Silver halide photographic material

A novel silver halide photographic material is provided, comprising a hydrophilic colloidal layer containing at least one dye represented by the following formula (I): ##STR1## wherein Y.sup.1 and Y.sup.2 each represents a chalcogen atom, --CH.dbd.CH--, --N(R.sup.10)--, or --C (R.sup.10)(R.sup.11)--, in which R.sup.10 and R.sup.11 each represents an alkyl group; Z.sup.1 and Z.sup.2 each represents a nonmetallic atom group necessary for forming a benzo condensed or naphtho condensed ring; R.sup.1 and R.sup.2 each represents an alkyl group; the plurality of L groups may be the same or different and each represents a methine group, with the proviso that at least one of the plurality of L groups represents a methine group substituted by --OR.sup.12, --N(R.sup.12)(R.sup.13), --SR.sup.12 or --CH(R.sup.14)(R.sup.15), in which R.sup.12 represents an alkyl or aryl group substituted by an acidic substituent, R.sup.13 represents a hydrogen atom or an alkyl or aryl group substituted by an acidic substituent, and R.sup.14 and R.sup.15 each represents a cyano group, a carboxylic acid group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, with the proviso that at least one of R.sup.14 and R.sup.15 contains an acidic substituent; X represents an anion; p represents an integer 0 or 1; r represents an integer 0 or 1; m represents an integer 2 or 3; and n represents an integer 1 or 2, with the proviso that when the dye forms an intramolecular salt, n is 1; and wherein the dye contains at least three acidic substituents.

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic material 
comprising a dyed hydrophilic colloidal layer. More particularly, the 
present invention relates to a silver halide photographic material 
comprising a hydrophilic colloidal layer containing a dye which exhibits 
absorption in the infrared region, is stable in photographic 
light-sensitive materials, exhibits a photochemical inertness and can 
easily be decolored in a photographic processing procedure. 
BACKGROUND OF THE INVENTION 
With silver halide photographic materials, it is a frequent practice to 
color the photographic emulsion layer or other layers for the purpose of 
absorbing light in a specific wavelength. 
When it is necessary to control the spectral composition of the light 
incident upon the photographic emulsion layer, a colored layer is provided 
on the side of the photographic emulsion layer on the photographic 
light-sensitive layer far from the support. Such a colored layer is called 
a filter layer. If a plurality of photographic emulsion layers are 
provided, as in a multi-layer color photographic light-sensitive material, 
such a filter layer may be provided between these photographic emulsion 
layers. 
For the purpose of inhibiting blur in the image caused by the reflection of 
light which has been scattered during or after the transmission through 
the photographic emulsion layer by the interface of the emulsion layer 
with the support or the surface of the photographic light-sensitive 
material opposite the emulsion layer and the subsequent re-entry of the 
light into the photographic emulsion layer, i.e., halation, a colored 
layer may be provided between the photographic emulsion layer and the 
support or the side of the support opposite the photographic emulsion 
layer. Such a colored layer is called an antihalation layer. In the case 
of a multi-layer color photographic light-sensitive material, such an 
antihalation layer may be provided between the various layers. 
In order to inhibit the drop of image sharpness due to the scattering of 
light in the photographic emulsion layer (generally referred to as 
"irradiation"), the photographic emulsion layer may be colored. 
Most of these layers to be colored comprise hydrophilic colloid. Therefore, 
these layers normally comprise a water-soluble dye incorporated therein in 
order to provide color. Such a dye needs to meet the following 
requirements: 
(1) to exhibit an appropriate spectral absorption depending on the purpose; 
(2) to be photochemically inert (i.e., to give no chemically adverse 
effects on the properties of the silver halide photographic material such 
as sensitivity drop, latent image regression and photographic fog); 
(3) to be insusceptible to decoloration or removal by dissolution in the 
photographic processing procedure which leaves a harmful color on the 
processed photographic light-sensitive material; and 
(4) to exhibit excellent stability over time in a solution or photographic 
light-sensitive material. 
As dyes meeting these requirements, many dyes which absorb visible light or 
ultraviolet rays are known. These dyes are suitable for the purpose of 
improving image quality in a conventional photographic element which has 
been sensitized to a wavelength range of 700 nm or less. In particular, 
triarylmethane and oxonol dyes are widely used in this connection. 
On the other hand, it has recently been desired to develop an antihalation 
and anti-irradiation dye which exhibits absorption in the infrared region 
for use in a photographic light-sensitive material which serves as a 
recording material sensitized to the infrared region such as a recording 
material for recording the output of a near infrared laser. 
One of the known methods for the exposure of such a photographic 
light-sensitive material is an image formation method by a so-called 
scanner process which comprises scanning an original image to provide an 
image signal according to which a silver halide photographic material is 
exposed to form a negative or positive image corresponding to the original 
image. In this method, the scanner process recording light source most 
preferably used is a semiconductor laser. The semiconductor laser is a 
small-sized and inexpensive laser that can be easily modulated. The 
semiconductor laser is also long-lived and emitts light in the infrared 
region as compared with a He-Ne laser and an argon laser. Therefore, when 
a photographic light-sensitive material sensitive to the infrared region 
is used, a brighter safelight can be used, which advantageously improves 
the handleability of the material. 
However, since there are no appropriate dyes which exhibit absorption in 
the infrared region and meet the foregoing requirements (1), (2), (3) and 
(4), especially (3) and (4), it is difficult to obtain an excellent 
photographic light-sensitive material which is highly sensitive to the 
infrared region and insusceptible to halation and irradiation. Thus, the 
properties of the excellent semiconductor laser cannot be made the best 
use of. 
Many efforts have heretofore been made to find a dye that meets the 
foregoing requirements. Many dyes have been proposed. 
For example, tricarbocyanine dyes are disclosed in JP-A-62-123454, 
JP-A-63-55544, JP-A-64-33547, and JP-A-3-171136 (The term "JP-A" as used 
herein means an "unexamined published Japanese patent application"), 
oxonol dyes are disclosed in JP-A-1-227148, melocyanine dyes are disclosed 
in JP-A-1-234844, tetraryl type polymethine dyes are disclosed in 
JP-A-2-216140, and indoaniline dyes are disclosed in JP-A-50-100116, 
JP-A-62-3250, and JP-A-2-259753. 
Nevertheless, it is difficult to find a dye that meets all the foregoing 
requirements. 
SUMMARY OF THE INVENTION 
It is therefore an object of the present invention to provide a dye that 
meets the foregoing requirements (1), (2), (3) and (4), and particularly 
to provide an infrared-sensitive silver halide photographic material which 
remains stable during storage and leaves little color after development. 
This and other objects of the present invention will become more apparent 
from the following detailed description and examples. 
The objects of the present invention are accomplished with a silver halide 
photographic material, comprising a support having thereon a hydrophilic 
colloidal layer containing at least one dye represented by the following 
formula (I): 
##STR2## 
wherein Y.sup.1 and Y.sup.2 each represents a chalcogen atom, 
--CH.dbd.CH--, --N(R.sup.10)--, or --C(R.sup.10)(R.sup.11)--; in which 
R.sup.10 and R.sup.11 each represents an alkyl group; 
Z.sup.1 and Z.sup.2 each represents a nonmetallic atom group 
necessary for forming a benzo condensed or naphtho condensed ring; 
R.sup.1 and R.sup.2 each represents an alkyl group; 
the plurality of L groups may be the same or different and each represents 
a methine group, with the proviso that at least one of the plurality of L 
groups represents a methine group substituted by --OR.sup.12, 
--N(R.sup.12)(R.sup.13), --SR.sup.12, or --CH(R.sup.14)(R.sup.15); in 
which R.sup.12 represents an alkyl or aryl group substituted by an acidic 
substituent, R.sup.13 represents a hydrogen atom or an alkyl or aryl group 
substituted by an acidic substituent, and R.sup.14 and R.sup.15 each 
represents a cyano group, a carboxylic acid group, an acyl group, an 
alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a 
sulfonyl group or a sulfamoyl group, with the proviso that at least one of 
R.sup.14 and R.sup.15 contains an acidic substituent; 
X represents an anion; 
p represents an integer 0 or 1; 
r represents an integer 0 or 1; 
m represents an integer 2 or 3; and 
n represents an integer 1 or 2, with the proviso that when the dye forms an 
intramolecular salt, n is 1; 
and wherein the dye contains at least three acidic substituents. 
DETAILED DESCRIPTION OF THE INVENTION 
Formula (I) will be further described hereinafter. Examples of the 
chalcogen atom represented by Y.sup.1 or Y.sup.2 include oxygen, sulfur, 
selenium, and tellurium. R.sup.10 and R.sup.11 may be the same or 
different and each represents a substituted or unsubstituted alkyl group, 
preferably an alkyl group having from 1 to 5 carbon atoms (E.g., methyl, 
ethyl, n-propyl, n-butyl, n-pentyl) which may contain substituents such as 
a sulfonic acid group, a carboxylic acid group and a hydroxyl group. 
R.sup.1 and R.sup.2 have the same meaning as the alkyl group as defined 
above for R.sup.10, preferably an alkyl group having from 1 to 5 carbon 
atoms substituted by a sulfonic acid or carboxylic acid group (e.g., 
3-sulfopropyl, 4-sulfobutyl, 2-carboxyethyl). 
The term "acidic substituent" as used herein means a "sulfonic acid group, 
carboxylic acid group or phosphonic acid group". The term "sulfonic acid 
group" as used herein means a "sulfo group or salt thereof". The term 
"carboxylic acid group" as used herein means a "carboxyl group or salt 
thereof". The term "phosphonic acid group" as used herein means a 
"phosphono group or salt thereof". Examples of these salts include salts 
of alkaline metal such as sodium and potassium, and organic ammonium salts 
such as ammonium salt, triethylammonium salt, tributylammonium salt, 
pyridinium salt, and tetrabutylammonium salt. 
The benzo condensed or naphtho condensed ring formed by nonmetallic atom 
groups represented by Z.sup.1 and Z.sup.2 may be substituted by a halogen 
atom (e.g., Cl, F, Br), a substituted amino group (e.g., dimethylamino, 
diethylamino, di(4-sulfobutyl)amino, di(2-carboxyethyl)amino), a hydroxyl 
group, a sulfonic acid group, a carboxylic acid group or a substituted or 
unsubstituted alkyl group having from 1 to 5 carbon atoms (e.g., methyl, 
ethyl, propyl (substituents are preferably a sulfonic acid group, a 
carboxylic acid group and a hydroxyl group)) which is connected to the 
ring directly or a divalent connecting group. Preferred examples of the 
divalent connecting group include --O--, --NHCO--, --NHSO.sub.2 --, 
--NHCO.sub.2 --, --NHCONH--, --COO--, --CO--, and --SO.sub.2 --. More 
preferably, the benzo condensed or naphtho condensed ring is substituted 
by a sulfonic acid or carboxylic acid group. 
The alkyl group represented by R.sup.12 as a substituent on the L groups 
represents an alkyl group having from 1 to 5 carbon atoms substituted by a 
sulfonic acid or carboxylic acid group (e.g., carboxymethyl, 
2-carboxyethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl). The aryl group 
represented by R.sup.12 is preferably a phenyl or naphthyl group which may 
be substituted by a sulfonic acid or carboxylic acid group, and which may 
be further substituted by an alkyl group (as defined above), a halogen 
atom (F, Cl, Br), a hydroxyl group or an amino group (which have the same 
meaning as the foregoing substituted amino group or may be substituted by 
an alkylcarbonyl or arylcarbonyl group as defined lager). 
The alkyl and aryl groups represented by R.sup.13 as substituents on the L 
groups have the same meaning as those defined with reference to R.sup.12. 
The acyl group represented by R.sup.14 or R.sup.15 as a substituent on the 
L groups contains the alkyl group defined with reference to R.sup.10 or 
the aryl group defined with reference to R.sup.12. 
The alkyl moiety in the alkoxycarbonyl group represented by R.sup.14 or 
R.sup.15 as a substituent on the L groups has the same meaning as the 
alkyl group represented by R.sup.10. The aryl moiety in the 
aryloxycarbonyl group represented by R.sup.14 or R.sup.15 has the same 
meaning as the aryl group represented by R.sup.12. 
The carbamoyl group, sulfonyl group or sulfamoyl group represented by 
R.sup.14 or R.sup.15 on the L groups may be substituted by the alkyl group 
as defined with reference to R.sup.10 or the aryl group as defined with 
reference to R.sup.12. 
At least one of R.sup.14 and R.sup.15 is substituted by an acidic 
substituent. Further, at least three acidic substituents are contained in 
the dye. 
Examples of anion represented by X include a halogen ion (e.g., Cl.sup.-, 
Br.sup.-, I.sup.-), a p-toluenesulfonic acid ion, an ethylsulfric acid 
ion, PF.sub.6.sup.-, BF.sub.4.sup.-, and ClO.sub.4.sup.-. 
Preferably, the dyes of formula (I) are represented by formula (II) below. 
Thus, the objects of the present invention are accomplished with a silver 
halide photographic material, comprising a hydrophilic colloidal layer 
containing at least one dye represented by the following formula (II): 
##STR3## 
wherein Z.sup.1 and Z.sup.2 each represents a nonmetallic atom group 
necessary for forming a benzo condensed or naphtho condensed ring; 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represents an 
alkyl group; the plurality of L groups may be the same or different and 
each represents a methine group, with the proviso that at least one of the 
plurality of L groups represents a methine group substituted by 
--OR.sup.12, --N(R.sup.12)(R.sup.13), --SR.sup.12, or 
--CH(R.sup.14)(R.sup.15); in which R.sup.12 represents an alkyl or aryl 
group substituted by an acidic substituent, R.sup.13 represents a hydrogen 
atom or an alkyl or aryl group substituted by an acidic substituent, and 
R.sup.14 and R.sup.15 each represents a cyano group, a carboxylic acid 
group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a 
carbamoyl group, a sulfonyl group or a sulfamoyl group, with the proviso 
that at least one of R.sup.14 and R.sup.15 contains an acidic substituent; 
X represents an anion; 
m represents an integer 2 or 3; and 
n represents an integer 1 or 2, with the proviso that when the dye forms an 
intramolecular salt, n is 1; 
and wherein the dye contains at least four acidic substituents. 
The various substituents in formula (II) have the same meaning as that 
defined in formula (I) . However, the alkyl group represented by R.sup.3 
to R.sup.6 has the same meaning as that defined with reference to 
R.sup.10. 
Preferably the dyes of formula (II) are represented by formula (III) below. 
Thus, the objects of the present invention is further accomplished with a 
silver halide photographic material, comprising a hydrophilic colloidal 
layer containing at least one dye represented by the following formula 
(III): 
##STR4## 
wherein Z.sup.1 and Z.sup.2 each represents a nonmetallic atom group 
necessary for forming a benzo condensed or naphtho condensed ring; 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represents an 
alkyl group; R.sup.7 and R.sup.9 each represents a hydrogen atom or a 
nonmetallic atom group necessary for forming a 5- or 6-membered ring by 
connecting to each other; 
R.sup.8 represents --OR.sup.12, --N(R.sup.12)(R.sup.13), --SR.sup.12, or 
--CH(R.sup.14)(R.sup.15); in which R.sup.12 represents an alkyl or aryl 
group substituted by an acidic substituent, R.sup.13 represents a hydrogen 
atom or an alkyl or aryl group substituted by an acidic substituent, and 
R.sup.14 and R.sup.15 each represents a cyano group, a carboxylic acid 
group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a 
carbamoyl group, a sulfonyl group or a sulfamoyl group, with the proviso 
that at least one of R.sup.14 and R.sup.15 contains an acidic substituent; 
X represents an anion; and 
n represents an integer 1 or 2, with the proviso that when the dye forms an 
intramolecular salt, n is 1; 
and wherein the dye contains at least four acidic substituents. 
The substituents in formula (III) have the same meaning as those defined in 
formula (II). 
Moreover, the objects of the present invention are accomplished with a 
silver halide photographic material as defined above, 
wherein R.sup.8 in formula (III) is --SR.sup.16, in which R.sup.16 
represents an alkyl or aryl group substituted by a sulfonic acid or 
carboxylic acid group, and R.sup.7 and R.sup.9 are connected to each other 
to form a 5- or 6-membered ring. 
The alkyl group and aryl group represented by R.sup.16 have the same 
meaning as that defined with reference to R.sup.12. 
Specific examples of the compound of the present invention are shown below, 
but the present invention should not be construed as being limited 
thereto: 
__________________________________________________________________________ 
##STR5## 
Compound No. 
R.sup.17 
__________________________________________________________________________ 
(1) SCH.sub.2 CO.sub.2 K 
(2) 
##STR6## 
(3) 
##STR7## 
(4) SCH.sub.2 CH.sub.2 CO.sub.2 K 
(5) SCH.sub.2 CH.sub.2 SO.sub.3 K 
(6) 
##STR8## 
__________________________________________________________________________ 
##STR9## 
Compound No. 
R.sup.17 
__________________________________________________________________________ 
(7) 
##STR10## 
(8) CH(CO.sub.2 K).sub.2 
(9) 
##STR11## 
(10) 
##STR12## 
(11) 
##STR13## 
(12) 
##STR14## 
(13) 
##STR15## 
(14) 
##STR16## 
(15) 
##STR17## 
(16) 
##STR18## 
(17) NHCH.sub.2 CH.sub.2 SO.sub.3 K 
(18) 
##STR19## 
(19) OCH.sub.2 CH.sub.2 SO.sub.3 K 
(20) 
##STR20## 
(21) 
##STR21## 
(22) 
##STR22## 
(23) OCH.sub.2 CO.sub.2 K 
__________________________________________________________________________ 
##STR23## 
Compound No. 
R.sup.17 
__________________________________________________________________________ 
(24) SCH.sub.2 CO.sub.2 K 
(25) 
##STR24## 
(26) 
##STR25## 
(27) 
##STR26## 
(28) 
##STR27## 
__________________________________________________________________________ 
##STR28## 
Compound No. 
R.sup.17 
__________________________________________________________________________ 
(29) SCH.sub.2 CO.sub.2 K 
(30) 
##STR29## 
(31) 
##STR30## 
(32) 
##STR31## 
(33) CH(CO.sub.2 K).sub.2 
(34) 
##STR32## 
__________________________________________________________________________ 
##STR33## 
Compound No. 
R.sup.17 
__________________________________________________________________________ 
(35) SCH.sub.2 CO.sub.2 K 
(36) 
##STR34## 
(37) NHCH.sub.2 CO.sub.2 K 
(38) 
##STR35## 
(39) SCH.sub.2 CH.sub.2 CO.sub.2 K 
__________________________________________________________________________ 
Compound (40) 
##STR36## 
Compound (41) 
##STR37## 
Compound (42) 
##STR38## 
Compound (43) 
##STR39## 
Compound (44) 
##STR40## 
Compound (45) 
##STR41## 
__________________________________________________________________________ 
##STR42## 
Compound No. 
Y.sup.3 
R.sup.18 
__________________________________________________________________________ 
(46) S SCH.sub.2 CO.sub.2 K 
(47) Te 
##STR43## 
(48) Se 
##STR44## 
(47) O SCH.sub.2 CO.sub.2 K 
(50) 
##STR45## 
##STR46## 
__________________________________________________________________________ 
Compound (51) 
##STR47## 
Compound (52) 
##STR48## 
Compound (53) 
##STR49## 
Compound (54) 
##STR50## 
__________________________________________________________________________ 
##STR51## 
Compound No. 
R.sup.19 q 
__________________________________________________________________________ 
(55) SCH.sub.2 CO.sub.2 K 
2 
(56) SCH.sub.2 CH.sub.2 CO.sub.2 K 
2 
(57) 
##STR52## 
2 
(58) SCH.sub.2 CH.sub.2 SO.sub.3 K 
3 
(59) 
##STR53## 
3 
(60) SCH.sub.2 CO.sub.2 K 
3 
__________________________________________________________________________ 
Examples of the synthesis of the dye of the present invention are given 
below. 
(Synthesis of Compound (1) of the present invention) 
3 g of Dye Compound (16) disclosed in EP-A-0430244 (corresponding to 
JP-A-3-171136) was dissolved in 15 ml of water. To the solution were added 
0.8 ml of triethylamine and 0.33 g of thioglycolic acid. The reaction 
mixture was then stirred at room temperature for 1 hour. After the 
completion of the reaction, the reaction product was filtered off, and 
then recrystallized from a mixture of methyl alcohol and potassium 
acetate. 
Yield: 0.9 g 
.lambda.max: 813.7 nm (H.sub.2 O) 
.epsilon.: 1.74.times.10.sup.5 
Dye Compound (16) disclosed in EP-A-0430244: 
##STR54## 
(Synthesis of Compound (20) of the present invention) 
1.3 g of Compound (20) was prepared in the same manner as mentioned above 
from 2 g of Dye Compound (16) disclosed in EP-A-0430244 (corresponding to 
JP-A-3-171136). 
.lambda.max: 782.0 nm (H.sub.2 O) 
.epsilon.: 2.01.times.10.sup.5 
Other dyes can be similarly synthesized. 
The dyes of formulae (I), (II) and (III) are incorporated preferably in a 
light-sensitive or light-insensitive hydrophilic colloidal layer coating 
solution in the form of a solution in an appropriate solvent (e.g., water, 
alcohol such as methanol and ethanol, methyl cellosolve, mixture thereof) 
or in the form of an aqueous decomposition product. Two or more of these 
dyes may be used in combination. 
The preferred amount of the foregoing dye to be used is generally from 
10.sup.3 g/m.sup.2 to 2.5 g/m.sup.2, preferably 10.sup.3 g/m.sup.2 to 1.0 
g/m.sup.2, of photographic material. 
The photographic dyes of formulae (I), (II) and (III) are effective for the 
purpose of inhibiting irradiation. If used for this purpose, these dyes 
are mainly incorporated in the emulsion layer. 
The photographic dyes of formulae (I), (II) and (III) are also effective 
for the purpose of inhibiting halation. If used for this purpose, these 
dyes are incorporated in the side of the support or between the support 
and the emulsion layer. 
The photographic dyes of formulae (I), (II) and (III) can also be 
advantageously used as filter dyes. 
In the present invention, the dyes represented by formulae (I), (II) and 
(III) are preferably used in combination with a binder. 
Examples of hydrophilic colloidal materials to be used as binders include 
gelatin, substitute for gelatin, collodion, gum arabic, cellulose ester 
derivatives such as alkylester of carboxylated cellulose, hydroxyethyl 
cellulose and carboxymethylhydroxyethyl cellulose, synthetic resins such 
as amphoteric polymers disclosed in U.S. Pat. No. 2,949,442, polyvinyl 
alcohol, and other materials known to those skilled in the art. 
Examples of alternative high molecular gelatins include a copolymer of 
acrylamine and methacrylic acid, a copolymer of allylamine and acrylic 
acid, a hydrolyzable copolymer of allylamine, methacrylic acid and vinyl 
acetate, a copolymer of allylamine, acrylic acid and styrene, and a 
copolymer of allylamine, methacrylic acid and acrylonitrile. 
The photographic light-sensitive material of the present invention may be 
in the form of a black-and-white photographic light-sensitive material as 
well as a color photographic light-sensitive material. 
The specific constitution of the present invention will be further 
described hereinafter. 
The halogen composition of the silver halide emulsion to be used in the 
present invention may be any of silver bromide, silver bromochloride, 
silver bromochloroiodide, and the like, provided that the silver chloride 
content is not more than 50 mol %. Preferably, it is a silver 
bromochloride having a silver chloride content of 50 mol % or less, 
preferably from 5 mol % to 40 mol %. 
This is because the fixability of the photographic light-sensitive material 
can be raised by increasing the silver chloride content, but the increase 
in the silver chloride content causes a sensitivity drop, as described in 
Japanese Patent Application No. 3-266934. 
The silver halide grains to be used in the present invention are preferably 
finely divided (e.g., preferably 0.7 .mu.m or less, more preferably 0.5 
.mu.m or less) 
The silver halide grains to be used in the present invention may be any of 
a cube, octahedron, tetradecahedron, tablet and sphere or mixture thereof, 
preferably cube, tetradecahedron or tablet. 
The preparation of silver halide grains to be used in the present invention 
can be accomplished by any suitable method disclosed in P. Glafkides, 
Chimie et Physique Photographique (published by Paul Montel, 1967), G. F. 
Duffin, Photographic Emulsion Chemistry (published by The Focal Press, 
1966), and V. L. Zelikman et al., Making and Coating Photographic 
Emulsion, (published by The Focal Press, 1964). 
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 the 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. 
In order to provide a uniform grain size, a method which comprises changing 
the rate at which a silver nitrate for halogenated alkali is added 
depending on the growth speed of grains as disclosed in British Patent 
1,535,016, and JP-B-48-36890 and JP-B-52-16364 or a method which comprises 
changing the concentration of an aqueous solution as disclosed in British 
Patent 4,242,445, and JP-A-55-158124 may be used to allow grains to grow 
rapidly within the critical saturation degree. 
The silver halide grains to be used in the present invention may have a 
so-called core/shell structure having a halogen composition differing from 
the inner portion to the surface layer. 
The formation of the silver halide emulsion of the present invention may be 
carried out in the presence of a silver halide solvent such as 
tetra-substituted thiourea and organic thioether compound. 
Preferred examples of tetra-substituted thiourea silver halide solvents 
which can be used in the present invention include those described in 
JP-A-53-82408 and JP-A-55-77737. 
Examples of organic thioether silver halide solvents which may preferably 
be used in the present invention include a compound containing at least 
one group, wherein an oxygen atom and a sulfur atom are separated by an 
ethylene group (e.g., --O--CH.sub.2 CH.sub.2 --S--) as disclosed in U.S. 
Pat. No. 3,574,628 (JP-B-47-11386), and a chain thioether compound 
containing an alkyl group (the alkyl group contains at least two 
substituents selected from hydroxyl group, amino group, carboxyl group, 
amide group and sulfon group) at both ends as disclosed in JP-A-54-155828 
(U.S. Pat. No. 4,276,374). 
The amount of silver halide solvent to be incorporated in the system 
depends on the kind of compounds used and the desired grain size and 
halogen composition and is preferably from 10.sup.-5 to 10.sup.-2 mol per 
mol of silver halide. 
If the grain size exceeds the desired value due to the use of a silver 
halide solvent, the desired grain size can be obtained by (1) altering the 
temperature at which the grains are formed, (2) changing the time at which 
a silver salt solution, and (3) adding a halogen salt solution to the 
system, and other factors. 
In the present invention, a water-soluble iridium compound can be used. 
Examples of such a water-soluble iridium compound include a halogenated 
iridium (III) compound, a halogenated iridium (IV) compound, and an 
iridium complex salt having a halogen, amine, oxalate or the like as a 
ligand (e.g., hexachloroiridium (III) or (IV) complex salt, 
hexamineiridium (III) or (IV) complex salt and trioxalate iridium (III) or 
(IV) complex salt). In the present invention, any trivalent compound and 
tetravalent compound among these compounds may be used in combination. 
These iridium compounds may be used in the form of a solution in water or 
other appropriate solvent. In order to stabilize the iridium compound 
solution, a commonly used method, i.e., a method which comprises the 
addition of an aqueous solution of hydrogen halide (e.g., hydrochloric 
acid, bromic acid, fluoric acid) or alkali halide (e.g., KCl, NaCl, KBr, 
NaBr) may be used. Instead of using such a water-soluble iridium, silver 
halide grains which have been previously doped with iridium may be added 
to and dissolved in the system during the preparation of the silver halide 
grains of the present invention. 
The total amount of iridium compounds of the present invention to be 
incorporated in the system is 10.sup.-8 mol or more, preferably 
1.times.10.sup.-8 to 1.times.10.sup.-5 mol, most preferably 
5.times.10.sup.-8 to 5.times.10.sup.-6 mol per mol of eventually produced 
silver halide. 
The addition of these compounds to the system may be properly effected at 
any step during the preparation of the silver halide emulsion and before 
the coating of the emulsion. In particular, these compounds are preferably 
added to the system during the formation of silver halide grains so that 
these compounds are incorporated in the silver halide grains. Further, a 
compound containing the group VIII atoms other than iridium and an iridium 
compound may be used in combination. 
The silver halide photographic emulsion of the present invention may be 
chemically sensitized with a gold compound (hereinafter referred to as 
"gold-sensitized") to attain high sensitivity and low photographic fog. 
The gold sensitization may be normally effected by stirring the emulsion 
with s gold sensitizer at a temperature of 40.degree. C. or higher for a 
predetermined period of time. 
As the gold sensitizer for the foregoind gold sensitization a gold compound 
commonly used as a gold sensitizer may be used. The oxidation number of 
such a gold sensitizer may be either +1 or +3. Typical examples of such a 
gold sensitizer include chloroauric acid, potassium chloroaurate, auric 
trichloride, potassium auric thiocyanate, potassium iodoaurate, 
tetracyanoauric acid, ammonium aurothiocyanate, and pyridyltrichlorogold. 
The amount of such a gold sensitizer to be added depends on the various 
conditions but is generally from 1.times.10.sup.-7 mol to 
5.times.10.sup.-4 mol per mol of silver halide. 
The silver halide photographic emulsion of the present invention may be 
subjected to chemical sensitization in combination with sulfur 
sensitization to further attain a high sensitivity and a low photographic 
fog. 
The sulfur sensitization may be normally effected by stirring the emulsion 
with a sulfur sensitizer at a temperature of 40.degree. C. or higher for a 
predetermined period of time. 
A known compound may be used as a sulfur sensitizer. Examples of such a 
sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, 
cystine, p-toluenethiosulfonate, and rhodanine. Besides these compounds, 
sulfur sensitizers disclosed in U.S. Pat. Nos. 1,574,944, 2,410,689, 
2,278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,422,869, 
JP-B-56-24937 (The term "JP-B" as used herein means an "examined Japanese 
patent publication"), and JP-A-55-45016 can be used. The amount of the 
sulfur sensitizer to be added only needs to be large enough to effectively 
increase the sensitivity of the emulsion. It greatly depends on various 
conditions such as pH, temperature and size of silver halide grains but is 
preferably from 1.times.10.sup.-7 mol to 5.times.10.sup.-4 mol per mol of 
silver halide. 
For the chemical ripening, it is not necessary to limit the time and order 
of the addition of sulfur sensitizer and gold sensitizer. For example, 
these compounds may be added simultaneously or at different times during 
the initial period of the chemical ripening (preferably) or during the 
progress of the chemical ripening. These compounds may be added to the 
system in the form of solution in water or an organic solvent miscible 
with water, such as methanol, ethanol and acetone, singly or in admixture. 
When sulfur sensitization with a thiosulfate, selenium sensitization with a 
selenium compound, and gold sensitization are effected in combination, the 
effects of the present invention can be effectively attained. 
The chemical sensitizer which can be effectively used in the present 
invention may be a selenium compound as disclosed in the prior art 
patents. An unstable selenium compound and/or stable selenium compound may 
be added to the system which is then stirred at a temperature of 
40.degree. C. or higher for a predetermined period of time. 
A preferred unstable selenium compound is a compound disclosed in 
JP-B-41-15748, and JP-B-43-13489, JP-A-4-25832, and JP-A-4-109240. 
Specific examples of such an unstable selenium compound include 
isoselenocyanates (e.g., aliphatic isoselenocyanates such as 
allylisoselenocyanate), selenoureas, selenoketones, selenoamides, 
selenocarboxylic acids (e.g., 2-selenopropionic acid, 2-selenobutyric 
acid), selenoesters, diacylselenides (e.g., 
bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, 
phosphineselenides, and colloidal metallic selenium. 
Preferred examples of unstable selenium compounds have been given above, 
but these examples are not restrictive. For the unstable selenium compound 
which serves as a sensitizer for photographic emulsion, its structure is 
not particularly important to those skilled in the art, provided that it 
is unstable. It is generally understood that the organic moiety of the 
selenium sensitizer molecule only serves to carry selenium and allow it to 
occur in the emulsion in an unstable form. In the present invention, 
unstable selenium compounds having such a wide function can be 
advantageously used. 
The stable selenium compound to be used in the present invention may be a 
compound disclosed in JP-B-46-4553, JP-B-52-34492, and JP-B-52-34491. 
Examples of such a stable selenium compound include selenious acid, 
potassium selenocyanide, selenazoles, quaternary salts of selenazoles, 
diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 
2-selenazolidine dione, 2-selenoxazolidine thione, and derivatives 
thereof. 
The sensitizing dye sensitive to 600 nm or higher which may preferably be 
used exhibits an optimum spectral sensitivity to He-Ne laser or 
semiconductor laser. Such sensitizing dyes preferably include a 
sensitizing dye disclosed in JP-A-3-15049, page 12, upper left column to 
page 21, lower left column; JP-A-3-20730, page 4, lower left column to 
page 15, lower left column; EP-A-420011, page 4, line 21 to page 6, line 
54; EP-A-420012, page 4, line 12 to page 10, line 33; EP-A-443466; U.S. 
Pat. No. 4,975,362; JP-A-2-157749, pp. 13-38; JP-A-3-171136, pp. 8-12; and 
JP-A-62-215272, pp. 22-38. Particularly preferred among these sensitizing 
dyes are dyes represented by formulae [I], [II] and [III] disclosed in 
JP-A-3-171136, pp. 8-12. However, if used singly, these sensitizing dyes 
cannot provide a sufficient spectral sensitizing efficiency. As the amount 
of such a sensitizing dye to be used is increased, the inherent 
desensitization tends to decrease. In order to cope with this difficulty, 
a supersensitizing agent may be used in combination with these sensitizing 
dyes as is well known in the art. Such a supersensitizing agent is 
disclosed in JP-B-60-45414, and JP-B-46-10473, and JP-A-59-192242. 
These sensitizing dyes may be used singly or in combination. Such a 
combination of sensitizing dyes is often used for the purpose of 
supersensitization. In combination with such a sensitizing dye, a dye 
which does not exhibit a spectral sensitizing effect itself or a substance 
which does not substantially absorb visible light and exhibits a 
supersensitizing effect may be incorporated in the emulsion. 
Examples of useful sensitizing dyes, combination of supersensitizing dyes 
and supersensitizing substances are described in Research Disclosure No. 
17643, vol. 176 (December 1978), JP-B-49-25500, JP-B-43-4933, 
JP-A-59-19032, and JP-A-59-192242. 
The optimum content of the sensitizing dye of the present invention having 
an absorption in the wavelength range of 600 nm or more may preferably be 
selected depending on the grain diameter, halogen composition and method 
and extent of chemical sensitization of silver halide emulsion, the 
relationship between the layer in which the compound of the present 
invention is incorporated and the silver halide emulsion, the kind of fog 
inhibiting compound used, etc. The testing method for the selection of the 
optimum value is well known by those skilled in the art. In general, the 
sensitizing dye of the present invention may preferably be used in amount 
an of 10.sup.-7 to 1.times.10.sup.-2 mol, more preferably 10.sup.-6 to 
5.times.10.sup.-3 mol, per mol of silver halide. 
Supersensitizing agents which may be used include compounds disclosed in 
JP-A-3-15049, pp. 22-25, and JP-A-62-123454, pp. 15-20. 
The light-sensitive material of the present invention may comprise various 
compounds for the purpose of inhibiting fogging during the preparation, 
storage or photographic processing of light-sensitive material or 
stabilizing photographic properties. In particular, many compounds known 
as fog inhibitors or stabilizers can be used. Examples of these fog 
inhibitors or stabilizers include azoles such as benzothiazolium salt, 
nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, 
mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, 
aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines, 
mercaptotriazoles, thioketo compounds such as oxazolinethione, azaindenes 
such as triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted 
(1,3,3a,7)tetrazaindenes), and pentaazaindenes, benzenethiosulfonic acid, 
benzenesulfinic acid, and benzenesulfonic amide. 
In particular, polyhydroxybenzene compounds may preferably be used to 
improve pressure resistance without impairing sensitivity. These 
polyhydroxybenzene compounds are preferably compounds having any of the 
following structures: 
##STR55## 
wherein X and Y each represents --H, --OH, a halogen atom, --OM (in which 
M represents an alkaline metal ion), an alkyl group, a phenyl group, an 
amino group, a carbonyl group, a sulfone group, a sulfonated phenyl group, 
a sulfonated alkyl group, a sulfonated amino group, a sulfonated carbonyl 
group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, 
a hydroxyphenyl group, a hydroxyalkyl group, an alkylether group, an 
alkylphenyl group, an alkylthioether group, or a phenylthioether group, 
preferably --H, --OH, --Cl, --Br, --COOH, --CH.sub.2 CH.sub.2 COOH, 
--CH.sub.3, --CH.sub.2 CH.sub.3 --CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, 
--OCH.sub.3, --CHO, --SO.sub.3 Na, --SO.sub.3 H, --SCH.sub.3, 
##STR56## 
X and Y may be the same or different. 
The polyhydroxybenzene compound may be incorporated in the emulsion layer 
or other layers in the photographic light-sensitive material. The 
effective amount of the polyhydroxybenzene compound to be incorporated is 
from 10.sup.-5 mol to 1 mol, more preferably from 10.sup.-3 mol to 
10.sup.-1 mol. 
The photographic light-sensitive material prepared according to the present 
invention may comprise a water-soluble dye incorporated in the hydrophilic 
colloidal layer as a filter dye or for the purpose of inhibiting 
irradiation or other various purposes. Examples of such a water-soluble 
dye include an oxonol dye, a hemioxonol dye, a styryl dye, a melocyanine 
dye, a cyanine dye, and an azo dye. Particularly useful among these 
water-soluble dyes are an oxonol dye, a hemioxonol dye, a cyanine dye, and 
a melocyanine dye. 
The photographic light-sensitive material of the present invention may 
comprise a developing agent such as polyalkylene oxide or ether, ester or 
amine derivative thereof, thioether compound, thiomorpholines, quaternary 
ammonium salts, urethane derivatives, urea derivatives, imidazole 
derivatives, 3-pyrazolidones and aminophenols incorporated in the 
photographic emulsion layer for the purpose of enhancing the sensitivity 
or contrast or accelerating development. 
In particular, 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone) are preferred. Such a 
developing agent is normally used in an amount of 5 g/m.sup.2 or less, 
preferably from 0.01 g/m.sup.2 to 0.2 g/m.sup.2. 
The photographic emulsion and light-insensitive hydrophilic colloid of the 
present invention may contain an inorganic or organic film hardener. For 
example, activated vinyl compounds (e.g., 
1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methylether, 
N,N-methylenebis-[.beta.-(vinylsulfonyl)propionamide]), activated halogen 
compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids 
(e.g., mucochloric acid), N-carbamoylpyridinium salts 
(1-morpholino(carbonyl-3-pyridinio)methanesulfonate), and haloamidinium 
salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 
2-naphthalenesulfonate) may be used singly or in combination. In 
particular, activated vinyl compounds as disclosed in JP-A-53-41220, 
JP-A-53-57257, JP-A-59-162546, and JP-A-60-80846 and activated halides as 
disclosed in U.S. Pat. No. 3,325,287 are preferred. 
The photographic emulsion layer or other hydrophilic colloidal layers in 
the light-sensitive material prepared according to the present invention 
may comprise various surface active agents for the purpose of facilitating 
coating, inhibiting electrification, emulsion dispersion and adhesion, and 
improving sliding properties and photographic properties (e.g., 
accelerating development, improving contrast, sensitization). 
Examples of such surface active agents nonionic surface active agents such 
as saponin (steroid series), alkylene oxide derivatives (e.g., 
polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, 
polyethylene glycol alkyl ether or polyethylene glycol alkylaryl ether, 
polyethylene glycol ester, polyethylene glycol sorbitan ester, 
polyalkylene glycol alkylamine or amide, polyethylene oxide addition 
product of silicone), glycidol derivatives (e.g., polyglyceride 
alkenylsuccinate, alkylphenol polyglyceride), aliphatic ester of 
polyvalent alcohol, or alkylester of saccharide; anionic surface active 
agents containing acid groups such as carboxyl group, sulfo group, phospho 
group, ester sulfate group or ester phosphate group (e.g., 
alkylcarboxylate, alkylsulfonate, alkylbenzenesulfonate, 
alkylnaphthalenesulfonate, alkylsulfuric ester, alkylphosphoric ester, 
N-acyl-N-alkyltaurine, sulfosuccinic ester, sulfoalkyl 
polyoxyethylenealkylphenylether, polyoxyethylenealkylphosphoric ester); 
amphoteric surface active agents such as amino acid salt, 
aminoalkylsulfonic acid, aminoalkylsufuric or phosphoric ester, 
alkylbetaine and amine oxide; and cationic surface active agents such as 
alkylamine salt, aliphatic or aromatic quaternary ammonium salt, 
heterocyclic quaternary ammonium salt (e.g., pyridinium, imidazolium), and 
aliphatic or heterocyclic group-containing phosphonium or sulfonium salt. 
For the purpose of antistatic treatment, a fluorine-containing surface 
active agent disclosed in JP-A-60-80849 may preferably be used. 
The photographic light-sensitive material of the present invention may 
comprise a matting agent such as silica, magnesium oxide and polymethyl 
methacrylate in the photographic emulsion layer or other hydrophilic 
colloidal layers for the purpose of inhibiting adhesion. 
The light-sensitive material to be used in the present invention may 
comprise a water-insoluble or slightly water-soluble synthetic polymer 
dispersion for the purpose of stabilizing dimension. For example, alkyl 
(meth)acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth)acrylate, and 
the like, may be used singly or in combination. Furthermore, a polymer 
comprising as a monomeric component a combination of these acrylic acids, 
methacrylic acids, and the like, may be used. 
As a condensation agent or a protective colloid for the photographic 
emulsion gelatin may be advantageously used. Other hydrophilic colloids 
can also be used. For example, proteins such as gelatin derivative, graft 
polymer of gelatin and other high molecular compounds, albumin and casein; 
cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl 
cellulose and cellulose sulfuric ester; saccharide derivatives such as 
sodium alginate and starch derivative; and various synthetic hydrophillic 
high molecular compounds such as single polymer and copolymer, e.g., 
polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl 
pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, 
polyvinyl imidazole, and polyvinyl pyrazole. 
As gelatin, a lime-treated gelatin as well as acid-treated gelatin, gelatin 
hydrolyzate and enzymatic decomposition product of gelatin can be used. 
The silver halide emulsion layer to be used in the present invention may 
comprise a polymer latex such as alkyl acrylate. 
The support for the photographic light-sensitive material of the present 
invention may be cellulose triacetate, cellulose diacetate, 
nitrocellulose, polystyrene, polyethylene terepthalate paper, 
baryta-coated paper, polyolefin-coated paper or the like. 
The developing agent to be incorporated in the developer of the present 
invention preferably contains dihydroxybenzenes or 3-pyrazolidones, more 
preferably hydroquinone, 1-phenyl-3-pyrazolidone or 
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, to provide high 
sensitivity. 
Examples of sulfites which can be used as preservatives in the present 
invention include sodium sulfite, potassium sulfite, lithium sulfite, 
ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium 
formaldehydebisulfite. Such a sulfite can preferably be used in an amount 
of 0.25 mol/l or more, more preferably 0.4 mol/l or more. The upper limit 
of the amount of such a sulfite to be used is preferably 2.5 mol/l, more 
preferably 1.2 mol/l. 
Examples of alkaline agents used to adjust a pH value include pH adjustors 
or buffers such as sodium hydroxide, potassium hydroxide and sodium 
carbonate. 
Other additives can include development inhibitors such as boric acid, 
borax, sodium bromide, potassium bromide and potassium iodide; organic 
solvents such as ethylene glycol, diethylene glycol, triethylene glycol, 
dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and 
methanol; and fog inhibitors or black pepper inhibitors such as mercapto 
compounds (e.g., 1-phenyl-5-mercaptotetrazole, sodium 
2-mercaptobenzimidazole-5-sulfonate ), indazole compounds (e.g., 
5-nitroindazole), and benztriazole compounds (e.g., 5-methylbenztriazole). 
There can be further contained color toners, surface active agents, 
antifoaming agents, film hardeners, and amino compounds disclosed in 
JP-A-56-106244 and JP-A-61-267759 and JP-A-2-208652. 
The developer of the present invention may comprise a compound disclosed in 
JP-A-56-24347 as a silver stain inhibitor, a compound disclosed in 
JP-A-62-212651 as an uneven development inhibitor, and a compound 
disclosed in JP-A-61-267759 as a dissolution aid. 
The developer to be used in the present invention may comprise boric acid 
disclosed in JP-A-62-186259 or saccharides (e.g., saccharose), oxims 
(e.g., acetoxim) or phenols (e.g., 5-sulfosalicylic acid) disclosed in 
JP-A-60-93433 as buffer. 
The processing method of the present invention may be effected in the 
presence of a polyalkylene oxide. In order to incorporate such a 
polyalkylene oxide in the developer, a polyethylene glycol having a mean 
molecular weight of 1,000 to 6,000 may preferably be used in an amount of 
0.1 g/l to 10 g/l. 
The fixing solution may contain a water-soluble aluminum compound as a film 
hardener in addition to a fixing agent. Further, the fixing solution may 
optionally contain an acidic aqueous solution containing acetic acid and a 
dibasic acid (e.g., tartaric acid, citric acid, a salt thereof), 
preferably having a pH value of 3.8 or more, more preferably from 4.0 
to6.5. 
As the fixing agent, sodium thiosulfate, ammonium thiosulfate or the like 
may be used. In order to improve fixing speed, ammonium thiosulfate is 
particularly preferred. The amount of the fixing agent to be used can be 
properly altered but is normally from 0.1 mol/l to 5 mol/l. 
The water-soluble aluminum salt which serves mainly as a film hardener in 
the fixing solution is a compound known as a film hardener for acidic 
film-hardening fixing solution, such as aluminum chloride, aluminum 
sulfate and potassium alum. 
As the dibasic acid, tartaric acid, citric acid or a derivative thereof, 
can be used singly or in combination. Such a compound may be effectively 
incorporated in an amount of 0.005 mol or more, preferably 0.01 mol to 
0.03 mol, per l of fixing solution. 
Specific examples of such a dibasic acid include tartaric acid, potassium 
tartrate, sodium tartrate, sodium potassium tartrate, ammonium tartrate, 
and potassium ammonium tartrate. 
Examples of useful citric acid or derivatives thereof in the present 
invention include citric acid, sodium citrate, and potassium citrate. 
The fixing solution may optionally further contain a preservative (e.g., 
sulfite, bisulfite), a pH buffer (e.g., acetic acid, boric acid), a pH 
adjustor (e.g., ammonia, sulfuric acid), an image preservability improver 
(e.g., potassium iodide), and a chelating agent. The pH buffer may be used 
in an amount of 10 g/l to 40 g/l, preferably 18 g/l to 25 g/l because the 
pH value of the developer is high. 
The washing water may contain a mildewproofing agent (e.g., compound as 
disclosed in Horiguchi, Bokin Bobai no Kagaku (Chemistry of Sterilization 
and Mildewproofing), and JP-A-62-115154), a washing accelerator (e.g., 
sulfite), a chelating agent, and the like. 
In accordance with the foregoing process, the photographic light-sensitive 
material which has been developed and fixed is then rinsed and dried. The 
rinsing is effected to remove substantially all of silver salts which have 
been dissolved by fixing. The rinsing is preferably effected at a 
temperature of 20.degree. C. to 50.degree. C. for 10 seconds to 3 minutes. 
The drying is effected at a temperature of 40.degree. C. to 100.degree. C. 
The drying time can be properly altered by the ambient conditions but is 
normally from 5 seconds to 3.5 minutes. 
A roller conveyor type automatic developing machine as described in U.S. 
Pat. Nos. 3,025,779 and 3,545,971 may be used to develop in the present 
invention. It is referred to as "roller conveyor type processor" herein. 
The roller conveyor type processor consists of four zones, i.e., 
development, fixing, rinsing and drying. The process used with the present 
invention does not exclude other procedures (e.g., stop) but most 
preferably follows the four procedures. 
The replenishment rate of the rinsing water may be 1,200 ml/m.sup.2 or less 
(including 0 ml/m.sup.2). 
The case where the replenishment rate of the rinsing water (or stabilizing 
solution) is 0 ml/m.sup.2 means a so-called reservoir rinsing process. As 
an approach for reducing the replenishment rate, there has long been known 
a multi-stage countercurrent process (e.g., 2-stage, 3-stage). 
In order to cope with problems caused when the replenishment rate of the 
rinsing water is small, the following approaches can be combined to 
provide excellent processing properties. 
The rinsing bath or stabilizing bath may further contain an isothiazoline 
compound disclosed in R. T. Kreiman, J. Image. Tech., vol. 10, No. 6, page 
242 (1984), Research Disclosure, vol. 205, No. 20526 (May, 1981) and Ibid, 
vol. 228, No. 22845 (April, 1983) or a compound disclosed in 
JP-A-61-115154 and JP-A-62-209532 as a microbiocide. Moreover, the rinsing 
bath or stabilizing bath may contain compounds disclosed in Hiroshi 
Horiguchi, Bokin Bobai no Kagaku (Chemistry of Sterilization and 
Mildewproofing), Sankyo Shuppan, 1982, Bokin Bobai Gijutsu Handbook 
(Handbook of Sterilization and Mildewproofing Techniques), Nihon Bokin 
Bobai Gakkai, (Hakuhodo, 1986), L. E. West, "Water Quality Criteria", 
Photo Sci & Eng., vol 9, No. 6 (1965), M. W. Beach, "Microbiological 
Growths in Motion Picture Processing", SMPTE Journal, vol. 85 (1976), and 
R. O. Deegan, "Photo Processing Wash Water Biocides", J. Imaging Tech., 
vol. 10, No. 6 (1984). 
In the process used with the present invention, if rinsing is conducted 
with a small amount of water, a washing tank with a squeeze roller or 
crossover roller as disclosed in JP-A-63-18350 and JP-A-62-287252 is 
preferably provided. 
Further, the overflow solution from the washing tank or stabilizing tank 
caused by the replenishment of mildewproofing water into the washing tank 
or stabilizing tank depending on the processing according to the present 
invention may be entirely or partially reused for a processing solution 
having a fixing capacity as its preceding processing step as described in 
JP-A-60-235133 and JP-A-63-129343. In order to inhibit uneven bubbling, 
which is readily caused when the rinse is effected with a small amount of 
water and/or inhibit the transfer of the processing components attached to 
the squeeze roller to the processed film, a water-soluble surface active 
agent or anti-foaming agent may be added. 
In order to inhibit the stain with a dye eluted from the photographic 
light-sensitive material, a dye adsorbent described in JP-A-63-163456 may 
be provided in the washing tank. 
The photographic light-sensitive material of the present invention can 
exhibit excellent adaptability to rapid processing by an automatic 
developing machine for a total processing time of from 15 seconds to 60 
seconds. 
In the rapid development process used with the present invention, the 
development and fixing temperature and time are from 25.degree. C. to 
50.degree. C. and 25 seconds or less, preferably from 30.degree. C. to 
40.degree. C. and from 4 seconds to 15 seconds, respectively. 
In the present invention, the photographic light-sensitive material which 
has been developed and fixed is then subjected to rinsing or 
stabilization. The rinsing may be effected in a 2-stage or 3-stage 
countercurrent rinsing process to save water. If the rinsing is effected 
with a small amount of washing water, a squeeze roller washing tank is 
preferably provided. The overflow liquid from the rinsing bath or 
stabilizing bath may be partially or entirely re-used as a fixing solution 
as described in JP-A-60-235133. This advantageously reduces the amount of 
waste liquid. 
In the present invention, the photographic light-sensitive material which 
has been developed, fixed and rinsed is then dried through a squeeze 
roller. The drying is effected at a temperature of 40.degree. C. to 
80.degree. C. for 4 seconds to 30 seconds. 
The "total processing time" as defined herein means a total time elapsed 
between the point at which the tip of the film enters the inlet of the 
automatic developing machine and the point at which it leaves the outlet 
of a drying zone via a developing bath, a connecting zone, a fixing bath, 
a connecting zone, a rinsing bath, and a connecting zone. 
The silver halide photographic material of the present invention can 
comprise a reduced amount of a gelatin as a binder in the emulsion layer 
and protective layer without causing pressure fog and thus can be 
developed without lowering developing speed, fixing speed and drying speed 
even in a rapid processing with a total processing time of 15 seconds to 
60 seconds. 
If the photographic light-sensitive material of the present invention is a 
color photographic light-sensitive material, it may preferably comprise 
cyan, magenta and yellow couplers disclosed in JP-A-2-285345, pp. 100-129. 
For coupler dispersants and coupler dispersion methods, reference can be 
made to JP-A-2-285345, pp. 129-132. For the processing of the color 
photographic light-sensitive material, reference can be made to 
JP-A-2-285345, from page 144, line 8 to page 168, line 11. For the 
scanning exposure light source, reference can be made to JP-A-2-285345, 
page 168, line 12 to page 170, line 9. For the layer configuration of the 
color photographic light-sensitive material, reference can be made to 
JP-A-2-285345, page 171, line 1 to page 172.

The present invention will be further described in the following examples, 
but the present invention should not be construed as being limited 
thereto. 
In the following examples, amounts are by weight unless otherwise 
indicated. 
EXAMPLE 1 
1. Preparation of silver halide emulsion 
34 g of gelatin was dissolved in 850 ml of water and kept at a temperature 
of 65.degree. C. To the solution were then added 1.7 g of sodium chloride, 
0.1 g of potassium bromide, and 70 mg of the following compound (A) as a 
silver halide solvent: 
EQU HO--(CH.sub.2).sub.2 --S--(CH.sub.2).sub.2 --S--(CH.sub.2).sub.2 --OH(A) 
To the solution were then added 500 ml of an aqueous solution containing 
170 g of silver nitrate and 500 ml of an aqueous solution containing 
potassium hexachloroiridiumate (III) in such an amount that the molar 
ratio of iridium to produced silver halide is 5.times.10.sup.-7, 12 g Of 
sodium chloride and 98 g of potassium bromide by a double jet process to 
prepare a monodisperse emulsion of cubic silver bromochloride grains 
having a mean grain size of 0.35 .mu.m. The emulsion was then desalted. 50 
g of gelatin was then added to the emulsion. The pH value and pAg value of 
the emulsion were then adjusted to 6.5 and 8.1, respectively. The emulsion 
was then subjected to chemical sensitization with 2.5 mg of sodium 
thiosulfate and 5 mg of chloroauric acid at a temperature of 65.degree. C. 
To the emulsion was then added 0.2 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. The emulsion was then rapidly 
cooled and solidified (Emulsion A). 
A monodisperse emulsion of cubic silver bromochloride grains having a mean 
grain size of 0.3 .mu.m was prepared in the same manner as Emulsion A 
except that the gelatin solution was heated to a temperature of 40.degree. 
C. The emulsion thus obtained was then desalted. To the emulsion was then 
added 50 g of gelatin. The pH value and pAg value of the emulsion were 
thus adjusted to 6.5 and 8.1, respectively. The emulsion was then 
subjected to chemical sensitization with 2.5 mg of sodium thiosulfate and 
5 mg of chloroauric acid at a temperature of 65.degree. C. To the emulsion 
was then added 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. The 
emulsion was then rapidly cooled and solidified to prepare Emulsion B. 
2. Preparation of emulsion coating solution 
Emulsion (A) and Emulsion (B) were mixed in a weight ratio of 1:1. To the 
mixture were then added the following additives (figure indicates amount 
added per mol of silver halide): 
______________________________________ 
(Formulation of emulsion coating solution) 
a. Spectral sensitizing dye [2] 
1.0 .times. 10.sup.-4 
mol 
b. Supersensitizer [3] 0.7 .times. 10.sup.-3 
mol 
c. Preservability improver [4] 
1 .times. 10.sup.-3 
mol 
d. Polyacrylamide (molecular amount: 
7.5 g 
40,000) 
e. Dextran 7.5 g 
f. Trimethylolpropan 1.6 g 
g. Sodium polystyrenesulfonate 
1.2 g 
h. Latex of poly(ethyl acrylate/ 
12 g 
methacrylic acid) 
i. N,N'-ethylenebis- 3.0 g 
(vinylsulfonacetamide) 
j. 1-Phenyl-5-mercapto-tetrazole 
50 mg 
Spectral sensitizing dye [2] 
##STR57## 
Supersensitizer [3] 
##STR58## 
Preservability improver [4] 
##STR59## 
______________________________________ 
3. Preparation of coating solution for surface protective layer for 
emulsion layer 
A vessel was heated to a temperature of 40.degree. C. Additives having the 
following formulations were then added to the system to prepare a coating 
solution. 
______________________________________ 
(Formulation of coating solution for surface protective 
layer for emulsion layer) 
a. Gelatin 100 g 
b. Polyacrylamide (molecular weight: 
12 g 
40,000) 
c. Sodium polystyrenesulfonate 
0.6 g 
(molecular weight: 600,000) 
d. N,N'-ethylenebis- 2.2 g 
(vinylsulfonacetamide) 
e. Finely divided polymethyl 2.7 g 
methacrylate grains (mean grain 
size: 2.0 .mu.m) 
f. Sodium t-octylphenoxyethoxy- 
1.8 g 
ethanesulfonate 
g. C.sub.16 H.sub.33 O(CH.sub.2 CH.sub.2 O).sub.10 H 
4.0 g 
h. Sodium polyacrylate 6.0 g 
i. C.sub.8 F.sub.17 SO.sub.3 K 
70 mg 
j. C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)(CH.sub.2 CH.sub.2 
O).sub.4 (CH.sub.2).sub.4 SO.sub.3 Na 
70 mg 
k. NaOH(1N) 6 ml 
l. Methanol 90 ml 
m. Compound [5] 0.06 g 
##STR60## 
______________________________________ 
4. Preparation of coating solution for backing layer 
A vessel was heated to a temperature of 40.degree. C. Additives having the 
following formulations were then added to the System to prepare a coating 
solution for back layer. 
__________________________________________________________________________ 
(Formulation of coating solution for back layer) 
a. Gelatin 100 g 
b. Dye [A] 4.2 g 
c. Sodium polystyrenesulfonate 
1.2 g 
d. Latex of poly(ethyl acrylate/methacrylic acid) 
5 g 
e. N,N'-ethylenebis- 4.8 g 
(vinylsulfonacetamide) 
f. Compound [5] 0.06 g 
g. Dye [B] 0.3 g 
h. Dye [C] 0.05 g 
i. Colloidal silica 15 g 
Dye [A] 
##STR61## 
Dye [B] 
##STR62## 
Dye [C] 
##STR63## 
__________________________________________________________________________ 
5. Preparation of coating solution for surface protective layer on back 
layer 
A vessel was heated to a temperature of 40.degree. C. Additives having the 
following formulations were then added to the system to prepare a coating 
solution. 
(Formulation of coating solution for surface protective layer on back 
layer) 
______________________________________ 
a. Gelatin 100 g 
b. Sodium polystyrenesulfonate 
0.5 g 
c. N,N'-ethylenebis- 1.9 g 
(vinylsulfonacetamide) 
d. Finely divided polymethyl- 
4 g 
methacrylate grains 
(average grain size: 4.0 .mu.m) 
e. Sodium t-octylphenoxyethoxy- 
2.0 g 
ethanesulfonate 
f. NaOH (1N) 6 ml 
g. Sodium polyacrylate 2.4 g 
h. C.sub.16 H.sub.33 O--(CH.sub.2 CH.sub.2 O).sub.10 --H 
4.0 g 
i. C.sub.8 F.sub.17 SO.sub.3 K 
70 mg 
j. C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)(CH.sub.2 CH.sub.2 
O).sub.4 (CH.sub.2).sub.4 -- 
70 mg 
SO.sub.3 Na 
k. Methanol 150 ml 
l. Compound [5] 0.06 g 
______________________________________ 
6. Preparation of photographic light-sensitive material 
(Photographic Light-sensitive Material Specimen 1) 
The aforementioned backing layer coating solution was coated on one side of 
a polyethylene terephthalate support along with the coating solution for 
surface protective layer for backing layer in such an amount that the 
total coated amount of gelatin reached 3.0 g/m.sup.2. Subsequently, the 
aforementioned emulsion coating solution and surface protective layer 
coating solution were coated on the other side of the support in an amount 
such that the total coated amount of silver and the coated amount of 
gelatin in the surface protective layer reached 2.3 g/m.sup.2 and 1.0 
g/m.sup.2, respectively. 
Further, Photographic Light-sensitive Material Specimens 2 to 9 were 
prepared in the same manner as Specimen 1 except that Dye [A] was replaced 
by Comparative Dyes [D] and [E] and Dyes (1), (3), (4), (24), (34) and 
(58) of the present invention, respectively, in the same amount. 
##STR64## 
7. Evaluation of storage stability 
The thus obtained photographic light-sensitive material specimens as set 
forth in Table 1 were allowed to stand at a temperature of 50.degree. C. 
and a relative humidity of 70% for 5 days. These specimens were then 
measured for reflection spectrum from which the percentage absorbance 
change of each dye at the absorbance maxima wavelength (absorbance after 
storage at 50.degree. C. and 70% RH/absorbance before storage at 
50.degree. C. and 70% RH) was determined. The results are set forth in 
Table 1. 
8. Evaluation of decolorability 
The photographic light-sensitive material specimens as set forth in Table 1 
were processed for image formation and then measured for reflection 
spectrum on the white background. The absorbance at the absorption maxima 
before and after the image formation processing for each dye was compared 
to determine the percentage color remaining of the dye. The results are 
set forth in Table 1. 
The photographic light-sensitive material specimens 1 to 9 were allowed to 
stand at a temperature of 25.degree. C. and a relative humidity of 60% for 
7 days after coating, subjected to scanning exposure by means of a 830 nm 
semiconductor laser at room temperature for 10.sup.-7 seconds, and then 
developed with the following developer [I] and fixing solution [I] by 
means of a roller conveyor type automatic developing machine. The 
development time was 7 seconds, the fixing time was 7 seconds, the rinsing 
time was 4 seconds, and the dehydration/drying time was 11 seconds. The 
conveying speed was 3,000 mm/min. 
______________________________________ 
Formulation of Developer [I] 
Potassium hydroxide 29 g 
Sodium sulfite 31 g 
Potassium sulfite 44 g 
Ethylenetriaminetetraacetic acid 
1.7 g 
Boric acid 1 g 
Hydroquinone 30 g 
Diethylene glycol 29 g 
1-Phenyl-3-pyrazolidone 1.5 g 
Glutaraldehyde 4.9 g 
5-Methylbenzotriazole 60 mg 
5-Nitroindazole 0.25 g 
Potassium bromide 7.9 g 
Acetic acid 18 g 
Water to make 1,000 ml 
pH 10.3 
Formulation of Fixing Solution [I] 
Ammonium thiosulfate 140 g 
Sodium sulfite 15 g 
Disodium ethylenediaminetetraacetate 
20 mg 
dihydrate 
Sodium hydroxide 7 g 
Aluminum sulfate 10 g 
Boric acid 10 g 
Sulfuric acid 3.9 g 
Acetic acid 15 g 
Water to make 1,000 ml 
pH 4.30 
______________________________________ 
The results are set forth in Table 1. 
TABLE 1 
______________________________________ 
Photographic Color 
light-sensitive Dye remaining 
remaining 
material Dye (%) (%) Remarks 
______________________________________ 
1 [A] 65.0 2.8 Comparison 
2 [D] 75.0 4.2 Comparison 
3 [E] 76.0 5.3 Comparison 
4 (1) 82.0 2.2 Invention 
5 (3) 83.0 2.2 Invention 
6 (4) 85.3 2.3 Invention 
7 (24) 98.0 2.3 Invention 
8 (55) 82.7 2.0 Invention 
9 (58) 94.7 1.8 Invention 
______________________________________ 
The results set forth in Table 1 show that the dyes of the present 
invention have excellent stability and exhibit little residual color. 
Thus, it can be seen that the photographic light-sensitive material of the 
present invention exhibit an excellent storage stability as well as little 
color remaining after image formation processing. 
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.