensitive and has remarkable 
pressure resistance at the same time. 
Further, when compared with comparative emulsion Em-4, Em-5 of the present 
invention can provide still higher sensitivity and low fog by folding, 
less image density reduction by scratching with a fine needle, and can 
prevent increase of fog due to scratching in a swollen state by means of 
increasing the temperature and pAg in the reaction system in a thin layer 
forming process. 
Further, when compared with comparative emulsion Em-5, Em-7 of the present 
invention can provide an emulsion which is high sensitive and, at the same 
time, which has high resistance against various pressures by means of 
regulating iodide composition and providing pure silver iodide layer as 
the outermost layer. It is apparent from emulsions Em-3 and Em-5 that the 
relationship between the iodide content of host grains and the amount of 
iodide to be added in a dissolution process is very important. 
EXAMPLE 2 
Multilayer color photographic material Sample No. 201 was prepared using 
the emulsion according to the present invention described in Example 1 in 
the photographic material shown below. Sample Nos. 202 to 207 were 
prepared by replacing Em-1 in the tenth layer with Em-2 to Em-7, 
respectively. 
1) Support 
The support used in this example was prepared according to the following 
manner. 
100 weight parts of polyethylene-2,6-naphthalate polymer and 2 weight parts 
of Tinuvin P. 326 (product of Ciba Geigy AG), as an ultraviolet absorbing 
agent, were dried, then melted at 300.degree. C., subsequently, extruded 
through a T-type die, and stretched 3.3 times in a machine direction at 
140.degree. C. and then 3.3 times in a transverse direction at 130.degree. 
C., and further thermally fixed for 6 seconds at 250.degree. C. and the 
PEN film having the thickness of 90 .mu.m was obtained. Appropriate 
amounts of blue dyes, magenta dyes and yellow dyes were added to the PEN 
film (I-1, I-4, I-6, I-24, I-26, I-27 and II-5 disclosed in Journal of 
Technical Disclosure (Kokai-Giho), No. 94-6023). Further, the film was 
wound on to a stainless steel spool having a diameter of 20 cm and 
provided heat history at 110.degree. C. for 48 hours to obtain a support 
reluctant to get curling habit. 
2) Coating of undercoat layer 
After both surfaces of the above support were subjected to corona 
discharge, UV discharge and glow discharge treatments, on each side of the 
support an undercoat solution having the following composition was coated 
(10 ml/m.sup.2, using a bar coater): 0.1 g/m.sup.2 of gelatin, 0.01 
g/m.sup.2 of sodium a-sulfo-di-2-ethylhexylsuccinate, 0.04 g/m.sup.2 of 
salicylic acid, 0.2 g/m.sup.2 of p-chlorophenol, 0.012 g/m.sup.2 of 
(CH.sub.2 .dbd.CHSO.sub.2 CH.sub.2 CH.sub.2 NHCO).sub.2 CH.sub.2, and 0.02 
g/m.sup.2 of polyamide-epichlorohydrin polycondensation product. The 
undercoat layer was provided on the hotter side at the time of stretching. 
Drying was conducted at 115.degree. C. for 6 minutes (the temperature of 
the roller and transporting device of the drying zone was 115.degree. C.). 
3) Coating of backing layer 
On one side of the above support after undercoat layer coating, an 
antistatic layer, a magnetic recording layer and a libricating layer 
having the following compositions were coated as backing layers. 
3-1) Coating of antistatic layer 
0.2 g/m.sup.2 of a dispersion of fine grain powder of a stannic 
oxide-antimony oxide composite having the average grain size of 0.005 
.mu.m and specific resistance of 5 .OMEGA..cm (the grain size of the 
second agglomerate: about 0.08 .mu.m), 0.05 g/m.sup.2 of gelatin, 0.02 
g/m.sup.2 of (CH.sub.2 .dbd.CHSO.sub.2 CH.sub.2 CH.sub.2 NHCO).sub.2 
CH.sub.2, 0.005 g/m.sup.2 of polyoxyethylene-p-nonylphenol (polymerization 
degree: 10) and resorcin were coated. 
3-2) Coating of magnetic recording layer 
0.06 g/m.sup.2 of cobalt-.gamma.-iron oxide which was coating-treated with 
3-polyoxyethylene-propyloxytrimethoxysilane (polymerization degree: 15) 
(15 wt %) (specific surface area: 43 m.sup.2 /g, major axis: 0.14 .mu.m, 
minor axis: 0.03 .mu.m, saturation magnetization: 89 emu/g, Fe.sup.+2 
/Fe.sup.+3 is 6/94, the surface was treated with 2 wt %, respectively, 
based on the iron oxide, of aluminum oxide and silicon oxide), 1.2 
g/m.sup.2 of diacetyl cellulose (dispersion of the iron oxide was carried 
out using an open kneader and a sand mill), 0.3 g/m.sup.2 of C.sub.2 
H.sub.5 C[CH.sub.2 OCONH-C.sub.6 H.sub.3 (CH.sub.3)NCO].sub.3 as a curing 
agent, with acetone, methyl ethyl ketone and cyclohexanone as solvents, 
were coated with a bar coater to obtain a magnetic recording layer having 
the film thickness of 1.2 .mu.m. As matting agents, silica grains (0.3 
.mu.m) and an aluminum oxide abrasive (0.15 .mu.m) coating-treated with 
3-polyoxyethylene-propyloxytrimethoxysilane (polymerization degree: 15) 
(15 wt %) were added each in an amount of 10 mg/m.sup.2. Drying was 
conducted at 115.degree. C. for 6 minutes (the temperature of the roller 
and transporting device of the drying zone was 115.degree. C.). The 
increase of the color density of D.sup.B of the magnetic recording layer 
by X-light (a blue filter) was about 0.1, and saturation magnetization 
moment of the magnetic recording layer was 4.2 emu/g, coercive force was 
7.3.times.10.sup.4 A/m, and rectangular ratio was 65%. 
3-3) Preparation of lubricating layer 
Diacetyl cellulose (25 mg/m.sup.2), and a mixture of C.sub.6 H.sub.13 
CH(OH)C.sub.10 H.sub.20 COOC.sub.40 H.sub.81 (Compound a, 6 
mg/m.sup.2)/C.sub.50 H.sub.101 O(CH.sub.2 CH.sub.2 O).sub.16 H (Compound 
b, 91 mg/m.sup.2) were coated. This mixture of Compound a/Compound b was 
dissolved in xylene/propylene monomethyl ether (1/1) by heating at 
105.degree. C., and poured into propylene monomethyl ether (10 time 
amount) at room temperature and dispersed, and further dispersed in 
acetone (average grain size: 0.01 .mu.m), then added to the coating 
solution. Silica grains (0.3 .mu.m), as a matting agent, and aluminum 
oxide (0.15 .mu.m) coated with 3-polyoxyethylene-propyloxytrimethoxysilane 
(polymerization degree: 15) (15 wt %), as an abrasive were added each in 
an amount of 15 mg/m.sup.2. Drying was conducted at 115.degree. C. for 6 
minutes (the temperature of the roller and transporting device of the 
drying zone was 115.degree. C.). The thus-obtained lubricating layer 
showed excellent characteristic of dynamic friction coefficient of 0.06 (a 
stainless steel hard ball, diameter: 5 mm, load: 100 g, speed: 6 cm/min), 
static friction coefficient of 0.07 (a clip method), and the lubricating 
property with the surface of the emulsion described below provided dynamic 
friction coefficient of 0.12. 
4) Coating of light-sensitive laver 
Next, each layer having the following composition was multilayer coated on 
the opposite side of the above obtained backing layer and a color negative 
film was prepared as Sample No. 201. 
Composition of Light-Sensitive Layer 
The main components for use in each layer are classified as follows: 
ExC: Cyan Coupler 
ExM: Magenta Coupler 
ExY: Yellow Coupler 
ExS: Sensitizing Dye 
UV: Ultraviolet Absorber 
HBS: High Boiling Point Organic Solvent 
H: Hardening Agent for Gelatin 
The numeral corresponding to each component indicates the coated weight in 
unit of g/m.sup.2, and the coated weight of silver halide is shown as the 
calculated weight of silver. Further, in the case of a sensitizing dye, 
the coated weight is indicated in unit of mol per mol of silver halide in 
the same layer. 
______________________________________ 
First Layer: Antihalation Layer 
Black Colloidal Silver 0.09 as silver 
Gelatin 0.70 
Second Layer: Antihalation Layer 
Black Colloidal Silver 0.09 as silver 
Gelatin 1.00 
ExM-1 0.12 
ExF-1 2.0 .times. 10.sup.-3 
Solid Dispersion Dye ExF-2 
0.030 
Solid Dispersion Dye ExF-3 
0.040 
HBS-1 0.15 
HBS-2 0.02 
Third Layer: Interlayer 
ExC-2 0.05 
Polyethyl Acrylate Latex 0.20 
Gelatin 0.70 
Fourth Layer: Low Sensitivity Red-Sensitive Emulsion 
Layer 
Silver Iodobromide Emulsion A 
0.20 as silver 
Silver Iodobromide Emuision B 
0.23 as silver 
Silver Iodobromide Emulsion C 
0.10 as silver 
ExS-1 3.8 .times. 10.sup.-4 
ExS-2 1.6 .times. 10.sup.-5 
ExS-3 5.2 .times. 10.sup.-4 
ExC-1 0.17 
ExC-2 0.02 
ExC-3 0.030 
ExC-4 0.10 
ExC-5 0.020 
ExC-6 0.010 
Cpd-2 0.025 
HBS-1 0.10 
Gelatin 1.10 
Fifth Layer: Middle Sensitivity Red-Sensitive Emulsion 
Layer 
Silver Iodobromide Emulsion C 
0.15 as silver 
Silver Iodobromide Emulsion D 
0.46 as silver 
ExS-1 4.0 .times. 10.sup.-4 
ExS-2 2.1 .times. 10.sup.-5 
ExS-3 5.7 .times. 10.sup.-4 
ExC-1 0.14 
ExC-2 0.02 
ExC-3 0.03 
ExC-4 0.090 
ExC-5 0.02 
ExC-6 0.01 
Cpd-4 0.030 
Cpd-2 0.05 
HBS-1 0.10 
Gelatin 0.75 
Sixth Layer: High Sensitivity Red-Sensitive Emulsion 
Layer 
Silver Iodobromide Emulsion E 
1.30 as silver 
ExS-1 2.5 .times. 10.sup.-4 
ExS-2 1.1 .times. 10.sup.-5 
ExS-3 3.6 .times. 10.sup.-4 
ExC-1 0.12 
ExC-3 0.11 
ExC-6 0.020 
ExC-7 0.010 
Cpd-2 0.050 
Cpd-4 0.020 
HBS-1 0.22 
HBS-2 0.050 
Gelatin 1.40 
Seventh Layer: Interlayer 
Cpd-1 0.060 
Solid Dispersion Dye ExF-4 
0.030 
HBS-1 0.040 
Polyethyl Acrylate Latex 0.15 
Gelatin 1.10 
Eighth Layer: Low Sensitivity Green-Sensitive Emulsion 
Layer 
Silver Iodobromide Emulsion F 
0.22 as silver 
Siiver Iodobromide Emulsion G 
0.35 as silver 
ExS-7 6.2 .times. 10.sup.-4 
ExS-8 1.4 .times. 10.sup.-4 
ExS-4 2.7 .times. 10.sup.-5 
ExS-5 7.0 .times. 10.sup.-5 
ExS-6 2.7 .times. 10.sup.-4 
ExM-3 0.410 
ExM-4 0.086 
ExY-1 0.070 
ExY-5 0.0070 
HBS-1 0.30 
HBS-3 0.015 
Cpd-4 0.010 
Gelatin 0.95 
Ninth Layer: Middle Sensitivity Green-Sensitive 
Emulsion Layer 
Silver Iodobromide Emulsion G 
0.48 as silver 
Silver Iodobromide Emulsion H 
0.48 as silver 
ExS-4 4.8 .times. 10.sup.-5 
ExS-7 9.3 .times. 10.sup.-4 
ExS-8 2.1 .times. 10.sup.-5 
ExC-8 0.0020 
ExM-3 0.115 
ExM-4 0.035 
ExY-1 0.010 
ExY-4 0.010 
ExY-5 0.0050 
Cpd-4 0.011 
HBS-1 0.13 
HBS-3 4.4 .times. 10.sup.-3 
Gelatin 0.80 
Tenth Layer: High Sensitivity Green-Sensitive Emulsion 
Layer 
Emulsion Em-1 1.30 as silver 
ExS-4 4.5 .times. 10.sup.-5 
ExS-7 5.3 .times. 10.sup.-4 
ExS-8 1.2 .times. 10.sup.-4 
ExC-1 0.021 
ExM-1 0.010 
ExM-2 0.030 
ExM-5 0.0070 
ExM-6 0.0050 
Cpd-3 0.017 
Cpd-4 0.040 
HBS-1 0.25 
Polyethyl Acrylate Latex 0.15 
Gelatin 1.33 
Eleventh Layer: Yellow Filter Layer 
Yellow Colloidal Silver 0.015 as silver 
Cpd-1 0.16 
Solid Dispersion Dye ExF-5 
0.060 
Solid Dispersion Dye ExF-6 
0.060 
Oil-Soluble Dye ExF-7 0.010 
HBS-1 0.60 
Gelatin 0.60 
Twelfth Layer: Low Sensitivity Blue-Sensitive Emulsion 
Layer 
Silver Iodobromide Emulsion I 
0.09 as silver 
Silver Iodobromide Emulsion J 
0.10 as siiver 
Silver Iodobromide Emulsion K 
0.25 as silver 
ExS-9 8.4 .times. 10.sup.-4 
ExC-1 0.03 
ExC-8 7.0 .times. 10.sup.-3 
ExY-1 0.050 
ExY-2 0.75 
ExY-3 0.40 
ExY-4 0.040 
Cpd-2 0.10 
Cpd-4 0.01 
Cpd-3 4.0 .times. 10.sup.-3 
HBS-1 0.28 
Gelatin 2.10 
Thirteenth Layer: High Sensitivity Blue-Sensitive 
Emulsion Layer 
Silver Iodobromide Emulsion L 
0.58 as silver 
ExS-9 3.5 .times. 10.sup.-4 
ExY-2 0.070 
ExY-3 0.070 
ExY-4 0.0050 
Cpd-2 0.10 
Cpd-3 1.0 .times. 10.sup.-3 
Cpd-4 0.02 
HBS-1 0.075 
Gelatin 0.55 
Fourteenth Layer: First Protective Layer 
Silver Iodobromide Emulsion M 
0.10 as silver 
UV-1 0.13 
UV-2 0.10 
UV-3 0.16 
UV-4 0.025 
ExF-8 0.001 
ExF-9 0.002 
HBS-1 5.0 .times. 10.sup.-2 
HBS-4 5.0 .times. 10.sup.-2 
Gelatin 1.8 
Fifteenth Layer: Second Protective Layer 
H-1 0.40 
B-1 (diameter: 1.7 .mu.m) 0.06 
B-2 (diameter: 1.7 .mu.m) 0.09 
B-3 0.13 
ES-1 0.20 
Gelatin 0.70 
______________________________________ 
Further, W-1 to W-3, B-4 to B-6, F-1 to F-18, iron salt, lead salt, gold 
salt, platinum salt, palladium salt, iridium salt and rhodium salt were 
appropriately included in each layer to improve storage stability, 
processing properties, pressure resistance, fungicidal and biocidal 
properties, antistatic properties and coating properties. 
TABLE 4 
__________________________________________________________________________ 
Projected 
Average 
Variation 
Area 
Average 
Diameter 
Coefficient 
Diameter 
AgI Corresponding 
of the 
Corresponding 
Diameter/ 
Content 
to Sphere 
Grain Size 
to Circle 
Thickness 
Emulsion 
(%) (.mu.m) 
(%) (.mu.m) 
Ratio 
Tabularity 
__________________________________________________________________________ 
A 3.7 0.37 13 0.43 2.3 12 
B 3.7 0.43 19 0.58 3.2 18 
C 5.0 0.55 20 0.86 6.2 45 
D 5.4 0.66 23 1.10 7.0 45 
E 4.7 0.85 22 1.36 5.5 22 
F 3.7 0.43 19 0.58 3.2 18 
G 5.4 0.55 20 0.86 6.2 45 
H 5.4 0.66 23 1.10 7.0 45 
I 3.7 0.37 19 0.55 4.6 38 
J 3.7 0.37 19 0.55 4.6 38 
K 8.8 0.64 23 0.85 5.2 32 
L 6.3 1.05 20 1.46 3.7 9 
M 1.0 0.07 -- -- 1.0 -- 
__________________________________________________________________________ 
In Table 4: 
(1) Emulsions I to L were reduction sensitized during preparation of the 
grains using thiourea dioxide and thiosulfonic acid according to the 
examples of JP-A2-191938. 
(2) Emulsions C to E, G and H were gold, sulfur, and selenium sensitized, 
respectively, in the presence of the spectral sensitizing dyes which are 
described at each light-sensitive layer and sodium thiocyanate according 
to the examples of JP-A-3-237450. 
(3) Low molecular weight gelatin was used in the preparation of the tabular 
grains according to the examples of JP-A-1-158426. 
(4) In tabular grains, there were observed such dislocation lines as 
disclosed in JP-A-3-237450, using a high voltage electron microscope. 
(5) Emulsions A to E, G, H, I to L contain optimal amount of Rh, Ir and Fe. 
Tabularity means the value defined by the equation D.sub.c /t.sup.2, 
taking the diameter corresponding to circle of the projected area of the 
tabular grain as D.sub.c and the average thickness of the tabular grain as 
t. 
Preparation of Dispersion of Organic Solid Dispersion Dye 
ExF-2 shown below was dispersed according to the following method. That is, 
21.7 ml of water, 3 ml of a 5% aqueous solution of sodium 
p-octylphenoxyethoxyethoxyethanesulfonate, and 0.5 g of a 5% aqueous 
solution of p-octyl-phenoxypolyoxyethylene ether (polymerization degree: 
10) were put in a pot mill having a capacity of 700 ml, and 5.0 g of Dye 
ExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added 
thereto and the content was dispersed for 2 hours. The vibrating ball mill 
which was used was BO type ball mill manufactured by Chuo Koki. The 
content was taken out after dispersion and added to 8 g of a 12.5% aqueous 
solution of gelatin and the beads were removed by filtration and the 
gelatin dispersion of the dye was obtained. The average grain size of fine 
grains of the dye was 0.44 .mu.m. 
Solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained in the same 
manner. The average grain sizes of fine grains of the dyes were 0.24 
.mu.m, 0.45 .mu.m and 0.52 .mu.m, respectively. ExF-5 was dispersed 
according to the microprecipitation dispersion method disclosed in Working 
Example 1 of EP-A-549489. The average grain size was 0.06 .mu.m. 
##STR3## 
The thus prepared photographic material was cut to a size of 24 mm in width 
and 160 cm in length, and two perforations of 2 mm square at an interval 
of 5.8 mm were provided 0.7 mm inside from one side width direction in the 
length direction of the photographic material. The sample provided with 
this set of two perforations at intervals of 32 mm was prepared and 
encased in the plastic film cartridge explained in FIG. 1 to FIG. 7 in 
U.S. Pat. No. 5,296,887. 
FM signals were recorded between the above perforations of the sample from 
the side of the magnetic recording layer coated on the support using a 
head capable of in and out of 2,000 turns with head gap of 5 .mu.m at a 
feed rate of 100 mm/s. 
After FM signals were recorded, the emulsion surface was subjected to 
entire and uniform exposure of 1,000 cms and each process was conducted 
according to the following method, and each sample was put in the above 
plastic film cartridge again. 
Sample Nos. 201 to 207 cut to a width of 35 mm and photographed with a 
camera were processed (running process) at a rate of m.sup.2 per a day for 
15 days as follows. 
Each processing was conducted using an automatic processor FP-360B 
manufactured by Fuji Photo Film Co., Ltd. according to the following step. 
Further, the processor was modified so that the overflow from the 
bleaching bath was discharged to the waste solution tank not to flow to 
the after bath. FP-360B processor carried the evaporation compensating 
means disclosed in Hatsumei Kyokai Kokai Giho No. 94-4992. 
The processing step and the composition of each processing solution are as 
follows. 
______________________________________ 
Processing Step 
Processing 
Replenishment* 
Processing Temperature 
Amount 
Step Time (.degree. C.) 
(ml) 
______________________________________ 
Color Development 
2 min 45 sec 
38 45 
Bleaching 1 min 00 sec 
38 20 
The overflow 
from the 
bleaching tank 
was all 
introduced into 
the bleach- 
fixing tank. 
Bleach-Fixing 
3 min 15 sec 
38 30 
Washing (1) 
40 sec 35 countercurrent 
system from 
(2) to (1) 
Washing (2) 
1 min 00 sec 
35 30 
Stabilization 
40 sec 38 20 
Drying 1 min 15 sec 
55 
______________________________________ 
*Replenishinent rate: per 1.1 meter of a 35 mm wide photographic material 
(corresponding to a 24 ex. film) 
The composition of each processing solution is described below. 
______________________________________ 
Tank 
Solution Replenisher 
Color Developing Solution 
(g) (g) 
______________________________________ 
Diethylenetriaminepentaacetic 
1.0 1.1 
Acid 
1-Hydroxyethylidene-1,1- 
2.0 2.0 
diphosphonic Acid 
Sodium Sulfite 4.0 4.4 
Potassium Carbonate 30.0 37.0 
Potassium Bromide 1.4 0.7 
Potassium Iodide 1.5 mg -- 
Hydroxylamine Sulfate 
2.4 2.8 
4-[N-Ethyl-N-(.beta.-hydroxyethyl)- 
4.5 5.5 
amino]-2-methylaniline Sulfate 
Water to make 1.0 l 1.0 l 
pH (adjusted with potassium 
10.05 10.10 
hydroxide and sulfuric acid) 
______________________________________ 
Replenisher and 
tank solution 
Bleaching Solution (unit: g) 
______________________________________ 
Ammonium Ethylenediaminetetraacetato 
120.0 
Ferrate Dihydrate 
Disodium Ethylenediaminetetraacetate 
10.0 
Ammonium Bromide 100.0 
Ammonium Nitrate 10.0 
Bleach Accelerator 0.005 mol 
(CH.sub.3).sub.2 N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2 
--N(CH.sub.3).sub.2.2HCl 
Aqueous Ammonia (27%) 15.0 ml 
Water to make 1.0 l 
pH (adjusted with aqueous ammonia 
6.3 
and nitric acid) 
______________________________________ 
Tank 
Solution Replenisher 
Bleach-Fixing Solution 
(g) (g) 
______________________________________ 
Ammonium Ethylenediaminetetra- 
50.0 -- 
acetato Ferrate Dihydrate 
Disodium Ethylenediaminetetra- 
5.0 2.0 
acetate 
Sodium Sulfite 12.0 20.0 
Aqueous Solution of Ammonium 
240.0 ml 400.0 
ml 
Thiosulfate (700 g/liter) 
Aqueous Ammonia (27%) 
6.0 ml 
Water to make 1.0 l 1.0 l 
pH (adjusted with aqueous ammonia 
7.2 7.3 
and acetic acid) 
______________________________________ 
Washing Water (replenisher and tank solution) 
City water was passed through a mixed bed column packed with an H-type 
strongly acidic cation exchange resin (Amberlite IR-120B of Rohm & Haas) 
and an OH-type anion exchange resin (Amberlite IR-400 of Rohm & Haas) and 
treated so as to reduce the calcium ion and magnesium ion concentrations 
to 3 mg/liter or less, subsequently 20 mg/liter of sodium isocyanurate 
dichloride and 0.15 g/liter of sodium sulfate were added thereto. The pH 
of this washing water was in the range of from 6.5 to 7.5. 
______________________________________ 
Stabilizing Solution (replenisher and tank solution) 
(unit: g) 
______________________________________ 
Sodium p-Toluenesulfinate 0.03 
Polyoxyethylene-p-monononylphenyl 
0.2 
Ether (average polymerization degree: 
10) 
Disodium Ethylenediaminetetraacetate 
0.05 
1,2,4-Triazole 1.3 
1,4-Bis(1,2,4-triazol-1-ylmethyl)- 
0.75 
piperazine 
Water to make 1.0 l 
pH 8.5 
______________________________________ 
After each sample was wedgewise exposed by white light and processed as 
described above, the density was measured. 
The sensitivity of the tenth layer was evaluated from the exposure amount 
giving the density of minimum density +0.1 of the magenta density. As for 
the evaluation of pressureability, the above-described three kinds of 
tests were conducted. The results obtained are shown in Table 5 below. 
As is apparent from the results in Table 5, Sample Nos. 204 and 205 using 
the emulsion of the present invention materialized a multilayer color 
photographic material having high sensitivity and pressure resistance 
against various external pressures as well. 
TABLE 5 
__________________________________________________________________________ 
Pressure 
.DELTA.Pressure Fog in a 
Desensitization 
Relative 
.DELTA.Fog due to Folding 
Swollen State 
due to Fine Needle 
Sensitivity 
(fog after application 
(fog after application 
(existence of pressure 
Sample Emulsion 
Fog + 0.1 
of pressure) - (fog before 
of pressure) - (fog before 
desensitization in 
Sample No. 
No. (magenta) 
application of pressure) 
application of pressure) 
magenta image) 
__________________________________________________________________________ 
201 Em-1 100 +0.40 +0.15 absent 
(Comparison) 
202 Em-2 92 +0.55 +0.40 present 
(Comparison) 
203 Em-3 107 +1.00 +0.30 present 
(Comparison) 
204 Em-4 120 +0.20 +0.40 absent 
(Invention) 
205 Em-5 158 +0.20 +0.15 absent 
(Invention) 
206 Em-6 105 +0.50 +0.30 present 
(Comparison) 
207 Em-7 180 +0.15 +0.10 absent 
(Invention) 
__________________________________________________________________________ 
A silver halide photographic material which is high sensitive and less in 
fluctuation in photographic properties due to a stress can be obtained 
using the emulsion produced according to the present invention. 
While the invention has been described in detail and with reference to 
specific examples thereof, it will be apparent to one skilled in the art 
that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.