Silver halide color photographic material

A novel silver halide color photographic material comprising on a support at least one light-sensitive emulsion layer and at least one hydrophilic colloidal layer containing a white pigment between said support and said light-sensitive emulsion layer is provided, wherein (i) said white pigment is incorporated in such an amount that the coated amount thereof in said hydrophilic colloidal layer is in the range of 2 g/m.sup.2 or more, at least one of layers constituting said light-sensitive emulsion layer comprises a silver halide emulsion having a silver chloride content of 90 mol % or more and containing at least one of metal complexes of Fe, Ru, Re, Os and Ir in silver halide grains and at least one mercapto heterocyclic compound, (ii) said white pigment is incorporated in such an amount that the density thereof is in the range of 20% by weight or more, at least one of layers constituting said light-sensitive emulsion layer comprises silver bromochloride emulsion grains or silver chloride emulsion grains having a silver chloride content of 90 mol % or more sensitized with a gold compound, and either said light-sensitive layer or said light-insensitive layer comprises at least one of specific compounds represented by the general formulae (I) to (IX) as is defined in claims, or (iii) said white pigment is incorporated in such an amount that the density thereof in said hydrophilic colloidal layer is in the range of 20% by weight or more, at least one of layers constituting said light-sensitive emulsion layer comprises silver bromochloride emulsion grains or silver chloride emulsion grains containing substantially no silver iodide and having a silver chloride content of 95 mol % or more, and the film pH and film pAg of said light-sensitive material are in the range of 5.0 to 6.5 and 6.0 to 10.0, respectively.

FIELD OF THE INVENTION 
The present invention relates to a silver halide color photographic 
material. More particularly, the present invention relates to a silver 
halide color photographic material excellent in image sharpness and 
storage stability. The present invention further relates to a silver 
halide color photographic material which can undergo a highly rapid 
processing, exhibits a high sharpness and is little subject to sensitivity 
drop in the portion to which a mechanical strength had been applied before 
exposure and sensitivity drop during the storage in the form of 
photographic light-sensitive material. Moreover, the present invention 
relates to a silver halide color photographic material which can undergo a 
highly rapid processing, exhibits a high sharpness, and is subject to a 
small sensitivity change against the humidity fluctuations upon exposure 
and the fluctuations of time interval between exposure and development. 
BACKGROUND OF THE INVENTION 
Commercially available silver halide photographic materials and image 
formation methods using these photographic light-sensitive materials are 
diversified and find application in all fields. The halogen composition of 
silver halide emulsions to be incorporated in these photographic 
light-sensitive materials, particularly photographic light-sensitive 
materials for picture taking, mostly comprises silver bromoiodide mainly 
composed of silver bromide for the purpose of attaining a high 
sensitivity. Products for use in a market having a strong demand for rapid 
delivery of large amounts of prints, such as photographic light-sensitive 
materials for color photographic paper, comprise silver bromide or silver 
bromochloride substantially free of silver iodide under the necessity of 
expediting the development speed. 
In recent years, a silver bromochloride emulsion having a relatively high 
silver chloride content has been put into practical use to meet the demand 
for the improvement of the processability of color photographic papers. 
For example, a remarkable enhancement of the development speed has been 
attained as disclosed in JP-A-64-26837 (the term "JP-A" as used herein 
means an "unexamined published Japanese patent application"). 
On the other hand, rapidly processable silver halide photographic materials 
which provide a high picture quality have been desired in the art. 
Silver halide photographic materials are normally subjected to continuous 
processing by an automatic developing machine installed in laboratories. 
In order to accomplish services for customers, it is required that 
photographic light-sensitive materials be developed and returned to the 
customers within the day of application. Further, it has recently be even 
required that photographic light-sensitive materials be returned to the 
customers within a hour from the time of application. Thus, the demand for 
rapid processing is growing. Further, the reduction in the processing time 
provides an enhancement of productivity, enabling a cost reduction. This 
also requires rapid processing. 
In this situation, it has been known that the crystal form, size and 
composition of silver halide grains in the emulsion to be incorporated in 
the photographic light-sensitive materials have a great effect on the 
development speed, etc. It has been further known that the halogen 
composition of silver halide grains has a particularly great effect on the 
development speed, and a remarkable development speed is shown 
particularly when a high silver chloride coherent emulsion having a high 
silver chloride content is used. 
On the other hand, with respect to picture quality, a further enhancement 
of sharpness has been expected for the purpose of thoroughly attaining the 
desired properties of color negative films or meeting the demand for 
diversified exposure systems caused by the expansion of a use of color 
prints. In the latter case, a high sharpness has been recently required 
for the purpose of reproducing ordinary photographic images as well as 
images requiring a high contrast in a small area such as graphic and 
character. 
One of the requirements for color photographic light-sensitive materials is 
"high density recording". In order to thoroughly provide high density 
recording, the color photographic light-sensitive materials must exhibit a 
high sharpness. Thus, various techniques for enhancing sharpness have been 
developed depending on the demand for photographic light-sensitive 
materials and the application form thereof and have been actually applied. 
As factors lowering the sharpness in photographic light-sensitive materials 
there have been known two phenomena, i.e., halation caused by the 
reflection of incident light at the interface between emulsion layer and 
support or the interface between support and air and irradiation caused by 
the scattering of light by silver halide grains themselves. 
As a method for improving sharpness there has been known an approach which 
comprises the coloring of constituent layers of a photographic 
light-sensitive material with a dye or the like as described in U.S. Pat. 
No. 3,625,694. 
Further, a method which comprises dyeing a specific layer in a photographic 
light-sensitive material with a fine solid dye dispersion is disclosed in, 
e.g., JP-A-2-282244. 
However, the method which comprises the use of a dye to improve sharpness 
is disadvantageous in that the processed photographic light-sensitive 
material shows much stain on the white background. Accordingly, the amount 
of the dye to be incorporated cannot be increased high enough to 
thoroughly improve sharpness. In particular, when the photographic 
light-sensitive material is rapidly processed, the dye used can easily 
remain in the processed prints, causing more stain on the white 
background. 
In silver halide color photographic materials, stain on the white 
background is a key to the quality of the white background of the image. 
It also adds to color turbidity in color images or impairs the visual 
sharpness. In particular, when a reflective support is used, the 
reflective density of stain is theoretically emphasized several times its 
transmission density. Accordingly, even minute stain can remarkably 
impairs the image quality. Thus, the elimination of stain on the white 
background is an important assignment. 
A method which comprises coating a colloidal silver-containing layer to 
improve sharpness is disclosed in, e.g., JP-A-2-84637. However, this 
method is similarly disadvantageous in that when the photographic 
light-sensitive material is rapidly processed, the residual amount of 
silver at blix step is increased, causing a stain increase on the white 
background. 
As an effective approach for improving sharpness there has been known a 
method which comprises providing a white pigment-containing layer on a 
support. For example, JP-A-3-156454 discloses a method which comprises a 
high density dispersion of titanium oxide grains in a waterproof resin 
layer to improve sharpness. 
The inventors tried the foregoing approach. As a result, it was found that 
although stain on the white background is not worsened, the rise in the 
density of the white pigment to an extent to improve sharpness causes a 
remarkable drop of the strength of the waterproof resin layer and a 
remarkable deterioration of the smoothness of the coated layer. 
An approach for dispersing a white pigment in a hydrophilic colloidal layer 
to improve sharpness is disclosed in, e.g., JP-A-59-177542 and 
JP-A-57-64235. 
The inventors tried the foregoing approach. As a result, the white pigment 
density can be raised without causing the aforementioned troubles, 
enabling a thorough enhancement of sharpness. However, the use of the 
foregoing approach is disadvantageous in that a photographic 
light-sensitive material particularly suitable for rapid processing 
comprising a silver halide emulsion having a silver chloride content of 95 
mol % or higher shows a great sensitivity drop when exposed under high 
humidity conditions and a great sensitivity change with the fluctuations 
of the time interval between exposure and development. Accordingly, this 
approach was found greatly disadvantageous in the supply of prints having 
a stable quality to customers. 
A high silver chloride content color photographic material which has been 
improved in its sharpness by the foregoing methods is disadvantageous in 
that it is subject to sensitivity drop on the portion to which a 
mechanical force has been applied before exposure. This results in the 
density drop in the finished image on that portion. In particular, it is 
likely that the photographic light-sensitive material can be bent when 
handled with hands or can be twisted when carried through an automatic 
exposure and developing machine. In any case, the application of such a 
mechanical force to the photographic light-sensitive material can occur in 
an unspecified place. This results in an appreciable noise in the image 
that disadvantageously lowers the commercial value of color prints as 
image data. 
Further, such a high silver chloride content color photographic material 
which has been improved in its sharpness by the foregoing methods was 
found disadvantageous in that it is subject to latent image instability. 
That is, such a photographic light-sensitive material is subject to 
gradual sensitivity drop during the storage in the form of photographic 
light-sensitive material and sensitivity change with the fluctuations of 
the time between the completion of exposure and the beginning of 
development. The sensitivity change during the storage probably makes it 
difficult to effect exposure under constant conditions, disadvantageously 
giving a heavy burden in keeping the quality of finished color prints 
constant. 
The inventors made a study to overcome the foregoing disadvantages. As a 
result, it was found that the sensitivity drop on the portion to which a 
mechanical force has been applied before exposure depends on the degree of 
sulfur sensitization of emulsion, i.e., increase or decrease in the amount 
of a sulfur sensitizer or length of after-ripening time. It was also found 
that the rise in the degree of sulfur sensitization (i.e., rise in the 
amount of a sulfur sensitizer or extension of the after-ripening time) 
makes that portion less subject to sensitivity drop but makes that portion 
more subject to fog on the contrary. The fog on that portion results in an 
undesired noise on the white background. Accordingly, it is necessary that 
a chemical sensitization causing neither sensitivity drop nor fog be 
effected. 
The inventors also made studies on silver halide color photographic 
materials having a relatively high sharpness, particularly color 
photographic papers. As a result, it was found that a photographic 
light-sensitive material comprising a white pigment-containing hydrophilic 
colloidal layer coated on a support is subject to the rise in fog density 
after a prolonged storage. This fog density rise after a prolonged storage 
in the form of unprocessed photographic light-sensitive material becomes 
remarkable when a color developer contaminated with a blix solution at a 
processing step is used. Taking into account the possibility of the 
fluctuations of the storage time between the preparation of the 
photographic light-sensitive materials and the processing in laboratories 
and the composition of the processing solutions used in laboratories, this 
is a great problem in the practical use. 
The rapid delivery of prints having a high sharpness and a stable quality 
to customers is an important assignment from the standpoint of the current 
market need for silver halide color photographic materials. 
JP-A-2-20853 discloses that the doping of a high silver chloride content 
emulsion with a hexacoordinated complex of Re, Ru or Os having at least 4 
cyano ligands can provide a high sensitization. JP-A-1-105940 discloses 
that a high silver chloride content emulsion having a silver bromide-rich 
region selectively doped with iridium can provide an emulsion which 
exhibits excellent reciprocity law characteristics without impairing the 
latent image stability for several hours after exposure. JP-A-3-132647 
discloses that the use of a high silver chloride content emulsion 
containing ferric or ferrous ions provides a high sensitivity and a high 
contrast and causes little sensitivity change with the fluctuations of 
illumination or temperature upon exposure and little desensitization under 
pressure. JP-A- 4-9034 and JP-A-4-9035 disclose that the use of a high 
silver chloride content emulsion containing a specific metal complex 
having at least two cyan ligands provides little reciprocity law failure, 
an excellent latent image stability and little pressure fog. 
JP-A-62-253145 discloses that the incorporation of metallic ions in a high 
silver chloride content emulsion having a high silver bromide-containing 
phase provides a silver halide photographic material suitable for rapid 
processing which exhibits little pressure fog or desensitization. 
These prior art approaches on high silver chloride content emulsions 
containing metal dopants give no teaching of the inhibition of the fog 
density rise after a prolonged storage which becomes particularly 
remarkable when the photographic light-sensitive materials are processed 
with a color developer contaminated with a blix solution. 
SUMMARY OF THE INVENTION 
It is therefore an object of the present invention to provide an excellent 
silver halide color photographic material which can inhibit the 
aforementioned disadvantages. 
The aforementioned object of the present invention will become more 
apparent from the following detailed description and examples. 
The aforementioned object of the present invention is accomplished with (i) 
a silver halide color photographic material comprising on a support at 
least one light-sensitive emulsion layer, wherein at least one hydrophilic 
colloidal layer containing a white pigment in such an amount that the 
coated amount thereof is in the range of 2 g/m.sup.2 or more is provided 
between said support and said light-sensitive emulsion layer, and at least 
one of layers constituting said light-sensitive emulsion layer comprises a 
silver halide emulsion having a silver chloride content of 90 mol % or 
more and containing at least one of metal complexes of Fe, Ru, Re, Os and 
Ir in silver halide grains and at least one mercapto heterocyclic 
compound; (ii) a silver halide color photographic material comprising on a 
support a photographic layer comprising at least one yellow dye-forming 
coupler-containing light-sensitive silver halide emulsion layer, at least 
one magenta dye-forming coupler-containing light-sensitive silver halide 
emulsion layer, at least one cyan dye-forming coupler-containing 
light-sensitive silver halide emulsion layer, and at least one 
light-insensitive hydrophilic colloidal layer, wherein (1) at least one of 
layers constituting said light-sensitive silver halide emulsion layer 
comprises silver bromochloride emulsion grains having a silver chloride 
content of 90 mol % or more or silver chloride emulsion grains, which are 
sensitized with a gold compound, (2) a hydrophilic colloidal layer 
containing a white pigment in such an amount that the density thereof is 
in the range of 20% by weight or more is provided between said support and 
the nearest silver halide emulsion layer, and (3) either said 
light-sensitive emulsion layer or said light-insensitive layer comprises 
at least one of compounds represented by the following general formulae 
(I) to (IX): 
##STR1## 
wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.8 and R.sup.9 
each represents a hydrogen atom, alkyl group or aryl group; R.sup.7 
represents a hydrogen atom, alkyl group, aryl group, nitro group, carboxyl 
group, sulfo group, sulfamoyl group, hydroxyl group, halogen atom, alkoxy 
group or thiazolyl group; R.sup.10 represents an alkylene group or arylene 
group; R.sup.11, R.sup.12 and R.sup.13 each represents a halogen atom or 
alkyl group; R.sup.14 and R.sup.15 each represents a hydrogen atom, alkyl 
group, aryl group or nitrogen-containing heterocyclic residue; R.sup.16 
and R.sup.17 each represents a hydrogen atom, halogen atom, alkyl group, 
aryl group or aryloxy group, with the proviso that R.sup.16 and R.sup.17 
may be connected to each other to form a benzene ring; R.sup.18 represents 
a hydrogen atom or alkyl group; R.sup.19 represents an alkyl group or aryl 
group; Y represents a halogen atom; Z.sup.1 represents a nonmetallic atom 
group necessary for the formation of a thiazolyl ring; Z.sup.2 represents 
a nonmetallic atom group necessary for the formation of a 6-membered ring; 
n represents an integer 0 or 1; and m represents an integer 1 or 2; (iii) 
a silver halide color photographic material comprising on a support at 
least one yellow-developable silver halide emulsion layer, at least one 
magenta-developable silver halide emulsion layer, and at least one 
cyan-developable silver halide emulsion layer, wherein at least one of 
said silver halide emulsion layers comprises silver bromochloride emulsion 
grains or silver chloride emulsion grains containing substantially no 
silver iodide and having a silver chloride content of 95 mol % or more, at 
least one hydrophilic colloidal layer containing a white pigment in such 
an amount that the density thereof is in the range of 20% by weight or 
more is provided between said support and the nearest developable silver 
halide emulsion layer, and the film pH and film pAg of said 
light-sensitive material are in the range of 5.0 to 6.5 and 6.0 to 10.0, 
respectively; a silver halide color photographic material as defined in 
the foregoing clause (ii), wherein there is incorporated instead of or in 
combination with at least one compound of general formulae (I) to (IX) at 
least one aminoglycocide selected from the group consisting of gentamicin, 
amikacin, tobramycin, dibekacin, arbekacin, micronomicin, icepamicin, 
sisomicin, netilmicin and astromicin or at least one of compounds 
represented by the foregoing general formulae (VII) to (IX); a silver 
halide color photographic material as defined above or defined in the 
foregoing clause (ii), wherein at least one of layers constituting the 
photographic constituent layers provided on the support has a colored 
layer decolorable upon development; a silver halide color photographic 
material as defined in the foregoing clause (iii), wherein the coated 
amount of said white pigment to be incorporated in said hydrophilic 
colloidal layer is in the range of 2 g/m.sup.2 or more; or a silver halide 
color photographic material as defined in the foregoing clause (iii), 
wherein said silver bromochloride emulsion grains are formed by adding to 
a system containing initially formed silver halide grains bromide 
ion-releasing compounds and/or bromine-releasing compounds in the total 
amount of 0.0005 to 0.05 mol per mol of the finally formed silver halide 
at any time of the grain formation procedure when any portion of the grain 
corresponding to 20% by volume or less of the whole grain is formed and/or 
at any time between the completion of the grain formation and the coating 
thereof on said support.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention will be further described hereinafter. 
In the silver halide color photographic material (i) as disclosed above, 
when a hydrophilic colloidal layer containing a white pigment is coated on 
a support, it is necessary that the coated amount of the white pigment be 
in the range of 2 g/m.sup.2 or more, preferably 4 g/m.sup.2 or more, more 
preferably. 8 g/m.sup.2 or more. The upper limit of the coated amount of 
the white pigment is preferably 40 g/m.sup.2, though not specifically 
limited. 
The "coated amount of white pigment" as specified herein indicates the 
value including an amount of various surface treating agents or dispersion 
stabilizers which are optionally incorporated in the white pigment for the 
purpose of improving its dispersibility or like purposes. 
The proportion of the white pigment in the hydrophilic binder in the 
hydrophilic colloidal layer containing the white pigment can be 
arbitrarily predetermined in the range satisfying the aforementioned 
conditions but may be 10% by weight or more, preferably 20% by weight or 
more, more preferably 40% by weight or more, most preferably 70% by weight 
or more. Its upper limit is preferably 99% by weight, though not 
specifically limited. 
The thickness of the hydrophilic colloidal layer containing a white pigment 
can be predetermined by the above specified content and coated amount but 
is preferably in the range of 0.5 to 10 .mu.m. 
Examples of the white pigment to be incorporated in the photographic 
light-sensitive material (i) of the present invention include titanium 
dioxide, barium sulfate, lithopone, carmina white, calcium carbonate, 
silica white, antimony trioxide, titanium phosphate, zinc oxide, white 
lead, and gypsum. Particularly effective among these pigments is titanium 
dioxide. Titanium dioxide to be used in the present invention may be of 
either rutile type or anatase type. Titanium dioxide to be used in the 
present invention may also be a product of either the sulfate process or 
the chloride process. 
The grain diameter of the white pigment grains to be incorporated in the 
hydrophilic colloidal layer may be in the range of 0.1 .mu.m to 1.0 .mu.m, 
preferably 0.2 .mu.m to 0.3 .mu.m as calculated in terms of average grain 
size. 
In the photographic light-sensitive material (i) of the present invention, 
as the binder (hydrophilic colloid) constituting the hydrophilic colloidal 
layer containing a white pigment, the silver halide emulsion layer and the 
light-insensitive interlayer there may be preferably used a gelatin. If 
necessary, other hydrophilic colloids may be used in an arbitrary 
proportion instead of gelatin. 
Examples of such other hydrophilic colloids include gelatin derivatives, 
graft polymers of gelatin and other polymers, proteins such as albumin and 
casein, cellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethyl 
cellulose, cellulose sulfate), saccharides such as sodium alginate and 
starch derivative, and various kinds of synthetic polymers such as 
polyvinyl alcohol, partially acetalated polyvinyl alcohol, 
poly(N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, 
polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole. 
In the photographic light-sensitive material (i) of the present invention, 
the white pigment-containing hydrophilic colloidal layer may comprise 
various materials for use in general photographic light-sensitive 
materials incorporated therein besides white pigment and binder. For 
example, a surface active agent as coating aid, a film hardener, a dye, a 
fog inhibitor or the like may be used. Further, a high boiling organic 
solvent which has been dispersed in the form of fine oil drops may be 
incorporated in the white pigment-containing hydrophilic colloidal layer. 
When a dispersion of such a high boiling organic solvent is incorporated 
in the white pigment-containing hydrophilic colloidal layer, various 
oil-soluble materials (e.g., fluorescent brightening agent) may be 
dissolved therein and incorporated in the dispersion. 
The photographic light-sensitive material (i) of the present invention 
comprises a support, at least one light-sensitive emulsion layer coated on 
the support, a light-insensitive layer such as color mixing inhibiting 
layer and protective layer, and a hydrophilic colloidal layer containing a 
white pigment. 
In the photographic light-sensitive material (i) of the present invention, 
the hydrophilic colloidal layer containing a white pigment is provided 
interposed between the support and the light-sensitive emulsion layer. 
Examples of the support to be used in the photographic light-sensitive 
material (i) of the present invention include a paper made of natural 
pulp, a synthetic pulp, etc., a baryta paper, a paper coated with a resin 
such as a polyolefin (e.g., polyethylene, polypropylene) and polyester, 
etc., a synthetic high molecular film such as polyethylene, polypropylene, 
polystyrene, polycarbonate, hard polyvinylchloride and polyethylene 
terephthalate, and a natural high molecular film such as cellulose 
diacetate, cellulose triacetate and nitrocellulose. 
The photographic light-sensitive material (i) of the present invention may 
be in an embodiment in which the white pigment is incorporated only in the 
hydrophilic colloidal layer and is not incorporated in a resin 
constituting the support, e.g., a resin to be coated on a paper support, 
or a resin film as the support itself or in another embodiment in which 
the white pigment is incorporated in the hydrophilic colloidal layer as 
well as the resin constituting the support. 
In the photographic light-sensitive material (i) of the present invention, 
if a reflective type support is used, the reflective type support is 
preferably a paper support coated with a waterproof resin layer on both 
sides thereof, at least one of the waterproof resin layers containing fine 
grains of white pigment. These white pigment grains are preferably 
contained in the waterproof resin layer in a density of 12% by weight or 
more, more preferably 14% by weight or more. As such light reflecting 
white pigment grains there are preferably used grains obtained by 
thoroughly kneading white pigment grains in the presence of a surface 
active agent, and optionally treating the surface of the pigment grains 
with a divalent, trivalent or tetravalent alcohol. 
These white pigment grains are preferably dispersed uniformly in the 
reflective layer without aggregation. The size of its distribution can be 
determined by measuring the percentage (%) (Ri) of the area occupied by 
fine grains projected on a unit area. The fluctuation coefficient of the 
percent area occupation (% ) can be determined by calculating the ratio 
(s/R) of the standard deviation s of Ri to the average value (R) of Ri. In 
the present invention, the fluctuation coefficient of the percent area 
occupation (%) of pigment fine grains is preferably in the range of 0.15 
or less, more preferably 0.12 or less, particularly 0.08 or less. 
In the support of the material (i) of the present invention, the surface 
roughness on the central line on the side on which a light-sensitive layer 
is set forth is preferably in the range of 0.14 .mu.m or less. 
In preparing the photographic light-sensitive material (i) of the present 
invention, there may be used a support having a surface with a diffused 
reflectivity of the second kind. The term "diffused reflectivity of the 
second kind" as used herein means a "diffused reflectivity obtained by 
roughening a mirror-like surface so that the surface is divided into 
minute surfaces facing in different directions". Regarding the roughness 
of the surface of a diffused reflectivity of the second kind, the 
three-dimensional average roughness with respect to the central surface is 
in the range of 0.1 to 2 .mu.m, preferably 0.1 to 1.2 .mu.m. The frequency 
of the surface roughness is preferably in the range of 0.1 to 2,000 
cycle/mm, more preferably 50 to 600 cycle/mm for the roughness of 0.1 
.mu.m or more. For the details of such a support, reference can be made to 
JP-A-2-239244. 
On the white pigment-containing hydrophilic colloidal layer may be coated a 
light-sensitive emulsion layer directly or via one or more 
light-insensitive hydrophilic colloidal layers. If light-insensitive 
hydrophilic colloidal layers are provided, the total thickness of these 
layers is preferably in the range of 5 .mu.m or less, more preferably 2 
.mu.m or less. These light-insensitive hydrophilic colloidal layers may 
optionally contain various photographically useful materials. Examples of 
such photographically useful materials include a surface active agent as 
coating aid, a film hardener, a dye, and a fog inhibitor. Further, a 
colloidal silver, a solid dispersion of dye or a cationic polymer dyed 
with a dye may be incorporated in these light-insensitive hydrophilic 
colloidal layers to form colored layers decolorable upon development. 
Alternatively, a high boiling organic solvent dispersed in the form of 
fine oil drops may be incorporated in these light-insensitive hydrophilic 
colloidal layers. Such a high boiling organic solvent may contain a 
photographically useful material such as oil-soluble color mixing 
inhibitor, fluorescent brightening agent and ultraviolet absorbent 
dissolved therein. 
The photographic light-sensitive material (i) of the present invention 
preferably contains a dye decolorable upon processing as described in EP 
0337490A2, pp. 27-76, (particularly oxonol dye, cyanine dye) in the 
hydrophilic colloidal layer for the purpose of inhibiting irradiation or 
halation or improving fastness to safelight. 
Some of these water-soluble dyes cause deterioration in the color 
separation or fastness to safelight when used in an increased amount. As 
dyes which can be used without deteriorating the color separation there 
may be preferably used water-soluble dyes as described in Japanese Patent 
Application Nos. 03-310143, 03-310189, and 03-310139. 
The photographic light-sensitive material (i) of the present invention 
preferably comprises a colored layer decolorable upon processing instead 
of or in combination with such a water-soluble dye. The colored layer 
decolorable upon processing to be used in the present invention may be 
provided in direct contact with an emulsion layer or via an interlayer 
containing a processing color mixing inhibitor such as gelatin and 
hydroquinone. The colored layer is preferably disposed under an emulsion 
layer which is developed to the same primary color as the color of the 
colored layer (support side). All colored layers which correspond to the 
respective primary colors may be individually provided. Alternatively, 
only some of these colored layers may be selectively provided. Further, a 
single colored layer which has been colored so as to correspond to a 
plurality of primary colors can be provided. In respect to the optical 
reflection density of the colored layer, the optical density value at the 
wavelength in the exposure wavelength range (400 nm to 700 nm visible 
light range for commonly used printer exposure or wavelength of the 
scanning exposure light source used) at which the highest optical density 
is given is preferably in the range of 0.2 to 3.0, more preferably 0.5 to 
2.5, particularly 0.8 to 2.0. 
The formation of the colored layer can be accomplished by any conventional 
known methods. Examples of such known methods include a method which 
comprises the use of a dye as described in JP-A-2-282244, upper right 
column, page 3 to page 8, a method as described in JP-A-3-7931, upper 
right column, page 3--lower right column, page 11 which comprises 
incorporating a dye in a hydrophilic colloidal layer in the form of solid 
fine dispersion, a method which comprises mordanting a cation polymer with 
an anionic dye, a method which comprises allowing a dye to be adsorbed to 
fine grains of silver halide or the like to be fixed in a layer, and a 
method which comprises the use of a colloidal silver as described in 
JP-A-1-239544. As the method which comprises dispersing finely divided dye 
grains in a solid form there may be used a method as described in 
JP-A-2-308244, pp. 4-13, which comprises the incorporation of a finely 
divided dye powder that is substantially insoluble in water at pH 6 or 
less but is substantially soluble in water at pH 8 or more. An example of 
the method which comprises mordanting a cationic polymer with an anionic 
dye is described in JP-A-2-84637, pp. 18-26. A method for preparing 
colloidal silver as a light absorbent is described in U.S. Pat. Nos. 
2,688,601, and 3,459,563. Preferred among these methods are the method 
which comprises the incorporation of finely divided dye grains and the 
method which comprises the use of colloidal silver. 
The silver halide emulsion grains to be incorporated in the photographic 
light-sensitive material (i) of the present invention contain a metal 
complex of Fe, Ru, Re, Os or Ir. 
The amount of such a metal complex to be incorporated depends much on the 
kind of the metal complex used but is preferably in the range of 10.sup.-9 
mol to 10.sup.-2 mol, most preferably 10.sup.-8 mol to 10.sup.-4 mol per 
mol of silver halide. 
The metal complex to be incorporated in the photographic light-sensitive 
material (i) of the present invention may be added to the system at any 
step during the preparation of silver halide grains, i.e., nucleation, 
growth of nuclei, physical ripening, before or after chemical 
sensitization. The metal complex may be batch-wise added to the system 
several times. Such a metal complex is preferably used in the form of 
solution in water or a proper solvent. 
In particular, the metal complex to be incorporated in the photographic 
light-sensitive material (i) of the present invention is preferably an 
iridium complex. Examples of trivalent or tetravalent iridium complex to 
be used in order to incorporate iridium complexes in the silver halide 
emulsion grains will be given below, but the effects of the present 
invention should not be construed as being limited thereto. 
Hexachloroiridium (III) or (IV) complex salts, hexaamine iridium (III) or 
(IV) complex salts 
The amount of such an iridium complex to be incorporated is preferably in 
the range of 1.times.10.sup.-9 mol to 1.times.10.sup.-4 mol, most 
preferably 1.times.10.sup.-8 mol to 1.times.10.sup.-5 mol per mol of 
silver halide, except for iridium complexes having at least two cyano 
ligands as exemplified below. 
As the metal complex to be incorporated in the silver halide emulsion 
grains for use in the photographic light-sensitive material (i) of the 
present invention there may be preferably used at least one selected from 
the group consisting of metal complexes of Fe, Ru, Re., Os and Ir having 
at least two cyano ligands. Such a metal complex can be represented by the 
following general formula [C-I]: 
EQU [M.sub.1 (CN).sub.6-a L.sub.a ].sup.n [C- 1] 
wherein M.sub.1 represents Fe, Ru, Re, Os or Ir; L represents a ligand 
other than CN; "a" represents an integer 0, 1 or 2; and n represents an 
integer -2, -3 or -4. 
Specific examples of the metal complex having at least two cyano ligands to 
be used in the present invention will be given below. As paired ions to be 
incorporated in such a metal complex there may be preferably used ammonium 
ion and alkaline metal ions such as sodium ion and potassium ion. 
[Fe(CN).sub.6 ].sup.-4, [Fe(CN).sub.6 ].sup.-3, [Ru(CN).sub.6 ].sup.-4, 
[Ru(CN).sub.5 F].sup.-4, [Ru(CN).sub.4 F.sub.2 ].sup.-4, [Ru(CN).sub.5 
Cl].sup.-4, [Ru(CN).sub.4 Cl.sub.2 ].sup.-4, [Ru(CN).sub.5 (OCN)].sup.-4, 
[Ru(CN).sub.5 (SCN)].sup.-4, [Ru(CN).sub.6 ].sup.-4, [Re(CN).sub.5 
Br].sup.-4, [Re(CN).sub.4 Br.sub.2 ].sup.-4, [Os(CN).sub.6 ].sup.-4, 
[Os(CN).sub.6 I].sup.-4, [Os(CN).sub.4 I.sub.2 ].sup.-4, [Ir(CN).sub.6 
].sup.-3, [Ir(CN).sub.5 (N.sub.3)].sup.-3, [Ir(CN).sub.5 (H.sub.2 
O)].sup.-3 
The content of the at least one metal complex having at least two cyano 
ligands selected from the group consisting of metal complexes of Fe, Ru, 
Re, Os and Ir to be incorporated in the photographic light-sensitive 
material (i) is preferably in the range of 1.times.10.sup.-6 mol or more, 
and to 1.times.10.sup.-3 mol or less, more preferably 5.times.10.sup.-6 
mol or more and 5.times.10.sup.4 mol per mol of silver halide. 
The aforementioned metal complex having at least two cyano ligands to be 
incorporated in the photographic light-sensitive material (i) of the 
present invention may be added to the system at any step during the 
preparation of silver halide grains, i.e., nucleation, growth, physical 
ripening, before or after chemical sensitization. The metal complex may be 
batch-wise added to the system several times. In the present invention, 
50% or more of all the content of the aforementioned metal complex having 
at least two cyano ligands incorporated in the silver halide grains are 
present in the surface layer of grains which accounts for 50% or less of 
the volume thereof. The term "surface layer of grains which accounts for 
50% or less of the volume thereof" as used herein means the surface 
portion of a grain which accounts for 50% or less, preferably 40% or less, 
more preferably 20% or less of the volume of one grain. A metal 
complex-free layer may be further provided outside the above specified 
surface layer containing a metal complex. 
Such a metal complex may be added in the form of solution in water or a 
proper solvent directly to a reaction solution during the formation of 
silver halide grains or to an aqueous solution of silver halide, aqueous 
solution of silver salt or other solutions for the formation of silver 
halide grains so that it is incorporated in the silver halide grains thus 
formed. An alternative preferable approach is to dissolve silver halide 
grains containing a metal complex and to precipitate these silver halide 
from the solution thus obtained on other silver halide grains to 
incorporate the metal complex into silver halide grains. 
The halogen composition of the silver halide grains to be incorporated in 
the photographic light-sensitive material (i) of the present invention 
needs to have a silver chloride content of 90 mol % or more. The silver 
halide grains preferably comprise silver bromochloride substantially free 
of silver iodide, in which 95 mol % or more of total amount of silver 
halide is silver chloride. "Substantially free of silver iodide" as used 
herein indicates a silver iodide content of 1.0 mol % or less. More 
preferably, the silver halide grains comprises silver bromochloride 
substantially free of silver iodide, in which 98 mol % or more of total 
amount of silver halide is silver chloride, or silver chloride. 
The silver halide grains to be incorporated in the photographic 
light-sensitive material (i) of the present invention preferably comprises 
a localized phase having a silver bromide content of more than at least 10 
mol %. The location of a localized phase having a higher silver bromide 
content than the substrate needs to be in the vicinity of the surface of 
the grains in order to attain the effects of the present invention and 
from the standpoint of pressure properties and dependence on the 
composition of processing solutions. The term "vicinity of the surface of 
the grains" as used herein means the position located within 1/5, 
preferably 1/10 of the grain size of the silver halide grain used from the 
top surface thereof. The most preferable localized phase having a higher 
silver bromide content than the substrate is one having a silver bromide 
content of more than at least 10 mol % epitaxially grown on the corner of 
a cubic or tetradecahedral silver chloride grain. 
The silver bromide content of such a localized phase is preferably more 
than 10 mol %. If the silver bromide content is too high, the photographic 
light-sensitive material may be provided with photographically undesirable 
properties. For example, the photographic light-sensitive material may be 
desensitized under pressure or may be subject to a great change in 
sensitivity and gradation due to the fluctuations of the composition of 
processing solutions. Taking into account these problems, the silver 
bromide content of the localized phase having a high silver bromide 
content is preferably in the range of 10 mol % to 70 mol %, most 
preferably 20 mol % to 50 mol %. The silver bromide content of the 
localized phase having a high silver bromide content can be analyzed by 
X-ray diffractometry (as described in "Shinjikken Kagaku Koza 6; Kozo 
Kaiseki", Nihon Kagakukai, Maruzen) 
The aforementioned localized phase preferably comprises silver in an amount 
of 0.1 mol % to 20 mol %, 0.5 mol % to 7 mol % of the total amount of 
silver constituting the silver halide grains of the present invention. 
The interface of such a localized phase with other phases may have a 
definite phase interface or may have a transition region having a gradual 
gradation of halogen composition. 
The formation of such a localized phase can be accomplished by various 
methods. For example, a soluble silver salt and a soluble halogen salt can 
be reacted with each other by the single jet process or double jet process 
to form a localized phase. Alternatively, a conversion method by which 
silver halide grains which have been already formed are converted to 
silver halide grains having a lower solubility product may be used to form 
a localized phase. For example, a water-soluble bromide solution may be 
added to host cubic or tetradecahedral silver halide grains, or finely 
divided silver bromochloride or silver bromide grains having a smaller 
average grain size and a higher silver bromide content than the host 
grains may be mixed with the host grains, and then ripened to form a 
localized phase. 
The formation of such a localized phase is preferably effected in the 
presence of an iridium compound. This means that an iridium compound is 
supplied into the reaction system at the same time with, shortly before or 
shortly after the supply of silver or halogen to be used for the formation 
of a localized phase. For example, if a solution of a water-soluble 
bromide is added to the system to form a localized phase, it is a 
preferable conduct that an iridium compound has been previously 
incorporated in the solution, or another solution containing an iridium 
compound and the solution of water-soluble bromide are simultaneously 
added to the system. If finely divided silver halide grains having a 
smaller average grain diameter and a higher silver bromide content than 
host silver halide grains are mixed with the host grains, and then ripened 
to form a localized phase, it is a preferable conduct that an iridium 
compound has been previously incorporated in the finely divided silver 
halide grains having a high silver bromide content. The iridium compound 
may be added to the system during a formation of phases other than such a 
formation of the localized phase. However, the localized phase is 
preferably formed with at least 50 mol %, more preferably at least 80 mol 
% of the total amount of iridium added. 
In the photographic light-sensitive material (i) of the present invention, 
the silver halide emulsion is preferably subjected to sulfur sensitization 
and/or gold sensitization, optionally in combination with reduction 
sensitization. 
The sulfur chemical sensitization to be used for the photographic 
light-sensitive material (i) of the present invention can be effected with 
a sulfur-containing compound reactive with an active gelatin or silver 
(e.g., thiosulfate, thioureas, mercapto compounds, rhodanines). Specific 
examples of such a sulfur-containing compound are described in U.S. Pat. 
Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, and 3,656,955. 
The silver halide grains to be incorporated in the photographic 
light-sensitive material (i) of the present invention may have either or 
both of (100) planes and (111) planes or planes of higher order. The 
silver halide grains to be incorporated in the photographic 
light-sensitive material (i) of the present invention preferably comprise 
cubes or tetradecahedrons mainly having (100) planes. 
The size of the silver halide grains to be incorporated in the photographic 
light-sensitive material (i) of the present invention may be within a 
commonly specified range but is preferably in the range of 0.1 .mu.m to 
1.5 .mu.m as calculated in terms of average grain diameter. The grain 
diameter distribution may be either polydisperse or monodisperse, 
preferably monodisperse. In the grain size distribution, which represents 
the degree of monodispersibility, the ratio (s/d) of the statistic 
standard deviation (s) to the average grain size (d) is preferably in the 
range of 0.2 or less, more preferably 0.15 or less. Further, two or more 
kinds of monodisperse emulsions may be preferably used in admixture. 
As the mercapto heterocyclic compound to be incorporated in the 
photographic light-sensitive material (i) of the present invention there 
can be preferably used a compound represented by the following general 
formula (IA): 
##STR2## 
wherein Q represents an atomic group necessary for the formation of a 5- 
or 6-membered heterocycle or 5- or 6-membered heterocycle condensed with 
benzene rings; and M represents a cation. 
The compound represented by the general formula (IA) will be further 
described hereinafter. 
Examples of the heterocycle represented by Q include imidazole ring, 
tetrazole ring, thiazole ring, oxazole ring, selenazole ring, 
benzoimidazole ring, naphthoimidazole ring, benzothiazole ring, 
naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, and 
benzoxazole ring. Examples of the cation represented by M include hydrogen 
ion, alkaline metal (e.g., sodium, potassium) ion, and ammonium ion. 
Preferred among the compounds represented by the general formula (IA) are 
mercapto compounds represented by the following general formulae (IA-1), 
(IA-2), (IA-3) and (IA-4): 
##STR3## 
wherein R.sub.A represents a hydrogen atom, alkyl group, alkoxy group, 
aryl group, halogen atom, carboxyl group or salt thereof, sulfo group or 
salt thereof, or amino group; Z represents --NH--, --O-- or --S--; and M 
is as defined in the general formula (IA). 
##STR4## 
wherein Ar represents 
##STR5## 
R.sub.B represents an alkyl group, alkoxy group, carboxyl group or salt 
thereof, sulfo group or salt thereof, hydroxyl group, amino group, 
acylamino group, carbamoyl group or sulfonamide group; n represents an 
integer 0 to 2; and M is as defined in the general formula (IA). 
In the foregoing general formulae (IA-1) and (IA-2), examples of the alkyl 
group represented by R.sub.A or R.sub.B include methyl, ethyl, and butyl. 
Examples of the alkoxy group represented by R.sub.A or R.sub.B include 
methoxy, and ethoxy. Examples of the salts of carboxyl or sulfo group 
represented by R.sub.A or R.sub.B include sodium salts and ammonium salts 
of carboxyl and sulfo groups. 
In the general formula (IA-1), examples of the aryl group represented by 
R.sub.A include phenyl and naphthyl. Examples of the halogen atom 
represented by R.sub.A include chlorine atom and bromine atom. 
In the general formula (IA-2), examples of the acylamino group represented 
by R.sub.B include methylcarbonylamino, and benzoylamino. Examples of the 
carbamoyl group represented by Rs include ethyl carbamoyl, and phenyl 
carbamoyl. Examples of the sulfonamide group represented by R.sub.B 
include methyl sulfonamide, and phenyl sulfonamide. 
The foregoing alkyl group, alkoxy group, aryl group, amino group, acylamino 
group, carbamoyl group, and sulfonamide group may further contain 
substituents. Examples of substituents for, e.g., amino group include 
alkylcarbamoyl-substituted amino group, i.e., alkyl-substituted ureido 
group. 
##STR6## 
wherein Z represents --N(R.sub.A1)--, oxygen atom or sulfur atom; R 
represents a hydrogen atom, alkyl group, aryl group, alkenyl group, 
cycloalkyl group, --SR.sub.A1, --N(R.sub.A2)R.sub.A3, --NHCOR.sub.A4, 
--NHSO.sub.2 R.sub.A5 or heterocyclic group; R.sub.A1 represents a 
hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, 
--COR.sub.A4 or --SO.sub.2 R.sub.A5 ; R.sub.A2 and R.sub.A3 each 
represents a hydrogen atom, alkyl group or aryl group; R.sub.A4 and 
R.sub.A5 each represents an alkyl group or aryl group; and M is as defined 
in the general formula (IA). 
Examples of the alkyl group represented by R, R.sub.A1, R.sub.A2, R.sub.A3, 
R.sub.A4 or R.sub.A5 include methyl, benzyl, ethyl, and propyl. Examples 
of the aryl group represented by R, R.sub.A1, R.sub.A2, R.sub.A3, R.sub.A4 
or R.sub.A5 include phenyl, and naphthyl. 
Examples of the alkenyl group represented by R and R.sub.A1 include 
propenyl. Examples of the cycloalkyl group represented by R and R.sub.A1 
include cyclohexyl. Examples of the heterocyclic group represented by R 
include furyl, and pyridinyl. 
The alkyl group and aryl group represented by R, R.sub.A1, R.sub.A2, 
R.sub.A3, R.sub.A4 or RAS, the alkenyl group and cycloalkyl group 
represented by R or R.sub.A1, and the heterocyclic group represented by R 
may further contain substituents. 
##STR7## 
wherein R and M are as defined in the general formula (IA-3); and R.sub.B1 
and R.sub.B2 have the same meaning as R.sub.A1 and R.sub.A2 in the general 
formula (IA-3), respectively. 
Specific examples of the compound represented by the general formula (IA) 
will be given below, but the present invention should not be construed as 
being limited thereto. 
______________________________________ 
I-1-1 
##STR8## 
I-1-2 
##STR9## 
I-1-3 
##STR10## 
I-1-4 
##STR11## 
I-1-5 
##STR12## 
I-1-6 
##STR13## 
I-1-7 
##STR14## 
I-1-8 
##STR15## 
I-2-1 
##STR16## 
I-2-2 
##STR17## 
I-2-3 
##STR18## 
I-2-4 
##STR19## 
I-2-5 
##STR20## 
I-2-6 
##STR21## 
______________________________________ 
##STR22## 
Exemplary 
Compound R M 
______________________________________ 
I-3-1 C.sub.2 H.sub.5 H 
I-3-2 CH.sub.2CHCH.sub.2 
H 
I-3-3 CHCHCH.sub.2CB.sub.3 
H 
I-3-4 C.sub.7 H.sub.15 H 
I-3-5 C.sub.9 H.sub.19 Na 
I-3-6 
##STR23## H 
I-3-7 C.sub.4 H.sub.9 (t) 
H 
I-3-8 
##STR24## H 
I-3-9 
##STR25## H 
I-3-10 
##STR26## H 
I-3-11 
##STR27## H 
I-3-12 
##STR28## NH.sub.4 
I-3-13 NHCOCH.sub.3 H 
I-3-14 
##STR29## H 
I-3-15 N(CH.sub.3).sub.3 
H 
I-3-16 
##STR30## H 
I-3-17 
##STR31## H 
I-3-18 SCH.sub.3 H 
I-3-19 
##STR32## H 
I-3-20 SH H 
I-3-21 H H 
I-3-22 C.sub.2 H.sub.5 H 
I-3-23 C.sub.4 H.sub.9 (t) 
H 
I-3-24 C.sub.6 H.sub.13 H 
I-3-25 
##STR33## H 
I-3-26 
##STR34## H 
I-3-27 
##STR35## H 
I-3-28 
##STR36## H 
I-3-29 
##STR37## H 
I-3-30 NH.sub.2 H 
I-3-31 CH.sub.2 CHCH.sub.2 
H 
I-3-32 SH H 
I-3-33 NHCOC.sub.2 H.sub.5 
H 
______________________________________ 
##STR38## 
Exemplary 
Compound 
R R.sub.A1 M 
______________________________________ 
I-3-34 C.sub.2 H.sub.5 
H H 
I-3-35 CH.sub.3 CH.sub.3 H 
I-3-36 CH.sub.3 
##STR39## H 
I-3-37 NHCOCH.sub.3 CH.sub.3 H 
I-3-38 
##STR40## 
##STR41## H 
I-3-39 NHCOCH.sub.3 COCH.sub.3 H 
I-3-40 NHCOCH.sub.3 
##STR42## H 
______________________________________ 
##STR43## 
Exemplary 
Compound 
R R.sub.B1 
R.sub.B2M 
______________________________________ 
I-4-1 C.sub.2 H.sub.5 CH.sub.3 
CH.sub.3H 
I-4-2 
##STR44## CH.sub.3 
CH.sub.3H 
I-4-3 NH.sub.2 H 
##STR45## 
I-4-4 
##STR46## CH.sub.3 
C.sub.4 H.sub.9H 
I-4-5 NHCOCH.sub.3 CH.sub.3 
CH.sub.3H 
I-4-6 
##STR47## CH.sub.3 
CH.sub.3H 
I-4-7 
##STR48## CH.sub.3 
C.sub.3 H.sub.7 (i)H 
I-4-8 
##STR49## 
______________________________________ 
The amount of the compound represented by the general formula (IA) to be 
incorporated in the system is preferably in the range of 1.times.10.sup.-5 
to 5.times.10.sup.-2 mol, more preferably 1.times.10.sup.-4 to 
1.times.10.sup.-2 mol per mol of silver halide. The method for the 
addition of the compound represented by the general formula (IA) is not 
specifically limited. The compound of the general formula (IA) may be 
added to the system during the formation, physical ripening or chemical 
ripening of silver halide grains or during the preparation of the coating 
solution. 
As the binder or protective colloid to be used for the photographic 
light-sensitive material (i) of the present invention there may be 
advantageously used a gelatin. Other hydrophilic colloids may be used 
singly or in combination with such a gelatin. An example of such a gelatin 
which can be preferably used is a low calcium gelatin having a calcium 
content of 800 ppm or less, more preferably 200 ppm or less. In order to 
prevent various mold and bacteria from proliferating in the hydrophilic 
colloidal layer to deteriorate the image, it is preferred that an 
antifungal substance as described in JP-A-63-271247 be incorporated in the 
system. 
The photographic light-sensitive material (i) of the present invention may 
be exposed to visible light or infrared rays. The exposure can be carried 
out under low intensity or high intensity. A preferred example of the high 
intensity exposure method is a laser scanning exposure process with an 
exposure time of less than 1.times.10.sup.-4 seconds, more preferably less 
than 1.times.10.sup.-6 seconds per pixel. 
A bandstop filter as described in U.S. Pat. No. 4,880,726 is preferably 
used upon exposure. This eliminates light color mixing, providing a 
remarkable improvement in the color reproducibility. 
A photographic light-Sensitive material which has been exposed is then 
subjected to a commonly used color development process. The photographic 
light-sensitive material of the present invention which has been exposed 
is preferably subjected to color development followed by blix for the 
purpose of rapid processing. In particular, if the aforementioned high 
silver chloride content emulsion is used, the pH value of the blix 
solution is preferably in the range of about 6.5 or less, more preferably 
about 6 or less for the purpose of accelerating desilvering. 
As the silver halide emulsion, other materials (e.g., additives) and 
photographic constituent layers (layer configuration) which can be used in 
the photographic light-sensitive material (i) of the present invention, 
and processing methods and processing additives to be used in the 
processing of the photographic light-sensitive material (i) of the present 
invention there may be preferably used those described in the following 
patents, particularly EP0,355,660A2 (corresponding to JP-A-2-139544). 
__________________________________________________________________________ 
Photographic 
constituent 
JP-A-62-215272 
JP-A-2-33144 EPO,355,660A2 
__________________________________________________________________________ 
Silver halide 
Line 6, upper right column, 
Line 16, upper right column, 
Line 53, p. 45-line 
emulsion 
p. 10-line 5, lower left 
p. 28-line 11, lower right 
3, p 47/lines 20-22, 
column, p. 12/last line 
column, p. 29/lines 2-5, 
p. 47 
4, lower right column, 
p. 30 
p. 12-line 17, upper 
left column, p. 13 
Silver halide 
Lines 6-14, lower left 
-- -- 
solvent column, p. 12/last line 3, 
upper right column- 
last line, lower left 
column, p. 18 
Chemical 
Last line 3, lower right 
Line 12-last line, 
Lines 4-9, p. 47 
sensitizer 
column-last line 5, lower 
lower right column, 
right column, p. 12/line 
p. 29 
1, lower right column, 
p. 18-last line 9, upper 
right column, p. 22 
Spectral 
Last line 8, upper right 
Lines 1-13, upper 
Lines 10-15, p. 47 
sensitizer 
column, p. 22-last 
left column, p. 30 
(spectral 
line, p. 38 
sensitizing 
method) 
Emulsion 
Line 1, upper left column, 
Line 14, upper left column- 
Lines 16-19, p. 47 
stabilizer 
p. 39-last line, upper 
line 1, upper right, 
right column, p. 72 
p. 30 
Development 
Line 1, lower left column, 
-- -- 
accelerator 
p. 72-line 3, upper 
right column, p. 91 
Color coupler 
Line 4, upper right column, 
Line 14, upper right column, 
Lines 15-27, p. 4/ 
(cyan, magenta, 
p. 91-line 6, upper left 
p. 3-last line, upper 
line 30, p. 5- 
yellow coupler) 
column, p. 121 
left column, p. 35 
last line, p. 28/ 
lines 29-31, p. 45/ 
line 23, p. 47- 
line 50, p. 63 
Color Line 7, upper left column, 
-- -- 
intensifier 
p. 121-line 1, upper 
right column, p. 125 
Ultraviolet 
Line 2, upper right column, 
Line 14, upper right column, 
Lines 22-31, p. 65 
absorbent 
p. 125-last line, lower 
p. 37-line 11, upper left 
left column, p. 127 
column, p. 38 
Discoloration 
Line 1, lower right column, 
Line 12, upper right column, 
Line 30, p. 4-line 
inhibitor 
p. 127-line 8, lower left 
p. 36-line 19, upper lower 
23, p. 5/line 1, 
(image column, p. 137 
column, p. 37 p. 29-line 25, 
stabilizer) p. 45/lines 33-40, 
P. 45/lines 2-21, 
p. 65 
High boiling 
Line 9, lower left column, 
Line 14, lower right column, 
Lines 1-51, p. 64 
and/or low 
p. 137-last line, upper 
p. 35-last line 4, upper 
boiling organic 
right column, p. 144 
left column, p. 36 
solvent 
Process for 
Line 1, lower left column, 
Line 10, lower right column, 
Line 51, p. 63-line 
dispersion 
p. 144-line 7, upper right 
p. 27-last line, upper 
56, p. 64 
of photographic 
column, p. 146 
left column, p. 28/line 
additives 12, lower right column- 
line 7, upper right 
column, p. 36 
Film Line 8, upper right column, 
-- -- 
hardener 
p. 146-line 4, lower left 
column, p. 155 
Developing 
Line 5, lower left column, 
agent p. 155-line 2, lower right 
precursor 
column, p. 155 
Development 
Lines 3-9, lower right 
-- -- 
inhibitor- 
column, p. 155 
releasing 
compound 
Support Line 19, lower right column, 
Line 18, upper right 
Line 29, p. 66- 
p. 155-line 14, upper 
column, p. 38-line 3, 
line 13, p. 67 
left column, p. 156 
upper left column, p. 39 
Constitution 
Line 15, upper left column, 
Lines 1-15, upper right 
Lines 41-52, p. 45 
of light- 
p. 156-line 14, lower 
column, p. 28 
sensitive 
right column, p. 156 
layer 
Dye Line 15, lower right column, 
Line 12, upper left column,- 
Lines 18-22, p. 66 
p. 156-last line, lower 
line 7, upper right 
right column, p. 184 
column, p. 38 
Discoloration 
Line 1, upper left column, 
Lines 8-11, upper right 
Line 57, p. 64- 
inhibitor 
p. 185-line 3, lower 
column, p. 36 line 1, p. 65 
right column, p. 188 
Gradation 
Lines 4-8, lower right 
-- -- 
adjustor 
column, p. 188 
Stain Line 9, lower right column, 
Last line, upper left 
Line 32, p. 65-line 
inhibitor 
p. 188-line 10, lower 
column-line 13, lower 
17, p. 66 
right column, p. 193 
right column, p. 37 
Surface Line 1, lower left column, 
Line 1, upper right column, 
-- 
active p. 201-last line, upper 
p. 18-last line, lower 
agent right column, p. 210 
right column, p. 24/last 
line 10, lower left column- 
line 9, lower right column, 
p. 27 
Fluorine- 
Line 1, lower left column, 
Line 1, upper left column, 
-- 
containing 
p. 210-line 5, lower 
p. 25-line 9, lower 
compound 
left column, p. 222 
right column, p. 27 
(antistatic 
agent, coating 
aid, lubricant, 
adhesion 
inhibitor) 
Binder Line 6, lower left column, 
Lines 8-18, upper right 
Lines 23-28, p. 66 
(hydrophilic 
p. 222-last line, upper 
column, p. 38 
colloid) 
left column, p. 225 
Thickening 
Line 1, upper right column, 
-- -- 
agent p. 225-line 2, upper right 
column, p. 227 
Antistatic 
Line 3, upper right column, 
-- -- 
agent p. 227-line 1, upper left 
column, p. 230 
Polymer latex 
Line 2, upper left column, 
-- -- 
p. 240-last line, p. 239 
Matting agent 
Line 1, upper left column, 
-- -- 
p. 240-last line, upper 
right column, p. 240 
Photographic 
Line 7, upper right column, 
Line 4, upper left column, 
Line 14, p. 67-line 
processing 
p. 3-line 5, upper right 
p. 39-last line, upper 
28, p. 69 
method column, p. 10 left column, p. 42 
(processing 
step, additives, 
etc.) 
__________________________________________________________________________ 
Note 
The contents cited in JPA-62-215272 include the contents described in the 
written amendment of procedure dated March 16, 1987 attached thereto. 
Among the above mentioned color couplers, as yellow couplers there may 
also be preferably used socalled short wave type yellow couplers as 
disclosed in JPA-63-231451, JPA-63-123047, JPA-63-241547, JPA-1-173499, 
JPA-1-213648, and JPA-1-250944. 
The cyan, magenta or yellow coupler is preferably emulsion-dispersed in an 
aqueous solution of a hydrophilic colloid in the form of an impregnation 
in a loadable latex polymer (as described in U.S. Pat. No. 4,203,716) in 
the presence (or absence) of a high boiling organic solvent as tabulated 
above or in the form of a solution with a water-insoluble and organic 
solvent-soluble polymer. 
Examples of the water-insoluble and organic solvent-soluble polymer which 
can be preferably used include single polymers or copolymers as described 
in U.S. Pat. No. 4,857,449, 7th column to 15th column, and WO88/00723, pp. 
12-30. More preferably, methacrylate or acrylamide polymers, particularly 
acrylamide polymers may be used in the light of dye image stability. 
The photographic light-sensitive material (i) of the present invention 
preferably comprises a dye image preservability-improving compound as 
described in EO0,277,589A2 in combination with these couplers, 
particularly pyrazoloazole coupler or pyrrolotriazole coupler. 
In particular, a compound as described in the above cited patents which 
undergoes chemical bonding to an aromatic amine developing agent remaining 
after color development to produce a chemically inert and substantially 
colorless compound and/or another compound as described in the above cited 
patents which undergoes chemical bonding to an oxidation product of an 
aromatic amine color developing agent remaining after color development to 
produce a chemically inert and substantially colorless compound may be 
preferably used singly or in combination to inhibit the occurrence of 
stain or other side effects caused by the formation of developed dyes by 
the reaction of a color developing agent or its oxidation product 
remaining in the film with a coupler in the storage after processing. 
As cyan couplers there may be preferably used 3-hydroxypyridine cyan 
couplers as disclosed in European Patent (EP) 0,333,185A2 (particularly 
those which have been rendered two-equivalent by incorporating a 
chlorine-separatable group in four-equivalent Coupler (42) exemplified as 
a specific example, Coupler (6), Coupler (9)), cyclic active methylene 
cyan couplers as disclosed in JP-A-64-32260 (particularly Coupler Examples 
3, 8, 34 exemplified as specific examples), pyrrolopyrazole cyan couplers 
as disclosed in EO0,456,226A1, pyrroloimidazole cyan couplers as disclosed 
in EP0,484,909, or pyrrolotriazole cyan couplers as disclosed in 
EP0,488,248, and EP0,491,197A1 besides diphenylimidazole cyan couplers as 
disclosed in JP-A-2-33144. Particularly preferred among these cyan 
couplers are pyrrolotriazole cyan couplers. 
As yellow couplers there may be preferably used besides the compounds as 
tabulated above acylacetamide yellow couplers having a 3- to 5-membered 
cyclic structure in the acyl group as disclosed in EP0,447,969A1, 
malondianilide yellow couplers as disclosed in EP0,482,552A1, or 
acylacetamide yellow couplers having a dioxane structure as disclosed in 
U.S. Pat. No. 5,118,599. Particularly preferred among these yellow 
couplers are acylacetamide yellow couplers having 
1-alkylcyclopropane-1-carbonyl group as acyl group, and malondianilide 
yellow couplers in which one of the anilide group forms an indoline ring. 
These couplers may be used singly or in combination. 
As the magenta coupler to be incorporated in the photographic 
light-sensitive material (i) of the present invention there can be used a 
5-pyrazolone magenta coupler or pyrazoloazole magenta coupler as disclosed 
in known articles as tabulated above. Particularly preferred among these 
magenta couplers are pyrazolotriazole couplers having a secondary or 
tertiary alkyl group directly connected to the 2, 3 or 6-position of the 
pyrazolotriazole ring as disclosed in JP-A-61-65245, pyrazoloazole 
couplers Containing a sulfonamide group in the molecule as disclosed in 
JP-A-61-65246, pyrazoloazole couplers containing an 
alkoxyphenylsulfonamide ballast group as disclosed in JP-A-61-147254, and 
pyrazoloazole couplers containing an alkoxy group or aryloxy group in the 
6-position as disclosed in EP226,849A and 294,785A in the light of color 
hue, image stability, color developability, etc. 
As the processing method for the color photographic light-sensitive 
material of the present invention and processing material for use in the 
processing method there may be preferably used those disclosed in 
JP-A-2-207250, line 1, lower right column, page 26--line 9, upper right 
column, page 34, and JP-A-4-97355, line 17, upper left column, page 
5--line 20, lower right column, page 18, other than those tabulated above. 
The hydrophilic colloidal layer containing a white pigment in the 
photographic light-sensitive material (ii) of the present invention will 
be described hereinafter. 
When the hydrophilic colloidal layer containing a white pigment is coated 
on the support, the density of the white pigment in the hydrophilic 
colloidal layer needs to be in the range of 20% by weight or more, 
preferably 40% by weight or more, most preferably 70% by weight or more. 
The upper limit of the density of the white pigment is not specifically 
defined but is preferably in the range of 99% by weight or less. 
The coated amount of the white pigment can be arbitrarily predetermined 
such that it satisfies the aforementioned conditions but is preferably in 
the range of 1 g/m.sup.2 or more, more preferably 2 g/m.sup.2 or more, 
most preferably 6 g/m.sup.2 or more in order to enhance the sharpness. The 
limit of the coated amount of the white pigment is not specifically 
defined but is preferably in the range of 40 g/m.sup.2 or less. 
The thickness of the white pigment-containing hydrophilic colloidal layer 
can be predetermined by the above specified content and coated amount but 
is preferably in the range of 0.5 .mu.m to 10 .mu.m. 
As the white pigment to be incorporated in the photographic light-sensitive 
material (ii) of the present invention there can be used one similar to 
that used in the photographic light-sensitive material (i) of the present 
invention. 
The grain diameter of the white pigment grains to be incorporated in the 
hydrophilic colloidal layer may be in the range of 0.1 .mu.m to 1.0 .mu.m, 
preferably 0.2 .mu.m to 0.3 .mu.m as calculated in terms of average grain 
size. 
In the present invention, as the hydrophilic colloid (binder) constituting 
the hydrophilic colloidal layer containing a white pigment, the silver 
halide emulsion layer, the light-insensitive interlayer, etc. there may be 
preferably used a gelatin. If necessary, other hydrophilic colloids may be 
used in an arbitrary proportion instead of gelatin. 
Examples of such hydrophilic colloids which can be used include the same 
hydrophilic colloids as described with reference to the photographic 
light-sensitive material (i). 
In the photographic light-sensitive material (ii) of the present invention, 
the white pigment-containing hydrophilic colloidal layer may comprise 
various materials to be commonly incorporated in photographic 
light-sensitive materials as described with reference to the photographic 
light-sensitive material (i) besides the white pigment and binder. 
The photographic light-sensitive material (ii) of the present invention 
comprises a support, at least one light-sensitive emulsion layer coated on 
the support, a light-insensitive layer such as color mixing inhibiting 
layer and protective layer, and a hydrophilic colloidal layer containing a 
white pigment. 
In the photographic light-sensitive material (ii) of the present invention, 
the hydrophilic colloidal layer containing a white pigment is provided 
interposed between the support and the light-sensitive emulsion layer. 
As the support carrying the hydrophilic colloidal layer containing a white 
pigment there can be used one similar to that used in the photographic 
light-sensitive material (i). From the standpoint of the expedition of the 
development of photographic light-sensitive material, the support is 
preferably waterproof. In other words, a waterproof resin-coated paper or 
a high molecular film is preferably used. Alternatively, a support having 
a surface with a diffused reflectivity of the second kind may be used as 
in the case of the photographic light-sensitive material (i). 
The photographic light-sensitive material (ii) of the present invention may 
be in an embodiment in which the white pigment is incorporated only in the 
hydrophilic colloidal layer and is not incorporated in the resin 
constituting the support, e.g., resin to be coated on paper support, or 
resin film as the support itself or in another embodiment in which the 
white pigment is incorporated in the hydrophilic colloidal layer as well 
as the resin constituting the support. 
On the white pigment-containing hydrophilic colloidal layer may be coated a 
light-sensitive emulsion layer directly or via one or more 
light-insensitive hydrophilic colloidal layers. If light-insensitive 
hydrophilic colloidal layers are provided, the total thickness of these 
layers is preferably in the range of 5 .mu.m or less, more preferably 2 
.mu.m or less. These light-insensitive hydrophilic colloidal layers may 
optionally comprise various photographically useful materials as used in 
the photographic light-sensitive material (i). Further, a colloidal 
silver, a solid dispersion of dye or a cationic polymer dyed with a dye 
may be incorporated in these light-insensitive hydrophilic colloidal 
layers to form colored layers decolorable upon development as described 
with reference to the photographic light-sensitive material (i). 
Alternatively, a high boiling organic solvent dispersed in the form of 
fine oil drops. Such a high boiling organic solvent may comprise a 
photographically useful material such as oil-soluble color mixing 
inhibitor, fluorescent brightening agent and ultraviolet absorbent 
dissolved therein. 
In addition to the use of such a white pigment, the disposition of a 
colored layer decolorable upon development in any position in the 
hydrophilic colloidal layer group coated on the light-sensitive layer side 
of the support provides an improvement in the sharpness of the 
photographic light-sensitive material (ii). 
For the disposition of the colored layer decolorable upon processing in the 
photographic light-sensitive material (ii) of the present invention, 
reference can be made to the photographic light-sensitive material (i). 
In respect to the optical reflection density of the colored layer, the 
optical density value at the wavelength in the visible light wavelength 
range of 400 nm to 700 nm at which the highest optical density is given is 
preferably in the range of 0.2 or more and 3.0 or less, more preferably 
0.5 or more and 2.5 or less, particularly 0.8 or more and 2.0 or less. The 
formation of the colored layer can be accomplished by any conventional 
known methods. Examples of such known methods include a method which 
comprises dispersing a dye in the solid form, a method which comprises 
mordanting a cation polymer with an anionic dye, a method which comprises 
allowing a dye to be adsorbed on finely divided grains of silver halide or 
the like, and then fixing the dye in a layer, and a method which comprises 
the use of a colloidal silver. As the method which comprises dispersing 
finely divided dye grains in the solid form there may be used a method as 
described in JP-A-2-308244, pp. 4-13, which comprises the incorporation of 
a finely divided dye powder that is substantially insoluble in water at pH 
6 or less but is substantially soluble in water at pH 8 or more. An 
example of the method which comprises mordanting a cationic polymer with 
an anionic dye is described in JP-A-2-84637, pp. 18-26. A method for 
preparing colloidal silver as a light absorbent is described in U.S. Pat. 
Nos. 2,688,601, and 3,459,563. Preferred among these methods are the 
method which comprises the incorporation of finely divided dye grains and 
the method which comprises the use of colloidal silver. 
Another aspect of the photographic light-sensitive material (ii) of the 
present invention is that the photographic light-sensitive material is 
subjected to chemical sensitization with a gold compound as previously 
mentioned. 
Preferred examples of such a gold sensitizer include compounds as disclosed 
in U.S. Pat. Nos. 2,399,083, 2,540,085, 2,540,086, and 2,597,856. Specific 
examples of such compounds include tetrachloroauric acid and salts 
thereof, potassium aurocyanate, potassium aurothiocyanate, and gold 
sulfide. Gold sensitization may be effected with the combined use of a 
thiocyanate to intensify its effect. As described in JP-B-59-11892, the 
combined use of a tetra-substituted thiourea compound is also useful. 
The amount of such a gold sensitizer to be used can be selected from 
1.times.10.sup.-8 mol to 1.times.10.sup.-5 mol per mol of silver such that 
enhance the sensitivity/fog ratio. With the combined use of a chemical 
sensitization inhibitor, only a small amount of a gold sensitizer can 
provide a high sensitivity with little fog. A relatively small amount of a 
gold sensitizer is preferably used depending on the desired sensitivity. 
The conditions under which sensitization is effected with a gold compound 
(pH, pAg, temperature, time) is not specifically limited. For example, the 
pH value is preferably in the range of 3.0 to 8.5, particularly 5.0 to 
7.5. The pAg value is preferably in the range of 4.5 or more, more 
preferably 6.5 or more, further preferably 7.0 or more. The temperature is 
preferably in the range of 40.degree. C. to 85.degree. C., particularly 
45.degree. C. to 75.degree. C. The time is preferably in the range of 10 
minutes to 200 minutes, particularly 30 minutes to 120 minutes. 
Examples of sulfur sensitizers to be used in the photographic 
light-sensitive material of the present invention as defined in the clause 
(ii) include thiosulfates, sulfinates, thioureas, thiazoles, rhodanines, 
and other compounds as disclosed in U.S. Pat. Nos. 1,574,944, 2,410,689, 
2,728,668, and 3,656,955. Further, sulfur-containing compounds as 
disclosed in U.S. Pat. Nos. 3,857,711, 2,466,018, and 4,054,457 may be 
used. 
The optimum amount of the sulfur sensitizer to be used in combination the 
gold sensitizer can be selected depending on the conditions such as grain 
size, chemical sensitization temperature, pAg and pH. Specifically, it is 
in the range of 1.times.10.sup.-7 mol to 1.times.10.sup.-4 mol, preferably 
5.times.10.sup.-7 to 1.times.10.sup.-4 mol, more preferably 
5.times.10.sup.-7 mol to 1.times.10.sup.-5 mol per mol of silver. 
The chemical sensitization of the photographic light-sensitive material 
(ii) of the present invention may be effected by the aforementioned 
chemical sensitization method in combination with a chemical sensitization 
with a chalcogen sensitizer other than sulfur sensitizer (e.g., selenium 
sensitization with a selenium compound, tellurium sensitization with a 
tellurium compound), a noble sensitization other than gold sensitization, 
a reduction sensitization or the like. As compounds to be used in the 
chemical sensitization method there may be preferably used those described 
in JP-A-62-215272, lower right column, page 18--upper right column, page 
22. 
In the chemical sensitization of the photographic light-sensitive material 
(ii) of the present invention, an emulsion comprising high silver chloride 
content grains having a localized phase whose silver bromide content is 
higher than the other portion is preferably subjected to gold 
sensitization, particularly sulfur sensitization and gold sensitization in 
combination, in the presence of a compound for controlling chemical 
sensitization. 
The compounds represented by the general formulae (I) to (IX) will be 
further described hereinafter. 
In these general formulae, the alkyl group, alkylene group, aryl group, 
arylene group, alkoxy group, aryloxy group, sulfamoyl group, thiazolyl 
group and other nitrogen-containing heterocyclic residues represented by 
R.sup.2 to R.sup.9, and R.sup.11 to R.sup.19 may be further substituted. 
Specific examples of these groups and halogen atoms will be given below, 
but the present invention should not be construed as being limited 
thereto. Halogen atom (e.g., fluorine, chlorine, bromine ), alkyl group 
(e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 
dodecyl, cyclopentyl, cyclohexyl, benzyl, phenethyl), aryl group (e.g., 
phenyl, naphthyl, 4-methylphenyl), nitrogen-containing heterocyclic 
residue (e.g., pyridyl, imidazolyl, piperidyl, morpholino), alkoxy group 
(e.g., methoxy, ethoxy, butoxy), aryloxy group (e.g., phenoxy, 
2-naphthyloxy), sulfamoyl group (e.g., unsubstituted sulfamoyl, 
N,N-dimethylsulfamoyl, N-phenylsulfamoyl), alkylene group (e.g., 
methylene, ethylene, --(CH.sub.2).sub.6 --, --(CH.sub.2).sub.8 --), 
arylene group (e.g., phenylene) 
The number of the repeating unit represented by the general formula (IV) is 
preferably 4 to 100 and more preferably 10 to 30. 
Preferred among the compounds represented by the general formulae (I) to 
(IX) are those represented by the general formulae (II), (VII), (VIII) and 
(IX). Further preferred among these compounds are those represented by the 
general formulae (VII), (VIII), and (IX). 
Specific examples of the compounds represented by the general formulae (I) 
to (IX) to be used in the present invention will be given below, but the 
present invention should not be construed as being limited thereto. 
##STR50## 
In the present invention, the compounds represented by the general formulae 
(I) to (IX) may be incorporated in any layer such as silver halide 
emulsion layer and gelatin interlayer. 
The amount of the compound represented by the general formulae (I) to (IX) 
to be incorporated is preferably in the range of 5.times.10.sup.-7 to 
2.times.10.sup.-3 mol/m.sup.2, more preferably 5.times.10.sup.-6 to 
5.times.10.sup.-4 mol/m.sup.2. These compounds are preferably incorporated 
in the photographic light-sensitive material (ii) of the present invention 
in the form of solution in an organic solvent such as methanol, ethanol, 
ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, 
ethanolamine, diethanolamine and triethanolamine or in the form of 
emulsion (emulsified product). 
Particularly preferred among the aforementioned aminoglycocides to be used 
in the present invention are gentamicines. Specific examples of typical 
gentamicines will be given below. 
Compound No. 
1 (Gentamicine A.sub.2) 
2 (Gentamicine A) 
3 (Gentamicine A.sub.1) 
4 (Gentamicine B) 
5 (Gentamicine X.sub.2) 
6 (Antibiotic JI-20A) 
7 (Gentamicine B.sub.1) 
8 (Antibiotic G418) 
9 (Antibiotic JI-20B) 
10 (Gentamicine C.sub.1) 
11 (Gentamicine C.sub.1a) 
12 (Gentamicine C.sub.2) 
13 (Gentamicine C.sub.2a) 
14 (Gentamicine C.sub.2b) 
As the aminoglycocides to be used in the present invention there may be 
used ones commercially available. For the properties of these 
aminoglycocides, reference can be made to "THE MERCK INDEX AN ENCYCLOPEDIA 
OF CHEMICALS, DRUGS, AND BIOLOGICALS", 11th ed., 1989, MERCK & CO. INC. 
For the preparation method for these aminoglycocides, reference can be made 
to U.S. Pat. Nos. 3,091,572, and 3,136,704 with respect to gentamicins, 
U.S. Pat. No. 3,781,268 with respect to amikacins, U.S. Pat. No. 
4,107,424, and German Patent 2,350,169 with respect to arbekacins, German 
Patent 2,135,191 with respect to dibekacins, U.S. Pat. No. 4,002,742 with 
respect to icepamicins, U.S. Pat. No. 4,045,298, and German Patent 
2,326,781 with respect to micronomicins, U.S. Pat. Nos. 4,002,742, and 
4,029,882, and German Patent 2,437,160 with respect to netilmicins, and 
U.S. Pat. No. 3,832,286 with respect to sisomicins. 
The aminoglycocides to be incorporated in the photographic light-sensitive 
material (ii) of the present invention may be incorporated in at least one 
of, preferably all of silver halide emulsion layers to be coated on the 
support and previously exemplified auxiliary layers. 
These aminoglycocides may be preferably added to a coating solution 
containing a hydrophilic colloid in the form of aqueous solution, 
The amount of these aminoglycocides to be used is preferably in the range 
of about 0.01 to 20 mg/m.sup.2, more preferably 0.1 to 5 mg/m.sup.2. 
The color photographic light-sensitive material (ii) of the present 
invention can comprise a light-sensitive emulsion layer having at least 
one yellow-developable silver halide emulsion layer, at least one 
magenta-developable silver halide emulsion layer and at least one 
cyan-developable silver halide emulsion layer coated on a support. In the 
configuration of general color photographic papers, a color coupler which 
forms a dye having a color complementary to that of the light to which the 
silver halide emulsion is sensitive can be incorporated in the system to 
provide subtractive color reproduction. In the configuration of general 
color photographic papers, the silver halide emulsion grains are 
spectrally sensitized with blue-sensitive, green-sensitive and 
red-sensitive spectral sensitizing dyes in the order according to that of 
the aforementioned color-developable layers, and then coated on a support 
in this order. However, the order of arrangement may be different from the 
aforementioned order. In particular, from the standpoint of rapid 
processing, a light-sensitive layer containing silver halide grains having 
the greatest average grain size may be preferably provided as an uppermost 
layer. Alternatively, the lowermost layer may be preferably an 
infrared-sensitive silver halide emulsion layer from the standpoint of 
preservability under irradiation. 
In a further alternative embodiment, the light-sensitive layers and the 
color hue of developed dyes may have correlations other than above 
specified. Further, at least one infrared-sensitive silver halide emulsion 
layer may be incorporated in the photographic light-sensitive material 
(ii) of the present invention. 
The silver halide grains to be incorporated in at least one of (preferably 
all of) the silver halide emulsion layers in the photographic 
light-sensitive material (ii) of the present invention may comprise silver 
bromochloride having a silver chloride content of 90 mol % or more or 
silver chloride. The silver chloride content of the silver halide grains 
is preferably in the range of 95 mol % or more, more preferably 98 mol % 
or more. 
In order to expedite the development processing time, the photographic 
light-sensitive material (ii) of the present invention is preferably free 
of silver iodide. The term "substantially free of silver iodide" as used 
herein indicates a silver iodide content of 1 mol % or less, preferably 
0.2 mol % or less. On the other hand, for the purpose of enhancing the 
high intensity sensitivity, the spectrally sensitized sensitivity or the 
storage stability of the photographic light-sensitive material, high 
silver chloride content grains containing 0.01 to 3 mol % of silver iodide 
on the surface thereof as disclosed in JP-A-3-84545 may be preferably 
used. 
The halogen composition of emulsion may be the same or different from grain 
to grain. The use of an emulsion having the same halogen composition among 
grains advantageously provides easy uniformalization of the properties of 
grains. 
The halogen composition distribution in the silver halide emulsion grain 
can be properly selected from the group consisting of so-called uniform 
type structure in which the halogen composition is the same anywhere, 
so-called laminated structure in which the halogen composition differs 
from the core to the shell (monolayer or multi-layers), and structure in 
which nonlayer portions having different halogen compositions are 
localized inside or on the surface of grains (portions having different 
halogen compositions are connected to the edge, corner or surface of the 
grains). 
In order to obtain a high sensitivity, the latter two structures are 
preferred to the uniform structure from the standpoint of pressure 
resistance. If the silver halide grains have such a structure, the border 
of the portions having different compositions may be a definite one or an 
indefinite one where a mixed crystal is formed by the difference in the 
halogen composition or a positively continuous structural change. 
The high silver chloride content emulsion to be incorporated in the 
photographic light-sensitive material (ii) of the present invention 
preferably comprises silver bromide phase localized inside and/or on 
silver halide grains in a layer or non-layer form as mentioned above. The 
halogen composition of the aforementioned localized phase preferably has a 
silver bromide content of at least 10 mol %, more preferably 20 mol % to 
100 mol %. 
The silver bromide content of the silver bromide localized phase can be 
analyzed by X-ray diffractometry (as described in "Shinjikken Kagaku Koza 
6; Kozo Kaiseki", Nihon Kagakukai, Maruzen). 
These localized phases may be preferably present inside the grains, on the 
edge or corner of the surface of the grains, or on the surface of the 
grains. A preferred example is a localized phase epitaxially grown on the 
corner of grains. 
It is also effective to further enhance the silver chloride content of the 
silver halide emulsion for the purpose of reducing the replenishment rate 
of the developer. In this case, a substantially pure silver chloride 
emulsion having a silver chloride content of 98 mol % to 100 mol % may be 
preferably used. 
The average grain size (number-average value of grain sizes as calculated 
in terms of diameter of circle having the same area as that of projected 
area of grains) of silver halide grains contained in the silver halide 
emulsion to be used in the present invention is preferably in the range of 
0.1 .mu.m to 2 .mu.m. 
The grain size distribution is preferably so-called monodisperse, as 
represented by a fluctuation coefficient (obtained by dividing the 
standard deviation of grain size distribution by the average grain size) 
as small as 20% or less, preferably 15% or less and more preferably 10% or 
less. For the purpose of obtaining a great latitude, several kinds of the 
aforementioned monodisperse emulsions may be preferably blended for one 
layer or may be preferably coated in multiple layers. 
The silver halide grains to be contained in the photographic emulsion may 
have a regular crystal form such as cube, octahedron and tetradecahedron, 
an irregular crystal form such as sphere and tablet or composite thereof. 
The silver halide grains also may comprise a mixture of grains having 
various crystal forms. In the present invention, grains having the 
aforementioned regular crystal forms are contained in a weight proportion 
of 50% or more, preferably 70% or more, more preferably 90% or more. 
Besides these emulsions, an emulsion comprising tabular grains having an 
average aspect ratio (diameter in terms of circle/thickness) of 5 or more, 
preferably 8 or more, in a proportion of 50% by weight or more of the 
total grains as calculated in terms of projected area may be preferably 
used. 
The preparation of emulsion to be used in the present invention can be 
accomplished by any suitable method as disclosed in P. Glafkides, "Chimie 
et Physique Photographique", Paul Montel, 1967, G. F. Duffin, 
"Photographic Emulsion Chemistry", The Focal Press, 1966, and V. L. 
Zelikman et al., "Making and Coating Photographic Emulsion", The Focal 
Press, 1964. In some detail, the emulsion can be prepared by any of the 
acid process, the neutral process, the ammonia process, etc. The reaction 
between a soluble silver salt and a soluble halogen salt can be carried 
out by any of a single jet process, a double jet process, a combination 
thereof, and the like. A method in which grains are formed in the presence 
of excess silver ions (so-called reverse mixing method) may be used. 
Further, a so-called controlled double jet process, in which a pAg value 
of a liquid phase in which silver halide grains are formed is maintained 
constant, may also be used. According to the controlled double jet 
process, a silver halide emulsion having a regular crystal form and an 
almost uniform grain size can be obtained. 
The localized phase or substrate of the silver halide grains to be 
incorporated in the photographic light-sensitive material (ii) of the 
present invention may preferably comprise diverse metal ions or complex 
ions thereof. Preferred metal ions can be selected from the group 
consisting of ions of metals belonging to the groups VIII and IIb in the 
periodic table or complexes thereof, lead ions and thallium ions. The 
localized phase can mainly comprise metal ions selected from the group 
consisting of iridium, rhodium and ferric or ferrous ions or complex ions 
thereof. The substrate can mainly comprise metal ions selected from the 
group consisting of osmium, iridium, rhodium, platinum, ruthenium, 
palladium, cobalt, nickel and ferric or ferrous ions or complex ions in 
combination. The kind and concentration of metal ions in the localized 
phase may be different from those of the substrate. A plurality of kinds 
of metals can be used. In particular, iron and iridium compounds are 
preferably incorporated in the silver bromide localized phase. 
These metal ion-supplying compounds may be incorporated in the localized 
phase and/or other portion (substrate) of the silver halide grains of the 
present invention by adding these metal ion-supplying compounds in the 
form of dispersion in aqueous solution of gelatin, aqueous solution of 
halide, aqueous solution of silver salt or other aqueous solutions to the 
system, or by adding these metal ion-supplying compounds to the system in 
the form of solution of finely divided silver halide grains containing 
metal ions, during the formation of silver halide grains. 
The incorporation of metal ions to be used in the photographic 
light-sensitive material (ii) of the present invention in the emulsion 
grains can be effected at any time before, during or shortly after the 
formation of grains depending ion the position of metal ions in the grain 
in which these metal ions are to be incorporated. 
The silver halide emulsion to be incorporated in the photographic 
light-sensitive material (ii) of the present invention may comprise 
various compounds or precursors thereof for the purpose of inhibiting fog 
during the preparation, storage or photographic processing of the 
photographic light-sensitive material. Specific examples of such compounds 
which can be preferably used in the present invention include those 
described in the above cited JP-A-62-215272, pp. 39-72. Further, 
5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue contains at 
least one electron-withdrawing group) as disclosed in EP0447647 may be 
preferably used. 
Spectral sensitization is effected for the purpose of providing the 
emulsion in the various layers in the photographic light-sensitive 
material (ii) of the present invention with the spectral sensitivity to 
the respective desired wavelength range. 
As spectral sensitizing dyes to be used in the spectral sensitization to 
blue, green and red light ranges in the photographic light-sensitive 
material (ii) of the present invention there may be used those described 
in F. M. Harmer, "Heterocyclic compounds--Cyanine dyes and related 
compounds", John Wiley & Sons, New York, London, 1964. Specific preferred 
examples of such a compound and spectral sensitization method which can be 
preferably used include those described in the above cited JP-A-62-215272, 
upper right column, page 22 to page 38. As the red-sensitive spectral 
sensitizing dye for silver halide emulsion grains having a high silver 
chloride content, spectral sensitizing dyes as disclosed in JP-A-3-123340 
are particularly preferred from the standpoint of stability, adsorption, 
dependence on temperature upon exposure, etc. 
If the photographic light-sensitive material of the present invention as 
defined in the clause (ii) is spectrally sensitized in the infrared range 
at a high efficiency, a sensitizing dye as disclosed in JP-A-3-15049, 
upper left column, page 12--lower left column, page 21, and JP-A-3-20730, 
lower left column, page 4--lower left column, page 15, EP0,420,011, line 
21, page 4-- line 54, page 6, EP0,420,012, line 12, page 4--line 33, page 
10, EP0,443,466, and U.S. Pat. No. 4,975,362 can be preferably used. 
When such a spectral sensitizing dye is incorporated in the silver halide 
emulsion, it may be directly dispersed in the emulsion or may be added to 
the emulsion in the form of solution in water, methanol, ethanol, 
propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol or the like, 
singly or in admixture. Alternatively, such a spectral sensitizing dye may 
be added to the emulsion in the form of aqueous solution with an acid or 
base present therein as disclosed in JP-B-44-23389, JP-B-44-27555, and 
JP-B-57-22089 or in the form of aqueous solution or colloidal dispersion 
with a surface active agent present therein as disclosed in U.S. Pat. Nos. 
3,822,135, and 4,006,025. Further, such a spectral sensitizing dye may be 
dissolved in a solvent substantially non-miscible with water such as 
phenoxyethanol, dispersed in water or a hydrophilic colloid, and then 
added to the emulsion. As described in JP-A-53-102733, and JP-A-58-105141, 
such a spectral sensitizing dye may be added to the emulsion in the form 
of dispersion in a hydrophilic colloid. 
The time at which such a spectral sensitizing dye is added to the emulsion 
may be any stage which has heretofore been known effective. In particular, 
it may be added to the emulsion before or during the formation of silver 
halide emulsion grains, between shortly after the formation of grains and 
before the rinse, before or during the chemical sensitization, between 
shortly after the chemical sensitization and solidification by cooling of 
the emulsion, or during the preparation of coating solution. 
In general, it may be conducted between the completion of the chemical 
sensitization and before the coating. As described in U.S. Pat. Nos. 
3,628,969, and 4,225,666, such a spectral sensitizing dye may be added to 
the emulsion at the same time with a chemical sensitizer so that spectral 
sensitization and chemical sensitization are simultaneously effected. As 
described in JP-A-58-113928, it may be conducted prior to the chemical 
sensitization. Further, such a spectral sensitizing dye may be added to 
the emulsion before the completion of precipitation of silver halide 
grains to initiate spectral sensitization. Moreover, as taught in U.S. 
Pat. No. 4,225,666, such a spectral sensitizing dye may be batch-wise 
added to the system. In other words, a part of the spectral sensitizing 
dye may be added to the system prior to chemical sensitization, and the 
residual part of the spectral sensitizing dye may be added to the system 
after chemical sensitization. In accordance with a further method taught 
in U.S. Pat. No. 4,183,756, such a spectral sensitizing dye may be added 
to the system at any stage during the formation of silver halide grains. 
Particularly preferred among these stages in which the spectral sensitizing 
dye can be added to the system is before rinse or chemical sensitization. 
The amount of such a spectral sensitizing dye to be added depends much on 
the circumstances. It is preferably in the range of 0.5.times.10.sup.-6 
mol to 1.0.times.10.sup.-2 mol, more preferably 1.0.times.10.sup.-6 mol to 
5.0.times.10.sup.-3 mol per mol of silver halide. 
In the photographic light-sensitive material (ii) of the present invention, 
when a sensitizing dye having a spectrally sensitized sensitivity, 
particularly in the range of from red region to infrared region is used, 
it is preferred that a compound as described in JP-A-2-157749, lower right 
column, page 13--lower right column, page 22 is used together. The use of 
such a compound provides a specific enhancement of the preservability and 
processing stability of the photographic light-sensitive material and the 
effect of supersensitizing the photographic light-sensitive material. In 
particular, Compounds (IV), (V) and (VI) described in the above cited 
patent are preferably used together therewith. The amount of such a 
compound to be incorporated is in the range of 0.5.times.10.sup.-5 mol to 
5.0.times.10.sup.-2 mol, preferably 5.0.times.10.sup.-5 mol to 
5.0.times.10.sup.-3 mol per mol of silver halide. Its advantageous range 
is in the range of 0.1 to 10,000 times, preferably 0.5 to 5,000 times the 
molar quantity of sensitizing dye. 
The photographic light-sensitive material (ii) of the present invention may 
be exposed to visible light or infrared light. Exposure may be carried out 
by a low intensity exposure process or a high intensity exposure process. 
In a preferred embodiment of the latter case, laser scanning exposure 
process with an exposure time of 10.sup.-4 seconds or less, preferably 
10.sup.-6 or less per pixel may be preferably used. 
A band stop filter as disclosed in U.S. Pat. No. 4,880,726 may be 
preferably used for exposure. This removes light stain, providing a 
remarkable enhancement of color reproducibility. 
The photographic light-sensitive material (ii) which has been exposed to 
light may be subjected to a commonly used color development, preferably 
followed by blix for the purpose of expediting the processing. In 
particular, if the aforementioned emulsion having a high silver chloride 
content is used, the pH value of the blix solution is preferably in the 
range of about 6.5 or less, more preferably about 6 or less for the 
purpose of accelerating the desilvering procedure. 
As silver halide emulsions and other materials (additives) to be 
incorporated in the light-sensitive material (ii) of the present 
invention, photographic constituent layers of the light-sensitive material 
(ii) of the present invention (layer configuration), and processing 
methods and processing additives to be used in the processing of the 
light-sensitive material (ii) of the present invention there can be 
preferably used those described in JP-A-62-215272, and JP-A-2-33144, and 
EP0,355,660A2 corresponding to JP-A-2-139544 as in the photographic 
light-sensitive material (i). 
The dispersion method of cyan, magenta and yellow couplers is the same as 
used in the case of the photographic light-sensitive material (i). 
Water-insoluble and organic solvent-soluble polymers, dye 
stability-improving compounds to be used in combination with couplers, 
compounds which undergo chemical bonding to an aromatic amine developing 
agent remaining after color development to produce a chemically inert and 
substantially colorless compound and/or another compounds which undergo 
chemical bonding to an oxidation product of an aromatic amine color 
developing agent remaining after color development to produce a chemically 
inert and substantially colorless compound are also used in the 
photographic light-sensitive material (ii) of the present invention, in 
the same way as in the case of the photographic light-sensitive material 
(i) of the present invention. 
As the cyan, yellow and magenta couplers to be incorporated in the 
photographic light-sensitive material (ii) of the present invention there 
can be used the same couplers as used in the photographic light-sensitive 
material (i) of the present invention. 
As the processing method for the color photographic light-sensitive 
material (ii) of the present invention there preferably be used besides 
those tabulated above processing materials and processing methods as 
described in JP-A-2-207250, line 1, lower right column, page 26--line 9, 
upper right column, page 34, and JP-A-4-97355, line 17, upper left column, 
page 5--line 20, lower right column, page 18. 
In the photographic light-sensitive material (iii) of the present 
invention, a hydrophilic colloidal layer containing a white pigment is 
provided on a support, the appropriate coated amount of the white pigment 
being in the range of 0.5 g/m.sup.2 or more, preferably 2 g/m.sup.2 or 
more, more preferably 4 g/m.sup.2 or more, and most preferably 8 g/m.sup.2 
or more. The upper limit of the coated amount of the white pigment is not 
specifically defined but is preferably 40 g/m.sup.2 or less. 
The "coated amount of white pigment" as specified herein indicates the 
value including an amount of various surface treatments or dispersion 
stabilizers which are optionally incorporated in the white pigment for the 
purpose of improving its dispersibility or like purposes. 
The density of the white pigment in the hydrophilic colloidal layer is 
preferably in the range of 40% by weight or more, most preferably 70% by 
weight or more. The upper limit of the density of the white pigment is not 
specifically defined but is preferably in the range of 99% by weight or 
less. 
The thickness of the white pigment-containing hydrophilic colloidal layer 
can be predetermined by the above specified content and coated amount but 
is preferably in the range of 0.5 .mu.m to 10 .mu.m, more preferably 2 
.mu.m to 5 .mu.m. 
For the kind and grain diameter of white pigments to be incorporated in the 
photographic light-sensitive material (iii) of the present invention, 
reference can be made to the case of the photographic light-sensitive 
material (i). 
In the photographic light-sensitive material (iii) of the present 
invention, as the binder (hydrophilic colloid) constituting the 
hydrophilic colloidal layer containing a white pigment, there may 
preferably be used a gelatin. If necessary, other hydrophilic colloids may 
be used in an arbitrary proportion instead of gelatin. 
Examples of such a hydrophilic colloid include those described with 
reference to the photographic light-sensitive material (i). 
In the photographic light-sensitive material (iii) of the present 
invention, the white pigment-containing hydrophilic colloidal layer may 
contain various materials to be commonly incorporated in photographic 
light-sensitive materials as described with reference to the photographic 
light-sensitive material (i) besides the white pigment and binder. 
The photographic light-sensitive material (iii) of the present invention 
comprises a support, at least one light-sensitive emulsion layer coated on 
the support, a light-insensitive layer such as color mixing inhibiting 
layer and protective layer, and a hydrophilic colloidal layer containing a 
white pigment. 
In the photographic light-sensitive material (iii) of the present 
invention, the hydrophilic colloidal layer containing a white pigment is 
provided interposed between the support and the light-sensitive emulsion 
layer. 
As the support carrying the hydrophilic colloidal layer containing a white 
pigment there can be used one being the same as that used in the 
photographic light-sensitive material (i). From the standpoint of the 
expedition of the development of photographic light-sensitive material, 
the support is preferably waterproof. In other words, a waterproof 
resin-coated paper or a high molecular film is preferably used. 
Alternatively, a support having a surface with a diffused reflectivity of 
the second kind may be used as in the case of the photographic 
light-sensitive material (i). 
The photographic light-sensitive material (iii) of the present invention 
may be in an embodiment in which the white pigment is incorporated only in 
the hydrophilic colloidal layer and is not incorporated in the resin 
constituting the support, e.g., resin to be coated on paper support, or 
resin film as the support itself or in another embodiment in which the 
white pigment is incorporated in the hydrophilic colloidal layer as well 
as the resin constituting the support. 
On the white pigment-containing hydrophilic colloidal layer may be coated a 
light-sensitive emulsion layer directly or via one or more 
light-insensitive hydrophilic colloidal layers. If light-insensitive 
hydrophilic colloidal layers are provided, the total thickness of these 
layers is preferably in the range of 5 .mu.m or less, more preferably 2 
.mu.m or less. These light-insensitive hydrophilic colloidal layers may 
optionally contain various photographically useful materials as used in 
the photographic light-sensitive material (i) of the present invention. 
For instance, a surfactant as a coating aid, hardening agent, dye, fogging 
inhibitor, etc. may be contained. Further, a colloidal silver, a solid 
dispersion of dye or a cationic polymer dyed with a dye may be 
incorporated in these light-insensitive hydrophilic colloidal layers to 
form colored layers decolorable upon development as described with 
reference to the photographic light-sensitive material (i) of the present 
invention. Alternatively, a high boiling organic solvent dispersed in the 
form of fine oil drops. Such a high boiling organic solvent may contain a 
photographically useful material such as oil-soluble color mixing 
inhibitor, fluorescent brightening agent and ultraviolet absorbent 
dissolved therein. 
For the disposition of the colored layer decolorable upon processing of the 
photographic light-sensitive material (iii) of the present invention, 
reference can be made to the photographic light-sensitive material (i) of 
the present invention. 
For the optical reflective density of the colored layer and the method for 
the formation of the colored layer, reference can be made to those for the 
photographic light-sensitive material (i) of the present invention as is 
disclosed above. As the method which comprises dispersing finely divided 
dye grains in the solid form there may be used a method as described in 
JP-A-2-308244, pp. 4-13, which comprises the incorporation of a finely 
divided dye powder that is substantially insoluble in water at pH 6 or 
less but is substantially soluble in water at pH 8 or more. An example of 
the method which comprises mordanting a cationic polymer with an anionic 
dye is described in JP-A-2-84637, pp. 18-26. A method for preparing 
colloidal silver as a light absorbent is described in U.S. Pat. Nos. 
2,688,601, and 3,459,563. Preferred among these methods are the method 
which comprises the incorporation of finely divided dye grains and the 
method which comprises the use of colloidal silver. 
The film pH value of the silver halide color photographic light-sensitive 
material (iii) of the present invention is the pH value of all 
photographic constituent layers obtained by coating the coating solution 
on a support and therefore doesn't necessarily coincide with the pH value 
of the coating solution. 
The film pH value of the photographic light-sensitive material of the 
present invention can be determined by the method as described in 
JP-A-61-245153. Specifically, the measurement process comprises the 
following procedures: (1) 0.05 cc of pure water is added dropwise to the 
surface of the photographic light-sensitive material on the silver halide 
emulsion side; and (2) After 3 minutes, the film pH value of the material 
is measured by means of a film pH measuring electrode (GS-165F available 
from Toa Denpa K.K.). In the present invention, the film pH value of the 
material as determined by this method is in the range of 5.0 to 6.5. 
The film pH value of the material can be optionally adjusted with an acid 
(e.g., sulfuric acid, citric acid) or an alkali (e.g., sodium hydroxide, 
potassium hydroxide). 
If the film pH value of the material falls below 5.0, it causes a 
disadvantage that the film hardening is prohibited or the sensitivity is 
lowered. On the contrary, if the film pH value of the material exceeds 
6.5, it disadvantageously leads to desensitization upon exposure under 
high humidity conditions or sensitivity fluctuation with the change of the 
time interval between the completion of exposure and the beginning of 
processing. 
The film pAg value of the silver halide color photographic light-sensitive 
material of the present invention is the pAg value of all photographic 
constituent layers obtained by coating the coating solution on a support 
and therefore doesn't necessarily coincide with the pAg value of the 
coating solution. 
The film pAg value of the photographic light-sensitive material of the 
present invention can be determined by the following method. Specifically, 
the measurement process comprises the following procedures: (1) 20 ul of 
pure water is added dropwise to the surface of the photographic 
light-sensitive material on the silver halide emulsion side; and (2) After 
1 minute, the film pAg value of the material is measured by means of a 
film pAg measuring electrode (GS-165F available from Toa Denpa K.K.). 
In order to convert the potential thus obtained to pAg, a calibration curve 
obtained from the measured potential of the following solution can be 
used: 
______________________________________ 
Solution No. 
pAg Preparation method 
______________________________________ 
1 2 0.17 g of AgNO.sub.3 is dissolved in 
water to make 100 ml; 
2 3 Water is added to 5 ml of 
Solution 1 to make 50 ml; 
3 4 Water is added to 5 ml of 
Solution 2 to make 50 ml; 
4 5 Water is added to 5 ml of 
Solution 3 to make 50 ml; 
5 -- 2.38 g of KBr is dissolved in 
water to make 100 ml; 
6 -- Water is added to 5 ml of 
Solution 5 to make 50 ml; 
7 -- Water is added to 5 ml of 
Solution 6 to make 50 ml; 
8 11.67 5 ml of Solution 4 and 5 ml of 
Solution 5 are mixed; 
9 10.67 5 ml of Solution 4 and 5 ml of 
Solution 6 are mixed; 
10 9.67 5 ml of Solution 4 and 5 ml of 
Solution 7 are mixed 
______________________________________ 
In the present invention, the film pAg value thus determined is in the 
range of 6.0 to 10.0, preferably 7.0 to 9.0, more preferably 7.2 to 8.7. 
The film pAg value of the material can be optionally adjusted with a 
water-soluble halide (e.g., sodium chloride, potassium bromide) or a 
water-soluble silver salt (e.g., silver nitrate). 
If the film pAg value of the material exceeds 10.0, it causes a 
disadvantage that the sensitivity is reduced. On the contrary, if the film 
pAg value of the material falls below 6.0, it disadvantageously leads to 
desensitization upon exposure under high humidity conditions or 
sensitivity fluctuation with the change of the time interval the 
completion of exposure and the beginning of processing. 
The silver halide emulsion grains to be incorporated in the photographic 
light-sensitive material (iii) of the present invention comprise silver 
bromochloride or silver chloride having a silver chloride content of 95 
mol % or more substantially free of silver iodide. Further, the silver 
bromochloride emulsion grains may be preferably formed by adding a bromide 
ion-releasing compound and/or bromine-releasing compound to the system in 
the total amount of 0.0005 mol to 0.05 mol per mol of the finally formed 
silver halide at any time of the grain formation when any portion of the 
grain corresponding to 20% by volume or less of the whole grain is formed 
and/or at any time between the completion of the formation of grains and 
the coating on the support to reduce the humidity dependence upon exposure 
and further enhance the latent image stability. 
When a water-soluble bromide is added to silver chloride or silver 
bromochloride grains, silver bromide having a small solubility product is 
deposited on the grains to cause a so-called halogen conversion reaction. 
Accordingly, the silver bromide content of the grains is determined by the 
total amount of the water-soluble bromide thus added and the original 
silver bromide contained in the grains. 
In the photographic light-sensitive material (iii) of the present 
invention, the eventually formed emulsion grains need to have a silver 
chloride content of 95 mol % or more, and the added amount of the 
water-soluble bromide is preferably in the range of 0.0005 mol to 0.05 mol 
per mol of silver halide. The halogen composition of the emulsion grains 
to which the water-soluble bromide has not yet been added may be either 
pure silver chloride or silver bromochloride. The halogen composition may 
be predetermined such that the total silver bromide content is not more 
than 5 mol % even after water-soluble bromide is added. 
If the silver bromide content of the silver halide grains exceeds 5 mol %, 
it prevents the photographic light-sensitive material from being rapidly 
processed. 
The process for the preparation of the silver halide emulsion to be used in 
the photographic light-sensitive material (iii) of the present invention 
comprises the steps of forming silver halide grains by the reaction of a 
water-soluble silver salt with a water-soluble halide, physically ripening 
the silver halide grains, removing the resulting water-soluble salts 
(desilvering and rinsing), and then chemically sensitizing the emulsion. 
If the emulsion of the present invention is subjected to spectral 
sensitization, a spectral sensitizing dye may be added to the system at 
any steps in the aforementioned procedures. 
The silver halide emulsion thus obtained is then mixed with coupler 
dispersions as dye-forming elements, stabilizers, coating aids such as 
surface active agent and viscosity modifier, gelatin, etc. to prepare a 
coating solution. 
If a bromide ion-releasing compound and/or bromine-releasing compound is 
added to the system during the formation of grains, it may be preferably 
conducted for a period during which any 20% by volume or less of the 
grains is formed. The period during which these compounds are added to the 
system may be momentary. The bromide ion-releasing compound and/or 
bromine-releasing compound may be continuously or discontinuosly added to 
the system. If these compounds are discontinuously added to the system, 
the sum of the periods during which they are added to the system should be 
not more than the period during which any 20% by volume or less of the 
grains is formed. If these compounds are added to the system for more than 
the period during which any 20% by volume or less of the grains is formed, 
the aforementioned effects can hardly be attained. These compounds are 
preferably added to the system for the period during which any portion of 
10% by volume or less, more preferably 5% by volume or lessor the grains 
is formed. The time at which these compounds are added to the system is 
preferably after the formation of 50% by volume or more, more preferably 
80% by volume or more of the whole silver halide grains has completed. 
In the photographic light-sensitive material (iii) of the present 
invention, the time at which the bromide ion-releasing compound and/or 
bromine-releasing compound are added to the system is preferably between 
the completion of the formation of grains and the beginning of preparation 
of the coating solution, more preferably between the beginning of the 
chemical sensitization and the beginning of preparation of the coating 
solution. 
The addition of such a bromide ion-releasing compound and/or 
bromine-releasing compound provides an effective inhibition of 
desensitization caused upon exposure under high humidity conditions with a 
hydrophilic colloidal layer containing a white pigment as disclosed 
herein. If the added amount of these compounds is too great, it 
disadvantageously causes desensitization under pressure. 
The amount of the bromide ion-releasing compound and/or bromine-releasing 
compound to be incorporated in the photographic light-sensitive material 
(iii) of the present invention is preferably in the range of 0.0005 mol to 
0.05 mol, more preferably 0,001 mol to 0.02 mol per mol of silver halide. 
If the addition of these compounds is batch-wise conducted, the sum of the 
added amounts of these compounds only needs to be within the above 
specified range. 
As the bromide ion-releasing compound and/or bromine-releasing compound 
there may be preferably used a water-soluble bromide in the form of 
alkaline metal salt (e.g., Na, K, Li salts) or ammonium salt thereof. 
Further, finely divided silver bromide grains having a smaller grain 
diameter than host grains or finely divided silver bromochloride grains 
having a high silver bromide content may be preferably used. Moreover, 
compounds as described in JP-A-1-285942 may be preferably used. The grain 
diameter of the finely divided silver bromide grains or finely divided 
silver bromochloride grains is required to be smaller than that of host 
grains and may be preferably in the range of about 0.05 .mu.m or less. 
The color photographic light-sensitive material of the present invention as 
defined in the clause (iii) can comprise a light-sensitive emulsion layer 
having at least one yellow-developable silver halide emulsion layer, at 
least one magenta-developable silver halide emulsion layer and at least 
one cyan-developable silver halide emulsion layer coated on a support. In 
the configuration of general color photographic papers, a color coupler 
which forms a dye having a color complementary to that of the light to 
which the silver halide emulsion is sensitive can be incorporated in the 
system to provide subtractive color reproduction. In the configuration of 
general color photographic papers, the silver halide emulsion grains are 
spectrally sensitized with blue-sensitive, green-sensitive and 
red-sensitive spectral sensitizing dyes in the order according to that of 
the aforementioned color-developable layers, and then coated on a support 
in this order. However, the order of arrangement may be different from the 
aforementioned order. In particular, from the standpoint of rapid 
processing, a light-sensitive layer containing silver halide grains having 
the greatest average grain size may be preferably provided as an uppermost 
layer. Alternatively, the lowermost layer may be preferably a 
magenta-developable silver halide emulsion layer from the standpoint of 
preservability under irradiation. 
In a further alternative embodiment, the light-sensitive layers and the 
color hue of developed dyes may have correlations other than that above 
specified. 
The silver halide grains to be incorporated in the photographic 
light-sensitive material of the present invention as defined in the clause 
(iii) may comprise silver bromochloride or silver chloride having a silver 
chloride content of 95 mol % or more and being substantially free of 
silver iodide. The silver chloride content of the silver halide grains is 
preferably in the range of 98 mol % or more. 
The term "substantially free of silver iodide" as used herein indicates a 
silver iodide content of 1 mol % or less, preferably 0.2 mol % or less. On 
the other hand, for the purpose of enhancing the high intensity 
sensitivity, the spectrally sensitized sensitivity or the storage 
stability of the photographic light-sensitive material, high silver 
chloride content grains containing 0.01 to 3 mol % of silver iodide on the 
surface thereof as disclosed in JP-A-3-84545 may be preferably used in 
some cases. 
The halogen composition of emulsion may be the same or different from grain 
to grain. The use of an emulsion having the same halogen composition among 
grains advantageously provides easy uniformalization of the properties of 
grains. 
For the halogen composition distribution in the silver halide emulsion 
grains to be incorporated in the photographic light-sensitive material 
(iii) of the present invention, reference can be made to the case of the 
photographic light-sensitive material (ii). 
The high silver chloride content emulsion to be incorporated in the 
photographic light-sensitive material of the present invention as defined 
in the material (iii) preferably comprises silver bromide phase localized 
inside and/or on silver halide grains in a layer or non-layer form as 
mentioned above. The halogen composition of the aforementioned localized 
phase preferably has a silver bromide content of at least 10 mol %, more 
preferably 20 mol % to 100 mol %. 
For the analysis of the silver bromide content of the silver bromide 
localized phase and the preferred location of the localized phase, 
reference can be made to the case of the photographic light-sensitive 
material (ii). 
It is also effective to further enhance the silver chloride content of the 
silver halide emulsion for the purpose of reducing the replenishment rate 
of the developer. In this case, a substantially pure silver chloride 
emulsion having a silver chloride content of 98 mol % to 100 mol % may 
also be preferably used. 
For the preferred average grain size and grain size distribution of silver 
halide grains to be incorporated in the silver halide emulsion used in the 
photographic light-sensitive material (iii) of the present invention, 
reference can be made to the case of the photographic light-sensitive 
material (ii). For the purpose of obtaining a wide latitude, several kinds 
of the aforementioned monodisperse emulsions may be preferably blended for 
one layer or may be preferably coated in multiple layers. 
For the crystal form of the silver halide grains to be incorporated in the 
photographic emulsion, reference can be made to the case of the 
photographic light-sensitive material (ii). In the material (iii) of the 
present invention, grains having the aforementioned regular crystal forms 
are contained in a weight proportion of 50% or more, preferably 70% or 
more, more preferably 90% or more. 
Besides these emulsions, an emulsion comprising tabular grains having an 
average aspect ratio (diameter, in terms of circle/thickness) of 5 or 
more, preferably 8 or more, in a proportion of 50% by weight or more of 
the total grains as calculated in terms of projected area may be 
preferably used. 
For the method for the preparation of the silver bromochloride emulsion or 
silver chloride emulsion to be used in the photographic light-sensitive 
material (iii) of the present invention, reference can be made to the case 
of the photographic light-sensitive material (ii). 
The localized phase or substrate of the silver halide grains to be 
incorporated in the photographic light-sensitive material (iii) of the 
present invention may preferably comprise diverse metal ions or complex 
ions thereof. Preferred metal ions can be selected from the group 
consisting of ions of metals belonging to the groups VIII and IIb in the 
periodic table or complexes thereof, lead ions and thallium ions. The 
localized phase can mainly comprise metal ions selected from the group 
consisting of iridium, rhodium and ferric or ferrous ions or complex ions 
thereof. The substrate can mainly comprise metal ions selected from the 
group consisting of osmium, iridium, rhodium, platinum, ruthenium, 
palladium, cobalt, nickel and ferric or ferrous ions or complex ions in 
combination. The kind and concentration of metal ions used in the 
localized phase may be different from those of the substrate. A plurality 
of kinds of metals can be used. In particular, iron and iridium compounds 
are preferably incorporated in the silver bromide localized phase. 
These metal ion-supplying compounds may be incorporated in the localized 
phase and/or other portion (substrate) of the silver halide grains of the 
present invention by adding these metal ion-supplying compounds in the 
form of dispersion in aqueous solution of gelatin, aqueous solution of 
halide, aqueous solution of silver salt or other aqueous solutions to the 
system, or by adding these metal ion-supplying compounds to the system in 
the form of solution of finely divided silver halide grains containing 
metal ions, during the formation of silver halide grains. 
The incorporation of metal ions to be used in the photographic 
light-sensitive material (iii) of the present invention to the emulsion 
grains can be effected at any time before, during or shortly after the 
formation of grains depending on the position of metal ions in the grain 
in which these metal ions are to be incorporated. 
The silver halide emulsion to be used in the present invention is normally 
subjected to chemical sensitization and spectral sensitization. 
The chemical sensitization of the photographic light-sensitive material 
(iii) of the present invention may be effected by a chemical sensitization 
with a chalcogen sensitizer e.g., sulfur sensitization in which unstable 
sulfur compound is representatively used, selenium sensitization with a 
selenium compound, tellurium sensitization with a tellurium compound), a 
noble sensitization represented by gold sensitization, a reduction 
sensitization or the like. As compounds to be used in the chemical 
sensitization method there may be preferably used those described in 
JP-A-62-215272, lower right column, page 18--upper right column, page 22. 
The emulsion to be used in the photographic material (iii) of the present 
invention is preferably of a so-called surface latent image type in which 
latent images are formed mainly on the surface of grains. 
The silver halide emulsion to be incorporated in the photographic 
light-sensitive material (iii) of the present invention may comprise 
various compounds or precursors thereof for the purpose of inhibiting fog 
as in the case of the photographic light-sensitive material (ii). Specific 
examples of these compounds include those described with reference to the 
photographic light-sensitive material (ii). 
Spectral sensitization is effected for the purpose of providing the 
emulsion in the various layers in the photographic light-sensitive 
material (iii) of the present invention with the spectral sensitivity to 
the respective desired wavelength range. 
As spectral sensitizing dyes to be used in the spectral sensitization to 
blue, green and red light ranges in the photographic light-sensitive 
material (iii) of the present invention there may be used those described 
with reference to the photographic light-sensitive material (ii). Specific 
preferred examples of such a compound and spectral sensitization method 
which can be preferably used include those described in the above cited 
JP-A-62-215272, upper right column, page 22 to page 38. As the 
red-sensitive spectral sensitizing dye for silver halide emulsion grains 
having a high silver chloride content, spectral sensitizing dyes as 
disclosed in JP-A-3-123340 are particularly preferred from the standpoint 
of stability, adsorption, dependence on temperature upon exposure, etc. 
If the photographic light-sensitive material of the present invention as 
defined in the clause (iii) is spectrally sensitized in the infrared range 
at a high efficiency, a sensitizing dye as disclosed in JP-A-3-15049, 
upper left column, page 12--lower left column, page 21, and 3-20730, lower 
left column, page 4--lower left column, page 15, EP0,420,011, line 21, 
page 4--line 54, page 6, EP0,420,012, line 12, page 4--line 33, page 10, 
EP0,443,466, and U.S. Pat. No. 4,975,362 can be preferably used. 
When such a spectral sensitizing dye is incorporated in the silver halide 
emulsion, it may be directly dispersed in the emulsion or may be added to 
the emulsion in the form of solution in water, methanol, ethanol, 
propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol or the like, 
Singly or in admixture. Alternatively, such a spectral sensitizing dye may 
be added to the emulsion in the form of aqueous solution under the 
presence of an acid or base as disclosed in JP-B-44-23389, JP-B-44-27555, 
and JP-B-57-22089 or in the form of aqueous solution for colloidal 
dispersion with a surface active agent present therein as disclosed in 
U.S. Pat. Nos. 3,822,135, and 4,006,025. Further, such a spectral 
sensitizing dye may be dissolved in a solvent substantially non-miscible 
with water such as phenoxyethanol, dispersed in water or a hydrophilic 
colloid, and then added to the emulsion. As described in JP-A-53-102733, 
and JP-A-58-105141, such a spectral sensitizing dye may be added to the 
emulsion in the form of dispersion in a hydrophilic colloid. 
The time at which such a spectral sensitizing dye is added to the emulsion 
may be any stage which has heretofore been known effective. In particular, 
it may be added to the emulsion before or during the formation of silver 
halide emulsion grains, between shortly after the formation of grains and 
before the rinse, before or during the chemical sensitization, between 
shortly after the chemical sensitization and solidification of by cooling 
the emulsion or during the preparation of coating solution. 
In general, it may be conducted between the completion of the chemical 
sensitization and before the coating. As described in U.S. Pat. Nos. 
3,628,969, and 4,225,666, such a spectral sensitizing dye may be added to 
the emulsion at the same time with a chemical sensitizer so that spectral 
sensitization and chemical sensitization are simultaneously effected. As 
described in JP-A-58-113928, it may be conducted prior to the chemical 
sensitization. Further, such a spectral sensitizing dye may be added to 
the emulsion before the completion of precipitation of silver halide 
grains to initiate spectral sensitization. Moreover, as taught in U.S. 
Pat. No. 4,225,666, such a spectral sensitizing dye may be batch-wise 
added to the system. In other words, a part of the spectral sensitizing 
dye may be added to the system prior to chemical sensitization, and the 
residual part of the spectral sensitizing dye may be added to the system 
after chemical sensitization. In accordance with a further method taught 
in U.S. Pat. No. 4,183,756, such a spectral sensitizing dye may be added 
to the system at any stage during the formation of silver halide grains. 
Particularly preferred among these stages in which the spectral sensitizing 
dye can be added to the system is before rinse or chemical sensitization. 
The amount of such a spectral sensitizing dye to be added depends much on 
the circumstances. It is preferably in the range of 0.5.times.10.sup.-6 
mol to 1.0.times.10.sup.-2 mol, more preferably 1.0.times.10.sup.-6 mol to 
5.0.times.10.sup.-3 mol per mol of silver halide. 
In the photographic light-sensitive material (iii) of the present 
invention, when a sensitizing dye having a spectrally sensitized 
sensitivity particularly in the range of from red region to infrared 
region is used, it is preferred that a compound as described in 
JP-A-2-157749, lower right column, page 13--lower right column, page 22 is 
used together. The use of such a compound provides a specific enhancement 
of the preservability and processing stability of the photographic 
light-sensitive material and the effect of supersensitizing the 
photographic light-sensitive material. In particular, Compounds (IV), (V) 
and (VI) described in the above cited patent are preferably used together 
therewith. The amount of such a compound to be incorporated is in the 
range of 0.5.times.10.sup.-5 mol to 5.0.times.10.sup.-2 mol, preferably 
5.0.times.10.sup.-5 mol to 5.0.times.10.sup.-3 mol per mol of silver 
halide. Its advantageous range is in the range of 0.1 to 10,000 times, 
preferably 0.5 to 5,000 times the molar quantity of sensitizing dye. 
The photographic light-sensitive material of the present invention as 
defined in the clause (iii) may be exposed to visible light or infrared 
light. Exposure may be carried out by a low intensity exposure process or 
a high intensity exposure process. In a preferred embodiment of the latter 
case, laser scanning exposure process with an exposure time of 10.sup.-4 
seconds or less, preferably 10.sup.-6 or less per pixel may be preferably 
used. 
A band stop filter as disclosed in U.S. Pat. No. 4,880,726 may be 
preferably used for exposure. This removes light stain, providing a 
remarkable enhancement of color reproducibility. 
The photographic light-sensitive material (iii) which has been exposed to 
light may be subjected to a commonly used color development, preferably 
followed by blix for the purpose of expediting the processing. In 
particular, if the aforementioned emulsion having a high silver chloride 
content emulsion is used, the pH value of the blix solution is preferably 
in the range of about 6.5 or less, more preferably about 6 or less for the 
purpose of accelerating the desilvering procedure. 
As silver halide emulsions and other materials (additives) to be 
incorporated in the photographic light-sensitive material (iii) of the 
present invention, photographic constituent layers of the light-sensitive 
material (iii) of the present invention (layer configuration), and 
processing methods and processing additives to be used in the processing 
of the photographic light-sensitive material (iii) of the present 
invention there can be preferably used those described in JP-A-62-215272, 
and JP-A-2-33144, and EP0,355,660A2 as in the photographic light-sensitive 
material (i). 
The cyan, magenta or yellow coupler is preferably emulsion-dispersed in an 
aqueous solution of a hydrophilic colloid in the form of an impregnation 
in a loadable latex polymer (as described in U.S. Pat. No. 4,203,716) in 
the presence (or absence) of a high boiling organic solvent as tabulated 
above or in the form of a solution together with a water-insoluble and 
organic solvent-soluble polymer. 
Examples of the water-insoluble and organic solvent-soluble polymer which 
can be preferably used include single polymers or copolymers as described 
in U.S. Pat. No. 4,857,449, 7th column--15th column, and WO88/00723, pp. 
12-30. More preferably, methacrylate or acrylamide polymers, particularly 
acrylamide polymers may be used in the light of dye image stability. 
The photographic light-sensitive material (iii) of the present invention 
preferably comprises a dye preservability-improving compound as described 
in EO0,277,589A2 in combination with these couplers, particularly in 
combination with pyrazoloazole coupler or pyrrolotriazole coupler. 
In particular, a compound as described in the above cited patents which 
undergoes chemical bonding to an aromatic amine developing agent remaining 
after color development to produce a chemically inert and substantially 
colorless compound and/or another compound as described in the above cited 
patents which undergoes chemical bonding to an oxidation product of an 
aromatic amine color developing agent remaining after color development to 
produce a chemically inert and substantially colorless compound may be 
preferably used singly or in combination to inhibit the occurrence of 
stain or other side effects caused by the formation of developed dyes by 
the reaction of a color developing agent or its oxidation product 
remaining in the film with a coupler in the storage after processing. 
As the cyan, yellow and magenta couplers to be incorporated in the 
photographic light-sensitive material (iii) of the present invention there 
can be used the same couplers as used in the photographic light-sensitive 
material (i) of the present invention. 
As the processing method for the color photographic light-sensitive 
material (iii) of the present invention there preferably be used besides 
those tabulated above processing materials and processing methods as 
described in JP-A-2-207250, line 1, lower right column, page 26--line 9, 
upper right column, page 34, and JP-A-4-97355, line 17, upper left column, 
page 5--line 20, lower right column, page 18. 
The present invention will be further described in the following examples, 
but the present invention should not be construed as being limited 
thereto. 
EXAMPLE 1 
32 g of a lime-treated gelatin was added to and dissolved in 800 cc of 
distilled water at a temperature of 40.degree. C. 5.76 g of sodium 
chloride was added to the solution. The solution was then heated to a 
temperature of 75.degree. C. A solution of 100 g of silver nitrate in 400 
cc of distilled water and a solution of 34.4 g of sodium chloride in 400 
cc of distilled water were added to the solution over 73 minutes with the 
temperature of the system being kept at 75.degree. C. A solution of 59.2 g 
of silver nitrate in 200 cc of distilled water and a solution of 17.1 g of 
sodium chloride in 200 cc of distilled water were added to the solution 
over 28 minutes with the temperature of the system being kept at 
75.degree. C. The system was then allowed to cool to 4.degree. C. 
Blue-sensitive sensitizing dyes A and B as described below were each added 
to the system in an amount of 2.times.10.sup.-4 mol per mol of silver 
halide. A solution of 0.8 g of silver nitrate in 100 cc of distilled water 
and a solution of 0.56 g of potassium bromide in 100 cc of distilled water 
were added to the solution over 10 minutes with the temperature of the 
system being kept at 40.degree. C. The material was then desalted and 
rinsed. The material was then subjected to optimum sulfur sensitization 
with 90 g of a lime-treated gelatin. The silver bromochloride emulsion 
thus obtained (silver bromide content: 0.5 mol %) was designated as 
Emulsion A. 
A silver bromochloride emulsion (silver bromide content: 0.5 mol %) was 
prepared as Emulsion B in the same manner as Emulsion A except that 
K.sub.2 IrCl.sub.6 was added to the potassium bromide Solution in an 
amount corresponding to of 1.0.times.10.sup.-6 mol per mol of finished 
silver bromochloride. 
A silver bromochlorideemulsion (silver bromide content: 0.5 mol %) was 
prepared as Emulsion C in the same manner as Emulsion A except that 
K.sub.4 Fe(CN).sub.6 was added to the sodium chloride solution to be added 
at the second time in an amount corresponding to 8.0.times.10.sup.-6 mol 
per mol of finished silver bromochloride. 
Silver bromochloride emulsions were prepared as Emulsions D, E, F and G in 
the same manner as Emulsion A except that the kind and amount of metal 
complexes to be added to the sodium chloride solution to be added at the 
second time were altered as set forth in Table A, respectively. 
TABLE A 
______________________________________ 
Kind of metal 
Amount of metal 
Emulsion complex complex.sup.1 
______________________________________ 
A None None 
B K.sub.2 IrCl.sub.6 
1.0 .times. 10.sup.-6 
C K.sub.4 Fe(CN).sub.6 
8.0 .times. 10.sup.-6 
D K.sub.4 Ru(CN).sub.6 
8.0 .times. 10.sup.-6 
E K.sub.4 Os(CN).sub.6 
8.0 .times. 10.sup.-6 
F K.sub.3 Ir(CN).sub.6 
1.5 .times. 10.sup.-5 
G K.sub.3 RuCl.sub.6 
1.0 .times. 10.sup.-7 
______________________________________ 
.sup.1 Added molar amount per mol of finished silver halide 
Emulsions A to G thus obtained were measured for grain shape, grain size 
and grain size distribution with their electron microscope photographs. 
The grain size was represented by the average value of the diameter of 
circles having the same area as the projected area of grains. The grain 
size distribution was obtained by dividing the standard deviation of grain 
diameters by the average grain size. Emulsions A to G all comprised cubic 
grains having a grain size of 0.70 .mu.m and a grain size distribution of 
0.09. When examined by a diffraction X-ray method, emulsions A to G 
exhibited a weak diffraction in the portion corresponding to a silver 
bromide content of 10 mol % to 40 mol %. 
The surface of a paper support laminated with polyethylene on both sides 
thereof for gelatin was subjected to corona discharge. On the paper 
support was provided an undercoating layer for gelatin containing sodium 
dodecylbenzenesulfonate. On the undercoating layer were coated various 
photographic constituent layers to prepare a multilayer color photographic 
paper having the following layer construction (Specimen 1). The coating 
solutions were prepared as follows: 
Preparation of 1st Layer Coating Solution 
153.0 g of a yellow coupler (ExY), 15.0 g of a dye image stabilizer 
(Cpd-1), 7.5 g of a dye image stabilizer (Cpd-2), and 16.0 g of a dye 
image stabilizer (Cpd-3) were dissolved in 180 cc of ethyl acetate, 25 g 
of a solvent (Solv-1) and 25 g of a solvent (Solv-2) to make a solution. 
The solution thus obtained was then emulsion-dispersed in 1,000 g of a 10% 
aqueous solution of gelatin containing 60 cc of sodium 
dodecylbenzenesulfonate and 10 g of citric acid to prepare Emulsified 
Dispersion A which was then mixed with Emulsion A to obtain a 1st layer 
coating solution. 
The coating solutions four the 2nd layer to the 7th layer were prepared in 
the same manner as the coating solution for the 1st layer. As gelatin 
hardener for each layer there was used sodium salt of 
1-oxy-3,5-dichloro-s-triazine. 
Dye image stabilizers Cpd-14 and Cpd-15 each were added to each layer in an 
amount to be 25.0 mg/m.sup.2 and 50.0 mg/m.sup.2 in total, respectively. 
As spectral sensitizing dyes to be incorporated in the various layers there 
were used the following compounds: 
##STR51## 
Further, the following compound was incorporated in the system in an amount 
of 2.6.times.10.sup.-3 mol per mol of silver halide. 
##STR52## 
In the green-sensitive emulsion layer was incorporated 
1-(5-methylureidophenyl)-5-mercaptotetrazole in an amount of 
7.7.times.10.sup.-4 mol per mol of silver halide. 
In the blue-sensitive emulsion layer and the green-sensitive emulsion layer 
was incorporated 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 
1.0.times.10.sup.-4 mol and 2.0.times.10.sup.-4 mol per mol of silver 
halide, respectively. 
For the purpose of inhibiting irradiation, to the emulsion layers were each 
added the following dyes (figures in the parenthesis indicate the coated 
amount): 
##STR53## 
The formulations of the various layers are set forth below. The figures 
indicate the coated amount (g/m2). The coated amount of silver halide 
emulsion is represented as calculated in terms of silver. 
Support 
Polyethylene-laminated paper [containing a white pigment (TiO.sub.2) and a 
bluish dye (ultramarine) in polyethylene on the 1st layer side] 
__________________________________________________________________________ 
1st layer (blue-sensitive emulsion layer) 
Silver bromochloride emulsion A as set forth above 
0.27 
Gelatin 1.36 
Yellow coupler (ExY) 0.79 
Dye image stabilizer (Cpd-1) 0.08 
Dye image stabilizer (Cpd-2) 0.04 
Dye image stabilizer (Cpd-3) 0.08 
Solvent (Solv-1) 0.13 
Solvent (Solv-2) 0.13 
2nd layer (color stain inhibiting layer) 
Gelatin 1.00 
Color mixing inhibitor (Cpd-4) 0.06 
Solvent (Solv-7) 0.03 
Solvent (Solv-2) 0.25 
Solvent (Solv-3) 0.25 
3rd layer (green-sensitive emulsion layer) 
Silver bromochloride emulsion (1:3 (Ag molar ratio) mixture of a 
0.13e 
size emulsion of cubic grains having an average size of 0.55 .mu.m with 
a grain size distribution fluctuation coefficient of 0.10 and a small 
size emulsion of cubic grains having an average size of 0.39 .mu.m with 
a grain size distribution fluctuation coefficient of 0.08, 0.8 mol % of 
silver bromide being localized partially on the surface of each 
emulsion and a balance comprising silver chloride) 
Gelatin 1.45 
Magenta coupler (ExM) 0.16 
Dye image stabilizer (Cpd-5) 0.15 
Dye image stabilizer (Cpd-2) 0.03 
Dye image stabilizer (Cpd-6) 0.01 
Dye image stabilizer (Cpd-7) 0.01 
Dye image stabilizer (Cpd-8) 0.08 
Solvent (Solv-3) 0.50 
Solvent (Solv-4) 0.15 
Solvent (Solv-5) 0.15 
4th layer (color stain inhibiting layer) 
Gelatin 0.70 
Color mixing inhibitor (Cpd-4) 0.04 
Solvent (Solv-7) 0.02 
Solvent (Solv-2) 0.18 
Solvent (Solv-3) 0.18 
5th layer (red-sensitive emulsion layer) 
Silver bromochloride emulsion (1:4 (Ag molar ratio) mixture of a 
0.20e 
size emulsion of cubic grains having an average size of 0.50 .mu.m 
with a grain size distribution fluctuation coefficient of 0.09 and a 
small 
size emulsion of cubic grains having an average size of 0.41 .mu.m with a 
grain size distribution fluctuation coefficient of 0.11, 0.8 mol % of 
silver bromide being localized partially on the surface of each emulsion 
and a balance comprising silver chloride) 
Gelatin 0.85 
Cyan coupler (ExC) 0.33 
Ultraviolet absorbent (UV-2) 0.18 
Dye image stabilizer (Cpd-9) 0.02 
Dye image stabilizer (Cpd-10) 0.02 
Dye image stabilizer (Cpd-11) 0.01 
Solvent (Solv-6) 0.22 
Dye image stabilizer (Cpd-8) 0.01 
Dye image stabilizer (Cpd-6) 0.01 
Solvent (Solv-1) 0.01 
Dye image stabilizer (Cpd-1) 0.33 
6th layer (ultraviolet absorbing layer) 
Gelatin 0.55 
Ultraviolet absorbent (UV-1) 0.38 
Dye image stabilizer (Cpd-12) 0.15 
Dye image stabilizer (Cpd-5) 0.02 
7th layer (protective layer) 
Gelatin 1.13 
Acryl-modified copolymer of polyvinyl 
0.05 
alcohol (modification degree: 17%) 
Liquid paraffin 0.02 
Dye image stabilizer (Cpd-13) 0.01 
__________________________________________________________________________ 
Yellow coupler (ExY) 
1:1 (molar ratio) mixture of 
##STR54## 
##STR55## 
and 
##STR56## 
Magenta coupler (ExM) 
##STR57## 
Cyan coupler (ExC) 
3:7 (molar ratio) of: 
##STR58## 
and 
##STR59## 
Dye image stabilizer (Cpd-1) 
##STR60## 
Dye image stabilizer (Cpd-2) 
##STR61## 
Dye image stabilizer (Cpd-3) 
##STR62## 
Color mixing inhibitor (Cpd-4) 
##STR63## 
Dye image stabilizer (Cpd-5) 
##STR64## 
Dye image stabilizer (Cpd-6) 
##STR65## 
Dye image stabilizer (Cpd-7) 
##STR66## 
Dye image stabilizer (Cpd-8) 
##STR67## 
Dye image stabilizer (Cpd-9) 
##STR68## 
Dye image stabilizer (Cpd-10) 
##STR69## 
Dye image stabilizer (Cpd-11) 
##STR70## 
Dye image stabilizer (Cpd-12) 
##STR71## 
Average molecular amount: approx. 60,000 
Dye image stabilizer (Cpd-13) 
##STR72## 
Preservative (Cpd-14) 
##STR73## 
Preservative (Cpd-15) 
##STR74## 
Ultraviolet absorbent (UV-1) 
1:5:10:5 (weight ratio) mixture of: 
##STR75## 
##STR76## 
##STR77## 
##STR78## 
Ultraviolet absorbent (UV-2) 
1:2:2 (weight ratio) mixture of: 
##STR79## 
##STR80## 
##STR81## 
Solvent (Solv-1) 
##STR82## 
Solvent (Solv-2) 
##STR83## 
Solvent (Solv-3) 
##STR84## 
Solvent (Solv-4) 
##STR85## 
Solvent (Solv-5) 
##STR86## 
Solvent (Solv-6) 
##STR87## 
Solvent (Solv-7) 
##STR88## 
Specimens 2 to 18 were prepared in the same manner as Specimen 1 
except that the presence of an undercoating hydrophilic colloidal layer 
as mentioned below between the support (polyethylene-laminated paper) and 
the 1st layer, the coated amount of titanium oxide (white pigment) in the 
hydrophilic colloidal layer, the kind of the silver halide emulsion to be 
incorporated in the 1st layer (blue-sensitive emulsion layer), and the 
kind of the compounds to be incorporated in the 1st layer were altered as 
set forth in Table B. Preparation of Coating Solution for Undercoating 
To 1.0 kg of a 10% aqueous solution of gelatin were added 400 g of a rutile 
type titanium white pigment having an average grain size of 0.23 .mu.m 
(Titan White R780 available from Ishihara Sangyo K.K.) and 4 l of water. 
To the material was then added 8 cc of a 5% aqueous solution of sodium 
dodecylbenzenesulfonate as a dispersant. The material was then subjected 
to dispersion under irradiation with ultrasonic wave. 
TABLE B 
__________________________________________________________________________ 
Undercoating hydrophilic 
colloidal layer 
Coated amount of Mercapto.sup.1 
Spatial 
white pigment 
Blue-sensitive 
heterocyclic 
frequency 
Specimen 
Presence 
(g/m.sup.2) 
layer emulsion 
compound 
(line/mm) 
.DELTA.D 
__________________________________________________________________________ 
1 No -- A I-2-6 14.0 0.000 
2 Yes 1.5 A I-2-6 15.0 0.000 
3 Yes 3 A I-2-6 19.5 0.020 
4 Yes 5 A I-2-6 25.5 0.025 
5 Yes 5 A None 23.5 0.030 
6 No -- B I-2-6 14.0 0.000 
7 Yes 5 B None 23.5 0.030 
8 Yes 5 B I-2-6 23.5 0.000 
9 Yes 5 C I-2-6 23.5 0.000 
10 Yes 1.5 D None 15.0 0.005 
11 Yes 1.5 D I-2-6 15.0 0.000 
12 Yes 3 D I-2-6 19.5 0.000 
13 Yes 5 D None 23.5 0.030 
14 Yes 5 D I-2-6 23.5 0.000 
15 Yes 10 D I-2-6 25.5 0.010 
16 Yes 5 E I-2-6 23.5 0.000 
17 Yes 5 F I-2-6 23.5 0.000 
18 Yes 5 G I-2-6 23.5 0.015 
__________________________________________________________________________ 
.sup.1 Added in an amount of 8 .times. 10.sup.-4 mol per mol of silver 
halide in the bluesensitive layer upon the preparation of the coating 
solution 
Specimens 1 to 7, 10, 11, and 13 were comparative while the others were 
according to the present invention. 
In order to examine the photographic light-sensitive materials thus 
prepared for magenta sharpness, the photographic light-sensitive materials 
were exposed to light through a sharpness measuring optical wedge and a 
green color filter, and then processed in accordance with the processing 
procedures as mentioned below. The sharpness was represented by the 
spatial frequency (line/mm) giving CTF 0.5. The more the spatial frequency 
value is, the higher is the sharpness. The reason why the sharpness of 
magenta is evaluated is that the human eye is more sensitive to magenta 
than to yellow and cyan. The results are set forth in Table B. 
In order to evaluate yellow fog density developed after a prolonged 
storage, these photographic light-sensitive materials were stored at a 
temperature of 35.degree. C. and a relative humidity of 55% for 2 weeks 
and another batch of these specimens were stored in a freezer (10.degree. 
C.) for 2 weeks. These specimens were then processed in accordance with 
the processing procedures as mentioned below. On the supposition that the 
color developer would have been actually contaminated with some blix 
solution, the processing was effected with the developer being 
intentionally contaminated with 0.3 cc/l of the blix solution. The rise in 
the yellow fog density was represented by the difference (AD) in fog 
density between the specimen stored in a freezer and another batch of the 
specimen stored at 35.degree. C./55% RH. The greater this difference value 
is, the greater is the rise in the yellow fog density developed after a 
prolonged storage. The reason why the yellow fog density is evaluated is 
that the silver halide emulsion in the blue-sensitive layer itself is 
subject to fog due to the emulsion design in color photographic papers. In 
addition, since the blue-sensitive layer is nearest to the white pigment 
layer and thus is further liable to be fogged, the yellow coupler in the 
blue-sensitive layer causes a remarkable yellow fog. 
______________________________________ 
Processing 
step Temperature 
Time 
______________________________________ 
Color development 
35.degree. C. 
45 sec. 
Blix 30-35.degree. C. 
45 sec. 
Rinse 1 30-35.degree. C. 
20 sec. 
Rinse 2 30-35.degree. C. 
20 sec. 
Rinse 3 30-35.degree. C. 
20 sec. 
Drying 70-80.degree. C. 
60 sec. 
______________________________________ 
The formulations of the various processing solutions were as follows: 
______________________________________ 
Color developer 
Water 800 ml 
Ethylenediamine-N,N,N,N-tetramethylene- 
1.5 g 
phosphonate 
Potassium bromide 0.015 g 
Triethanolamine 8.0 g 
Sodium chloride 1.4 g 
Potassium carbonate 25 g 
N-ethyl-N-(.beta.-methanesulfoamideethyl)-3- 
5.0 g 
methyl-4-aminoanilinesulfate 
N,N-bis(carboxymethyl)hydrazine 
4.0 g 
N,N-di(sulfoethyl)hydroxylamine.1Na 
4.0 g 
Fluorescent brightening agent 
1.0 g 
(Whitex 4B produced by Sumitomo 
Chemical Co., Ltd.) 
Water to make 1,000 ml 
pH (25.degree. C.) 10.05 
Blix solution 
Water 400 ml 
70% Ammonium thiosulfate 100 ml 
Sodium sulfite 17 g 
Ferric (III) ammonium ethylenediamine- 
55 g 
tetraacetate 
Ferric disodium ethylenediamine- 
5 g 
tetraacetate 
Ammonium bromide 40 g 
Water to make 1,000 ml 
pH (25.degree. C.) 6.0 
______________________________________ 
Washing Solution 
Ion-exchanged water (calcium and magnesium concentration: 3 ppm or less 
each) 
Table B shows that the rise in the undercoated amount of a white pigment 
provides a high sharpness but also provides an increase in the fog density 
after a prolonged storage (Specimens 1 to 4). It can be seen in the table 
that the rise in the fog density can be minimized only by mixing an 
emulsion containing a specific metal complex with a mercaptoheterocyclic 
compound (Specimens 8, 9, 12, 14 to 18). 
EXAMPLE 2 
32 g of a lime-treated gelatin was added to and dissolved in 800 cc of 
distilled water at a temperature of 40.degree. C. 3.3 g of sodium chloride 
was added to the solution. The solution was then heated to a temperature 
of 74.degree. C. A solution of 32.0 g of silver nitrate in 200 cc of 
distilled water and a solution of 11.0 g of sodium chloride in 200 cc of 
distilled water were added to the solution over 18 minutes with the 
temperature of the system being kept at 74.degree. C. A solution of 128.0 
g of silver nitrate in 560 cc of distilled water and a solution of 44.0 g 
of sodium chloride over 560 cc of distilled water were added to the 
solution in 50 minutes with the temperature of the system being kept at 
74.degree. C. K.sub.4 Fe(CN).sub.6 had been previously added to the sodium 
chloride solution to be added at the second time in an amount of 
5.0.times.10.sup.-6 mol per mol of finished silver bromochloride. The 
material was then desalted and rinsed. 90.0 g of a lime-treated gelatin 
was then-added to the material. Blue-sensitive sensitizing dyes A and B as 
used in Example 1 were each added to the system in an amount of 
2.0.times.10.sup.-4 mol per mol of silver halide. An emulsion of ultrafine 
silver bromide grains (grain size: 0.05 .mu.m; K2IrCl.sub.6 content: 
1.0.times.10.sup.-6 mol per mol of finished silver bromochloride emulsion) 
was added to the material in an amount of 0.4 mol % based on the molar 
amount of silver chloride as calculated in terms of silver bromide. The 
emulsion was then subjected to optimum gold-sulfur sensitization. The 
silver bromochloride emulsion thus obtained (silver bromide content: 0.4 
mol %) was used as Emulsion H. 
32 g of a lime-treated gelatin was added to and dissolved in 800 cc of 
distilled water at a temperature of 40.degree. C. 3.3 g of sodium chloride 
was added to the solution. The solution was then heated to a temperature 
of 74.degree. C. A solution of 32.0 g of silver nitrate in 200 cc of 
distilled water and a solution of 9.35 g of sodium chloride and 3.36 g of 
potassium bromide in 200 cc of distilled water were added to the solution 
over 28 minutes with the temperature of the system being kept at 
74.degree. C. A solution of 128.0 g of silver nitrate in 560 cc of 
distilled water and a solution of 37.4 g of sodium chloride and 13.4 g of 
potassium bromide in 560 cc of distilled water were added to the solution 
over 50 minutes with the temperature of the system being kept at 
74.degree. C. K.sub.4 Fe(CN).sub.6 and K.sub.2 IrCl.sub.6 had been 
previously added to the sodium chloride solution to be added at the second 
time in an amount of 5.0.times.10.sup.-6 mol and 1.0.times.10.sup.-6 mol 
per mol of finished silver bromochloride, respectively. The material was 
then desalted and rinsed. 90.0 g of a lime-treated gelatin was then added 
to the material. Blue-sensitive sensitizing dyes A and B as used in 
Example 1 were each added to the system in an amount of 
2.0.times.10.sup.-4 mol per mol of silver halide. The emulsion was then 
subjected to optimum gold-sulfur sensitization. The silver bromochloride 
emulsion thus obtained (silver bromide content: 15 mol %) was used as 
Emulsion I. 
Emulsions H and I thus obtained were measured for grain shape, grain size 
and grain size distribution from their electron microscope photographs. 
The grain size was represented by the average value of the diameter of 
circles having the same area as the projected area of grains. The grain 
size distribution was obtained by dividing the standard deviation of grain 
diameters by the average grain size. Both Emulsions H and I comprised 
cubic grains having a grain size of 0.71 .mu.m and a grain size 
distribution of 0.08. 
A photographic light-sensitive material was prepared as Specimen 19 in the 
same manner as Specimen 1 except that the formulations of the various 
layers (additives and coated amount)were altered as follows, The figure 
indicates the coated amount (g/m.sup.2), The coated amount of silver 
halide emulsion is represented as calculated in terms of silver, 
__________________________________________________________________________ 
Support 
Polyethylene-laminated paper 
[containing a white pigment (TiO.sub.2) and a bluish dye (ultramarine) in 
polyethylene 
on the 1st layer side] 
1st layer (blue-sensitive emulsion layer) 
Silver bromochloride emulsion H as set forth above 
0.30 
Gelatin 1.22 
Yellow coupler (ExY) 0.82 
Dye image stabilizer (Cpd-16) 0.19 
Solvent.(Solv-9) 0.18 
Solvent (Solv-1) 0.18 
Dye image stabilizer (Cpd-18) 0.06 
2nd layer (color stain inhibiting layer) 
Gelatin 0.64 
Color mixing inhibitor (Cpd-4) 0.10 
Solvent (Solv-2) 0.16 
Solvent (Solv-3) 0.08 
3rd layer (green-sensitive emulsion layer) 
Silver bromochloride emulsion (1:3 (Ag molar ratio) mixture of a large 
size 0.12 
emulsion of cubic grains having an average size of 0.55 .mu.m with a 
grain size 
distribution fluctuation coefficient of 0.10 and a small size emulsion of 
cubic grains 
having an average size of 0.39 gm with a grain size distribution 
fluctuation coefficient 
of 0.08, 0.8 mol % of silver bromide being localized partially on the 
surface of each 
emulsion and a balance comprising silver chloride) 
Gelatin 1.28 
Magenta coupler (ExM) 0.23 
Dye image stabilizer (Cpd-8) 0.03 
Dye image stabilizer (Cpd-5) 0.16 
Dye image stabilizer (Cpd-7) 0.02 
Dye image stabilizer (Cpd-2) 0.02 
Solvent (Solv-8) 0.40 
4th layer (ultraviolet-absorbing layer) 
Gelatin 1.41 
Ultraviolet absorbent (UV-3) 0.47 
Color mixing inhibitor (Cpd-4) 0.05 
Solvent (Solv-10) 0.24 
5th layer (red-sensitive emulsion layer) 
Silver bromochloride emulsion H 0.23 
Gelatin 1.04 
Cyan coupler (ExC-2) 0.32 
Dye image stabilizer (Cpd-8) 0.03 
Dye image stabilizer (Cpd-17) 0.03 
Ultraviolet absorbent (UV-2) 0.18 
Dye image stabilizer (Cpd-18) 0.40 
Dye image stabilizer (Cpd-19) 0.05 
Solvent (Solv-11) 0.14 
6th layer (ultraviolet absorbing layer) 
Gelatin 0.48 
Ultraviolet absorbent (UV-3) 0.16 
Color stain inhibitor (Cpd-4) 0.02 
Solvent (Solv-10) 0.08 
7th layer (protective layer) 
Gelatin 1.10 
Acryl-modified copolymer of polyvinyl alcohol 
0.17 
(modification degree: 17%) 
Liquid paraffin 0.03 
__________________________________________________________________________ 
Cyan coupler (ExC-2) -1:1 (molar ratio) mixture of: - 
##STR89## 
##STR90## 
Dye image stabilizer (Cpd-16) - 
##STR91## 
Dye image stabilizer (Cpd-17) - 
##STR92## 
Dye image stabilizer (Cpd-18) - 
##STR93## 
Dye image stabilizer (Cpd-19) -1:1 (weight ratio) mixture of: 
##STR94## 
Ultraviolet absorbent (UV-2) -4:2:4 (weight ratio) mixture of: 
##STR95## 
##STR96## 
##STR97## 
Solvent (Solv-8) -1:1 (volume ratio) mixture of: - 
##STR98## 
##STR99## 
Solvent (Solv-9) - 
##STR100## 
Solvent (Solv-10) - 
##STR101## 
Solvent (Solv-6) -80:20 (volume ratio) mixture of: - 
##STR102## 
##STR103## 
Specimens 20 to 27 were prepared in the same manner as Specimen 19 
except that the presence of three undercoating layers (1st undercoating 
layer, 2nd undercoating layer, and 3rd undercoating layer coated on the 
support in this order) as mentioned below between the support 
(polyethylene-laminated paper) and the 1st layer, the kind of the silver 
halide emulsion to be incorporated in the 1st layer (blue-sensitive 
emulsion layer), and the kind of the compounds to be incorporated in the 
To 1.0 kg of a 10% aqueous solution of gelatin were added 400 g of a rutile 
type titanium white pigment having an average grain size of 0.23 .mu.m 
(Titan White R780 available from Ishihara Sangyo K.K.) and 4 l of water. 
To the material was then added 8 cc of a 5% aqueous solution of sodium 
dodecylbenzenesulfonate as a dispersant. The material was then subjected 
to dispersion under irradiation with ultrasonic wave. The coated amount of 
the white pigment was adjusted to 5.5 g/m.sup.2. 
2nd Undercoating Layer 
A colloidal silver emulsion as described in Example 1 of JP-A-239544 was 
coated in an amount of 0.18 g/m.sup.2 as calculated in terms of silver. 
The coated amount of gelatin was 0.80 g/m.sup.2. 
3rd Undercoating Layer 
To 1.0 kg of a 10% aqueous solution of gelatin were added 2 l of water and 
8 cc of a 5% aqueous solution of sodium dodecylbenzenesulfonate as a 
dispersant. The emulsion was coated in such an amount that the coated 
amount of gelatin reached 0.7 g/m.sup.2. 
TABLE C 
______________________________________ 
Presence Blue- 
of three sensitive 
Mercapto.sup.1 
Spatial 
undercoating 
layer heterocyclic 
frequency 
Specimen 
layer emulsion compound (line/mm) 
.DELTA.D 
______________________________________ 
19 No H None 14.5 0.000 
20 No H I-2-5 14.5 0.000 
21 Yes H None 27.0 0.060 
22 Yes H I-2-5 27.0 0.010 
23 Yes H I-1-5 27.0 0.020 
24 Yes H I-3-33 27.0 0.020 
25 Yes H I-4-6 27.0 0.020 
26 No I I-2-5 14.5 0.050 
27 Yes I I-2-5 27.0 0.050 
______________________________________ 
.sup.1 Added in an amount of 7 .times. 10.sup.-4 mol per mol of silver 
halide in the bluesensitive layer in the same manner as in Example 1. 
Specimens 22 to 25 are according to the present invention and the others 
are comparisons. 
The photographic light-sensitive material specimens thus prepared were then 
evaluated for magenta sharpness and yellow fog density rise after a 
prolonged storage in the same manner as in Example 1. The results are set 
forth in Table C. 
Table C shows that the undercoating of a white pigment-containing layer and 
a colloidal silver-containing layer provides a high sharpness but also 
provides an increase in the fog density after a prolonged storage 
(comparison of Specimen 20 with Specimen 21 and comparison of Specimen 26 
with Specimen 27). It can be seen in the table that the rise in the fog 
density can be minimized only by mixing an emulsion containing a specific 
metal complex with a mercaptoheterocyclic compound (Specimens 22 to 25). 
On the other hand, this effect cannot be attained with a silver halide 
emulsion having a silver chloride content of 90 mol % or less (comparison 
of Specimen 26 with Specimen 27). 
EXAMPLE 3 
Emulsions J to N were prepared in the same manner as Emulsion C used in 
Example 1 except that the kind and addition amount of metal complex were 
changed as is shown below. 
______________________________________ 
Kind of metal 
Amount of metal 
Emulsion comples complex.sup.1 
______________________________________ 
J K.sub.2 RuCl.sub.5 (NO) 
2.0 .times. 10.sup.-8 
K K.sub.2 OsCl.sub.6 
1.0 .times. 10.sup.-7 
L K.sub.2 RuCl.sub.6 
2.0 .times. 10.sup.-7 
M K.sub.3 IrCl.sub.6 
4.0 .times. 10.sup.-8 
N K.sub.2 IrBr.sub.6 
2.0 .times. 10.sup.-8 
______________________________________ 
.sup.1 Added molar amount per mol of finished silver halide 
Speciments 28 to 32 were prepared in the same manner as Specimen 18 of 
Example 1 except that the blue-sensitive emulsion G is replaced by 
Emulsions J, K, L, M and N. The specimens thus obtained were processed and 
evaluated in the same manner as in Example 1 to evaluate sharpness 
(spatial frequency) and an increase of yellow fog density after a 
prolonged storage of the photographic material, i.e., .DELTA.D. 
The results thus obtained are shown in below. 
______________________________________ 
Spatial 
Specimen Emulsion Frequency .DELTA.D 
Remarks 
______________________________________ 
28 J 23.5 0.015 
Invention 
29 K 23.5 0.020 
Invention 
30 L 23.5 0.015 
Invention 
31 M 23.5 0.000 
Invention 
32 N 23.5 0.005 
Invention 
______________________________________ 
As is apparent from the results, the storage atability of the photographic 
material is remarkably improved when iridium complex is used among metal 
complexes. 
The results of Examples 1 to 3 show that the photographic light-sensitive 
material (i) of the present invention provides a silver halide color 
photographic material excellent in image sharpness and storage stability. 
EXAMPLE 4 
25 g of a lime-treated gelatin was added to and dissolved in 800 cc of 
distilled water at a temperature of 40.degree. C. 2.25 g of sodium 
chloride was added to the solution. The solution was then heated to a 
temperature of 70.degree. C. A solution of 5.0 g of silver nitrate in 140 
cc of distilled water and a solution of 1.7 g of sodium chloride in 140 cc 
of distilled water were added to the solution over 40 minutes with the 
temperature of the system being kept at 70.degree. C. A solution of 57.5 g 
of silver nitrate in 160 cc of distilled water and a solution of 19.8 g of 
sodium chloride in 160 cc of distilled water were added to the solution 
over 40 minutes with the temperature of the system being kept at 
70.degree. C. 
Further, a solution of 62.5 g of silver nitrate in 160 cc of distilled 
water and a solution of 21.5 g of sodium chloride in 160 cc of distilled 
water were added to the solution over 40 minutes with the temperature of 
the system being kept at 70.degree. C. The emulsion was then desalted and 
rinsed at a temperature of 40.degree. C. 76.0 g of a lime-treated gelatin 
was added to the emulsion. The pH and pAg values of the emulsion were 
properly adjusted. 
The emulsion was then heated to a temperature of 50.degree. C. A 
blue-sensitive sensitizing dye as set forth below was then added to the 
emulsion in an amount of 3.times.10.sup.-4 mol per mol of silver halide. 
The emulsion was then subjected to optimum sulfur sensitization with 
triethylthiourea. The silver chloride emulsion was used as Emulsion B101. 
Preparation of Emulsion B102 
Emulsion B102 was prepared in the same manner as Emulsion B101 except that 
the optimum chemical sensitization was effected with tetrachloroauric acid 
and triethylthiourea in combination. 
Preparation of Emulsion B103 
Emulsion B103 was prepared in the same manner as Emulsion B101 except that 
an emulsion of finely divided silver bromide grains having a grain size of 
0.05 .mu.m was added in an amount as calculated in terms of 
5.times.10.sup.-3 mol before the chemical sensitization with 
triethylthiourea and followed by an optimal chemical sensitization with 
the combination of tetrachloroauric acid and triethylthiourea. Potassium 
hexachloroiridiumate (IV) had been previously added to the emulsion of 
finely divided silver bromide grains in an amount of 10 mg per mol of 
silver bromide. 
Preparation of Emulsion B104 
Emulsion B104 was prepared in the same manner as Emulsion B101 except that 
the optimum chemical sensitization was effected with tetrachloroauric 
acid. 
Preparation of Emulsion B105 
Emulsion B105 was prepared in the same manner as Emulsion B104 except that 
an emulsion of finely divided silver bromide grains having a grain size of 
0.05 .mu.m was added in an amount as calculated in terms of 
5.times.10.sup.-3 mol of silver bromide before the optimum chemical 
sensitization was effected with tetrachloroauric acid, and followed by 
optimal chemical sensitization with tetrachloroauric acid. Potassium 
hexachloroiridiumate (IV) had been previously added to the emulsion of 
finely divided silver bromide grains in an amount of 10 mg per mol of 
silver bromide. 
Emulsions B101 to B105 thus obtained were measured for grain shape, grain 
size and grain size distribution from their electron microscope 
photographs. 
The grain size was represented by the average value of the diameter of 
circles having the same area as the projected area of grains. The grain 
size distribution was obtained by dividing the standard deviation of grain 
diameters by the average grain size. Emulsions B101 to B105 comprised 
sharply edged cubic grains having a grain size of 0.92 .mu.m and a grain 
size distribution of 0.11. 
The surface of a paper support laminated with polyethylene on both sides 
thereof was subjected to corona discharge. On the paper support was 
provided a gelatin undercoating layer containing sodium 
dodecylbenzenesulfonate. On the undercoating layer were coated various 
photographic constituent layers to prepare a multilayer color photographic 
paper having the following layer construction (Specimen 104). The coating 
solutions were prepared as follows: 
Preparation of 1st Layer Coating Solution 
To 1.0 kg of a 10% aqueous solution of gelatin were added 400 g of a rutile 
type titanium white pigment having an average grain size of 0.23 .mu.m 
(Titan White R780 available from Ishihara Sangyo K.K. ) and 4 l of water. 
To the material was then added 8 cc of a 5% aqueous solution of sodium 
dodecylbenzenesulfonate as a dispersant. The material was then subjected 
to dispersion under irradiation with ultrasonic wave. 
Preparation of 2nd Layer Coating Solution 
153.0 g of a yellow coupler (ExY), 15.0 g of a dye image stabilizer 
(Cpd-1), 7.5 g of a dye image stabilizer (Cpd-2), and 16.0 g of a dye 
image stabilizer (Cpd-3) were dissolved in 180 cc of ethyl acetate, 25 g 
of a solvent (Solv-1) and 25 g of a solvent (Solv-2) to make a solution. 
The solution thus obtained was then emulsion-dispersed in 1,000 g of a 10% 
aqueous solution of gelatin containing 60 cc of sodium 
dodecylbenzenesulfonate and 10 g of citric acid to prepare Emulsion 
Dispersion A. 
Emulsion A was then mixed with Emulsion B101 to obtain a 2nd layer coating 
solution having the composition as set forth below. 
The coating solutions for the 3rd layer to the 8th layer were prepared in 
the same manner as the coating solution for the 2nd layer. As gelatin 
hardener for each layer there was used sodium salt of 
1-oxy-3,5-dichloro-s-triazine. 
The silver bromochloride emulsions to be incorporated in the various 
photographic light-sensitive emulsion layers comprised the same spectral 
sensitizing dyes as used in Example 1, respectively. 
In the blue-sensitive emulsion layer, the green-sensitive emulsion layer 
and the red-sensitive emulsion layer was incorporated 
1-(5-methylureidephenyl)-5-mercaptotetrazole in an amount of 
3.4.times.10.sup.-4 mol, 9.7.times.10.sup.-4 mol and 5.5.times.10.sup.-4 
mol per mol of silver halide, respectively. 
In the blue-sensitive emulsion layer and the green-sensitive emulsion layer 
was incorporated 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 
1.0.times.10.sup.-4 mol and 2.0.times.10.sup.-4 mol per mol of silver 
halide, respectively. For the purpose of inhibiting irradiation, to the 
emulsion layers were each added the following dyes (figures in the 
parenthesis indicate the coated amount): 
##STR104## 
Layer construction 
The formulations of the various layers are set forth below. The figures 
indicate the coated amount (g/m.sup.2). The coated amount of silver halide 
emulsion is represented as calculated in terms of silver. 
Support 
Polyethylene-laminated paper [containing a white pigment (TiO.sub.2) in 
polyethylene on the 1st layer side in an amount of 4 g/m.sup.2 ] 
______________________________________ 
1st layer (white pigment-containing 
hydrophilic colloidal layer) 
TiO.sub.2 2.50 
Gelatin 0.63 
2nd layer (blue-sensitive emulsion layer) 
Silver bromochloride emulsion B101 
0.27 
as set forth above 
Gelatin 1.36 
Yellow coupler (ExY) 0.79 
Dye image stabilizer (Cpd-1) 
0.08 
Dye image stabilizer (Cpd-2) 
0.04 
Dye image stabilizer (Cpd-3) 
0.08 
Solvent (Solv-1) 0.13 
Solvent (Solv-2) 0.13 
3rd layer (color stain inhibiting layer) 
Gelatin 0.99 
Color mixing inhibitor (Cpd-4) 
0.08 
Solvent (Solv-2) 0.25 
Solvent (Solv-3) 0.25 
4th layer (green-sensitive emulsion layer) 
Silver bromochloride emulsion (6:4 
0.13 
(Ag molar ratio) mixture of a large 
size emulsion of cubic grains having 
an average size of 0.55 .mu.m with a grain 
size distribution fluctuation coefficient 
of 0.10 and a small size emulsion of cubic 
grains having an average size of 0.39 .mu.m 
with a grain size distribution fluctuation 
coefficient of 0.08, 0.8 mol % of silver 
bromide being localized partially on the 
surface of each emulsion and a balance 
comprising silver chloride) 
Gelatin 1.45 
Magenta coupler (ExM) 0.16 
Dye image stabilizer (Cpd-5) 
0.15 
Dye image stabilizer (Cpd-2) 
0.03 
Dye image stabilizer (Cpd-6) 
0.01 
Dye image stabilizer (Cpd-7) 
0.01 
Dye image stabilizer (Cpd-8) 
0.08 
Solvent (Solv-3) 0.50 
Solvent (Solv-4) 0.15 
Solvent (Solv-5) 0.15 
5th layer (color mixing inhibiting layer) 
Gelatin 0.70 
Color stain inhibitor (Cpd-4) 
0.04 
Dye image stabilizer (Cpd-5') 
0.02 
Solvent (Solv-2) 0.18 
Solvent (Solv-3) 0.18 
6th layer (red-sensitive emulsion layer) 
Silver bromochloride emulsion 
0.20 
(Emulsion R 101 comprising cubic grains 
having an average grain size of 0.55 .mu.m 
and a grain size fluctuation coefficient 
of 0.10, 0.8 mol % of silver bromide being 
localized partially on the surface of each 
emulsion and a balance comprising silver 
chloride) 
Gelatin 0.85 
Cyan coupler (ExC') 0.33 
Ultraviolet absorbent (UV-2) 
0.18 
Dye image stabilizer (Cpd-1) 
0.33 
Dye image stabilizer (Cpd-9) 
0.15 
Dye image stabilizer (Cpd-10) 
0.15 
Dye image stabilizer (Cpd-11) 
0.01 
Dye image stabilizer (Cpd-8) 
0.01 
Dye image stabilizer (Cpd-7) 
0.01 
Solvent (Solv-6) 0.22 
Solvent (Solv-1) 0.01 
7th layer (ultraviolet absorbing layer) 
Gelatin 0.55 
Ultraviolet absorbent (UV-1) 
0.40 
Dye image stabilizer (Cpd-12) 
0.15 
Dye image stabilizer (Cpd-5) 
0.02 
8th layer (protective layer) 
Gelatin 1.13 
Acryl-modified copolymer of polyvinyl 
0.15 
alcohol (modification degree: 17%) 
Liquid paraffin 0.03 
Dye image stabilizer (Cpd-14) 
0.01 
______________________________________ 
The chemical structure of the compounds of ExC' and Cpd-5' will be given 
below. Other chemical structures of the compounds used in Example 4 are 
the same as those used in Example 1. 
##STR105## 
Further, Specimens 101 to 103 and 105 to 123 were prepared in the same 
manner as Specimen 104 except that they had configurations as set forth in 
Table D. The coated amount of the white pigment in the 1st layer was 
adjusted by adjusting the amount of the white pigment to be incorporated 
in the coating solution. The coated amount of gelatin was adjusted 
constant among the specimens. The addition of the compounds represented by 
the general formulae (I) to (IX) was adjusted such that the total amount 
of the various compounds as set forth in Table D in each layer was 
3.times.10.sup.-4 mol. 
In order to evaluate the sensitivity drop due to the bending of the 
photographic light-sensitive material, the specimen was placed parallel to 
the direction of gradient of light by the optical wedge and folded 
downward for 1 second so that an angle made by the face of the specimen 
opposite the silver halide emulsion layer is 45.degree., in which the 
silver halide emulsion layer faces upward. 
In order to observe the sensitivity drop during the storage in the form of 
photographic light-sensitive material, the specimen was stored at a 
temperature of 35.degree. C. for 1 month after coating and another batch 
of the specimen was stored at a temperature of -10.degree. C. for 1 month. 
These specimens were then subjected to gradient exposure through an optical 
wedge and a blue filter by means of a sensitometer (Type FWH available 
from Fuji Photo Film Co., Ltd.; color temperature of light source: 
3,200.degree. K.). These specimens were then subjected to color 
development in accordance with the following processing procedures. 
In order to evaluate the latent image stability after storage, the 
specimens which had been stored at a temperature of 35.degree. C. for 1 
month after coating were subjected to color development in accordance with 
the following processing procedures 1 minute and 1 hour after exposure. 
In order to evaluate the sharpness, a wedge was prepared having a striped 
pattern made by the repetition of a transparent portion (density: 0.05) 
and a black portion (corresponding to background; density: 1.0) with an 
equal interval, varying a number of the black line from 10 to 100 with a 
decade within a 5 mm width. The specimens were subjected to contact 
exposure through the wedge in such a manner that the density of the 
background was a neutral gray represented by a reflective density of 0.4. 
These specimens were then subjected to color development in accordance 
with the following processing procedures: 
______________________________________ 
Processing Tank 
step Temperature 
Time Replenisher* 
capacity 
______________________________________ 
Color 35.degree. C. 
45 sec. 125 ml 2 l 
development 
Blix 30-35.degree. C. 
45 sec. 215 ml 2 l 
Rinse 30.degree. C. 
90 sec. 350 1 l 
Drying 70-80.degree. C. 
60 sec. 
______________________________________ 
*per m.sup.2 of lightsensitive material 
The formulations of the various processing solutions were as follows: 
______________________________________ 
Running 
Solution Replenisher 
______________________________________ 
Color developer 
Water 800 ml 800 ml 
Ethylenediamine-N,N,N',N'- 
1.5 g 2.0 g 
tetramethylenephosphonic acid 
Potassium bromide 0.015 g -- 
Triethanolamine 8.0 g 12.0 g 
Sodium chloride 1.4 g -- 
Potassium carbonate 
25 g 25 g 
N-ethyl-N-(.beta.-methanesulfon- 
5.0 g 7.0 g 
amidoethyl)-3-methyl-4-amino- 
aniline sulfate 
N,N-bis(carboxymethyl)- 
4.0 g 5.0 g 
hydrazine 
N,N-di(sulfoethyl)hydroxyl- 
4.0 g 5.0 g 
amine.1Na 
Fluorescent brightening agent 
1.0 g 2.0 g 
(Whitex 4B produced by Sumitomo 
Chemical Co., Ltd.) 
Water to make 1,000 ml 1,000 ml 
pH (25.degree. C.) 10.05 10.45 
Blix solution (running solution was 
used as replenisher) 
Water 400 ml 
Ammonium thiosulfate (700 g/l) 
100 ml 
Sodium sulfite 17 g 
Ferric ammonium ethylenediamine- 
55 g 
tetraacetate 
Disodium ethylenediaminetetraacetate 
5 g 
Ammonium bromide 40 g 
Water to make 1,000 ml 
pH (25.degree. C.) 6.0 
______________________________________ 
Washing Solution (Running Solution was Used Also as Replenisher) 
Ion-exchanged water (calcium and magnesium concentrations: 3 ppm each) 
The processed specimens were measured for yellow reflective density on the 
unbent portion and the bent portion. A so-called characteristic curve was 
then obtained from the measurements. The sensitivity was represented by 
the logarithm of the exposure giving a higher density by 0.5 than the fog 
density. For the evaluation of sensitivity drop, the sensitivity of the 
unfolded portion was subtracted from that of the folded portion. The 
sensitivity drop value was increased by 100 times. The results are set 
forth in Table D. 
In order to evaluate the latent image stability after storage in the form 
of photographic light-sensitive material, the sensitivity of the specimen 
which had been processed 1 minute after exposure was subtracted from that 
of another batch of the specimen which had been processed 1 hour after 
exposure. The sensitivity drop value was increased by 100 times. The 
results are set forth in Table D. 
In order to evaluate the sensitivity drop after storage in the form of 
photographic light-sensitive material, the specimens which had been stored 
at a temperature of 35.degree. C. for 1 month after coating and another 
batch of the specimens which had been stored at a temperature of 
-10.degree. C. for 1 month after coating were measured for sensitivity. 
The sensitivity of the specimens which had been stored at a temperature of 
-10.degree. C. was subtracted from that of the specimens which had been 
stored at a temperature of 35.degree. C. The sensitivity drop value was 
then increased by 100 times. The results are set forth in Table D. 
In order to evaluate the sharpness, the specimens which had been processed 
for the evaluation of sharpness were examined by 20 examiners for the 
maximum visually recognizable number of striped patterns. These examined 
values were then averaged to obtain a representative value of sharpness. 
The results are set forth in Table D. 
TABLE D 
__________________________________________________________________________ 
Blue-sensitive 
silver halide emulsion Latent 
1st Layer Silver image 
white bromide Sensitivity 
Sensitivity 
stability 
pigment 
Added Chemical 
localized drop due 
drop after 
after 
Specimen 
content 
compound sensitization 
phase 
Sharpness 
to bending 
storage 
storage 
Remarks 
__________________________________________________________________________ 
101 15% -- B101 
sulfur none 71.5 -6 -4 .+-.0 Comparative 
102 20% -- B101 
sulfur none 78.5 -8 -6 .+-.0 Comparative 
103 40% -- B101 
sulfur none 80.5 -10 -7 -1 Comparative 
104 80% -- B101 
sulfur none 83.0 -31 -8 -1 Comparative 
105 90% -- B101 
sulfur none 84.5 -52 -9 -2 Comparative 
106 -- -- B102 
gold.sulfur 
none 68.0 -1 -2 -2 Comparative 
107 20% -- B102 
gold.sulfur 
none 78.5 -2 -8 -3 Comparative 
108 40% -- B102 
gold.sulfur 
none 80.5 -3 -10 - 3 Comparative 
109 80% -- B102 
gold.sulfur 
none 83.0 -5 -13 -4 Comparative 
110 90% -- B102 
gold.sulfur 
none 84.5 -6 -15 -4 Comparative 
111 80% A-37/A-39* 
B102 
gold.sulfur 
none 83.0 -5 -2 -1 Present 
Invention 
112 80% A-37/A-39 
B103 
gold.sulfur 
present 
83.0 -5 -2 -1 Present 
Invention 
113 80% A-37/A-39 
B104 
gold none 83.0 -5 -1 -1 Present 
Invention 
114 80% A-37/A-39 
B105 
gold present 
83.0 -5 -1 -1 Present 
Invention 
115 80% A-5 B102 
gold.sulfur 
none 83.0 -5 -4 -2 Present 
Invention 
116 80% A-7 B102 
gold.sulfur 
none 83.0 -5 -3 -2 Present 
Invention 
117 80% A-18 B102 
gold.sulfur 
none 83.0 -5 -4 -2 Present 
Invention 
118 80% A-24 B102 
gold.sulfur 
none 83.0 -5 -4 -2 Present 
Invention 
119 80% A-27 B102 
gold.sulfur 
none 83.0 -5 -3 -2 Present 
Invention 
120 80% A-37 B102 
gold.sulfur 
none 83.0 -5 -4 -1 Present 
Invention 
121 80% A-38 B102 
gold.sulfur 
none 83.0 -5 -4 -1 Present 
Invention 
122 80% A-40 B102 
gold.sulfur 
none 83.0 -5 -2 -1 Present 
Invention 
123 20% A-40 B102 
gold.sulfur 
none 78.5 -2 -1 -1 Present 
Invention 
__________________________________________________________________________ 
*1:1 (molar ratio) mixture 
Table D shows that if the 1st layer is free of white pigment or comprises a 
white pigment in an amount of less than 20%, it causes a small sensitivity 
drop due to folding but provides a disadvantageously low sharpness 
(Specimens 101, 106). The specimens comprising an emulsion which has not 
been subjected to chemical sensitization with a gold compound show a great 
sensitivity drop due to folding when the white pigment content is 
increased (Specimens 103, 104, 105). Further, the specimens which have 
been subjected to chemical sensitization with a gold compound but are free 
of the compound of the present invention show a remarkable sensitivity 
drop after storage (Specimens 107 to 110). In other words, a silver halide 
photographic material which exhibits a small sensitivity drop due to 
folding before exposure, a high sharpness and a small sensitivity drop 
after storage in the form of photographic light-sensitive material can be 
formed only when a silver halide emulsion sensitized with a gold compound 
is coated in such an amount that the white pigment content in the 1st 
layer is 20% or more, with the compound of the present invention being 
incorporated therein (Specimens 111 to 123). 
EXAMPLE 5 
A specimen was prepared in the same manner as in Example 4 except that the 
layers as set forth in Table E were provided between the 1st layer and the 
2nd layer. The specimen was evaluated in the same manner as in Example 4. 
The results thus obtained were similar to that of Example 4. The maximum 
value of sharpness was about 5% greater than that of Example 4. 
TABLE E 
______________________________________ 
Support side 
Colored layer 
Black colloidal silver 
0.10 
Gelatin 0.99 
Color mixing inhibitor (Cpd-5) 
0.08 
Solvent (Solv-l) 0.16 
Solvent (Solv-4) 0.08 
Color mixing-inhibiting layer 
Gelatin 0.99 
Color mixing inhibitor (Cpd-5) 
0.08 
Solvent (Solv-1) 0.16 
Solvent (Solv-4) 0.08 
Emulsion layer side 
______________________________________ 
EXAMPLE 6 
A specimen was prepared in the same manner as Specimen 111 of Example 4 
except that a gentamicine (1:1:1 (weight ratio) mixture of Gentamicine C1, 
Gentamicine C.sub.1a and Gentamicine C.sub.2) was incorporated in the 
system in an amount of 0.5 mg/m.sup.2 instead of A-37/A-39 mixture. The 
specimen thus obtained was then evaluated for sensitivity drop due to 
bending and sensitivity drop after storage in the same manner as in 
Example 4. The results thus obtained were as good as Specimen 111. In 
particular, it was confirmed that the sensitivity drop after storage can 
be further minimized. 
Accordingly, the present invention provides a photographic light-sensitive 
material which can be rapidly processed and exhibits a high sharpness, a 
small sensitivity drop on the portion which has been under force before 
exposure and a small sensitivity drop after storage in the form of 
photographic light-sensitive material. 
EXAMPLE 7 
Preparation of Large Size Silver Halide Emulsion B1 for Blue-sensitive 
Silver Halide Emulsion Layer 
To a 3% aqueous solution of a lime-treated gelatin were added 3.3 g of 
sodium chloride and 3.2 ml of a 1% aqueous solution of 
N,N'-dimethylimidazolidine-2-thione. To the aqueous solution were added an 
aqueous solution containing 0.5 mol of silver nitrate and an aqueous 
solution containing 0.5 mol of sodium chloride at a temperature of 
66.degree. C. with vigorous stirring. To the material were then added an 
aqueous solution containing 0.45 mol of silver nitrate and an aqueous 
solution containing 0.45 mol of sodium chloride and an aqueous solution 
containing 0.45 mol of sodium chloride at a temperature of 72.degree. C. 
with vigorous stirring. To the material was then added a copolymer of 
isobutene-maleic acid-1-sodium salt at a temperature of 40.degree. C. to 
make sedimentation. The material was then washed with water and desalted. 
90.0 g of lime-treated gelatin was then added to the material. To the 
emulsion was then added a fine emulsion of silver bromide grains having a 
size of 0.05 .mu.m in an amount of 0.0053 mol as calculated in terms of 
silver to form a silver bromide-rich phase on the surface of grains. A 
blue-sensitive sensitizing dye was then added to the emulsion in an amount 
of 2.times.10.sup.-4 mol/mol Ag. The emulsion was then subjected to 
optimum chemical sensitization with a sulfur sensitizer 
(triethylthiourea). Further, 1-(5-methylureidophenyl)-5mercaptotetrazole 
was added to the emulsion in an amount of 5.times.10.sup.-4 mol/mol Ag. 
Emulsion B.sub.1 thus obtained was then determined for the grain shape, 
grain size and grain size distribution from its electron microphotograph. 
The emulsion grains were cubic. The grain size was 0.88 .mu.m. The grain 
size fluctuation coefficient was 0.10. The grain size is represented by 
the average of diameter of circles having the same area as the projected 
area of grains. The grain size fluctuation coefficient is obtained by 
dividing the standard deviation of grain sizes by the average grain size. 
Emulsions having different grain sizes were prepared by altering the 
temperature at which silver halide grains are formed, the time at which 
the aqueous solution of silver nitrate and the aqueous solution of sodium 
chloride were added, and the amount of the finely divided silver bromide 
grains to be added. A blue-sensitive sensitizing dye, a red-sensitive 
sensitizing dye or a green-sensitive sensitizing dye was then added to 
these emulsions to obtain a blue-sensitive small size emulsion, a 
red-sensitive emulsion, and a green-sensitive emulsion which were used 
later. 
In the silver bromochloride emulsion to be incorporated in the various 
light-sensitive emulsion layers were the following spectral sensitizing 
dyes, respectively. 
##STR106## 
Further, the following compound was incorporated in an amount of 
2.6.times.10.sup.-3 mol per mol of silver halide. 
##STR107## 
A paper support laminated with polyethylene on both sides thereof was 
subjected to corona discharge on its surface. A gelatin undercoating layer 
containing sodium dodecylbenzenesulfonate was coated on the surface of the 
support. Various photographic constituent layers were further coated on 
the undercoating layer to prepare a multi-layer color photographic paper 
having the following layer configuration (Specimen 1). The coating 
solution used had been prepared as follows: 
Preparation of 1st Layer (White Pigment-containing Layer) Coating Solution 
To 1.0 kg of a 10% aqueous solution of gelatin were added 400 g of a rutile 
type titanium white pigment having an average grain size of 0.23 .mu.m 
(Titan White R780 available from Ishihara Sangyo K.K.) and 4 l of water. 
To the material was then added 8 cc of a 5% aqueous solution of sodium 
dodecylbenzenesulfonate as a dispersant. The material was then subjected 
to dispersion under irradiation with ultrasonic wave. 
Preparation of 2nd Layer Coating Solution 
153.0 g of a yellow coupler (ExY), 15.0 g of a dye image stabilizer 
(Cpd-1), 7.5 g of a dye image stabilizer (Cpd-2), and 16.0 g of a dye 
image stabilizer (Cpd-3) were dissolved in 180 cc of ethyl acetate, 25 g 
of a solvent (Solv-1) and 25 g of a solvent (Solv-2) to make a solution. 
The solution thus obtained was then emulsion-dispersed in 1,000 g of a 10% 
aqueous solution of gelatin containing 60 cc of sodium 
dodecylbenzenesulfonate and 10 g of citric acid to prepare Emulsified 
Dispersion A. 
On the other hand, a silver bromochloride emulsion was prepared in the same 
manner as mentioned above (6:4 (silver molar ratio) mixture of large size 
cubic grain emulsion B1 having an average grain size of 0.88 .mu.m and a 
grain size fluctuation coefficient of 0.10 and small size cubic grain 
emulsion having an average grain size of 0.70 .mu.m and a grain size 
fluctuation coefficient of 0.08, each emulsion comprising 0.53 mol % 
silver bromide localized on the grain surface). 
Emulsion A was then mixed with the silver bromochloride emulsion thus 
obtained to obtain a 2nd layer coating solution having the composition as 
set forth below. 
The coating solutions for the other layers were prepared in the same manner 
as the coating solution for the 2nd layer. 
As gelatin hardener for each layer there was used sodium salt of 
1-oxy-3,5-dichloro-s-triazine. 
In the various layers were each incorporated Cpd-15 and Cpd-16 in an amount 
of 25.0 mg/m.sup.2 and 50.0 mg/m.sup.2, respectively. 
In the blue-sensitive emulsion and the red-sensitive emulsion was 
incorporated 1-(5-methylureidophenyl)-5-mercaptotetrazole in an amount of 
9.7.times.10.sup.-4 mol and 5.5.times.10.sup.-4 mol per mol of silver 
halide, respectively. 
In the blue-sensitive emulsion layer and the green-sensitive emulsion layer 
was incorporated 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 
1.0.times.10.sup.-4 mol and 2.0.times.10.sup.-4 mol per mol of silver 
halide, respectively. 
For the purpose of inhibiting irradiation, to the emulsion layers were each 
added the following dyes (figures in the parenthesis indicate the coated 
amount): 
##STR108## 
Layer Construction 
The formulations of the various layers are set forth below. The figures 
indicate the coated amount (g/m.sup.2). The coated amount of silver halide 
emulsion is represented as calculated in terms of silver. 
Support 
Polyethylene-laminated paper 
______________________________________ 
1st layer (white pigment-containing hydrophilic 
colloidal layer) 
Gelatin 1.13 
Titanium oxide white pigment 
4.50 
(packing of white pigment: 80 wt %) 
2nd layer (blue-sensitive emulsion layer) 
Silver bromochloride emulsion (6:4 
0.27 
(Ag molar ratio) mixture of a large 
size emulsion B1 of cubic grains having 
an average size of 0.88 .mu.m with a grain 
size distribution fluctuation coefficient 
of 0.10 and a small size emulsion B2 of 
cubic grains having an average size of 
0.70 .mu.m with a grain size distribution 
fluctuation coefficient of 0.08, 0.53 mol % 
of silver bromide being localized partial- 
ly on the surface of each emulsion) 
Gelatin 1.36 
Yellow coupler (ExY) 0.79 
Dye image stabilizer (Cpd-1) 
0.08 
Dye image stabilizer (Cpd-2) 
0.04 
Dye image stabilizer (Cpd-3) 
0.08 
Solvent (Solv-1) 0.13 
Solvent (Solv-2) 0.13 
3rd layer (color stain inhibiting layer) 
Gelatin 0.99 
Color mixing inhibitor (Cpd-4) 
0.08 
Solvent (Solv-2) 0.25 
Solvent (Solv-3) 0.25 
4th layer (green-sensitive emulsion layer) 
Silver bromochloride emulsion (6:4 
0.13 
(Ag molar ratio) mixture of a large 
size emulsion G1 of cubic grains having 
an average size of 0.55 .mu.m with a grain 
size distribution fluctuation coefficient 
of 0.10 and a small size emulsion G2 of 
cubic grains having an average size of 
0.39 .mu.m with a grain size distribution 
fluctuation coefficient of 0.08, 0.8 mol % 
of silver bromide being localized partial- 
ly on the surface of each emulsion) 
Gelatin 1.45 
Magenta coupler (ExM) 0.16 
Dye image stabilizer (Cpd-5) 
0.15 
Dye image stabilizer (Cpd-2) 
0.03 
Dye image stabilizer (Cpd-6) 
0.01 
Dye image stabilizer (Cpd-7) 
0.01 
Dye image stabilizer (Cpd-8) 
0.08 
Solvent (Solv-3) 0.50 
Solvent (Solv-4) 0.15 
Solvent (Solv-5) 0.15 
5th layer (color stain inhibiting layer) 
Gelatin 0.70 
Color stain inhibitor (Cpd-4) 
0.04 
Dye image stabilizer (Cpd-5') 
0.02 
Solvent (Solv-2) 0.18 
Solvent (Solv-3) 0.18 
6th layer (red-sensitive emulsion layer) 
Silver bromochloride emulsion (7:3 
0.20 
(Ag molar ratio) mixture of a large 
size emulsion R1 of cubic grains having 
an average size of 0.50 .mu.m with a grain 
size distribution fluctuation coefficient 
of 0.08 and a small size emulsion R2 of 
cubic grains having an average size of 
0.45 .mu.m with a grain size distribution 
fluctuation coefficient of 0.11, 0.5 mol % 
of silver bromide being localized partial- 
ly on the surface of each emulsion) 
Gelatin 0.85 
Cyan coupler (ExC) 0.33 
Ultraviolet absorbent (UV-2) 
0.18 
Dye image stabilizer (Cpd-1) 
0.33 
Dye image stabilizer (Cpd-9) 
0.15 
Dye image stabilizer (Cpd-10) 
0.15 
Dye image stabilizer (Cpd-11) 
0.01 
Dye image stabilizer (Cpd-8) 
0.01 
Dye image stabilizer (Cpd-7) 
0.01 
Solvent (Solv-6) 0.22 
Solvent (Solv-1) 0.01 
7th layer (ultraviolet absorbing layer) 
Gelatin 0.55 
Ultraviolet absorbent (UV-1) 
0.40 
Dye image stabilizer (Cpd-12) 
0.15 
Dye image stabilizer (Cpd-5) 
0.02 
8th layer (protective layer) 
Gelatin 1.13 
Acryl-modified copolymer of polyvinyl 
0.15 
alcohol (modification degree: 17%) 
Liquid paraffin 0.03 
Dye image stabilizer (Cpd-13) 
0.01 
______________________________________ 
The chemical structure of the compound of Cpd-5' is given below. Chemical 
structures of other compounds are the same as those used in Example 1. 
Dye Image Stabilizer (Cpd-5') 
##STR109## 
Specimens 2 to 15 were then prepared in the same manner as Specimen 1 
except that the coated amount of titanium oxide and the film pH were 
altered as set forth in Table F. The density of titanium oxide was 80% by 
weight for Specimens 2 to 5, and 11 to 15 and 15% by weight for Specimens 
6 to 10. The film pH value was adjusted by adding a 1N aqueous solution of 
sulfuric acid or sodium hydroxide to the coating solutions for the 
protective layer and color mixing-inhibiting layer. The film Ag value was 
adjusted to 8.0 for all the specimens by adjusting the amount of the 
aqueous solution of sodium chloride to be incorporated in the 2nd layer 
coating solution. 
Further, Specimens 16 to 20 were prepared as comparative specimens in the 
same manner as Specimen 1 except that the 1st layer was not coated and the 
polyethylene laminate on the emulsion side of the support comprised a 
titanium oxide white pigment incorporated therein in an amount of 16% by 
weight such that the coated amount of titanium oxide was 4.5 g/m.sup.2. 
TABLE F 
______________________________________ 
Coated amount 
of TiO.sub.2 
Specimen No. 
Film pH (g/m.sup.2) TiO.sub.2 coating method 
______________________________________ 
(1) 5.0 4.5 Coated as 1st layer 
(2) 6.0 4.5 Coated as 1st layer 
(3) 6.5 4.5 Coated as 1st layer 
(4) 4.0 4.5 Coated as 1st layer 
(5) 7.0 4.5 Coated as 1st layer 
(6) 4.0 1.5 Coated as 1st layer 
(7) 5.0 1.5 Coated as 1st layer 
(8) 6.0 1.5 Coated as 1st layer 
(9) 6.5 1.5 Coated as 1st layer 
(10) 7.0 1.5 Coated as 1st layer 
(11) 4.0 2.5 Coated as 1st layer 
(12) 5.0 2.5 Coated as 1st layer 
(13) 6.0 2.5 Coated as 1st layer 
(14) 6.5 2.5 Coated as 1st layer 
(15) 7.0 2.5 Coated as 1st layer 
(16) 4.0 4.5 Incorporated in 
polyethylene 
laminate 
(17) 5.0 4.5 Incorporated in 
polyethylene 
laminate 
(18) 6.0 4.5 Incorporated in 
polyethylene 
laminate 
(19) 6.5 4.5 Incorporated in 
polyethylene 
laminate 
(20) 7.0 4.5 Incorporated in 
polyethylene 
laminate 
______________________________________ 
For the evaluation of dependence on exposure temperature, these specimens 
were stored at humidities of 35% and 85% (temperature: 25.degree. C.) for 
30 minutes, and then subjected to gradationwise exposure for sensitometry 
through blue, green and red filters by means of a sensitometer (FWH, 
available from Fuji Photo Film Co., Ltd.; color temperature of light 
source: 3,200.degree. K.) under the respective conditions. The exposure 
was conducted in such a manner that an exposure of 250 CMS was reached in 
0.1 second. The sensitivity of these specimens were then compared. For the 
evaluation of the degree of desensitization upon exposure under high 
humidity, the sensitivity after storage at a humidity of 35% (S30) was 
subtracted from that after storage at a humidity of 85% (S85) to obtain a 
difference (S85-S30). 
In order to evaluate the sensitivity change with the fluctuations of the 
time between the completion of exposure and the beginning of development, 
the specimens were exposed to light in the same manner as mentioned above, 
stored at a temperature of 25.degree. C. and a relative humidity of 55% 
for 2 hours, and then examined for sensitivity change from before to after 
storage. For the evaluation of sensitivity change after storage, the 
sensitivity before storage was subtracted from that after storage. 
For the evaluation of sensitivity, the logarithm of the reciprocal of the 
exposure at which the processed photographic light-sensitive material 
gives a density of 1.0 was used. 
For the evaluation of sharpness, CTF value was used. CTF represents the 
attenuation of the amplitude with respect to the spatial frequency in the 
form of rectangular wave. The sharpness was represented by the spatial 
frequency (line/mm) which gives 50% CTF value. The greater this value is, 
the higher is the sharpness. 
The specimens which had been exposed to light were processed with the 
following processing solutions in the following processing procedures by 
means of a paper processing machine. 
______________________________________ 
Processing Tank 
step Temperature 
Time Replenisher* 
capacity 
______________________________________ 
Color 35.degree. C. 
45 sec. 161 ml 17 l 
development 
Blix 30-35.degree. C. 
45 sec. 215 ml 17 l 
Rinse 35.degree. C. 
90 sec. 350 ml 10 l 
Drying 70-80.degree. C. 
60 sec. 
______________________________________ 
*The replenishment rate is represented per m.sup.2 of lightsensitive 
material. 
The various processing solutions had the following compositions: 
______________________________________ 
Running 
Solution Replenisher 
______________________________________ 
Color developer 
Water 800 ml 800 ml 
Ethylenediamine-N,N,N',N'- 
1.5 g 2.0 g 
tetramethylenephosphonic acid 
Potassium bromide 0.015 g -- 
Triethanolamine 8.0 g 12.0 g 
Sodium chloride 1.4 g -- 
Potassium carbonate 
25 g 25 g 
N-ethyl-N-(.beta.-methanesulfon- 
5.0 g 7.0 g 
amidoethyl)-3-methyl-4-amino- 
anilinesulfate 
N,N-bis(carboxymethyl)- 
4.0 g 5.0 g 
hydrazine 
N,N-di(sulfoethyl)- 
4.0 g 5.0 g 
hydroxylamine.1Na 
Fluorescent-brightening agent 
1.0 g 2.0 g 
(WHITEX 4B, available from 
Sumitomo Chemical Co., Ltd.) 
Water to make 1,000 ml 1,000 ml 
pH (25.degree. C.) 10.05 10.45 
Blix solution (running solution was used 
also as replenisher) 
Water 400 ml 
Ammonium thiosulfate (700 g/l) 
100 ml 
Sodium sulfite 17 g 
Ammonium ethylenediaminetetraacetate 
55 g 
(III) 
Disodium ethylenediaminetetraacetate 
5 g 
Ammonium bromide 40 g 
Water to make 1,000 ml 
pH (25.degree. C.) 6.0 
______________________________________ 
Rinse Solution (Running Solution was Used Also as Replenisher) 
Ion-exchanged water (calcium and magnesium concentration: 3 ppm or less 
each) 
The results are set forth in Table G. The results indicate the sensitivity 
change and CTF value of the blue-sensitive emulsion layer. 
TABLE G 
______________________________________ 
Sensitivity 
change when 
Desensitization stored for 2 
degree upon hours after 
exposure at until exposure 
CTF high humidity 
Sensitivity 
processing 
Specimen No. 
(B) (B) (B) (B) 
______________________________________ 
(1) 24.0 -0.02 1.00 +0.02 
(2) 24.0 -0.02 1.01 +0.02 
(3) 24.0 -0.03 1.01 +0.03 
(4) 24.0 -0.03 0.91 +0.03 
(5) 24.0 -0.10 1.02 +0.12 
(6) 16.0 -0.02 0.90 +0.02 
(7) 16.0 -0.02 1.01 +0.02 
(8) 16.0 -0.02 1.01 +0.02 
(9) 16.0 -0.02 1.01 +0.02 
(10) 16.0 -0.08 1.01 +0.08 
(11) 22.0 -0.02 0.89 +0.02 
(12) 22.0 -0.02 1.01 +0.02 
(13) 22.0 -0.02 1.02 +0.02 
(14) 22.0 -0.02 1.01 +0.02 
(15) 22.0 -0.09 1.02 +0.12 
(16) 15.0 -0.02 0.90 +0.02 
(17) 15.0 -0.02 1.01 +0.02 
(18) 15.0 -0.02 1.01 +0.02 
(19) 15.0 -0.02 1.00 +0.05 
(20) 15.0 -0.04 1.01 +0.05 
______________________________________ 
(Note) 
Specimens 1 to 3, and 12 to 14 are according to the present invention 
while the others are comparative. 
Table G shows that the sharpness can be remarkably enhanced by providing a 
hydrophilic colloidal layer containing a white pigment of the present 
invention. However, this also causes the specimens having a film pH value 
of 6.0 or more to exhibit a great desensitization upon exposure under high 
humidity conditions and a great sensitivity change with the fluctuations 
of the time between the completion of exposure and the beginning of 
processing. (See Specimens 5, 10, 15) 
When the film pH value is adjusted to 4.0 or less, the sensitivity of the 
various emulsion layers are lowered. (See Specimens 4, 6, 11) 
When the coated amount of the white pigment is relatively small, it is 
little disadvantageous in the problems of the present invention such as 
dependence of exposure on humidity and latent image stability but gives a 
low sharpness. (See Specimens 7 to 9) 
When a white pigment is incorporated in the polyethylene laminate on the 
emulsion layer side of the support, the effect of enhancing sharpness is 
low even if the coated amount of the white pigment is increased. (See 
Specimens 16 to 20) 
A color photographic light-sensitive material which exhibits a high 
sharpness, a small desensitization upon exposure under high humidity 
conditions and a small sensitivity change with the fluctuations of the 
time between the completion of exposure and the beginning of processing 
can be obtained only by adjusting the film pH value to the value specified 
herein. (See Specimens 1 to 3, and 12 to 14) 
EXAMPLE 8 
Coating solutions for the 2nd layer were prepared in the same manner as in 
that for Specimens 1 and 5 of Example 7 except that instead of forming a 
silver bromide-rich layer from finely divided silver bromide grains during 
the preparation of silver halide emulsions B1 and B2, an aqueous solution 
of potassium bromide was added to the system at the time as set forth in 
Table H to alter the halogen composition of the silver halide emulsion. 
Using these coating solutions, Specimens 21 to 32 were prepared. For these 
specimens, the pAg value was adjusted to 8.0 in the same manner as used in 
Example 7. These specimens were then evaluated in the same manner as in 
Example 7. The results are set forth in Table I. 
TABLE H 
______________________________________ 
Specimen 
Time at which KBr 
Added amount of 
Film 
No. was added KBr (mol/mol Ag) 
pH 
______________________________________ 
(1) -- -- 5.0 
(2) -- -- 7.0 
(21) -- -- 7.0 
(Neither added finely 
divided silver bromide 
grains) 
(22) After the formation of 
0.0053 7.0 
grains, 3 minutes before 
the addition of sulfur 
sensitizer 
(23) After the addition of sulfur 
0.0053 7.0 
sensitizer, 20 minutes 
during chemical sensiti- 
zation 
(24) After the addition of 
0.00040 7.0 
chemical sensitization 
stopping agent, during the 
preparation of coating 
solution 
(25) After the addition of 
0.0053 7.0 
chemical sensitization 
stopping agent, during the 
preparation of coating 
solution 
(26) When the formation of 
0.0053 7.0 
grains is finished by 80% 
by volume 
(27) -- -- 5.0 
(Neither added finely 
divided silver bromide 
grains) 
(28) After the formation of 
0.0053 5.0 
grains, 3 minutes before 
the addition of sulfur sensi- 
tizer 
(29) After the addition of sulfur 
0.0053 5.0 
sensitizer, 20 minutes 
during chemical sensiti- 
zation 
(30) After the addition of 
0.00040 5.0 
chemical sensitization 
stopping agent, during the 
preparation of coating 
solution 
(31) After the addition of 
0.0053 5.0 
chemical sensitization 
stopping agent, during the 
preparation of coating 
solution 
(32) When the formation of 
0.0053 7.0 
grains is finished by 80% 
by volume 
______________________________________ 
(Note) 
In this experiment, the chemical sensitization was suspended at the time 
of addition of 1(5-methyl-ureidophenyl)-5-mercaptotetrazole during the 
preparation of the emulsion. 
TABLE I 
______________________________________ 
Desensitization 
Sensitivity change when 
degree upon stored for 2 hours 
Specimen exposure at after exposure until 
No. CTF (B) high humidity (B) 
processing (B) 
______________________________________ 
(1) 24.0 -0.03 +0.02 
(5) 24.0 -0.10 +0.12 
(21) 24.0 -0.20 +0.10 
(22) 24.0 -0.15 +0.12 
(23) 24.0 -0.15 +0.12 
(24) 24.0 -0.19 +0.11 
(25) 24.0 -0.15 +0.12 
(26) 24.0 -0.14 +0.12 
(27) 24.0 -0.04 +0.02 
(28) 24.0 .+-.0 +0.02 
(29) 24.0 .+-.0 +0.02 
(30) 24.0 -0.05 +0.02 
(31) 24.0 .+-.0 +0.02 
(32) 24.0 -0.01 +0.02 
______________________________________ 
(Note) 
Specimens 1, and 27 to 32 are according to the present invention while th 
others are comparative. 
Table I shows that the addition of a water-soluble bromide provides a 
remarkable attainment of the effects of the present invention. 
This effect can be attained with a gold-sulfur sensitized emulsion. 
EXAMPLE 9 
Specimens 33 to 37 were prepared in the same manner as Specimen 12 of 
Example 7 except that the proportion of gelatin and titanium oxide in the 
1st layer were altered to obtain titanium oxide packings as set forth in 
Table E, respectively. The coated amount of titanium oxide was adjusted to 
2.5 g/m.sup.2 for all the specimens. These specimens were then evaluated 
for sharpness in the same manner as in Example 7. The results are set 
forth in Table J. 
TABLE J 
______________________________________ 
Coated amount 
TiO.sub.2 packing 
of TiO.sub.2 CFT 
Specimen No. 
(wt %) (g/m.sup.2) Film pH 
(B) 
______________________________________ 
(12) 80 2.5 5.0 22.0 
(33) 60 2.5 5.0 21.0 
(34) 40 2.5 5.0 21.0 
(35) 20 2.5 5.0 20.0 
(36) 15 2.5 5.0 14.0 
(37) 10 2.5 5.0 12.0 
______________________________________ 
Table J shows that the specimens comprising a hydrophilic colloidal layer 
having a white pigment packing of less than 20% by weight exhibit a poor 
sharpness. 
In accordance with the present invention, a photographic light-sensitive 
material can be obtained which can be rapidly processed and exhibits a 
high sharpness, a small sensitivity change with the change in the humidity 
upon exposure and a small sensitivity change with the fluctuations of the 
time interval between the completion of exposure and the beginning of 
processing. 
EXAMPLE 10 
Specimens 38 to 54 were prepared in the same manner as Specimens 1, 2, 4, 
5, 6, 8, and 10 of Example 7 except that the amount of the aqueous 
solution of sodium chloride to be added to the 2nd layer coating solution 
was altered to obtain film pAg values as set forth in Table K, 
respectively. 
TABLE K 
______________________________________ 
Coated amount 
Specimen 
Film Film of TiO.sub.2 
TiO.sub.2 coating 
No. pH pAq (g/m.sup.2) 
method 
______________________________________ 
(2) 6.0 8.0 4.5 Coated as 1st layer 
(38) 6.0 5.8 4.5 Coated as 1st layer 
(39) 6.0 10.2 4.5 Coated as 1st layer 
(4) 4.0 8.0 4.5 Coated as 1st layer 
(40) 4.0 5.8 4.5 Coated as 1st layer 
(41) 4.0 10.2 4.5 Coated as 1st layer 
(5) 7.0 8.0 4.5 Coated as 1st layer 
(42) 7.0 5.8 4.5 Coated as 1st layer 
(43) 7.0 10.2 4.5 Coated as 1st layer 
(6) 4.0 8.0 1.5 Coated as 1st layer 
(44) 4.0 5.8 1.5 Coated as 1st layer 
(45) 4.0 10.2 1.5 Coated as 1st layer 
(8) 6.0 8.0 1.5 Coated as 1st layer 
(46) 6.0 5.8 1.5 Coated as 1st layer 
(47) 6.0 10.2 1.5 Coated as 1st layer 
(10) 7.0 8.0 1.5 Coated as 1st layer 
(48) 7.0 5.8 1.5 Coated as 1st layer 
(49) 7.0 10.2 1.5 Coated as 1st layer 
(1) 5.0 8.0 4.5 Coated as 1st layer 
(50) 5.0 5.8 4.5 Coated as 1st layer 
(51) 5.0 10.2 4.5 Coated as 1st layer 
(52) 6.0 9.5 4.5 Coated as 1st layer 
(53) 6.0 7.5 4.5 Coated as 1st layer 
(54) 6.0 6.5 4.5 Coated as 1st layer 
______________________________________ 
These specimens were evaluated in the same manner as in Example 7. 
The results are set forth in Table L. 
TABLE L 
______________________________________ 
Sensitivity 
change when 
Desensitization stored for 2 
degree upon hours after 
exposure at exposure until 
Specimen 
CTF high humidity 
Sensitivity 
processing 
No. (B) (B) (B) (B) 
______________________________________ 
(2) 24.0 -0.02 1.01 +0.02 
(38) 24.0 -0.02 0.91 +0.02 
(39) 24.0 -0.10 1.02 +0.10 
(4) 24.0 -0.03 0.91 +0.03 
(40) 24.0 -0.02 0.82 +0.02 
(41) 24.0 -0.03 0.93 +0.03 
(5) 24.0 -0.10 1.02 +0.12 
(42) 24.0 -0.09 0.99 +0.11 
(43) 24.0 -0.11 1.02 +0.12 
(6) 16.0 -0.02 0.90 +0.02 
(44) 16.0 -0.02 0.82 +0.02 
(45) 16.0 -0.02 0.91 +0.02 
(8) 16.0 -0.02 1.01 +0.02 
(46) 16.0 -0.02 1.01 +0.02 
(47) 16.0 -0.02 1.02 +0.02 
(10) 16.0 -0.08 1.01 +0.08 
(48) 16.0 -0.03 0.98 +0.03 
(49) 16.0 -0.08 1.01 +0.08 
(1) 24.0 -0.02 1.00 +0.02 
(50) 24.0 -0.02 0.91 +0.10 
(51) 24.0 -0.10 1.02 +0.10 
(52) 24.0 -0.02 0.98 +0.02 
(53) 24.0 -0.02 1.02 +0.02 
(54) 24.0 -0.03 1.01 +0.03 
______________________________________ 
(Note) 
Specimens 1, 2, and 52 to 54 are according to the present invention while 
the others are comparative. 
Table L shows that even when the film pH value is as specified herein, the 
sensitivity shows a drop if the film pAg value falls below 6.0. When the 
film pAg value exceeds 10.0, it causes a great desensitization upon 
exposure under high humidity conditions and a great sensitivity change 
with the fluctuations of the time between the completion of exposure and 
the beginning of processing. 
These results show that the effects of the present invention become 
remarkable with photographic light-sensitive materials having a high 
sharpness. 
While the invention has been described in detail and with reference to 
specific embodiments 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.