Silver halide photographic material and method for producing the same

A silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer containing silver halide grains, wherein the silver halide grains has been gold and chalcogen sensitized, and the partition rate of the gold in the silver halide grain side is not less than 10% and less than 40%, and a method for producing the silver halide photographic material.

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic material and 
the method for producing the same and, particularly, relates to producing 
a photographic material comprising a silver halide emulsion which is high 
sensitive, rapid in development progress, excellent in storage stability 
and processability, and easy to handle. 
BACKGROUND OF THE INVENTION 
Various performances are required of the photographic material in recent 
years, in particular, the improvement of sensitivity and storage stability 
is always required of the photographic materials for photographing and 
printing. 
On the other hand, the simplification and speedup of the development 
processing have been increasingly required and the reduction of the 
replenishment of the replenisher is also demanded. However, the 
improvement of sensitivity and storage stability of the photographic 
material and the reduction of the replenisher and speedup of the 
processing are often incompatible. For example, the representative and 
best-known technique of increasing sensitivity is to increase the iodide 
content of a silver halide emulsion and this is disclosed in various 
literature and patents. 
Examples of increasing sensitivity by iodide are disclosed, for example, in 
JP-A-48-51627, JP-A-2-193137 and JP-A-3-1211442 (the term "JP-A" as used 
herein refers to a "published unexamined Japanese patent application"). 
The use of silver iodide on the surface of a silver halide grain not only 
heightens the adsorption of a spectral sensitizing dye and increases 
sensitivity but also prevent the desorption of a dye under high 
temperature and high humidity conditions and improves the storage 
stability. That is, the adsorption of a dye is heightened by the halide 
conversion by iodide on the surface of a grain, and the formation site of 
the chemical sensitization speck is controlled by the site direct function 
of a dye, and this is a well known technique in the art as disclosed in 
JP-A-63-305343 and JP-A-3-121442. 
However, such a usage of silver iodide brings about not only the 
deterioration of the pressurability (pressure blackening), but also fog, 
fixing failure and remaining color of a dye due to the accumulation of the 
iodine ion in the processing solution, therefore, this is not desirable 
from the point of rapid processing and the reduced replenishing 
resistance. 
Thus, the harmful influences of increasing the content of silver iodide in 
silver halide with respect to processing solutions and the like are 
disclosed in detail, for example, in JP-A-2-225637, JP-A-3-121789, 
JP-A-3-135227 and JP-A-3-103639. 
On the other hand, the increase of the developing agent and the auxiliary 
developing agent in a developing solution and raising the pH and the 
temperature of a developing solution are effective to increase the 
activity of the processing solution. However, any of these methods is 
accompanied by the degradation of the processing solution with the lapse 
of time, low contrast and the increase of the generation of fog. 
Techniques of utilizing tabular grains to cope with these drawbacks are 
disclosed in U.S. Pat. Nos. 4,439,520 and 4,425,425. Also, there is 
disclosed in JP-A-58-111933 a photographic element for radiography which 
is endowed with a high covering power by using tabular grains to suppress 
swelling of the hydrophilic colloid layer to 200% or less and there is no 
use for additional hardening during processing. Further, techniques for 
improving the development progression and the sensitivity/fog ratio by 
controlling the development initiation point of the silver halide grains 
having {111} faces at the vertex and/or the edge and the neighborhood 
thereof of the grains are disclosed in JP-A-63-305343 and JP-A-1-77047. 
These known techniques are superior techniques for improving the 
development progression and useful. 
A large quantity of materials adsorbing onto a silver halide, such as a 
spectral sensitizing dye and the like, are necessary to control the 
development initiation point to obtain silver halide grains which can 
provide a sufficient photographic density in a short developing time of 10 
seconds or less using the above technique. However, the remaining color 
and fixing failure become conspicuous under the processing time of 35 
seconds or less of dry to dry time. 
Excessive chemical sensitization to obtain high sensitivity, in general, 
increases fog and extremely deteriorates the storage stability of the 
photographic material. In particular, in large grain size area, chemical 
sensitization has to be conducted until fog generates increasingly for 
achieving the increment of sensitivity corresponding to the increment of 
the surface area of the grain. Therefore, good sensitivity/fog ratio, 
development progression and storage stability cannot be obtained. 
The present inventors have noticed as a result of extensive studies the 
partition rate of the gold in the silver halide grain side, and found that 
good sensitivity/fog ratio, development progression and storage stability 
could be obtained when the partition rate of the gold in the silver halide 
grain side was low. The present inventors have found that good 
photographic performances and storage stability could be obtained by 
raising the partition rate of the gold in the silver halide grain side one 
time by carrying out chemical sensitization using gold, selenium and 
sulfur in combination, and then lowering the partition rate of the gold in 
the silver halide grain side by the desorption of a part of the gold by a 
compound which forms a stable complex with the gold. 
The technique for desorbing the gold from a silver halide emulsion by 
sodium sulfite is disclosed in L. Dupain-Klerkx and P. Faelens, The 
Journal of Photographic Science 35, pp. 136 to 144 (1987). However, the 
technique disclosed therein is a technique of bathing the silver halide 
emulsion coated after the completion of chemical sensitization to an 
aqueous sodium sulfite solution, which is not the addition of sodium 
sulfite to the silver halide emulsion during chemical sensitization. There 
is described, accordingly, that the gold in the binder phase is desorbed 
from the coated silver halide emulsion but the gold on the silver halide 
grain is not desorbed and 80% or more of the gold is distributed to the 
silver halide grain side in gold and sulfur sensitization. This point 
distinctly differs from the present invention. Further, this known example 
does not suggest at all that the emulsion of high sensitive and excellent 
in storage stability can be obtained by the desorption of the gold. In 
addition, only gold and sulfur sensitization is conducted in this known 
example, but the present inventors have found that the greatest effect of 
the present invention can be obtained, in particular, by gold and selenium 
sensitization. 
There is disclosed in JP-A-62-240951 that the removal of the gold 
sensitizer remaining in the binder phase after completion of the gold 
sensitization of the silver halide emulsion heightens the partition rate 
of the gold in the silver halide grain side of the emulsion and this 
contributes to the storage stability. However, this known example 
conducted only the removal of the gold in the binder phase and did not 
intend to desorb later the gold once distributed to the silver halide 
grain side. 
U.S. Pat. No. 3,442,653 discloses the addition of sulfite during chemical 
sensitization process simultaneously with gold sensitizer and stable 
selenium sensitizer to activate the stable selenium sensitizer in gold and 
selenium sensitization. The use of sulfite as a silver halide solvent to 
be added before the addition of a chemical sensitizer during chemical 
sensitization process is disclosed in JP-B-2-7445 (the term "JP-B" as used 
herein refers to an "examined Japanese patent publication"). The addition 
of sodium sulfite as a reducing material during chemical sensitization 
process before gold and sulfur sensitization is disclosed in 
JP-A-2-235043. However, all of these known examples are insufficient for 
the object of desorbing later the once reacted gold on the silver halide 
grains such as in the example mode of the present invention. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a photographic material 
which is excellent in sensitivity/fog ratio, shows high development 
progression, excellent in storage stability and good in sharpness. 
The above object of the present invention has been achieved by the 
following. 
(1) A silver halide photographic material comprising a support having 
thereon at least one silver halide emulsion layer, wherein the silver 
halide grains contained in said silver halide emulsion layer has been gold 
and chalcogen sensitized, and the partition rate of the gold in the silver 
halide grain side is 10% or more and less than 40%. 
(2) A method of producing a silver halide photographic material comprising 
a support having thereon at least one silver halide emulsion layer, 
wherein silver halide grains contained in the silver halide emulsion layer 
has been gold and chalcogen sensitized, and the partition rate of the gold 
in the silver halide grain side is made 10% or more and less than 40% by 
the addition of a compound which forms a complex with the gold after the 
partition rate of the gold in the silver halide grain side reached 50% or 
more in the chemical sensitization process. 
(3) The method of producing a silver halide photographic material as 
described in (2), wherein the compound which forms a complex with the gold 
is a compound having the stability constant of the gold and the complex 
salt of from 28 to 39. 
(4) The method of producing a silver halide photographic material as 
described in (2), wherein the compound which forms a complex with the gold 
is sulfite. 
(5) The silver halide photographic material as described in (1) to (4), 
wherein the silver halide emulsion has been gold and chalcogen sensitized, 
and the method of producing the same. 
(6) The silver halide photographic material as described in (1) to (5), 
wherein the silver halide grains are tabular grains having an average 
aspect ratio of 2 or more, and the method of producing the same. 
(7) The silver halide photographic material as described in (1) to (5), 
wherein the silver halide grains are tabular grains having an average 
aspect ratio of 2 or more, and an average silver iodide content is 1 mol % 
or less based on the entire silver content, and the method of producing 
the same.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention is described in detail below. 
A silver halide emulsion is, in general, prepared by mixing alkali halide 
and silver nitrate in the presence of gelatin, and through the process of 
any of the steps of below described known silver halide grain formation 
techniques, and the steps of physical ripening, cooling, washing, heating, 
chemical sensitization and cooling for solidification. Specifically 
speaking with the chemical sensitization, the silver halide emulsion 
prepared at first is desalted, washed, dispersed in new gelatin, and after 
the pH and pAg are adjusted, chemically sensitized by the addition of 
chemical sensitizers, typically gold sensitizers, more preferably gold 
sensitizers and chalcogen sensitizers. Various additives are added to the 
chemically sensitized emulsion and then the emulsion is coated on a 
support. 
The present invention is attained by desorbing a part of the gold 
partitioned to the chemically sensitized silver halide grain side after 
the addition of chemical sensitizers. 
The partition rate of the gold in the silver halide grain side in the 
present invention is 10% or more and less than 40%, more preferably 12% or 
more and less than 35%, and most preferably 15% or more and less than 30%. 
The partition rate of the gold in the silver halide grain side is defined 
as follows from the amount of the gold in the silver halide grain phase 
and the total amount of the gold in the silver halide emulsion phase 
determined by the methods described below: 
EQU (The partition rate of the gold in the silver halide grain side)=(The 
amount of the gold in the silver halide grain phase)/(The total amount of 
the gold in the silver halide emulsion phase) 
The determination of the amount of the gold in the silver halide grain 
phase and the determination of the total amount of the gold in the silver 
halide emulsion phase are specifically carried out according to the 
calorimetric analysis method, the atomic absorption method; the ICP 
emission spectral method, the neutron radioactivation method, the mass 
spectrometry and the like. 
More specifically, analysis can be conducted by operation (i), (ii) or 
(iii) described below. Further, the total amount of the gold in the silver 
halide emulsion phase may be the sum total of the gold amount in the 
silver halide grain phase and that in the binder phase, or may be the 
determined value of the gold by analyzing the total of the silver halide 
emulsion without conducting operation (i), (ii) or (iii), or further may 
be the total amount of the gold added to the silver halide emulsion. 
(i) When the silver halide emulsion to be analyzed is a silver halide 
emulsion dispersion before coating on a support, the silver halide 
emulsion dispersion is separated to the silver halide grain solid phase 
and the binder phase by a centrifugal separation method, and the amount of 
the gold sensitizer of each phase is determined according to the above 
analysis methods. 
(ii) When the emulsion to be analyzed is a coated film on a support, the 
film is swollen with water and peeled off from the support by enzyme 
decomposition or acid decomposition, the silver halide emulsion peeled off 
is separated to the silver halide grain solid phase and the binder phase 
by a centrifugal separation method, and the amount of the gold sensitizer 
of each phase is determined according to the above analysis methods. 
(iii) When the emulsion to be analyzed is a coated film on a support, the 
film is sufficiently washed with a diluted aqueous solution of sodium 
thiosulfate or potassium thiocyanate (e.g., a 0.01% aqueous solution) 
carefully so that the silver halide is not fixed. Thus, almost all the 
gold sensitizer in the binder phase is washed out. The amount of all the 
gold sensitizer in the film before and after sodium thiosulfate or 
potassium thiocyanate bath processing is determined to calculate the 
amount of the gold sensitizer in the silver halide grain phase and that in 
the binder phase. The details with respect to the operation (iii) are 
disclosed in P. A. Falens, Photographische Korrespondenz, Vol. 104, pp. 
137 to 146 (1968). 
The silver halide grains of the present invention are preferably such that 
the partition rate of the gold in the silver halide grain side is 
preferably lowered by the addition of a compound which forms a complex 
with the gold after the partition rate of the gold in the silver halide 
grain side becomes higher in the chemical sensitization process. The 
partition rate of the gold in the silver halide grain side immediately 
before the addition of a compound which forms a complex with the gold is 
preferably 50% or more, more preferably 55% or more, and most preferably 
60% or more. The partition rate of the gold in the silver halide grain 
side after the completion of the chemical sensitization is preferably 10% 
or more and less than 40%, more preferably 12% or more and less than 35%, 
and most preferably 15% or more and less than 30%. 
The ripening time from the addition of gold and chalcogen sensitizers to 
the addition of the compound which forms a complex with gold, necessary 
for making the partition rate of the gold in the silver halide grain side 
of not less than 50%, is not particularly limited, but generally strongly 
depends on, especially, the pAg of the emulsion, the silver halide grains 
used, the temperature in chemical sensitizing, and the chalcogen 
sensitizer used. 
The time from the addition of the compound which forms a complex with gold 
to the completion of the chemical sensitization, necessary for making the 
partition rate of the gold in the silver halide grain side of not less 
than 10% and less than 40%, is not particularly limited, but generally 
depends on the pAg of the emulsion, the silver halide grains used, the 
temperature in chemical sensitizing, and the chalcogen sensitizer used. 
A compound which forms a complex with the gold is preferably a compound 
having the stability constant of the gold and the complex salt of from 28 
to 39. Specific examples of such a compound include thiosulfate, sulfite, 
cyanide, etc., and particularly preferably sulfite. 
The amount of the compound which forms a complex with the gold for use in 
the present invention varies depending on the stability constant of the 
gold and the complex salt, the silver halide grains to be used, and the 
conditions of the chemical sensitization, but is from 10.sup.-8 to 
10.sup.-2 mol, preferably from 10.sup.-7 to 5.times.10.sup.-3 mol or so, 
per mol of the silver halide. 
The chemical sensitization in the present invention is used in combination 
of chalcogen sensitization such as sulfur sensitization, selenium 
sensitization and tellurium sensitization, with gold sensitization. 
Unstable sulfur compounds are used in sulfur sensitization, for example, 
the unstable sulfur compounds as disclosed in P. Glafkides, Chimie et 
Physique Photographique, 5th Edition, Paul Montel, 1987 and Research 
Disclosure, Vol. 307, No. 307105 can be used. Specific examples thereof 
include known sulfur compounds such as thiosulfate (e.g., hypo), thioureas 
(e.g., diphenylthiourea, triethylthiourea, 
N-ethyl-N'-(4-methyl-2-thiazolyl)thiourea, 
carboxymethyltrimethylthiourea), thioamides (e.g., thioacetamide), 
rhodanines (e.g., diethyl rhodanine, 5-benzylidene-N-ethyl rhodanine), 
phosphinesulfides (e.g., trimethylphosphinesulfide), thiohydantoins, 
4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (e.g., 
dimorpholinedisulfide, cystine, lenthionine), a mercapto compound (e.g., 
cysteine), polythionate, elemental sulfur and active gelatin. 
Unstable selenium compounds are used in sulfur sensitization, for example, 
the unstable selenium compounds as disclosed in JP-B-43-13489, 
JP-B-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and JP-A-5-40324 
can be used. Specific examples thereof include colloidal metal selenium, 
selenoureas (e.g., N,N-dimethylselenourea, 
trifluoromethylcarbonyl-trimethylselenourea, acetyltrimethylselenourea), 
selenoamides (e.g., selenoacetamide, N,N-diethylphenylselenoamide), 
phosphineselenides (e.g., triphenylphosphineselenide, 
pentafluorophenyltriphenylphosphineselenide), selenophosphates (e.g., 
tri-p-tolylselenophosphate, tri-n-butylselenophosphate), seleno ketones 
(e.g., selenobenzophenone), isoselenocyanates, selenocarboxylic acids, 
seleno esters, and diacylselenides. In addition, the non-unstable selenium 
compounds, e.g., selenites, potassium selenocyanide, selenazoles and 
selenides as disclosed in JP-B-46-4553 and JP-B-52-34492 can also be used. 
Unstable tellurium compounds are used in tellurium sensitization, for 
example, the unstable tellurium compounds as disclosed in Canadian Patent 
800,958, British Patents 1,295,462, 1,396,696, JP-A-4-204640, 
JP-A-4-271341, JP-A-4-333043 and JP-A-5-303157 can be used. Specific 
examples thereof include telluroureas (e.g., tetramethyltellurourea, 
N,N'-dimethylethylenetellurourea, N,N'-diphenylethylenetellurourea), 
phosphinetellurides (e.g., butyldiisopropylphosphinetelluride, 
tributylphosphinetelluride, tributoxyphosphinetelluride, 
ethoxydiphenylphosphinetelluride), diacyl(di)tellurides (e.g., 
bis(diphenylcarbamoyl)ditelluride, 
bis(N-phenyl-N-methylcarbamoyl)ditelluride, 
bis(N-phenyl-N-methylcarbamoyl)telluride, bis(ethoxycarbonyl)telluride), 
isotellurocyanates, telluroamides, tellurohydrazides, telluro esters 
(e.g., butylhexyltelluro ester), telluro ketones (e.g., 
telluroacetophenone), colloidal tellurium, (di)tellurides, and other 
tellurium compounds (e.g., potassium telluride, sodium 
telluropentathionate). 
The gold salts disclosed in the above P. Glafkides, Chimie et Physique 
Photographique, 5th Edition, Paul Montel, 1987, and Research Disclosure, 
Vol. 307, No. 307105 can be used in gold sensitization. Specifically, 
chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold 
sulfide, gold selenide, as well as the gold compounds as disclosed in U.S. 
Pat. Nos. 2,642,361, 5,049,484 and 5,049,485 can be used. Further, noble 
metals such as platinum, palladium, iridium can also be used. 
Chalcogen sensitization may be conducted alone or may be a combination of 
two or more, or may be combined with gold sensitization, a combination of 
selenium sensitization and gold sensitization is most preferred, a 
combination of sulfur sensitization, selenium sensitization and gold 
sensitization is also preferred. Reduction sensitization may be used in 
combination. 
The amount of the chalcogen sensitizer for use in the present invention 
varies depending on the silver halide grains to be used or chemical 
sensitization conditions, but is from 10.sup.-8 to 10.sup.-2 mol, 
preferably from 10.sup.-7 to 5.times.10.sup.-3 mol or so, per mol of the 
silver halide. 
The amount of the gold sensitizer for use in the present invention is from 
10.sup.-7 to 10.sup.-2 mol or so per mol of the silver halide. The amount 
of the noble metal sensitizer other than the gold sensitizer for use in 
the present invention may be from 10.sup.-7 to 10.sup.-2 mol or so per mol 
of the silver halide. The conditions of chemical sensitization in the 
present invention are not particularly limited but preferably the pAg is 
from 6 to 11, more preferably from 7 to 10, the pH is preferably from 4 to 
10, and the temperature is preferably from 40.degree. to 95.degree. C., 
more preferably from 45.degree. to 85.degree. C. 
The known reducing compounds as disclosed in the above P. Glafkides, Chimie 
et Physique Photoqraphique, 5th Edition, Paul Montel, 1987, and Research 
Disclosure, Vol. 307, No. 307105 can be used in reduction sensitization. 
Specifically, aminoiminomethanesulfinic acid (another name is thiourea 
dioxide), borane compounds (e.g., dimethylamineborane), hydrazine 
compounds (e.g., hydrazine, p-tolylhydrazine), polyamine compounds (e.g., 
diethylenetriamine, triethylenetetramine), stannous chloride, a silane 
compound, leductones (e.g., ascorbic acid), sulfite, an aldehyde compound, 
or hydrogen gas can be used. Reduction sensitization may be conducted at 
the atmosphere of high pH, or excessive silver ion (so-called silver 
ripening). 
Silver halide grains having any halide composition may be used in the 
present invention, for example, silver chloride, silver bromide, silver 
iodobromide, silver iodochloride, silver chlorobromide and silver 
iodochlorobromide, but is preferably the content of tabular silver iodide 
is 10 mol % or less of the entire silver amount, more preferably 5 mol % 
or less, and most preferably 1 mol % or less. There is no limitation on 
the grain size of the silver halide grains for use in the present 
invention, but it is from 0.05 .mu.m to 10 .mu.m, preferably from 0.1 
.mu.m to 3 .mu.m. 
The silver halide grains for use in the present invention may have a 
regular crystal form (regular crystal grains) such as a hexahedral, 
octahedral, dodecahedral, tetradecahedral, tetracosahedral or 
octatetracontahedral form, or an irregular crystal form such as a 
spherical or potato-like form, or may be various forms of grains which 
have one or more twin planes, but tabular grains having an average aspect 
ratio of 2 or more is most preferred. The aspect ratio herein is expressed 
by diameter/thickness ratio, the diameter is a diameter of a circle having 
an area corresponding to the projected area of the grain, and the 
thickness is represented by a distance between two parallel planes 
comprising the tabular silver halide grains. 
Tabular silver halide grains can be produced according to well known 
methods in the art in an arbitrary combination. 
For example, tabular silver halide grains can be obtained by forming a seed 
crystal comprising 40% or more by weight of tabular grains under the 
comparatively high pAg atmosphere of pBr 1.3 or less and growing the seed 
crystal by adding silver and halide solutions simultaneously while keeping 
the pBr at about the same value. 
Silver and halide solutions are preferably added so as not to generate new 
crystal nucleus during the grain growth. 
The size of tabular silver halide grains can be controlled by adjusting the 
temperature, selecting the kind and amount of the solvents, and 
controlling the addition speed of the silver salt and halide for use 
during grain growth. 
The grain size and the grain form (diameter/thickness ratio and the like), 
the grain size distribution and the grain growth speed can be controlled 
by using a silver halide solvent according to necessity during the 
production of tabular silver halide grains of the present invention. The 
amount used of the solvent is 10.sup.-3 to 1.0 wt %, particularly 
preferably from 10.sup.-2 to 10.sup.-1 wt %, of the reaction solution. 
For example, it is possible to make the grain size distribution 
monodisperse and to increase the speed of the grain growth with the 
increase of the amount of the solvent. On the other hand, the thickness of 
the grain tends to increase with the increase of the amount of the 
solvent. 
Ammonia, thioether and thioureas are frequently used as silver halide 
solvents. U.S. Pat. Nos. 3,271,157, 3,790,387 and 3,574,628 can be 
referred to with respect to thioethers. 
The methods of increasing the addition speed, amount and concentration of 
the silver salt solution (e.g., an aqueous AgNO.sub.3 solution) and the 
halide solution (e.g., an aqueous KBr solution) which are added to raise 
the speed of the grain growth during production of the tabular silver 
halide grains of the present invention are preferably used. 
With respect to these methods, British Patent 1,335,925, U.S. Pat. Nos. 
3,672,900, 3,650,757, 4,242,445, JP-A-55-142329 and JP-A-55-158124 can be 
referred to. 
In the layer containing the tabular silver halide grains of the present 
invention, the tabular grains having aspect ratio of 2 or more accounts 
for from 50% to 100%, preferably from 60% to 100%, more preferably from 
70% to 100%, in projected area ratio, based on the entire silver halide 
grains contained in the layer. 
The thickness of the layer containing the tabular silver halide grains is 
from 0.3 to 5.0 .mu.m, particularly preferably from 0.5 to 3.0 .mu.m. 
Other constitutions of the layer containing the tabular silver halide 
grains of the present invention, for example, a binder, a hardening agent, 
an antifoggant, a stabilizer for silver halide, a surfactant, a spectral 
sensitizing dye, a dye, an ultraviolet absorbing agent, a chemical 
sensitizer, and the like are not particularly limited and, for example, 
Research Disclosure, Vol. 176, pp. 22 to 28 (December, 1978) can be 
referred to. 
When the emulsion layer of the silver halide photographic material of the 
present invention contains grains other than tabular silver halide grains, 
any production methods hitherto known can be used, that is, the addition 
of an aqueous silver salt solution and an aqueous halide solution to the 
reaction vessel containing an aqueous gelatin solution with efficient 
stirring. Specifically, the preparation is feasible according to the 
methods disclosed in P. Glafkides, Chimie et Physique Photographigue, Paul 
Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal 
Press (1966), V. L. Zelikman, et al., Making and Coating Photographic 
Emulsion, The Focal Press (1964), and so on. That is, any process, such as 
an acid process, a neutral process, and an ammoniacal process, can be 
used. Any of a single jet method, a double jet method, and combinations of 
these methods can be used for reacting a soluble silver salt with a 
soluble halide. 
A so-called controlled double jet method, which is one form of a double jet 
method, in which the pAg of the liquid phase in which the silver halide is 
formed is maintained constant can also be used. Moreover, the method in 
which the rates of addition of the silver nitrate and the aqueous alkali 
halide solution are varied according to the grain growth rate as disclosed 
in British Patent 1,535,016, JP-B-48-36890 and JP-B-52-16364, and the 
method in which the concentrations of the aqueous solutions are varied as 
disclosed in U.S. Pat. No. 4,242,445 and JP-A-55-158124 are preferably 
used to rapidly grow grains within the range not exceeding the critical 
degree of saturation. These methods are preferably used because they do 
not generate new nuclei and silver halide grains grow uniformly. 
A method in which previously prepared fine grains are added to a reaction 
vessel to start nucleus formation and/or grain growth to thereby obtain 
silver halide grains in place of adding a silver salt solution and a 
halide solution to a reaction vessel is preferably used. This technique is 
disclosed in JP-A-1-183644, JP-A-1-183645, U.S. Pat. No. 4,879,208, 
JP-A-2-44335, JP-A-2-43534 and JP-A-2-43535. According to this method, 
uniform distribution of halogen ion in the emulsion grain crystal can be 
obtained and preferred photographic characteristics can be obtained. 
Emulsion grains of various structures can be used in the present invention. 
Grains comprising inside (core) part and outside (shell) part, that is, 
so-called core/shell type double structure grains, the triple structure 
grains as disclosed in JP-A-60-222844, or multilayer structure grains can 
be used. When producing emulsion grains having an inner structure, grains 
having a junction structure within the grains can also be produced not 
only the above described enveloped type structure. Examples thereof are 
disclosed in JP-A-59-133540, JP-A-58-108526, EP 199290A2, JP-B-58-24772 
and JP-A-59-16254. 
In a junction structure, the crystal to be joined having different 
composition from the host crystal can be grown at the edge or corner part, 
or on the surface of the host crystal. Such a junction crystal can be 
formed if the host crystal has a uniform halide composition throughout, or 
has a core/shell type structure. 
The combination of silver halide with silver halide can of course be formed 
as a junction structure but silver salt compounds not having a rock salt 
structure such as silver thiocyanate and silver carbonate can be combined 
with silver halide and can form a junction crystal. Further, non-silver 
salt compound such as PbO can be used, if they can form a junction 
structure. 
In the case of silver iodobromide grains of these structures, for example, 
in core/shell type grains, grains may have a structure in which the silver 
iodide content of the core part is high and the silver iodide content of 
the shell part is low, or conversely, grains may have a structure in which 
the silver iodide content of the core part is low and the silver iodide 
content of the shell part is high. Similarly, with respect to grains 
having a junction structure, the grains may have a structure in which the 
silver iodide content of the host crystal is high and the silver iodide 
content of the joined crystal is low, or the grains may have the converse 
structure. Further, when the grains have a non-uniform structure as 
described above, a boundary between the parts which differ in halide 
composition may have a clear interface, or the interface may be obscured 
by forming mixed crystals depending on the difference in halide 
composition. Also, a continuous change in structure may be made positively 
in the boundary. 
The grains of the silver halide emulsion for use in the present invention 
may be processed to have round shapes as disclosed in EP-0096727B1 and 
EP-0064412B1, or may be processed to improve the surface quality as 
disclosed in DE-2306447C2 and JP-A-60-221320. 
A surface latent image type silver halide emulsion is preferably used in 
the present invention, but an internal latent image type emulsion can also 
be used by selecting developing solutions and conditions of development. 
Also, a shallow internal latent image type emulsion covered with a thin 
shell can be used according to the purpose. 
The silver halide grain having a dislocation line is preferably used in the 
present invention. Such grains having dislocation lines are disclosed in 
U.S. Pat. No. 4,806,461. 
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt 
or a complex salt thereof, a rhodium salt or a complex salt thereof, or an 
iron salt or a complex salt thereof may be present during silver halide 
grain formation or physical ripening. 
The emulsion of the present invention is in general spectrally sensitized. 
The dyes which are used for spectral sensitization include, for example, 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 selenazoline nucleus, a pyrrole nucleus, 
an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole 
nucleus, a tetrazole nucleus, a pyridine nucleus, a tellurazole nucleus, 
etc.; 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 benzimidazole nucleus, a 
naphthoimidazole nucleus, a benzothiazole nucleus, a naphthothiazole 
nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a 
quinoline nucleus and a benzotellurazole nucleus can be used. These 
heterocyclic nucleus may be substituted on the carbon atoms. 
Nuclei which are usually utilized as nuclei having ketomethylene structures 
in merocyanine dyes can be applied to merocyanine and complex merocyanine 
dyes. Particularly useful nuclei which can be applied are a 5- or 
6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a 
thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a 
thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid 
nucleus, and a 2-thioselenazolidine-2,4-dione nucleus. 
These sensitizing dyes may be used alone or may be used in combination. A 
combination of a sensitizing dye is often used for the purpose of 
supersensitization. Representative 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, 3,614,609, 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, these sensitizing dyes may be used in combination with dyes which 
themselves do not show a spectral sensitizing function or materials 
substantially do not absorb visible light but show conspicuous increase of 
spectral sensitization when combined with sensitizing dyes, that is, the 
compounds known as supersensitizers. Representative examples of 
supersensitizers include the bispyridinium salt compounds disclosed in 
JP-A-59-142541, the stilbene derivatives disclosed in JP-B-59-18691, the 
water-soluble bromide and the water-soluble iodide such as the potassium 
bromide and the potassium iodide disclosed in JP-B-49-46932, the fused 
compounds of aromatic compound and formaldehyde, cadmium salts and 
azaindene compounds disclosed in U.S. Pat. No. 3,743,510. 
Sensitizing dyes are added after chemical ripening or before chemical 
ripening. The sensitizing dyes are most preferably added to the silver 
halide grains of the present invention during chemical ripening or before 
chemical ripening (for example, during grain formation, during physical 
ripening). 
Various compounds can be added to the photographic emulsion of the present 
invention for preventing generation of fog or stabilizing photographic 
performances during production, storage or processing of the photographic 
material. Such compounds include compounds known as an antifoggant or a 
stabilizer such as azoles, e.g., benzothiazolium salt, nitroindazoles, 
triazoles, benzotriazoles, benzimidazoles (particularly nitro- or 
halogen-substitution product); heterocyclic mercapto compounds, e.g., 
mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, 
mercaptothiadiazoles, mercaptotetrazoles (particularly, 
1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic 
mercapto compounds having water-soluble groups such as carboxyl groups or 
sulfone groups; thioketo compound, e.g., oxazolinethione; azaindenes, 
e.g., tetraazaindenes (particularly, 
4-hydroxy-substituted(1,3,3a,7)-tetraazaindenes); benzenethiosulfonic 
acids; and benzenesulfinic acid. 
A thiocyanic acid compound may be added to the emulsion layer for use in 
the present invention in an amount of 1.0.times.10.sup.-3 mol or more and 
less than 2.0.times.10.sup.-2 mol per mol of silver. The addition of the 
thiocyanic acid compound may be any step of grain formation, physical 
ripening, grain growth, chemical sensitization and coating, but the 
addition before chemical sensitization is preferred. 
As the thiocyanic acid compound for use during adjustment of the silver 
halide emulsion of the present invention, water-soluble salt such as a 
thiocyanic acid metal salt or an ammonium salt may be generally used, but 
in the case of a metal salt, precaution must be taken to use metal 
elements which do not adversely affect the photographic performances, for 
example, a potassium salt and a sodium salt are preferred. A hardly 
soluble salt such as AgSCN may be added in the form of fine grains. 
These antifoggants or stabilizers are usually added after chemical 
sensitization, but more preferably the addition time can be selected from 
the time during chemical sensitization or the time before the commencement 
of chemical sensitization. 
The silver halide emulsion produced according to the method of the present 
invention can be used, for example, for a color photographic material for 
photographing (a color negative film, a color reversal film), a 
photographic material for printing, a photographic material for X-ray use, 
a black-and-white photographic material for photographing, a material for 
photomechanical process, a photographic paper and the like. 
The various additives for use in photographic materials are not 
particularly limited other than described above and those described in the 
following corresponding places can be used. 
______________________________________ 
Item Places 
______________________________________ 
1) Silver halide line 6, right lower column, 
emulsion and the 
page 8 to line 12, right upper 
preparation method 
column, page 10 of JP-A-2- 
68539; line 10, right lower 
column, page 2 to line 1, right 
upper column, page 6 of JP-A-3- 
24537; line 16, left upper 
column, page 10 to line 19, left 
lower column, page 11 of JP-A-3- 
24537; and Japanese patent 
application Ser. No. 2-225637 
2) Method of chemical 
line 13, right upper column, page 
sensitization 10 to line 16, left upper column 
of JP-A-2-68539; and Japanese 
patent application Ser. No. 3-105035 
3) Antifoggant and 
line 17, left lower column, page 
stabilizer 10, to line 7, left upper column, 
page 11 of JP-A-2-68539; and line 
2, left lower column, page 3 to 
left lower column, page 4 of JP- 
A-2-68539 
4) Tone improving agent 
line 7, left lower column, page 2 
to line 20, left lower column, 
page 10 of JP-A-62-276539; and 
line 15, left lower column, page 
6 to line 19, right upper column, 
page 11 of JP-A-3-94249 
5) Spectral sensitizing 
line 4, right lower column, page 
dye 4 to right lower column, page 8 
of JP-A-2-68539 
6) Surfactant and line 14, left upper column, page 
antistatic agent 
11 to line 9, left upper column, 
page 12 of JP-A-2-68539 
7) Matting agent, line 10, left upper column, page 
sliding agent and 
12 to line 10, right upper 
plasticizer column, page 12 of JP-A-2-68539; 
and line 10, left lower column, 
page 14 to line 1, right lower 
column, page 14 of JP-A-2-68539 
8) Hydrophilic colloid 
line 11, right upper column, page 
12 to line 16, left lower column, 
page 12 of JP-A-2-68539 
9) Hardening agent 
line 17, left lower column, page 
12 to line 6, right upper column, 
page 13 of JP-A-2-68539 
10) Support from line 7 to line 20, right 
upper column, page 13 of JP-A-2- 
68539 
11) Crossover cut line 20, right upper column, page 
method 4 to right upper column, page 14 
of JP-A-2-264944 
12) Dye and mordant 
line 1, left lower column, page 
13 to line 9, left lower column, 
page 14 of JP-A-2-68539; and left 
lower column, page 14 to right 
lower column, page 16 of JP-A-3- 
24539 
13) Polyhydroxybenzenes 
left upper column, page 11 to 
left lower column, page 12 of JP- 
A-3-39948; and EP 452772A 
14) Layer structure 
JP-A-3-198041 
15) Development line 7, right upper column, page 
processing method 
16 to line 15, left lower column, 
page 19 of JP-A-2-103037; and 
line 5, right lower column, page 
3 to line 10, right upper column, 
page 6 of JP-A-2-115837 
______________________________________ 
EXAMPLE 1 
6.9 g of potassium bromide and 11.5 g of low molecular weight gelatin 
having an average molecular weight of 15,000 were added to 1 liter of 
water, and 22 cc of an aqueous solution of silver nitrate (silver nitrate: 
2.40 g) and 39 cc of an aqueous solution containing 5.9 g of potassium 
bromide were added, with stirring, to the vessel maintained at 74.degree. 
C. by a double jet method over 37 seconds. Subsequently, 26 g of gelatin 
was added thereto, then 104 cc of an aqueous solution of silver nitrate 
(silver nitrate: 11.6 g) was added over 11 minutes and 30 seconds. 18 cc 
of a 25% aqueous solution of ammonia was added to the mixture, and 
physical ripening was carried out for 10 minutes while maintaining the 
temperature at 74.degree. C., then 19 cc of a 100% solution of acetic acid 
was added. Subsequently, an aqueous solution containing 188 g of silver 
nitrate and an aqueous solution of potassium bromide were added by a 
controlled double jet method over 55 minutes with maintaining pAg at 8.4. 
The flow rate at this time was accelerated so that the final flow rate was 
2.8 times of the flow rate at the start of the addition. After the 
termination of addition, 44 cc of a 2N potassium thiocyanate solution was 
added. Physical ripening was carried out for 5 minutes while keeping the 
same temperature, then the temperature was lowered to 35.degree. C. and 
the soluble salts were removed by the precipitation method, then the 
temperature was raised to 40.degree. C. and 43 g of gelatin, 2.1 g of 
phenoxyethanol, and a tackifier were added thereto, and the pH and the pAg 
of the emulsion were adjusted to 6.1 and 7.8, respectively, using sodium 
hydroxide, potassium bromide and an aqueous silver nitrate solution. The 
temperature was raised to 56.degree. C., and immediately after the 
addition of an aqueous solution containing 0.084 g of potassium bromide 
and 5.4 mg of sodium ethylthiosulfonate, 0.11 mol %, based on the entire 
amount of silver, of AgI fine grains having a diameter of 0.03 gm was 
added. Subsequently, 0.76 g of calcium chloride was added, and 7 minutes 
after, 538 mg of Sensitizing A-1 and 2.1 mg of Sensitizing A-2 having the 
structural formulae shown below were added, and allowed to stand for 5 
minutes for adsorption, then 1.7 mg of chloroauric acid and 81 mg of 
potassium thiocyanate were added, then 0.28 mg of sodium thiosulfate and 
0.81 mg of selenium compound A-3 were further added and ripening was 
carried out for 60 minutes. Subsequently, 24 mg of sodium sulfite was 
added and further ripened, 105 minutes after the addition of the 
chloroauric acid, the reaction system was solidified by quenching. Thus, 
Emulsion T-1 was prepared. 
Emulsions T-2 to T-7 were prepared in the same manner as the preparation of 
T-1 except that the addition amounts and the time from the addition of the 
chloroauric acid to the addition of the sodium sulfite were changed as 
indicated in Table 1. Further, Emulsion T-8 was prepared in the same 
manner except that the selenium sensitizer was not added. 
Each of the thus obtained emulsion and the emulsion immediately before the 
addition of sodium sulfite (prepared separately by the same formulation) 
was separated to the binder phase and the silver halide grain phase by 
centrifugation. The amount of the gold of silver halide emulsion phase was 
determined by the atomic absorption method after dissolving the silver 
halide grains with an aqueous solution of ammonium thiosulfite, the 
partition rate of the gold in the silver halide grain side was calculated 
from the determined value of the gold in the binder phase. 
The partition rates of the gold in the silver halide grain side of 
Emulsions T-1 to T-8 are shown in Table 1. 
##STR1## 
TABLE 1 
__________________________________________________________________________ 
Time from the 
Partition Rate of 
Partition Rate of 
Addition of 
the Gold in the 
the Gold in the 
Addition 
Chloroauric 
Silver Halide Grain 
Silver Halide Grain 
Amount of 
Acid to the 
Side Immediately 
Side at the Time of 
Sodium 
Addition of 
before Addition of 
Completion of 
Sulfite 
Sodium Sulfite 
Sodium Sulfite 
Chemical Sensitization 
Emulsion 
(mg) (min) (%) (%) Remarks 
__________________________________________________________________________ 
T-1 24 60 70 25 Invention 
T-2 0 -- -- 70 Comparison 
T-3 24 -20 0 5 Comparison 
(before the 
addition of 
chloroauric 
acid) 
T-4 24 0 0 3 Comparison 
T-5 24 5 15 8 Comparison 
T-6 24 10 30 9 Comparison 
T-7 36 40 65 20 Invention 
T-8 24 60 70 5 Comparison 
__________________________________________________________________________ 
70% of the sum total of the projected area of the grains of the thus 
obtained emulsion comprised grains having an aspect ratio of 5 or more, 
and all the grains having an aspect ratio of 3 or more had an average 
projected area diameter of 1.9 .mu.m, a standard deviation coefficient of 
22%, an average grain thickness of 0.3 .mu.m, an average aspect ratio of 
7. 
Preparation of Coating Solution for Emulsion 
The following compounds were added to the above chemically sensitized 
emulsion in the amount described below per mol of the silver halide to 
prepare a coating solution. 
______________________________________ 
Gelatin (including gelatin in the emulsion) 
111 g 
Dextran (average molecular weight: 39,000) 
21.5 g 
Sodium Polyacrylate (average molecular 
5.1 g 
weight: 400,000) 
Sodium Polystyrenesulfonate 
1.2 g 
(average molecular weight: 600,000) 
Potassium Iodide 78 mg 
Hardening Agent, 1,2-Bis(vinyl- 
Amount added was 
sulfonylacetamido)ethane 
adjusted as to obtain 
a swelling rate of 230% 
Compound A-4 42.1 mg 
Compound A-5 10.3 g 
Compound A-6 0.11 g 
Compound A-7 8.5 mg 
Compound A-8 0.43 g 
(pH adjusted to 6.1 with NaOH) 
______________________________________ 
Compound A-4 
##STR2## 
Compound A-5 
##STR3## 
Compound A-6 
##STR4## 
Compound A-7 
##STR5## 
Compound A-8 
##STR6## 
Dye Emulsion a was added to the above coating solution as to provide a 
coating weight of Compound A-9 of 10 mg/m.sup.2 per one side. 
##STR7## 
60 g of the above Compound A-9, 62.8 g of 2,4-diaminophenol, 62.8 g of 
dicyclohexyl phthalate and 333 g of ethyl acetate were dissolved at 
60.degree. C. Then, 65 cc of a 5% aqueous solution of sodium 
dodecylbenzenesulfonate, 94 g of gelatin and 581 cc of water were added to 
the solution, and dispersed in an emulsion condition using a dissolver 
over 30 minutes. Then, 2 g of methyl p-hydroxybenzoate and 6 liters of 
water were added and the temperature was lowered to 40.degree. C. 
Subsequently, the emulsion was concentrated until the total weight reached 
2 kg using ultrafiltration labo module ACP1050 manufactured by Asahi Kasei 
Industry Co., Ltd., and 1 g of methyl p-hydroxybenzoate was added thereto 
to obtain Dye Emulsion a. 
Preparation of Coating Solution for Surface Protective Layer 
The surface protective layer was prepared so that the coating weight of 
each composition became as indicated below. 
______________________________________ 
Gelatin 0.780 g/m.sup.2 
Sodium Polyacrylate (average molecular 
0.025 g/m.sup.2 
weight: 400,000) 
Sodium Polystyrenesulfonate 
0.0012 g/m.sup.2 
(average molecular weight: 
600,000) 
Polymethyl Methacrylate 0.072 g/m.sup.2 
(average particle size: 3.7 .mu.m) 
Compound A-10 0.018 g/m.sup.2 
Compound A-11 0.037 g/m.sup.2 
Compound A-12 0.0068 g/m.sup.2 
Compound A-13 0.0032 g/m.sup.2 
Compound A-14 0.0012 g/m.sup.2 
Compound A-15 0.0022 g/m.sup.2 
Compound A-16 (Proxel) 0.0010 g/m.sup.2 
(pH adjusted to 6.8 with NaOH) 
______________________________________ 
Compound A-10 
##STR8## 
Compound A-11 
##STR9## 
Compound A-12 
##STR10## 
Compound A-13 
##STR11## 
Compound A-14 
##STR12## 
Compound A-15 
##STR13## 
Compound A-16 
##STR14## 
(1) Preparation of Dye Dispersion B for Subbing Layer 
The following Compound A-17 was treated by a ball mill according to 
JP-A-63-197943. 
##STR15## 
434 cc of water and 791 cc of a 6.7% aqueous solution of surfactant Triton 
X-200 (trade name) (TX-200) were put in a ball mill having a capacity of 2 
liters. 20 g of the dye was added to the solution. 400 ml of beads of 
zirconium oxide (ZrO.sub.2) (diameter: 2 mm) was added thereto and the 
content was pulverized over 4 days. After that, 160 g of 12.5% gelatin was 
added. After defoaming, ZrO.sub.2 beads were removed by filtration. As a 
result of the observation, the diameter of the pulverized dye accounted 
for a wide range of from 0.05 to 1.15 .mu.m and the average grain size was 
0.37 .mu.m. 
The dye grains of 0.9 .mu.m or more were removed by centrifugal operation. 
Thus, Dye Dispersion B was obtained. 
(2) Preparation of Support 
A biaxially stretched polyethylene terephthalate film having a thickness of 
175 .mu.m was corona discharged, the first subbing layer having the 
following composition was coated by a wire bar coater so that the coating 
amount reached 4.9 cc/m.sup.2, and then dried at 185.degree. C. for 1 
minute. 
Then, the first subbing layer was also coated on the opposite side 
similarly. The polyethylene terephthalate used contained 0.04 wt % of 
Compound A-9. 
______________________________________ 
Solution of Butadiene-Styrene Copolymer Latex 
158 cc 
(solid part: 40%, weight ratio of butadiene/ 
styrene = 31/69) 
4% Solution of Sodium 2,4-Dichloro-6-hydroxy- 
41 cc 
s-triazine 
Distilled Water 801 cc 
______________________________________ 
* In a latex solution, 0.4 wt %, based on the solid part of the latex, of 
Compound A-18 was contained as an emulsifying dispersant. 
##STR16## 
(3) Coating of Subbing Layer 
On the first subbing layers of the above both surfaces were coated the 
second subbing layer having the following composition so as to provide the 
coating amount indicated below, one by one using a wire bar coater at 
55.degree. C., and then dried. 
______________________________________ 
Gelatin 80 mg/m.sup.2 
Dye Dispersion B (as dye solid part) 
8 mg/m.sup.2 
Compound A-19 1.8 mg/m.sup.2 
Compound A-16 0.27 mg/m.sup.2 
Matting Agent (polymethyl methacrylate 
2.5 mg/m.sup.2 
having an average particle size of 2.5 .mu.m) 
Compound A-19 
C.sub.12 H.sub.25 O.paren open-st.CH.sub.2 CH.sub.2 O.paren close-st..sub. 
10 H 
______________________________________ 
##STR17## 
Preparation of Photographic Material 
On the above prepared support, the aforementioned emulsion layer and the 
surface protective layer were coated by a double extrusion method. The 
coating amount per one side was 1.75 g/m.sup.2. The coating amount of 
gelatin and the swelling rate calculated by freeze drying method by liquid 
nitrogen were adjusted by the gelatin and the hardening agent added to the 
emulsion layer. 
Thus, Coating Sample No. 1 to No. 8 corresponding to Emulsion T-1 to T-8 
were prepared. 
Evaluation of Photographic Performance 
Coating Sample Nos. 1 to 8 were exposed to green light, development 
processed with Developing Solution (I) at 35.degree. C. for 8 sec and 24 
sec, and fixed, washed and dried. 
Developinq Solution (I) 
______________________________________ 
1-Phenyl-3-pyrazolidone 
1.5 g 
Hydroxy 30 g 
5-Nitroindazole 0.25 g 
Potassium Bromide 3.0 g 
Anhydrous Sodium Sulfite 
50 g 
Sodium Hydroxide 30 g 
Boric Acid 5 g 
Glutaraldehyde 10 g 
Water to make 1 liter 
(pH was adjusted to 10.20) 
______________________________________ 
The reciprocal of the exposure amount providing a density of Fog+1.0 was 
taken as the sensitivity, and the Coating Sample No. 1 developed for 24 
sec. was taken as 100. 
Evaluation of Natural Aging 
Each Coating Sample was put in a closed container maintained at 50.degree. 
C. 68% RH for 5 days (forced aging). This sample and comparative sample 
(stored in a green room contained in a light-shielding box) were processed 
according to the same processing used for photographic evaluation and the 
density of fog part was measured. Natural aging was evaluated as fog rate. 
EQU (fog increase by forced aging)/{(maximum density)-(density of the 
support)}!.times.100 
The lower the fog rate, the better is the natural aging. The results are 
shown in Table 2. 
TABLE 2 
______________________________________ 
Coating Increase of Fog 
Sample Rate by 
No. Sensitivity Fog Forced Aging 
______________________________________ 
No. 1 100 0.18 2.5 
No. 2 80 0.25 9.3 
No. 3 20 0.19 3.0 
No. 4 25 0.20 3.1 
No. 5 28 0.21 4.2 
No. 6 30 0.23 4.7 
No. 7 105 0.19 2.3 
No. 8 22 0.20 3.0 
______________________________________ 
As can be seen from Table 2, the emulsion of the present invention shows 
excellent photographic performance. 
Further, as a result of the processing using an automatic processor 
described below the same thing was confirmed. 
Processing 
Automatic Processor: Drive motor and gear part of FPM-9000 manufactured by 
Fuji Photo Film Co., Ltd. were modified to raise the transporting speed 
Concentrated Developing Solution 
______________________________________ 
Potassium Hydroxide 56.6 g 
Sodium Sulfite 200 g 
Diethylenetriaminepentaacetic Acid 
6.7 g 
Potassium Carbonate 16.7 g 
Boric Acid 10 g 
Hydroquinone 83.3 g 
Diethylene Glycol 40 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3- 
22.0 g 
pyrazolidone 
5-Methylbenzotriazole 2 g 
Processing Aid-I 0.6 g 
##STR18## 
Water to make 1 liter 
(pH was adjusted to 10.60) 
______________________________________ 
Concentrated Fixing Solution 
______________________________________ 
Ammonium Thiosulfate 560 g 
Sodium Sulfite 60 g 
Disodium Ethylenediaminetetraacetate 
0.10 g 
Dihydrate 
Sodium Hydroxide 24 g 
Water to make 1 liter 
(pH was adjusted to 5.10 with acetic acid) 
______________________________________ 
At the beginning of development processing, each tank of the automatic 
processor was filled with the following processing solution. 
Developing tank: 33 ml of the above concentrated developing solution, 667 
ml of water, and a starter containing 2 g of potassium bromide and 1.8 g 
of acetic acid was added to adjust pH to 10.25 
Fixing tank: 200 ml of the above concentrated developing solution, and 800 
ml of water 
Processing speed: Dry to Dry: 35 sec 
Development temperature: 35.degree. C. 
Fixing temperature: 32.degree. C. 
Drying temperature: 55.degree. C. 
Replenishment rate: Developing solution: 21 ml/10.times.12 inch Fixing 
solution: 30 ml/10.times.12 inch 
Further, the processing by the following processor established the same 
fact. 
Developing Solution Formulation 
______________________________________ 
Part A 
Potassium Hydroxide 270 g 
Potassium Sulfite 1,125 g 
Diethylenetriaminepentaacetic Acid 
30 g 
Sodium Carbonate 450 g 
Boric Acid 75 g 
Hydroquinone 405 g 
4-Methy1-4-hydroxymethyl-1-phenyl-3- 
30 g 
pyrazolidone 
Diethylene Glycol 150 g 
1-(Diethylamino)ethyl-5-mercaptotetrazole 
1 g 
Water to make 4.7 liters 
Part B 
Triethylene Glycol 700 g 
5-Nitroindazole 4 g 
Acetic Acid 90 g 
1-Phenyl-3-pyrazolidone 50 g 
3,3'-Dithiobishydrocinnamic Acid 
6 g 
Water to make 850 ml 
Part C 
Glutaraldehyde 75 g 
Potassium Metabisulfite 75 g 
Water to make 850 ml 
______________________________________ 
Water was added to Part A, Part B and Part C to make 15 liters and made as 
replenisher formulations (pH at this time: about 10.5). Each of Parts A, B 
and C were filled in Fuji Film CEPROS-30 cartridge for developing solution 
and set in automatic processor CEPROS-30, and replenished every 10 sheets 
processing of 10.times.12 inch size film, 
Part A: 31.3 ml 
Part B: 5.7 ml 
Part C: 5.7 ml 
Water: 57.3 ml (Total 100 ml): replenished 10 ml per one sheet of quarter 
size 
150 g of KBr and 150 g of acetic acid were added to 1.5 liters of the above 
replenisher and this was used as the developing mother solution. CE-F1 
manufactured by Fuji Photo Film Co., Ltd. was used as a fixing solution. 
Running processing of 100 sheets of a quarter size (10 inch.times.12 inch) 
per one day was conducted using Fuji Medical X-ray Film Super HRS30, Super 
HRA30, Super HRHA30, Super HRL30, Super HRG30, MI-NP30, UR-1, UR-2, and 
LI-LM film for Fuji Laser Imager with CEPROS-30 automatic processor 
manufactured by Fuji Photo Film Co., Ltd. at 35.degree. C., Dry to Dry 
time of 46 sec. Excellent photographic performance and excellent washing 
ability with less remaining silver and remaining hypo were obtained. 
EXAMPLE 2 
6.2 g of gelatin having an average molecular weight of 15,000 and 6.9 g of 
potassium bromide were added to 1 liter of water, and an aqueous solution 
of silver nitrate containing 4.0 g of silver nitrate and an aqueous 
solution containing 5.9 g of potassium bromide were added, with stirring, 
to the vessel maintained at 40.degree. C. by a double jet method over 37 
seconds. Subsequently, an aqueous solution containing 18.6 g of gelatin 
was added thereto, then an aqueous solution containing 9.8 g of silver 
nitrate was added over 22 minutes and the temperature was raised to 
60.degree. C. 5.9 ml of a 25% aqueous solution of ammonia was added to the 
mixture, and after 10 minutes an aqueous solution containing 5.5 g of 
acetic acid was added. Subsequently, an aqueous solution containing 151 g 
of silver nitrate and an aqueous solution of potassium bromide were added 
by a controlled double jet method over 35 minutes with maintaining the 
potential at pAg 8.8. The flow rate at this time was accelerated so that 
the final flow rate was 14 times of the flow rate at the start of the 
addition. Potassium hexachloroiridate(III) was dissolved in this aqueous 
potassium bromide solution so as to reach the addition amount of 25 .mu.g. 
After the termination of addition, 15 ml of a 2N potassium thiocyanate 
solution was added. Then, the temperature was lowered to 35.degree. C. and 
the soluble salts were removed by the precipitation method, then the 
temperature was raised to 40.degree. C. and 35 g of gelatin, 85 mg of 
Proxel, and a tackifier were added thereto, and the pH and the pAg of the 
emulsion were adjusted to 6.1 and 7.8, respectively, using sodium 
hydroxide, potassium bromide and an aqueous silver nitrate solution. The 
temperature was raised to 56.degree. C., and immediately after the 
addition of 3 mg of sodium ethylthiosulfonate, 0.1 mol %, based on the 
entire amount of silver, of AgI fine grains having a diameter of 0.07 
.mu.m was added. Subsequently, 0.04 mg of thiourea dioxide was added, then 
1.2.times.10.sup.-3 mol/mol Ag of 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 7.2.times.10.sup.-4 mol/mol 
Ag of Compound A-1 were added. After 10 minutes, 0.52.times.10.sup.-5 
mol/mol Ag of triphenylphosphineselenide, 1.03.times.10.sup.-5 mol/molAg 
of sodium thiosulfate, 30 mg of potassium thiocyanate and 6 mg of 
chloroauric acid were added and ripening was carried out for 60 minutes. 
Subsequently, 24 mg of sodium sulfite was added and further ripened, 105 
minutes after the addition of the chloroauric acid, the reaction system 
was solidified by quenching. 93% of the sum total of the projected area of 
the grains of the thus obtained emulsion comprised grains having an aspect 
ratio of 3 or more, and all the grains having an aspect ratio of 3 or more 
had an average projected area diameter of 0.83 .mu.m, a standard deviation 
coefficient of 15%, an average grain thickness of 0.14 .mu.m, an average 
aspect ratio of 6.2. Thus, Emulsion T-9 was prepared. 
Emulsions T-10 to T-15 were prepared in the same manner as the preparation 
of T-9 except that the addition amounts and the time from the addition of 
the chloroauric acid to the addition of the sodium sulfite were changed as 
indicated in Table 3. Further, Emulsions T-16 and T-17 were prepared in 
the same manner except that equimolar amount of potassium thiocyanate 
(stability constant of gold and the complex salt: 20) and KBr (stability 
constant of gold and the complex salt: 15) were added in place of sodium 
sulfite in Emulsion T-9. 
Each of the thus obtained emulsion and the emulsion immediately before the 
addition of sodium sulfite (prepared separately by the same formulation) 
was separated to the binder phase and the silver halide grain phase by 
centrifugation. The amount of the gold of silver halide emulsion phase was 
determined by the atomic absorption method after dissolving the silver 
halide grains with an aqueous solution of ammonium thiosulfite, the 
partition rate of the gold in the silver halide grain side was calculated 
from the determined value of the gold in the binder phase. 
The partition rates of the gold in the silver halide grain side of 
Emulsions T-9 to T-17 are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Time from the 
Partition Rate of 
Partition Rate of 
Addition of 
the Gold in the 
the Gold in the 
Addition 
Chloroauric 
Silver Halide Grain 
Silver Halide Grain 
Amount of 
Acid to the 
Side Immediately 
Side at the Time of 
Sodium 
Addition of 
before Addition of 
Completion of 
Sulfite 
Sodium Sulfite 
Sodium Sulfite 
Chemical Sensitization 
Emulsion 
(mg) (min) (%) (%) Remarks 
__________________________________________________________________________ 
T-9 24 60 75 28 Invention 
T-10 0 -- -- 78 Comparison 
T-11 24 -15 0 6 Comparison 
(before the 
addition of 
chloroauric 
acid) 
T-12 24 0 0 7 Comparison 
T-13 24 5 10 8 Comparison 
T-14 24 15 40 9 Comparison 
T-15 12 70 85 29 Invention 
T-16 KSCN 60 75 70 Comparison 
18.5 
T-17 KBr 60 75 75 Comparison 
22.7 
__________________________________________________________________________ 
Preparation of Coating Solution for Emulsion 
Coating Solution for Emulsion 
The following compounds were added to the above chemically sensitized 
emulsion in the amount described below per mol of the silver halide to 
prepare a coating solution. 
______________________________________ 
Gelatin 85 g 
2,6-Bis(hydroxyamino)-4-diethylamino- 
72.0 mg 
1,3,5-triazine 
Dextran (average molecular weight: 39,000) 
3.9 g 
Sodium Polystyrenesulfonate 
0.7 g 
(average molecular weight: 600,000) 
Compound A-4 7.0 mg 
Compound A-7 16.0 mg 
Compound A-8 200 mg 
Sodium Hydroquinonemonosulfonate 
8.2 g 
Snowtex C (Nissan Chemical Co., Ltd.) 
10.5 g 
Ethyl Acrylate/Methacrylic Acid (97/3) 
9.7 g 
Copolymer Latex 
Gelatin adjusted so as to 
obtain a coating 
amount of emulsion layer 
of 2.6 g/m.sup.2 
Hardening Agent (1,3-bis (vinylsulfonyl- 
(adjusted so as to 
acetamido)-ethane) obtain swelling 
rate of 230%) 
______________________________________ 
Preparation of Coating Solution for Surface Protective Layer 
The surface protective layer was prepared so that the coating weight of 
each composition became as indicated below. 
______________________________________ 
Gelatin 650 mg/m.sup.2 
Sodium Polyacrylate (average molecular 
18 mg/m.sup.2 
weight: 400,000) 
Butyl Acrylate/Methacrylic Acid (4/6) 
120 mg/m.sup.2 
Copolymer Latex (average molecular weight: 120,000) 
Compound A-10 18 mg/m.sup.2 
Compound A-11 45 mg/m.sup.2 
Compound A-13 0.9 mg/m.sup.2 
Compound A-14 0.61 mg/m.sup.2 
Compound A-20 26 mg/m.sup.2 
##STR19## 
Compound A-15 1.3 mg/m.sup.2 
Polymethyl Methacrylate (average particle 
87 mg/m.sup.2 
size: 2.5 .mu.m) 
Proxel 0.5 mg/m.sup.2 
Potassium Polystyrenesulfonate 
0.9 mg/m.sup.2 
(average molecular weight: 600,000) 
(pH was adjusted to 7.4 with NaOH) 
______________________________________ 
Preparation of Coating Solution for Backing Layer 
Antihalation Layer 
Preparation of Dye Dispersion L 
Each 2.5 g of Compound A-9 and dicyclohexyl phthalate, 2,4-diaminophenol 
were dissolved in 50 cc of ethyl acetate, and this was mixed with 90 g of 
an aqueous gelatin solution containing 1.5 g of sodium 
dodecylbenzenesulfonate, 0.18 g of methyl p-hydroxybenzoate at 60.degree. 
C. and stirred in a homogenizer at high speed. After the completion of 
high speed stirring, reduced pressure processed using an evaporator at 
60.degree. C., and removed 90 wt % of ethyl acetate to thereby obtained 
Dye Dispersion L having an average grain size of 0.18 .mu.m. 
(2) Preparation of Coating Solution 
Coating solution 1 was prepared so that the coating weight of each 
composition became as indicated below. 
______________________________________ 
Gelatin 1.5 g/m.sup.2 
Dextran (molecular weight 39,000) 
0.3 g/m.sup.2 
Phosphoric Acid 5.2 mg/m.sup.2 
SnowteX C 0.5 g/m.sup.2 
Ethyl Acrylate/Methacrylic Acid (97/3) 
0.5 g/m.sup.2 
Copolymer Latex 
Proxel 4.2 mg/m.sup.2 
Dye Dispersion L 8.0 g/m.sup.2 
Compound A-21 100 mg/m.sup.2 
Compound A-22 42 mg/m.sup.2 
Compound A-23 23 mg/m.sup.2 
Hardening Agent 40 mg/m.sup.2 
(1,2-Bis(vinylsulfonylacetamido)ethane) 
Compound A-21 
##STR20## 
Compound A-22 
##STR21## 
Compound A-23 
##STR22## 
______________________________________ 
Surface Protective Layer 
Coating solution was prepared so that the coating weight of each 
composition became as indicated below. 
______________________________________ 
Gelatin 1,300 mg/m.sup.2 
Polymethyl Methacrylate 
(average grain size: 6.6 .mu.m) 
20 mg/m.sup.2 
(average grain size: 0.75 .mu.m) 
81 mg/m.sup.2 
Compound A-10 20 mg/m.sup.2 
Compound A-11 40 mg/m.sup.2 
Compound A-13 6 mg/m.sup.2 
Compound A-14 9 mg/m.sup.2 
Compound A-24 1.7 mg/m.sup.2 
Compound A-25 13 mg/m.sup.2 
Proxel 1.3 mg/m.sup.2 
Potassium Polystyrenesulfonate 
2 mg/m.sup.2 
(average molecular weight: 600,000) 
NaOH 2.5 mg/m.sup.2 
Compound A-24 C.sub.8 H.sub.17 SO.sub.3 K 
Compound A-25 
##STR23## 
______________________________________ 
The above average grain size is indicated as volume weighted average value. 
Preparation of Support 
A commercially available polyethylene terephthalate was biaxially stretched 
in usual manner, heat set was conducted and a film having a thickness of 
183 .mu.m was obtained. This support was corona discharged. The corona 
discharge treatment was carried out using solid state corona processor 
model 6 KVA available from Pillar Co., Ltd. which can treat the support of 
30 cm wide at a rate of 20 m/min. At that time, the treatment of 0.375 
KV.multidot.A.multidot.min/m.sup.2 was conducted to the support from the 
reading of the voltage and electric current. The discharge frequency at 
the treatment time was 9.6 KHz, gap clearance between the electrode and 
the induction roll was 1.6 mm. 
The first subbing layer having the following composition was coated by a 
wire bar coater so that the coating amount reached 5.1 cc/m.sup.2, and 
then dried at 175.degree. C. for 1 minute. Then, the first subbing layer 
was also coated on the opposite side similarly. The polyethylene 
terephthalate used contained 0.04 wt % of Compound A-9. 
______________________________________ 
Solution of Butadiene-Styrene Copolymer Latex 
79 cc 
(solid part: 40%, weight ratio of butadiene/ 
styrene = 31/35) 
4% Solution of Sodium 2,4-Dichloro-6-hydroxy- 
20.5 cc 
s-triazine 
Distilled Water 900.5 cc 
______________________________________ 
* In a latex solution, 0.4 wt %, based on the solid part of the latex, of 
Compound A-18 was contained. 
Preparation of Photographic Material 
On the above prepared support, the aforementioned back surface antihalation 
layer and the surface protective layer were coated, then on the opposite 
side of the support, an emulsion layer and the surface protective layer 
were coated by a double extrusion method to prepare a photographic 
material. The coating amount of silver on the emulsion layer side was 2.8 
g/m.sup.2. 
Evaluation of Photographic Performance 
After the photographic material was exposed from the emulsion layer side 
for 1 sec by emitting CRT (emitter P-45) for medical multicamera with 
gradual emission, the material was SP processed using Fuji Film ECPROS-30 
processor, developing solution CE-D30, fixing solution CE-F30 and washing 
temperature at 20.degree. C. The reciprocal of the exposure amount 
providing a density of Fog+1.0 was taken as the sensitivity, and the 
Coating Sample No. 9 was taken as 100. The evaluation of natural aging was 
carried out in the same manner as in Example 1. 
TABLE 4 
______________________________________ 
Coating Increase of Fog 
Sample Rate by 
No. Sensitivity Fog Forced Aging 
______________________________________ 
No. 9 100 0.17 2.4 
No. 10 75 0.26 9.5 
No. 11 15 0.21 3.3 
No. 12 20 0.22 3.1 
No. 13 23 0.22 4.0 
No. 14 35 0.24 5.2 
No. 15 108 0.18 2.6 
No. 16 60 0.23 7.0 
No. 17 20 0.20 3.0 
______________________________________ 
As can be seen from Table 4, the emulsion of the present invention showed 
excellent photographic performance. 
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.