Method of manufacturing silver halide emulsion

A method of manufacturing a silver halide emulsion, wherein reduction sensitization is performed by using at least one of ascorbic acid and derivatives thereof in a process of manufacturing a silver halide emulsion. The invention is further directed to a of manufacturing a silver halide emulsion, wherein reduction sensitization is performed by using at least one of ascorbic acid and derivatives thereof during precipitation of silver halide grains.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a method of manufacturing a silver halide 
photographic emulsion for providing a light-sensitive material with high 
sensitivity and low fogging density. The present invention also relates to 
a method of manufacturing a silver halide photographic emulsion for 
providing a light-sensitive material whose sensitivity and fogging density 
do not vary much upon storage. 
2. Description of the Related Art 
Basic properties required for a photographic silver halide emulsion are 
high sensitivity, low fogging density, and fine graininess. 
In order to increase the sensitivity of an emulsion, (1) to increase the 
number of photons absorbed by a single grain, (2) to increase the 
efficiency of converting photoelectrons generated by light absorption into 
a silver cluster (latent image), and (3) to increase development activity 
for effectively utilizing the obtained latent image, are required. 
Increasing the size increases the number of photons absorbed by a single 
grain but degrades image quality. Increasing the development activity is 
an effective means of increasing sensitivity. In the case of parallel 
development such as color development, however, the graininess is 
generally degraded. In order to increase the sensitivity without degrading 
graininess, it is most preferable to increase the efficiency of converting 
photoelectrons into a latent image, i.e., increase a quantum efficiency. 
In order to increase the quantum efficiency, a low-efficiency process such 
as recombination and latent image dispersion must be minimized. It is 
known that a reduction sensitization method of forming a small silver 
nucleus without development activity inside or on the surface of a silver 
halide is effective to prevent recombination. 
The method of reduction sensitization has been studied for a long time. 
Carroll, Lowe et al., and Fallens et al. disclose that a tin compound, a 
polyamine compound, and a thiourea dioxide-based compound are effective as 
a reduction sensitizer in U.S. Pat. Nos. 2,487,850 and 2,512,925 and 
British Patent 789,823, respectively. Collier compares properties of 
silver nuclei formed by various reduction sensitization methods in 
"Photographic Science and Engineering", Vol. 23, P. 113 (1979). Collier 
adopted methods of dimethylamineborane, stannous chloride, hydrazine, 
high-pH ripening, and low-pAg ripening. Reduction sensitization methods 
are also disclosed in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 
3,779,777, and 3,930,867. Not only selection of a reduction sensitizer but 
also improvements in a reduction sensitization method are described in 
JP-B-57-33572 and JP-B-58-1410 ("JP-B-" means examined Japanese patent 
application). In these disclosures, conventional reduction sensitizers are 
enumerated, and ascorbic acid is included therein. In these disclosures, 
however, a compound such as thiourea dioxide is considered to be 
preferable, and thiourea dioxide, silver ripening, and hydrazine are 
exemplified. Therefore, preferable properties of an ascorbic acid compound 
as a reduction sensitizer have not been yet found. Improvements are also 
disclosed in JP-A-57-179835 ("JP-A-" means unexamined published Japanese 
patent application). 
In order to realize reduction sensitization, a problem of storage stability 
must be solved. Techniques of improving storage stability of an emulsion 
subjected to reduction sensitization are disclosed in JP-A-57-82831 and 
JP-A-60-178445, but improvements have not reached a sufficient level. 
Regardless of a number of studies as described above, an increase in 
sensitivity is insufficient as compared with that obtained in hydrogen 
sensitization in which a light sensitive material is treated with hydrogen 
gas in a vacuum. This is reported by Moisar et al. in "Journal of Imaging 
Science", Vol. 29, P. 233 (1985). A demand has arisen for also improving 
in storage stability of a light-sensitive material containing a 
reduction-sensitized emulsion. 
The conventional techniques of reduction sensitization do not satisfy a 
recent demand for high sensitivity and high image quality of a 
photographic light-sensitive material. This is because, firstly, 
variations in sensitivity and fogging density are large when a 
light-sensitive material containing an emulsion subjected to reduction 
sensitization is stored. Secondly, an increase in sensitivity obtained by 
reduction sensitization is insufficient. 
SUMMARY OF THE INVENTION 
It is a first object of the present invention to provide a method of 
manufacturing an emulsion for providing a light-sensitive material with 
high sensitivity and low fogging density and, more particularly, to 
provide a method of manufacturing a light-sensitive material whose 
sensitivity and fogging density do not vary much upon storage and which 
has high sensitivity. 
It is a second object of the present invention to provide a color 
light-sensitive material, especially, a color photographic light-sensitive 
material with high sensitivity and low fogging density in which a 
performance variation is small upon storage. 
It is a third object of the present invention to provide a silver halide 
color photographic light-sensitive material having good graininess and 
sharpness and improved response to external pressure while maintaining 
high sensitivity. 
The above objects of the present invention are achieved by: 
(1) a silver halide color photographic light-sensitive material, wherein at 
least 50% of a total projected area of all silver halide grains in one 
emulsion layer containing silver halide grains reduction-sensitized by an 
ascorbic acid or at least one of the derivatives thereof are occupied by 
tabular silver halide grains having an average aspect ratio of not less 
than 3.0; and 
(2) a silver halide color photographic light-sensitive material, wherein at 
least 50% of a total projected surface area of all silver halide grains in 
one emulsion layer containing silver halide grains reduction-sensitized by 
an ascorbic acid or at least one of derivatives thereof in the presence of 
at least one of compounds represented by formulas (I), (II), and (III) are 
occupied by tabular silver halide grains having an average aspect ratio of 
not less than 3.0, 
EQU R--SO.sub.2 S--M (I) 
EQU R--SO.sub.2 S--R.sup.1 (II) 
EQU R--SO.sub.2 S--L.sub.m --SSO.sub.2 --R.sup.2 (III) 
The definitions of R, R.sup.1, R.sup.2, M and m in formulas (I), (II), and 
(III) are described below. 
Accordingly, the above objects of the present invention are achieved by 
performing reduction sensitization by using at least one of ascorbic acid 
and its derivatives in a process of manufacturing a silver halide 
emulsion, and by a color light-sensitive material comprising a transparent 
support having thereon at least one light-sensitive silver halide emulsion 
layer, wherein 50 weight percent or more of silver halide grains 
contained in the emulsion layer are the silver halide grains constituting 
the silver halide emulsion manufactured by the above method. 
More preferably, the above objects of the present invention are achieved by 
a method of manufacturing a silver halide emulsion in which reduction 
sensitization is performed by using at least one of ascorbic acid and its 
derivatives during precipitation of silver halide grains, a method of 
manufacturing a silver halide emulsion as in any one of the above methods, 
in which reduction sensitization is performed by using ascorbic acid or 
its derivative in an amount of 5.times.10.sup.-5 to 1.times.10.sup.-1 mol 
per mol of a silver halide, or a method of manufacturing a silver halide 
emulsion as in any one of the above methods, in which reduction 
sensitization is performed in the presence of at least one of compounds 
represented by formulas (I), (II), and (III). 
EQU R--SO.sub.2 S--M (I) 
EQU R--SO.sub.2 S--R.sup.1 (II) 
EQU R--SO.sub.2 S--L.sub.m --SSO.sub.2 --R.sup.2 (III) 
wherein R, R.sup.1, and R.sup.2 can be the same or different and represent 
an aliphatic group, an aromatic group, or a heterocyclic group, M 
represents a cation, L represents a divalent bonding group, and m 
represents 0 or 1. 
Compounds represented by formulas (I) to (III) can be polymers containing 
divalent groups derived from structures represented by formulas (I) to 
(III) as repeating units.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention will be described in detail below. 
Processes of manufacturing silver halide emulsions are roughly classified 
into, e.g., grain formation, desalting, chemical sensitization, and 
coating steps. Grain formation is further classified into e.g. nucleation, 
ripening, and precipitation substeps. These steps are performed not in the 
above-mentioned order but in a reverse order or repeatedly. "To perform 
reduction sensitization in a process of manufacturing silver halide 
emulsions" means that reduction sensitization can be basically performed 
in any step. The reduction sensitization can be performed during 
nucleation or physical ripening in the initial stage of grain formation, 
during precipitation, or before or after chemical sensitization. In the 
case of performing chemical sensitization including gold sensitization, 
sulfer sensitization, selenium sensitization or a mixture thereof, the 
reduction sensitization is perferably performed before the chemical 
sensitization so as not to produce an undesired fog. The reduction 
sensitization is most preferably performed during precipitation of silver 
halide grains. The method of performing the reduction sensitization during 
precipitation includes a method of performing the reduction sensitization 
while silver halide grains are grown by physical ripening or addition of a 
water-soluble silver salt and a water-soluble alkali halide and a method 
of performing the reduction sensitization while grain precipitation is 
temporarily stopped and then precipitating grains 
Examples of ascorbic acid and its derivative (to be referred to as an 
"ascorbic acid compound" hereinafter) are as follows. 
(A-1) L-ascorbic Acid 
(A-2) Sodium L-ascorbate 
(A-3) Potassium L-ascorbate 
(A-4) DL-ascorbic Acid 
(A-5) Sodium D-ascorbate 
(A-6) L-ascorbic acid 6-acetate 
(A-7) L-ascorbic acid 6-palmitate 
(A-8) L-ascorbic acid 6-benzoate 
(A-9) L-ascorbic acid 5,6-diacetate 
(A-10) L-ascorbic acid 5,6-O-isopropylidene 
In order to add the above ascorbic acid compounds in a process of 
manufacturing a silver halide emulsion of the present invention, they can 
be dispersed directly in an emulsion, or can be dissolved in a solvent or 
solvent mixture of, e.g., water, methanol, and ethanol and then added in 
the manufacturing process. 
It is desired that the ascorbic acid compound of the present invention is 
used in an amount much larger than a preferable addition amount of a 
conventional reduction sensitizer. For example, JP-B-57-33572 describes 
"an amount of a reducing agent normally does not exceed 
0.75.times.10.sup.-2 milli equivalent amount (8.times.10.sup.-4 mol/AgX 
mol) per gram of silver ions. An amount of 0.1 to 10 mg (10.sup.-7 to 
10.sup.-5 mol/AgX mol for ascorbic acid) per kg of silver nitrate is 
effective in many cases" (reduced values are calculated by the present 
inventors). U.S. Pat. No. 2,487,850 describes that "a tin compound can be 
used as a reduction sensitizer in an addition amount of 1.times.10.sup.-7 
to 44.times.10.sup.-6 mol". JP-A-57-179835 describes that it is suitable 
to add about 0.01 mg to about 2 mg of thiourea dioxide or about 0.01 mg to 
about 3 mg of stannous chloride per mol of a silver halide. A preferable 
addition amount of the ascorbic acid compound used in the present 
invention depends on factors such as grain size and halogen composition of 
an emulsion, temperature, ph, and pAg in emulsion preparation. The 
addition amount, however, is selected from a range of, preferably, 
5.times.10.sup.-5 mol to 1.times.10.sup.-1 mol, more preferably, 
5.times.10.sup.-4 mol to 1.times.10.sup.-2 mol, and most preferably, 
1.times.10.sup.-3 mol to 1.times.10.sup.-2 mol per mol of a silver halide. 
Although the ascorbic acid compound of the present invention can be added 
at any timing in an emulsion manufacturing process, it is most preferably 
added during grain precipitation. The ascorbic acid compound is preferably 
added at an arbitrary timing in grain formation though it can be added in 
a reaction vessel beforehand. In addition, a reduction sensitizer can be 
added in an aqueous solution of a water-soluble silver salt or 
water-soluble alkali halide to perform grain formation by using this 
aqueous solution. A method of adding a solution of the reduction 
sensitizer several times or continuously adding it over a long time period 
during grain growth is also preferable. 
Although a method of performing reduction sensitization by using the 
ascorbic acid compound of the present invention is superior to a 
conventional reduction sensitization method in sensitivity, fogging 
density, and age stability, it is sometimes more preferable to use the 
method of the present invention in combination with another reduction 
sensitization method. In this case, however, it is preferred that the 
other method is used as merely an auxiliary means of reduction 
sensitization and a main means of reduction sensitization is performed by 
the ascorbic acid compound. A method to be used in combination with the 
method of the present invention can be selected from a method of adding a 
known reducing agent to a silver halide emulsion, a method called silver 
ripening in which precipitating or ripening is performed in a low-pAg 
atmosphere of a pAg of 1 to 7, and a method called high pH ripening in 
which precipitating or ripening is performed in a high-pH atmosphere of a 
pH of 8 to 11. 
A method of adding a reduction sensitizer is preferable because the level 
of reduction sensitization can be precisely adjusted. 
As the reduction sensitizer, for example, stannous salt, amines and 
polyamines, a hydrazine derivative, formamidinesulfinic acid, a silane 
compound, and a borane compound are known. The ascorbic acid compound, 
however, can provide superior results to those obtained by the above known 
reduction sensitizers. 
In the present invention, it is preferred to perform reduction 
sensitization by using the ascorbic acid compound in a process of 
manufacturing a silver halide emulsion and to add at least one compound 
selected from compounds represented by formulas (I), (II), and (III) 
during the manufacturing process. 
EQU R--SO.sub.2 S--M (I) 
EQU R--SO.sub.2 S--R.sup.1 (II) 
EQU RSO.sub.2 S--L.sub.m --SSO.sub.2 --R.sup.2 (III) 
wherein R, R.sup.1, and R.sup.2 can be the same or different and represent 
an aliphatic group, an aromatic group, or a heterocyclic group, M 
represents a cation, L represents a divalent bonding group, m represents 0 
or 1. 
Thiosulfonic acid compounds represented by formulas (I), (II), and (III) 
will be described in more detail below. When R, R.sup.1 and R.sup.2 each 
represent an aliphatic group, it is a saturated or unsaturated, 
straight-chain, branched or cyclic aliphatic hydrocarbon group and is 
preferably alkyl having 1 to 22 carbon atoms or alkenyl or alkinyl having 
2 to 22 carbon atoms. These groups can have a substituent group. Examples 
of the alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 
2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, 
and t-butyl. 
Examples of the alkenyl are allyl and butenyl. 
Examples of the alkinyl are propargyl and butynyl. 
An aromatic group of R, R.sup.1, and R.sup.2 includes aromatic group of 
single-ring or condensed-ring and preferably has 6 to 20 carbon atoms. 
Examples of such an aromatic group are phenyl and naphthyl. These groups 
can have substituent group. 
A heterocyclic group of R, R.sup.1, and R.sup.2 includes a 3- to 
15-membered ring having at least one element of nitrogen, oxygen, sulfur, 
selenium, and tellurium and at least one carbon atom, preferably, a 3 to 
6-membered ring. Examples of the heterocyclic group are pyrrolidine, 
piperidine, pyridine, tetrahydrofurane, thiophene, oxazole, thiazole,, 
imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, 
benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole 
oxadiazole, and thiadiazole. 
Examples of the substituent group on R, R.sup.1, and R.sup.2 are an alkyl 
group (e.g., methyl, ethyl, and hexyl), an alkoxy group (e.g., methoxy, 
ethoxy, and octyloxy), an aryl group (e.g., phenyl, naphthyl, and tolyl), 
a hydroxyl group, a halogen atom (e.g., fluorine, chlorine, bromine, and 
iodine), an aryloxy group (e.g. phenoxy), an alkylthio group (e.g., 
methylthio and butylthio), an arylthio group (e.g. phenylthio), an acyl 
group (e.g. acetyl, propionyl, butyryl, and valeryl), a sulfonyl group 
(e.g. methyl sulfonyl and phenylsulfonyl), an acylamino group (e.g., 
acetylamino and benzaoylamino), a sulfonylamino group (e.g., 
methanesulfonylamino and benzenesulfonylamino), an acyloxy group (e.g., 
acetoxy and benzoxy), carboxyl, cyano, sulfo, amino, --SO.sub.2 SM (M 
represent a monovalent cation), and --SO.sub.2 R.sup.1. 
A divalent bonding group represented by L includes an atom or an atom group 
containing at least one of C, N, S, and O. Examples of L are alkylene, 
alkenylene, alkynylene, arylene, --O--, --S--, --NH--, --CO--, and 
--SO.sub.2 --. These divalent groups can be used singly or in a 
combination of two or more thereof. 
Preferably L represents a divalent aliphatic group or a divalent aromatic 
group. Examples of the divalent aliphatic of L are --CH.sub.2.sbsb.n (n=1 
to 12), --CH.sub.2 --CH.dbd.CH--CH.sub.2 --, --CH.sub.2 C.tbd.CCH.sub.2 
--, 
##STR1## 
and xylylene. Examples of the divalent aromatic group of L are phenylene 
and naphthylene. 
These substituent groups can have further substituent group 
above-mentioned. 
M is preferably a metal ion or an organic cation. Examples of the metal ion 
are a lithium ion, a sodium ion, and a potassium ion. Examples of the 
organic cation are an ammonium ion (e.g., ammonium, tetramethylammonium, 
and tetrabutylammonium), a phosphonium ion (e.g. tetraphenylphosphonium), 
and a guanidil group. 
When a compound represented by each of formulas (I) to (III) is a polymer, 
examples of its repeating unit are as follows: 
##STR2## 
Each of the above polymers can be a homopolymer or a copolymer with another 
copolymerizable monomer. 
Examples of a compound represented by formula (I), (II), or (III) are 
listed in Table A to be presented later. However, compounds are not 
limited to those in Table A. 
A compound represented by formula (I), (II), or (III) is preferably added 
in an amount of 10.sup.-7 to 10.sup.-1 mol per mol of a silver halide. The 
addition amount is more preferably 10.sup.-6 to 10.sup.-2 mol/molAg and 
most preferably 10.sup.-5 to 10.sup.-3 mol/molAg. 
A conventional method of adding an additive in a photographic emulsion can 
be adopted to add compounds represented by formulas (I) to (III) in a 
manufacturing process. For example, a water-soluble compound can be added 
in the form of an aqueous solution having an arbitrary concentration, and 
a water-insoluble or water-retardant compound is dissolved in an arbitrary 
organic solvent such as alcohols, glycols, ketones, esters, and amides, 
which is miscible with water and does not adversely affect photographic 
properties, and then added as a solution. 
A compound represented by formula (I), (II), or (III) can be added at any 
timing in a manufacturing process, e.g., during grain formation of a 
silver halide emulsion or before or after chemical sensitization. The 
compound is preferably added before or during reduction sensitization. The 
compound is most preferably added during grain precipitation. 
Although the compound can be added in a reaction vessel beforehand, it is 
preferably added at an arbitrary timing during grain formation. In 
addition, a compound represented by formula (I), (II), or (III) can be 
added in an aqueous solution of a water-soluble silver salt or 
water-soluble alkali halide to perform grain formation by using the 
aqueous solution. A method of adding a solution of a compound represented 
by formula (I), (II), or (III) several times or continuously adding it 
over a long time period during grain formation is also preferable. 
A compound most preferable in the present invention is represented by 
formula (I). 
A silver halide of any of silver bromide, silver iodobromide, silver 
iodochlorobromide, silver chlorobromide, and silver chloride can be used 
in a photographic emulsion layer of a photographic light-sensitive 
material used in the present invention. A preferable silver halide is 
silver iodobromide, silver bromide, or silver chlorobromide containing 30 
mol% or less of silver iodide. 
A silver halide grain to be used in the present invention can be selected 
from a regular crystal not including a twined crystal face and those 
describe in Japan Photographic Society ed., "Silver Salt Photographs, 
Basis of Photographic Industries", (Corona Co., P. 163) such as a single 
twined crystal including one twined crystal face, a parallel multiple 
twined crystal including two or more parallel twined crystal faces, and a 
non-parallel multiple twined crystal including two or more non-parallel 
twined crystal faces, in accordance with its application. In the case of a 
regular crystal, a cubic grain consisting of (100) faces, an octahedral 
grain consisting of (111) faces, and a dodecahedral grain consisting of 
(110) faces disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In 
addition, a grain having (hll), e.g., (211) faces, a grain having (hhl), 
e.g., (331) faces, a grain having (hk0), e.g., (210) faces, and a grain 
consisting of (hk1), e.g., (321) faces as reported in "Journal of Imaging 
Science", Vol. 30, P. 247, 1986 can be selectively used in accordance with 
an application although a preparation method must be improved. A grain 
including two or more types of faces, e.g., a tetradecahedral grain having 
both (100) and (111) faces, a grain having both (100) and (110) faces, and 
a grain having both (111) and (110) faces can be selectively used in 
accordance with an application. 
The grain of a silver halide can be a fine grain having a grain size of 0.1 
microns or less or a large grain having a projected surface area diameter 
of 10 microns. An emulsion can be a monodisperse emulsion having a narrow 
distribution or a polydisperse emulsion having a wide distribution. 
A so-called monodisperse silver halide emulsion having a narrow size 
distribution, i.e., in which 80% or more (the number or weight of grains) 
of all grains fall within the range of .+-.30% of an average grain size. 
In order to satisfy target gradation of a light-sensitive material, two or 
more types of monodisperse silver halide emulsions having different grain 
sizes can be coated in a single layer or overlapped in different layers in 
emulsion layers having substantially the same color sensitivity. 
Alternatively, two or more types of polydisperse silver halide emulsions 
or a combination of monodisperse and polydisperse emulsions can be mixed 
or overlapped. 
The photographic emulsions for use in the present invention can be prepared 
by using methods described in, for example, P. Glafkides, "Chimie et 
Physique Photographique", Paul Montel, 1967; Duffin, "Photographic 
Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., "Making 
and Coating Photographic Emulsion", Focal Press, 1964. That is, the 
photographic emulsion can be prepared by, e.g., an acid method, a 
neutralization method, and an ammonia method. Also, as a system for 
reacting a soluble silver salt and a soluble halide, a single mixing 
method, a double mixing method, or a combination thereof can be used. 
Also, a so-called back mixing method for forming silver halide grains in 
the presence of excessive silver ions can be used. As one system of the 
double mixing method, a so-called controlled double jet method wherein the 
pAg in the liquid phase, where the silver halide is generated, kept at a 
constant value can be used. According to this method, a silver halide 
emulsion having a regular crystal form and almost uniform grain sizes is 
obtained. 
The silver halide emulsion containing the above-described regular silver 
halide grains can be obtained by controlling the pAg and pH during grain 
formation. More specifically, such a method is described in "Photographic 
Science and Engineering", Vol. 6, 159-165 (1962); "Journal of Photographic 
Science", Vol. 12, 242-251 (1964); U.S. Pat. No. 3,655,394, and British 
Patent 1,413,748. 
A tabular grain having an aspect ratio of 3 or more can also be used in the 
present invention. The tabular grain can be easily prepared by methods 
described in, for example, Cleve, "Photography Theory and Practice", 
(1930), P. 131; Gutoff, "Photographic Science and Engineering", Vol. 14, 
PP. 248 to 257, (1970); and U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 
and 4,439,520 and British Patent 2,112,157. When the tabular grain is 
used, covering power and a color sensitizing efficiency of a sensitizing 
dye can be advantageously improved as described in detail in U.S. Pat. No. 
4,434,226. 
The tabular grains are preferably used in the emulsion of the present 
invention. In particular, tabular grains in which grains having aspect 
ratios of 3 to 8 occupy 50% or more of a total projected surface area are 
preferable. 
A crystal structure can be uniform, can have different halogen compositions 
inside and outside a crystal, or can be layered structure. These emulsion 
grains are disclosed in, e.g., British Patent 1,027,146, U.S. Pat. Nos. 
3,505,068 and 4,444,877, and Japanese Patent Application No. 58-248469. In 
addition, a silver halide having different compositions can be bonded by 
an epitaxial junction, or a compound other than a silver halide such as 
silver rhodanate or zinc oxide can be bonded. 
In the present invention, a tabular grain means a grain having a plurality 
of parallel twinned crystal faces and a tabular shape regardless of its 
aspect ratio. A grain having no twinned crystal face and having an aspect 
ratio of 2 or more is also included in the tabular grain. The latter grain 
includes a rectangular parallelepiped grain as reported in A. Mignot et 
al., "Journal of Cryst. Growth", Vol. 23, P. 207 (1974). 
In a tabular silver halide emulsion reduction-sensitized by an ascorbic 
acid compound, an aspect ratio means a ratio of a diameter of a silver 
halide grain with respect to its thickness. That is, the aspect ratio is a 
value obtained by dividing the diameter of each silver halide grain by its 
thickness. In this case, the diameter means a diameter of a circle having 
an area equal to a projected area of a grain upon observation of a silver 
halide emulsion by a microscope or electron microscope. Therefore, when 
the aspect ratio is 3 or more, the diameter of a circe is three times or 
more the thickness of a grain. 
An average aspect ratio is obtained as follows. That is, 1,000 silver 
halide grains of the emulsion are extracted at random to measure their 
aspect ratios, tabular grains corresponding to 50% of a total projected 
area are selected from those having larger aspect ratios, and a 
number-average of aspect ratios of the selected tabular grains is 
calculated. A number-average of a diameter or thickness of the tabular 
grains used to calculate the average aspect ratio is defined as an average 
grain size or average grain thickness, respectively. 
An example of an aspect ratio measuring method is a method of photographing 
a transmission electron micrograph by a replica technique to obtain a 
circle-equivalent diameter and a thickness of each grain. In this case, 
the thickness is calculated from the length of a shadow of the replica. 
The average aspect ratio of the tabular silver halide grains 
reduction-sensitized by the ascorbic acid compound is 3.0 or more, 
preferably, 3 to 20, more preferably, 4 to 15, and most preferably, 5 to 
10. In one emulsion layer, a ratio of a projected area occupied by tabular 
silver halide grains with respect to all silver halide grains is 50% or 
more, preferably, 70% or more, and more preferably, 85% or more. 
A silver halide photographic light-sensitive material having good sharpness 
can be obtained by using such an emulsion. The sharpness is good because a 
degree of light scattering caused by an emulsion layer using the above 
emulsion is much smaller than that of a conventional emulsion layer. This 
can be easily confirmed by an experiment method ordinarily used by those 
skilled in the art. The reason why the light scattering degree of an 
emulsion layer using the tabular silver halide emulsion is small is not 
clear. It can be assumed, however, that a major surface of the tabular 
silver halide emulsion grain is oriented parallel to the surface of a 
support. 
The average grain diameter of the tabular silver halide grains 
reduction-sensitized by the ascorbic acid compound is 0.2 to 10.0 .mu.m, 
preferably, 0.3 to 5.0 .mu.m, and more preferably, 0.4 to 3.0 .mu.m. The 
average grain thickness is preferably 0.5 .mu.m or less. In a more 
preferable silver halide photographic emulsion, the average grain size is 
0.4 to 3.0 .mu.m, the average grain thickness is 0.5 .mu.m or less, the 
aspect aspect ratio is 5 to 10, and 80% or more of a total projected area 
of all silver halide grains are occupied by tabular grains. 
The tabular silver halide grains reduction-sensitized by the ascorbic acid 
compound may be any of silver chloride, silver bromide, silver 
chlorobromide, silver iodobromide, and silver chloroiodobromide. More 
preferable examples are silver bromide, silver iodobromide having 20 mol % 
or less of silver iodide, and silver chloroiodobromide and silver 
chlorobromide having 50 mol % or less of silver chloride and 2 mol % or 
less of silver iodide. In a mixed silver halide, a composition 
distribution may be uniform or localized. 
The tabular silver halide emulsion of the present invention can be prepared 
by, for example, forming a seed crystal having 40% (weight) or more of 
tabular grains in a comparatively-high-pAg atmosphere in which a pBr is 
1.3 or less, and simultaneously adding silver and halogen solutions to 
grow the seed crystal while the pBr Value is maintained substantially the 
same level. In this grain growth step, it is preferred to add the silver 
and halogen solutions so that no new crystal nucleus is generated. 
In a tabular silver halide emulsion reduction-sensitized by the ascorbic 
acid compound, the size of emulsion grains can be adjusted, for example, 
by adjusting a temperature, selecting the type or quality of a solvent, 
and controlling addition rates of silver salts and halides used in grain 
formation. 
The silver halide emulsion of the present invention preferably has a 
distribution or structure of a halogen composition in its grain. A typical 
example is a core-shell type or double structured grain having different 
halogen compositions in the interior and surface layer of the grain as 
disclosed in, e.g., JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, and 
JP-A-61-75337. In such a grain, the shape of a core portion is sometimes 
identical to or sometimes different from that of the entire grain with a 
shell. More specifically, while the core portion is cubic, the grain with 
a shell is sometimes cubic or sometimes octahedral. On the contrary, while 
the core portion is octahedral, the grain with a shell is sometimes cubic 
or sometimes octahedral. In addition, while the core portion is a clear 
regular grain, the grain with a shell is sometimes slightly deformed or 
sometimes does not have any definite shape. Furthermore, not a simple 
double structure but a triple structure as disclosed in JP-A-60-222844 or 
a multilayered structure of more layers can be formed, or a thin layer of 
a silver halide having a different composition can be formed on the 
surface of a core-shell double structure grain. 
In order to give a structure inside the grain, a grain having not only the 
above surrounding structure but a so-called junction structure can be 
made. Examples of such a grain are disclosed in, e.g., JP-A-59-133540, 
JP-A-58-108526, EP 199290A2, JP-B-58-24772, and JP-A-59-16254. A crystal 
bonded having a composition different from that of a host crystal can be 
produced and bonded to an edge, corner, or face portion of the host 
crystal. Such a junction crystal can be formed regardless of whether the 
host crystal has a homogeneous halogen composition or a core-shell 
structure. 
The junction structure can be naturally made by a combination of silver 
halides. In addition, the junction structure can be made by combining a 
silver salt compound not having a rock salt structure, e.g., silver 
rhodanate or silver carbonate, with a silver halide. A non-silver salt 
compound such as PbO can also be used as long as the junction structure 
can be made. 
In a silver iodobromide grain having the above structure, e.g., in a 
core-shell type grain, the silver iodide content can be high at a core 
portion and low at a shell portion or vice versa. Similarly, in a grain 
having the junction structure, the silver iodide content can be high in a 
host crystal and relatively low in a junction crystal or vice versa. 
In a grain having the above structure, a boundary portion between different 
halogen compositions can be clear or unclear due to a crystal mixture 
formed by a composition difference. Alternatively, a continuous structure 
change can be positively made. 
The silver halide emulsion for use in the present invention can be 
subjected to a treatment for rounding a grain as disclosed in, e.g., 
EP-0096727B1 and EP-0064412B1 or a treatment of modifying the surface of a 
grain as disclosed in DE-2306447C2 and JP-A-60-221320. 
The silver halide emulsion for use in the present invention is preferably 
of a surface latent image type. An internal latent image type emulsion, 
however, can be used by selecting a developing solution or development 
conditions as disclosed in JP-A-59-133542. In addition, a shallow internal 
latent image type emulsion covered with a thin shell can be used in 
accordance with an application. 
A solvent for silver halide can be effectively used to promote ripening. 
For example, in a known conventional method, an excessive amount of 
halogen ions are supplied in a reaction vessel in order to promote 
ripening. Therefore, it is apparent that ripening can be promoted by only 
supplying a silver halide solution into a reaction vessel. In addition, 
another ripening agent can be used. A total amount of these ripening 
agents can be mixed in a dispersion medium in the reaction vessel before a 
silver salt and a halide are added therein, or they can be added in the 
reaction vessel together with one or more halides, a silver salt or a 
deflocculant. Alternatively, the ripening agents can be added singly in 
step of adding a halide and a silver salt. 
Examples of the ripening agent other than the halogen ion are ammonia, an 
amine compound and a thiocyanate such as an alkali metal thiocyanate, 
especially sodium or potassium thiocyanate and ammonium thiocyanate. 
In the present invention, it is very important to perform chemical 
sensitization represented by sulfur sensitization and gold sensitization 
because significant effects can be obtained upon chemical sensitization. A 
portion to be subjected to the chemical sensitization differs in 
accordance with the composition, structure, or shape of an emulsion grain 
or an application of the emulsion. That is, a chemical sensitization 
nucleus is embedded either inside a grain or in a shallow portion from the 
grain surface or formed on the surface of a grain. Although the present 
invention is effective in any case, the chemical sensitization nucleus is 
most preferably formed in a portion near the surface. That is, the present 
invention is more effective in the surface latent image type emulsion than 
in the internal latent image type emulsion. 
Chemical sensitization can be performed by using active gelatin as 
described in T. H. James, "The Theory of the Photographic Process", 4th 
ed., Macmillan, 1977, PP. 67 to 76. Alternatively, chemical sensitization 
can be performed at a pAg of 5 to 10, a pH of 5 to 8 and a temperature of 
30 to 80.degree. C by using sulfur, selenium, tellurium, gold, platinum, 
palladium or irridium, or a combination of a plurality of these 
sensitizers as described in Research Disclosure Vol. 120, No. 12,008 
(April, 1974), Research Disclosure Vol. 34, No. 13,452 (June, 1975), U.S. 
Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 
4,266,018, and 3,904,415, and British Patent 1,315,755. Chemical 
sensitization is optimally performed in the presence of a gold compound 
and a thiocyanate compound, a sulfur-containing compound described in U.S. 
Pat. Nos. 3,857,711, 4,266,018 and 4,054,457 or a sulfur-containing 
compound such as a hypo, thiourea compound and a rhodanine compound. 
Chemical sensitization can also be performed in the presence of a chemical 
sensitization assistant. An example of the chemical assistant is a 
compound known to suppress fogging and increase sensitivity in the 
chemical sensitization process such as azaindene, azapyridazine, and 
azapyrimidine. Examples of a chemical sensitization assistant modifier are 
described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, 
JP-A-58-126526 and G. F. Duffin, "Photographic Emulsion Chemistry", PP. 
138 to 143. 
The photographic emulsion for use in the present invention can contain 
various compounds in order to prevent fogging during manufacture, storage, 
or a photographic treatment of the light-sensitive marerial or to 
stabilize photographic properties. Examples of the compound known as an 
antifoggant or stabilizer are azoles, e.g., benzothiazolium salts, nitro 
imidazoles, nitrobenzimidazoles, chlorobenzimidazoles, 
bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, 
mercaptobenzimidazoles, mercaptothiaziazoles, aminotriazoles, 
benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (especially, 
1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriadines; a 
thioketo compound such as oxadrinthione; azaindenes, e.g., triazaindenes, 
tetraazaindenes (especially, 4-hydroxy-substituted 
(1,3,3a,7)tetraazaindenes), and pentaazaindenes. Examples are described in 
U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28660. 
The photographic emulsion for use in the present invention can be 
spectrally sensitized with, for example, methine dyes. Examples of the dye 
to be used are a cyanine dye, merocyanine dye, a composite cyanine dye, a 
composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a 
styryl dye, and hemioxonol dye. Most effective dyes are those belonging to 
a cyanine dye, a merocyanine dye, and a composite merocyanine dye. In 
these dyes, any nucleus normally used as a basic heterocyclic nucleus in 
cyanine dyes can be used. Examples of the nucleus are pyrroline nucleus, 
an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole 
nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a 
tetrazole nucleus, and a pyridine nucleus; a nucleus obtained by 
condensing an alicyclic hydrocarbon ring to each of the above nuclei; and 
a nucleus obtained by condensing an aromatic hydrocarbon ring to each of 
the above nuclei, e.g., an indolenine nucleus, a benzindolenine nucleus, 
an indole nucleus, a benzoxadole nucleus, a naphthooxazole nucleus, a 
benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole 
nucleus, a benzimidazole nucleus, and a quinoline nucleus. These nucei can 
have a substituent group on a carbon atom. 
For a merocyanine dye or composite merocyanine dye, a 5- or 6-membered 
heterocyclic nucleus, e.g., a pyrazoline-5-one nucleus, a thiohydantoin 
nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione 
nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be 
used as a nucleus having a ketomethylene structure. 
These sensitizing dyes can be used singly or in a combination of two or 
more thereof. A combination of the sensitizing dyes is often used 
especially in order to perform supersensitization. Typical examples of the 
combination are described in U.S. Pat. Nos. 2,688,545, 2,977,229, 
3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 
3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 
4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-4936 and 
JP-B-53-12375, and JP-A-52-110618 and JP-A-52-109925. 
The emulsion can contain, in addition to the sensitizing dye, a dye not 
having a spectral sensitizing effect or a substance substantially not 
absorbing visible light, having supersensitization. 
The dye can be added in the emulsion at any time conventionally known to be 
effective in emulsion preparation. Most ordinarily, the dye is added after 
completion of chemical sensitization and before coating. However, the dye 
can be added at the same time as a chemical sensitizer to simultaneously 
perform spectral sensitization and chemical sensitization as described in 
U.S. Pat. Nos. 3,628,969 and 4,225,666, added before chemical 
sensitization as described in JP-A-58-113928, or added before completion 
of silver halide grain precipitation to start spectral sensitization. In 
addition, as described in U.S. Pat. No. 4,225,666, the above compound can 
be separately added such that a portion of the compound is added before 
chemical sensitization and the remaining portion is added thereafter. That 
is, as described in U.S. Pat. No. 4,183,756, the compound can be added at 
any time during silver halide grain formation. 
An addition amount can be 4.times.10.sup.-6 to 8.times.10.sup.-3 mol per 
mol of silver halide. More preferably, when a silver halide grain size is 
a preferable size i.e. 0.1 to 1.2 .mu.m, an addition amount of about 
5.times.10.sup.-5 to 2.times.10.sup.-3 mol is more effective. 
The above various additives can be used in the light-sensitive material of 
the present invention. In addition to the above additives, however, 
various additives can be used in accordance with desired application. 
These additives are described in Research Disclosures, Item 17643 (Dec. 
1978) and Item 18716 (Nov. 1979) and they are summarized in the following 
table. 
______________________________________ 
Additives RD No. 17643 RD No. 18716 
______________________________________ 
1. Chemical page 23 page 648, right 
sensitizers column 
2. Sensitivity page 648, right 
increasing agents column 
3. Spectral sensiti- 
pages 23-24 page 648, right 
zers, super column to page 
sensitizers 649, right column 
4. Brighteners page 24 
5. Antifoggants and 
pages 24-25 page 649, right 
stabilizers pages 24-25 column 
6. Light absorbent, 
pages 25-26 page 649, right 
filter dye, ultra- column to page 
violet absorbents 650, left column 
7. Stain preventing 
page 25, page 650, left to 
agents right column right columns 
8. Dye image page 25 
stabilizer 
9. Hardening agents 
page 26 page 651, left 
column 
10. Binder page 26 page 651, left 
column 
11. Plasticizers, page 27 page 650, right 
lubricants column 
12. Coating aids, pages 26-27 page 650, right 
surface active column 
agents 
13. Antistatic agents 
page 27 page 650, right 
column 
______________________________________ 
In this invention, various color couplers can be used. Specific examples of 
these couplers are described in above-described Research Disclosure, No. 
17643, VII-C to VII-G as patent references. 
Preferred examples of a yellow coupler are described in, for example, U.S. 
Pat. Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739, 
and British Patents 1,425,020 and 1,476,760. 
Examples of a magenta coupler are preferably 5-pyrazolone and pyrazoloazole 
compounds, and more preferably, compounds described in, for example, U.S. 
Pat. Nos. 4,310,619 and 4,351,897, EP 73,636, U.S. Pat. Nos. 3,061,432 and 
3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, 
Research Disclosure No. 24230 (June 1984), JP-A-60-34659, and U.S. Pat. 
Nos. 4,500,630 and 4,540,654. 
Examples of a cyan coupler ar phenol and naphthol couplers, and preferably, 
those described in, for example, U.S. Pat. Nos. 4,052,212, 4,146,396, 
4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 
3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent 
Application (OLS) No. 3,329,729, EP 121,365A, U.S. Pat. Nos. 3,446,622, 
4,333,999, 4,451,559, and 4,427,767, and EP 161,626A. 
Preferable examples of a colored coupler for correcting additional, 
undesirable absorption of a colored dye are those described in Research 
Disclosure No. 17643, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. 
Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368. 
Preferable examples of a coupler capable of forming colored dyes having 
proper diffusibility ar those described in U.S. Pat. No. 4,366,237, 
British Patent 2,125,570, EP 96,570, and West German Patent Application 
(OLS) No. 3,234,533. 
Typical examples of a polymerized dye-forming coupler are described in U.S. 
Pat. Nos. 3,451,820, 4,080,211, and 4,367,282, and British Patent 
2,102,173. 
Couplers releasing a photographically useful residue upon coupling are 
preferably used in the present invention. DIR couplers, i.e., couplers 
releasing a development inhibitor are described in the patents cited in 
the above-described Research Disclosure No. 17643, VII-F, JP-A-57-151944, 
JP-A-57-154234, JP-A-60-184248, and U.S. Pat. No. 4,248,962. 
Preferable examples of a coupler imagewise releasing a nucleating agent or 
a development accelerator upon development are those described in British 
Patent 2,097,140, 2,131,188, and JP-A-59-157638 and JP-A-59-170840. 
Examples of a coupler which can be used in the light-sensitive material of 
the present invention are competing couplers described in, e.g., U.S. Pat. 
No. 4,130,427; poly-equivalent couplers described in, e.g., U.S. Pat. Nos. 
4,283,472, 4,338,393, and 4,310,618; DIR redox compound releasing 
couplers, described in, e.g., JP-A-60-185950 and JP-A-62-24252; couplers 
releasing a dye which turns to a colored form after being released 
described in EP 173,302A; bleaching accelerator releasing couplers 
described in, e.g., R.D. Nos. 11449 and 24241 and JP-A-61-201247; and a 
legand releasing coupler described in, e.g., U.S. Pat. No. 4,553,477. 
The couplers for use in this invention can be introduced in the 
light-sensitive materials by various known dispersion methods. 
Examples of a high-boiling solvent used in an oil-in-water dispersion 
method are described in, for example, U.S. Pat. No. 2,322,027. 
Examples of a high-boiling organic solvent to be used in the oil-in-water 
dispersion method and having a boiling point of 175.degree. C or more at 
normal pressure are phthalic esters (e.g., dibutylphthalate, 
dicyclohexylphthalate, and di-2-ethylhexylphthalate), phophates or 
phosphonates (e.g., triphenyl phosphate, tricresylphosphate, 
2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, and 
tri-2-ethylhexylphosphate), benzoates (e.g., 2-ethylhexylbenzoate, 
dodecylbenzoate, and 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., 
N,N-diethyldodecaneamide, N,N-diethyllaurylamide, and 
N-tetradecylpyrrolidone), alcohols or phenols (e.g., isostearylalcohol and 
2,4-di-tert-amylphenol), aliphatic carboxylates (e.g., 
bis(2-ethylhexyl)sebacate, dioctylazelate, glyceroltributylate, 
isostearyllactate, and trioctylcitrate), an aniline derivative (e.g., 
N,N-dibutyl-2-butoxy-5-tert-octylaniline), and hydrocarbons (e.g., 
paraffin, dodecylbenzene, and diisopropylnaphthalene). An organic solvent 
having a boiling point of about 30.degree. C. or more, and preferably, 
50.degree. C. to about 160.degree. C. can be used as a co-solvent. Typical 
examples of the co-solvent are ethyl acetate, butyl acetate, ethyl 
propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and 
dimethylformamide. 
Steps and effects of a latex dispersion method and examples of an loadable 
latex are described in, e.g., U.S. Pat. No. 4,199,363 and West German 
Patent Application (OLS) Nos. 2,541,274 and 2,541,230. 
The present invention can be applied to various color light-sensitive 
materials. Examples of the material are a color negative film for a 
general purpose or a movie, a color reversal film for a slide or a 
television, color paper, a color positive film, and color reversal paper. 
Preferably, in a color light-sensitive material comprising a transparent 
support having thereon at least one light sensitive silver halide emulsion 
layer, 50 weight percent or more of silver halide grains contained in said 
emulsion layer are the silver halide grains constituting the silver halide 
emulsion manufactured by the method of manufacturing a silver halide 
emulsion, wherein reduction sensitization is performed by using at least 
one of ascorbic acid and derivatives thereof in a process of manufacturing 
a silver halide emulsion. 
When the present invention is used as a material for color photography, the 
present invention can be applied to light-sensitive materials having 
various structures and to light-sensitive materials having combinations of 
layer structures and special color materials. 
Typical examples are: light-sensitive materials in which a coupling speed 
of a color coupler or diffusibility is combined with a layer structure, as 
disclosed in, e.g., JP-B-47-49031, JP-B-49-3843, JP-B-50-21248, 
JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043, JP-A-61-43743, 
and JP-A-61-42657; light-sensitive materials in which a single 
color-sensitive layer is divided into two or more layers, as disclosed in 
JP-B-49-15495 and U.S. Pat. No. 3,843,469; and light-sensitive materials, 
in which an arrangement of high- and low-sensitivity layers or layers 
having different color sensitivities is defined, as disclosed in 
JP-B-53-37017, JP-B-53-37018, JP-A-51-49027, JP-A-52-143016, 
JP-A-53-97424, JP-A-53-97831, JP-A-62-200350, and JP-A-59-177551. 
Examples of a support suitable for use in this invention are described in 
the above-mentioned RD. No. 17643, page 28 and ibid., No. 18716, page 647, 
right column to page 648, left column. 
The color photographic light-sensitive materials of this invention can be 
processed by ordinary processes as described, for example, in the 
above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., 
No. 18716, page 651, left to right columns. 
A color developer used in developing of the light-sensitive material of the 
present invention is, preferably, an aqueous alkaline solution containing 
as a main component an aromatic primary amine-based color developing 
agent. As the color developing agent, although an aminophenol-based 
compound is effective, a p-phenylenediamine-based compound is preferably 
used. Typical examples of the p-phenylenediamine-based compound are 
3-methyl-4-amino N,N-diethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylanline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyehtylaniline, and sulfates, 
hydrochlorides and p-toluenesulfonates thereof. These compounds can be 
used in a combination of two or more thereof in accordance with the 
desired application. 
In general, the color developer contains a pH buffering agent such as a 
carbonate, a borate or a phosphate of an alkali metal, and a development 
restrainer or an antifoggant such as a bromide, an iodide, a 
benzimidazole, a benzothiazole or a mercapto compound. If necessary, the 
color developer can also contain a preservative such as hydroxylamine, 
diethylhy droxylamine, a hydrazine sulfite, a phenylsemicarbazide, 
triethanolamine, a catechol sulfonic acid or a 
triethylenediamine(1,4-diazabicyclo[2,2,2]octane); an organic solvent such 
as ethyleneglycol or diethyleneglycol; a development accelerator such as 
benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; 
a dye forming coupler; a competing coupler; a fogging agent such as sodium 
boron hydride; an auxiliary developing agent such as 
1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating 
agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an 
alkylphosphonic acid or a phosphonocarboxylic acid. Examples of the 
chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic 
acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 
acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic 
acid, nitrilo-N,N,N-trimethylenephosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and 
ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof. 
In order to perform reversal development, black-and-white development is 
performed and then color development is performed. As a black-and-white 
developer, well-known black-and-white developing agents, e.g., a 
dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 
1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol 
can be used singly or in a combination of two or more thereof. 
The pH of the color developer and black-and-white developer is generally 9 
to 12. Although a replenishment amount of the developer depends on a color 
photographic light-sensitive material to be processed, it is generally 3 
liters or less per m.sup.2, of the light-sensitive material. The 
replenishment amount can be decreased to be 500 ml or less by decreasing a 
bromide ion concentration in a replenishing solution. In order to decrease 
the replenishment amount, a contact area of a processing tank with air is 
preferably decreased to prevent evaporation and oxidation of the solution 
upon contact with air. The replenishment amount can be decreased by using 
a means capable of suppressing an accumulation amount of bromide ions in 
the developer. 
The color development time is normally set between 2 to 5 minutes. The 
processing time, however, can be shortened by setting a high temperature 
and a high pH and using the color developing agent at a high 
concentration. 
The photographic emulsion layer is generally subjected to bleaching after 
color development. The bleaching can be performed either simultaneousy 
with fixing (bleach-fixing) or independently thereof. In addition, in 
order to increase the processing speed, bleach-fixing can be performed 
after bleaching. Also, processing can be performed in a bleach-fixing bath 
having two continuous tanks, fixing can be performed before bleach-fixing, 
or bleaching can be performed after bleach-fixing, in accordance with the 
desired application. Examples of the bleaching agent are a compound of a 
multivalent metal such as iron (III), cobalt (III), chromium (VI) and 
copper (II); a peroxide., a quinone; and a nitro compound. Typical 
examples of the bleaching agent are a ferricyanide; a dichromate; an 
organic complex salt of iron (III) or cobalt (III), e.g., a complex salt 
of an aminopolycarboxylic acid such as ethylened; aminetetraacetic acid, 
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 
methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and 
glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, 
tartaric acid or malic acid; a persulfate., a bromate; a permanganate; and 
a nitrobenzene. Of these compounds, an iron (III) complex salt of 
aminopolycarboxylic acid such as an iron (III) complex salt of 
ethylenediaminetetraacetic acid, and a persulfate are preferred because 
they can increase the processing speed and prevent an environmental 
contamination. The iron (III) complex salt of aminopolycarboxylic acid is 
effective in both the bleaching solution and bleach-fixing solution. The 
pH of the bleaching or bleach-fixing solution using the iron (III) complex 
salt of aminopolycarboxylic acid is normaly 5.5 to 8. In order to increase 
the processing speed, however, processing can be performed at a lower pH. 
A bleaching accelerator can be used in the bleaching solution, the 
bleach-fixing solution and their prebath, if necessary. Effective examples 
of the bleaching accelerator are described in, for example, U.S. Pat. No. 
3,893,858. A compound described in U.S. Pat. No. 4,552,834 is also 
preferable. These bleaching accelerators can be added in the 
light-sensitive material. These bleaching accelerators are effective 
especially in bleach-fixing of a photographic color light-sensitive 
material. 
Examples of the fixing agent are a thiosulfate, a thiocyanate, a 
thioether-based compound, a thiourea and a large amount of an iodide. Of 
these compounds, a thiosulfate, especially, ammonium thiosulfate can be 
used in a widest range of applications. As a preservative of the 
bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite 
adduct is preferred. 
The photographic light-sensitive material of the present invention is 
normally subjected to washing and/or stabilizing steps after desilvering. 
An amount of water used in the washing step can be arbitrarily determined 
over a broad range in accordance with the properties (e.g., a property 
determined by used material such as a coupler) of the light-sensitive 
material, the application of the photographic material, the temperature of 
the washing water, the number of water tanks (the number of stages), a 
replenishing scheme representing a counter or forward current, and other 
conditions. The relationship between the amount of water and the number of 
water tanks in a multi-stage counter-current scheme can be obtained by a 
method described in "Journal of the Society of Motion Picture and 
Television Engineers", Vol. 64, PP. 248-253 (May, 1955). 
According to the above-described multi-stage counter-current scheme, the 
amount of water used for washing can be greatly decreased. Since washing 
water stays in the tanks for a long period of time, however, bacteria 
multiply and floating substances can be undesirably attached to the 
light-sensitive material. In order to solve this problem in the process of 
the color photographic light-sensitive material of the present invention, 
a method of decreasing calcium and magnesium ions can be quite effectively 
utilized, as described in JP-A-61-131632. In addition, a germicide such as 
an isothiazolone compound and cyabendazole described in JP-A-57-8542, a 
chlorine-based germicide such as chlorinated sodium isocyanurate, and 
germicides such as benzotriazole described in Hiroshi Horiguchi, 
"Chemistry of Antibacterial and Antifungal Agents", Eiseigijutsu-Kai ed., 
"Sterilization, Antibacterial, and Antifungal Techniques for 
Microorganisms", and Nippon Bokin Bokabi Gakkai ed., "Cyclopedia of 
Antibacterial and Antifungal Agents". 
The pH of the water for washing the photographic light-sensitive material 
of the present invention is 4 to 9, and preferably, 5 to 8. The water 
temperature and the washing time can vary in accordance with the 
properties and applications of the light-sensitive material. Normally, the 
washing time is 20 seconds to 10 minutes at a temperature of 15.degree. C. 
to 45.degree. C., and preferably, 30 seconds to 5 minutes at 25.degree. C. 
to 40.degree. C. The light-sensitive material of the present invention can 
be processed directly by a stabilizing agent in place of washing. All 
known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 
can be used in such stabilizing processing. 
Stabilizing is sometimes performed subsequently to washing. An example is a 
stabilizing bath containing formation and a surface-active agnet to be 
used as a final bath of the photographic color light-sensitive material. 
Various chelating agents or antifungal agents can be added also in the 
stabilizing bath. 
An overflow solution produced upon washing and/or replenishment of the 
stabilizing solution can be reused in another step such as a desilvering 
step. 
The silver halide color light-sensitive material of the present invention 
can contain a color developing agent in order to simplify processing and 
increase the processing speed. 
The silver halide color light-sensitive material of the present invention 
can contain various 1-phenyl-3-pyrazolidones in order to accelerate color 
development, if necessary. Typical examples of the compound are described 
in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. 
Each processing solution in the present invention is used at a temperature 
of 10.degree. C. to 50.degree. C. Although the normal processing 
temperature is 33.degree. C. to 38.degree. C., processing can be 
accelerated at a high temperature to shorten the processing time, or image 
quality or stability of a processing solution can be improved at a lower 
temperature. In order to save silver for the light-sensitive material, 
processing using cobalt intensification or hydrogen peroxide 
intensification described in West German Patent No. 3,226,770 or U.S. Pat. 
No. 3,674,499 can be performed. 
The silver halide light-sensitive material of the present invention can 
also be applied to thermal development light-sensitive materials described 
in, e.g., U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, 
JP-A-61-238056, and EP 210,660A2. 
The present invention will be described in more detail below by way of its 
examples. 
EXAMPLE 1 
Double twined crystal grains comprising silver iodobromide and having an 
average iodide content of 24 mol % and an average sphere-equivalent 
diameter of 0.8 .mu.m were used as seed crystals to form an emulsion in an 
aqueous gelatin solution by a controlled double jet method, the emulsion 
comprising twined crystal grains comprising silver iodobromide and having 
an average sphere-equivalent diameter of 1.2 .mu.m, in which a core/shell 
ratio was 1:2, a shell iodide content was 2 mol %, and an average iodide 
content was 10 mol %. 
After grain formation, the emulsion was subjected to a normal 
desalting/washing step and redispersed under conditions of 40.degree. C., 
a pAg of 8.9, and a pH of 6.3, thereby preparing an emulsion Em-1. 
Thiosulfonic acid compounds 1-2, 1-6, and 1-16 listed in Table A were 
individually added in a reaction vessel in addition amounts listed in 
Table 1-1, one minute before shell formation was started, to perform grain 
formation, thereby preparing emulsions Em-2 to Em-4. 
TABLE 1-1 
______________________________________ 
Thiosulfonic Acid 
Addition Amount per 
Emulsion Compound Mol of Ag 
______________________________________ 
Em-2 1-2 3 .times. 10.sup.-5 mol 
Em-3 1-6 3 .times. 10.sup.-5 mol 
Em-4 1-16 3 .times. 10.sup.-5 mol 
______________________________________ 
When grain formation was performed following the same procedures as for 
Em-1, the reduction sensitizer A-1 (L-ascorbic acid) and tin chloride were 
added in addition amounts listed in Table 1-2 one minute after shell 
formation was started, thereby preparing emulsions Em-5 and Em-6. 
TABLE 1-2 
______________________________________ 
Reduction Sensi- 
Addition Amount per 
Emulsion tizer Mol of Ag 
______________________________________ 
Em-5 L-ascorbic Acid 
2 .times. 10.sup.-3 mol 
Em-6 Tin Chloride (II) 
1 .times. 10.sup.-5 mol 
______________________________________ 
When grain formation was performed following the same procedures as for 
Em-1, the thiosulfonic acid compounds 1-2, 1-6, and 1-16 were added one 
minute before shell formation was started, and optimal amounts of the 
reduction sensitizer L-ascrobic acid and tin chloride were added one 
minute after shell formation was started, thereby preparing emulsions Em-7 
to Em-12 of the present invention and comparative examples listed in Table 
1-3. 
TABLE 1-3 
______________________________________ 
Addition Thiosulfonic 
Addition 
Emul- Reduction Amount per Acid Amount per 
sion Sensitizer 
Mol of Ag Compound Mol of Ag 
______________________________________ 
Em-7 L-ascorbic 
2 .times. 10.sup.-3 mol 
1-2 3 .times. 10.sup.-5 mol 
Acid 
8 " " 1-6 " 
9 " " 1-16 " 
10 Tin 1 .times. 10.sup.-5 mol 
1-2 " 
Chloride 
11 " " 1-6 " 
12 " " 1-16 " 
______________________________________ 
The emulsions Em-1 to Em-12 of the present invention and comparative 
examples prepared as described above were subjected to optimal 
gold-plus-sulfur-sensitization by using sodium thiosulfate and chloroauric 
acid, thereby preparing emulsions. 
Emulsion and protective layers in amounts as listed in Table 1-4 were 
coated on triacetylcellulose film supports having undercoating layers. 
TABLE 1-4 
______________________________________ 
(1) Emulsion Layer 
Emulsion . . . emulsions 1 to 12 shown in Table 1-1 
to 1-3 (silver 1.7 .times. 10.sup.-2 mol/m.sup.2) 
Coupler (1.5 .times. 10.sup.-3 mol/m.sup.2) 
##STR3## 
Tricresylphosphate (1.10 g/m.sup.2) 
Gelatin (2.30 g/m.sup.2) 
(2) Protective Layer 
2,4-dichlorotriazine-6-hydroxy-s- 
(0.08 g/m.sup.2) 
triazine sodium salt 
Gelatin (1.80 g/m.sup.2) 
______________________________________ 
These samples were subjected to sensitometry exposure, thereby performing 
the following color development. 
The processed samples were subjected to density measurement by using a 
green filter. The results of obtained photographic properties are listed 
in Table 1-5. 
Development was performed under the following conditions at a temperature 
of 38.degree. C. 
______________________________________ 
1. Color Development 
2 min. 45 sec. 
2. Bleaching 6 min. 30 sec. 
3. Washing 3 min. 15 sec. 
4. Fixing 6 min. 30 sec. 
5. Washing 3 min. 15 sec. 
6. Stabilizing 3 min. 15 sec. 
______________________________________ 
The compositions of the processing solutions used in the above steps were 
as follows. 
______________________________________ 
Color Developer: 
Sodium Nitrilotriacetic Acid 
1.4 g 
Sodium Sulfite 4.0 g 
Sodium Carbonate 30.0 g 
Potassium Bromide 1.4 g 
Hydroxylamine Sulfate 2.4 g 
4-(N-ethyl-N-.beta.-hydroxyethylamino)- 
4.5 g 
2-methyl-aniline Sulfate 
Water to make 1 l 
Bleaching Solution: 
Sodium Bromide 160.0 g 
Ammonia Water (28%) 25.0 ml 
Iron (III) Sodium Ethylenediaminetetra- 
130 g 
acetate trihydrate 
Glacial Acetic Acid 14 ml 
Water to make 1 l 
Fixing Solution: 
Sodium Tetrapolyphosphate 2.0 g 
Sodium Sulfite 4.0 g 
Ammonium Thiosulfate (700 g/l) 
175.0 ml 
Sodium Bisulfite 4.6 g 
Water to make 1 l 
Stabilizing Solution: 
Formalin 8.0 ml 
Water to make 1 l 
______________________________________ 
In this case, a normal wedge exposure was performed for ten seconds and 
1/100 seconds. 
A light source was adjusted at a color temperature of 4,800.degree. K. by 
using a filter, and blue light was extracted by using a blue filter (BPN42 
(tradename): available from Fuji Photo Film Co. Ltd.). Sensitivities were 
compared at a point from a fogging density by an optical density of 0.2. 
The sensitivities are listed as relative sensitivities assuming that the 
sensitivity of a sample using the emulsion Em-1 is 100 (100 for both 
1/100" and 10"). Each fogging density was a value with respect to a 
non-exposed portion and the same for both 1/100" and 10"). 
As is apparent from Table 1-5, each emulsion of the present invention had 
low fogging density and high sensitivity (especially with low intensity). 
After samples 1 to 12 coated with the emulsions 1 to 12 were aged in the 
environment wherein temperature was 25.degree. C. and the humidity was 60% 
for 12 months, the sensitometry test was performed following the same 
procedures as described above. The results represented by relative 
sensitivities assuming that the sensitivity of the sample 1 before aging 
was 100 are listed in Table 1-6. According to each sample coated with the 
emulsion of the present invention, both a decrease in sensitivity and an 
increase in fogging density were small after aging, thereby realizing good 
storage stability. 
TABLE 1-5 
______________________________________ 
1/100" Sen- 
10" Sensi- Fogging 
Sample sitivity tivity Density 
Remarks 
______________________________________ 
1 100 100 0.20 Comparative 
Example 
2 83 78 0.18 Comparative 
Example 
3 81 75 0.19 Comparative 
Example 
4 75 70 0.18 Comparative 
Example 
5 121 130 0.19 Present 
Invention 
6 100 104 0.29 Comparative 
Example 
7 130 140 0.19 Present 
Invention 
8 128 135 0.18 Present 
Invention 
9 126 133 0.18 Present 
Invention 
10 120 126 0.23 Comparative 
Example 
11 120 126 0.22 Comparative 
Example 
12 115 120 0.26 Comparative 
Example 
______________________________________ 
TABLE 1-6 
______________________________________ 
1/100" Sen- 
10" Sensi- Fogging 
Sample sitivity tivity Density 
Remarks 
______________________________________ 
1* 100 100 0.20 Comparative 
Example 
1 95 93 0.21 Comparative 
Example 
2 82 76 0.17 Comparative 
Example 
3 80 73 0.17 Comparative 
Example 
4 73 68 0.17 Comparative 
Example 
5 120 128 0.19 Present 
Invention 
6 90 95 0.45 Comparative 
Example 
7 129 140 0.19 Present 
Invention 
8 128 133 0.19 Present 
Invention 
9 124 132 0.18 Present 
Invention 
10 101 110 0.33 Comparative 
Example 
11 98 105 0.34 Comparative 
Example 
12 95 103 0.36 Comparative 
Example 
______________________________________ 
*represents results of sensitometry obtained immediately after coating. 
When the same test was performed for each of the ascorbic acid compounds 
A-2 to A-10, the same effects were obtained. 
EXAMPLE 2 
In a process of forming an emulsion following the same procedures as the 
emulsion preparing method described in Example 1, 2.times.10.sup.-3 mol of 
L-ascorbic acid per mol of silver were added at the following addition 
times, thereby preparing emulsions. At the same time, 3.times.10.sup.-5 
mol of a thiosulfonic acid compound 1-2 per mol of silver were added 
during grain formation, one minute before shell formation was started, and 
after grain formation and before washing, thereby preparing emulsions. 
Addition Time of L-ascorbic Acid 
a Before grain formation was started 
b One minute after shell formation was started 
c Immediately after shell formation was completed 
d Immediately before chemical sensitization was started 
Addition Time of Thiosulfonic Acid Compound 
A One minute before shell formation was started 
B After grain formation and before washing 
The prepared emulsions were optimally subjected to chemical sensitization 
by gold-plus-sulfur to prepare emulsions 13 to 24 as listed in Table 2-1. 
TABLE 2-1 
______________________________________ 
L-ascorbic Acid 
Thiosulfonic Acid 
Emulsion Addition Time 
Addition Time 
______________________________________ 
13 a No Addition 
14 " A 
15 " B 
16 b No Addition 
17 " A 
18 " B 
19 c No Addition 
20 " A 
21 " B 
22 d No Addition 
23 " A 
24 " B 
______________________________________ 
These emulsions were coated following the same procedures as in Example 1 
to perform sensitometry estimation, thereby obtaining the results shown in 
Table 2-2. Similar to Example 1, sensitivities are estimated as relative 
sensitivities assuming that the sensitivity of Em-1 optimally subjected to 
gold-plus-sulfur sensitization is 100. 
TABLE 2-2 
______________________________________ 
Emul- 1/100" Sen- 
10" Sensi- Fogging 
sion sitivity tivity Density 
Remarks 
______________________________________ 
13 115 120 0.21 Present 
Invention 
14 125 130 0.20 Present 
Invention 
15 113 120 0.20 Present 
Invention 
16 121 130 0.19 Present 
Invention 
17 130 140 0.19 Present 
Invention 
18 126 133 0.20 Present 
Invention 
19 115 123 0.22 Present 
Invention 
20 120 126 0.21 Present 
Invention 
21 120 122 0.21 Present 
Invention 
22 110 115 0.22 Present 
Invention 
23 116 121 0.22 Present 
Invention 
24 115 120 0.20 Present 
Invention 
1 100 100 0.20 Comparative 
Example 
______________________________________ 
In this case, the emulsions Em-16 and Em-17 were prepared by adding the 
same ascorbic acid and thiosulfonic acid (I-2) at the same times as in the 
preparation of the emulsions Em-5 and Em-7, respectively. As is apparent 
from Tables 1-5 and 2-2, the emulsions Em-16 and Em-5 and the emulsions 
Em-17 and Em-7 had the same sensitivity and fogging density, respectively. 
That is, the effects of the present invention have good reproducibility. 
As is apparent from Table 2-2, each emulsion of the present invention had 
high sensitivity and low fogging density. When each coated sample wa aged 
following the same procedures as in Example 1 and its photographic 
properties were estimated, the same results as in Example 1 were obtained. 
EXAMPLE 3 
The following dyes were added to the chemically sensitized emulsions 
prepared in Example 1 as shown in Table 3-1, thereby preparing spectrally 
sensitized emulsions. 
The prepared emulsions were coated following the same procedures as in 
Example 1 to perform a sensitometry test. 
##STR4## 
______________________________________ 
Dye Group 1 (Red-Sensitive Dye) 
Sensitizing Dye IX 5.4 .times. 10.sup.-5 mol/molAg 
Sensitizing Dye II 1.4 .times. 10.sup.-5 mol/molAg 
Sensitizing Dye III 2.4 .times. 10.sup.-4 mol/molAg 
Sensitizing Dye IV 3.1 .times. 10.sup.-5 mol/molAg 
Dye Group 2 (Green-Sensitive Dye) 
Sensitizing Dye V 3.5 .times. 10.sup.-5 mol/molAg 
Sensitizing Dye VI 8.0 .times. 10.sup.-5 mol/molAg 
Sensitizing Dye VII 3.0 .times. 10.sup.-4 mol/molAg 
Dye Group 3 (Blue-Sensitive Dye) 
Sensitizing Dye VIII 
2.2 .times. 10.sup.-4 mol/molAg 
______________________________________ 
TABLE 3-1 
______________________________________ 
Spectrally Chemically Sensitized and 
Sensitized Spectrally Non-sensitized 
Sensitizing 
Emulsion Emulsion Dye Group 
______________________________________ 
Em - 25 Em - 1 1 
Em - 26 " 2 
Em - 27 " 3 
Em - 28 " 1 
Em - 29 " 2 
Em - 30 " 3 
Em - 31 Em - 7 1 
Em - 32 " 2 
Em - 33 " 3 
______________________________________ 
The sensitometry test was performed following the same procedures as in 
Example 1 except that the emulsions added with the red- or green-sensitive 
dyes were exposed by using a yellow filter (SC-52 (tradename): available 
from Fuji Photo Film Co. Ltd.) in place of the blue filter used in Example 
1 and the emulsions added with the blue-sensitive dye were exposed without 
using a filter. Table 3-2 shows sensitivities of Em-28 to Em-33 as 
relative sensitivities assuming that sensitivities of Em-25, Em-26, and 
Em-27 are 100 with respect to ten-sec and 1/100-sec exposures (Each 
fogging density is a value with respect to a non-exposed portion and was 
the same for both 1/100" and 10"). 
TABLE 3-2 
______________________________________ 
Emul- 1/100" Sen- 
10" Sensi- Fogging 
sion sitivity tivity Density 
Remarks 
______________________________________ 
Em-25 100 100 0.22 Comparative 
Example 
26 100 100 0.21 Comparative 
Example 
27 100 100 0.20 Comparative 
Example 
28 112 120 0 21 Present 
Invention 
29 115 122 0.20 Present 
Invention 
30 120 130 0.19 Present 
Invention 
31 115 120 0.20 Present 
Invention 
32 120 125 0.19 Present 
Invention 
33 125 135 0.20 Present 
Invention 
______________________________________ 
As is apparent from Table 3-2, each emulsion of the present invention had 
high sensitivity and low fogging density even after it was subjected to 
spectral sensitization. 
EXAMPLE 4 
A plurality of layers having the following compositions were coated on an 
undercoated triacetylcellulose film support to prepare a sample of a 
multilayer color light-sensitive material. 
Light-Sensitive Layer Composition 
Numerals corresponding to the respective components indicate coating 
amounts in units of g/m.sup.2. A coating amount of silver halide is 
represented in units of g/m.sup.2 of silver. A coating amount of the 
sensitizing dye is represented in units of mols per mol of the silver 
halide in the same layer. 
______________________________________ 
(Sample) 
______________________________________ 
Layer 1: Antihalation Layer 
Black Colloid Silver silver 0.18 
Gelatin 1.40 
Layer 2: Interlayer 
2,5-di-t-pentadecylhydroquinone 
0.18 
EX-1 0.07 
EX-3 0.02 
EX-12 0.002 
U-1 0.06 
U-2 0.08 
U-3 0.10 
HBS-1 0.10 
HBS-2 0.02 
Gelatin 1.04 
Layer 3: 1st Red-Sensitive Emulsion Layer 
Monodisperse Silver Iodobromide Emulsion 
silver 0.55 
(silver iodide = 6 mol %, average grain size = 
0.6 .mu.m, variation coefficient of grain size = 
0.15) 
Sensitizing Dye I 6.9 .times. 10.sup.-5 
Sensitizing Dye II 1.8 .times. 10.sup.-5 
Sensitizing Dye III 3.1 .times. 10.sup.-4 
Sensitizing Dye IV 4.0 .times. 10.sup.-5 
EX-2 0.350 
HBS-1 0.005 
EX-10 0.020 
Gelatin 1.20 
Layer 4: 2nd Red-Sensitive Emulsion Layer 
Tabular Silver Iodobromide Emulsion (silver 
silver 1.0 
iodide = 10 mol %, average grain size = 
0.7 .mu.m, average aspect ratio = 5.5, average 
thickness = 0.2 .mu.m) 
Sensitizing Dye I 5.1 .times. 10.sup.-5 
Sensitizing Dye II 1.4 .times. 10.sup.-5 
Sensitizing Dye III 2.3 .times. 10.sup.-4 
Sensitizing Dye IV 3.0 .times. 10.sup.-5 
EX-2 0.400 
EX-3 0.050 
EX-10 0.015 
Gelatin 1.30 
Layer 5: 3rd Red-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion I 
silver 1.60 
EX-3 0.240 
EX-4 0.120 
HBS-1 0.22 
HBS-2 0.10 
Gelatin 1.63 
Layer 6: Interlayer 
EX-5 0.040 
HBS-1 0.020 
Gelatin 0.80 
Layer 7: 1st Green-Sensitive Emulsion Layer 
Tabular Silver Iodobromide Emulsion (silver 
silver 0.40 
iodide = 6 mol %, average grain size = 0.6 .mu.m, 
average aspect ratio = 6.0, average thickness = 
0.15 .mu.m) 
Sensitizing Dye V 3.0 .times. 10.sup.-5 
Sensitizing Dye VI 1.0 .times. 10.sup.-4 
Sensitizing Dye VII 3.8 .times. 10.sup.-4 
EX-6 0.260 
EX-1 0.021 
EX-7 0.030 
EX-8 0.025 
HBS-1 0.100 
HBS-4 0.010 
Gelatin 0.75 
Layer 8: 2nd Green-Sensitive Emulsion Layer 
Monodisperse Silver Iodobromide Emulsion 
silver 0.80 
(silver iodide = 9 mol %, average grain size = 
0.7 .mu.m, variation coefficient of grain size = 
0.18) 
Sensitizing Dye V 2.1 .times. 10.sup.-5 
Sensitizing Dye VI 7.0 .times. 10.sup.-5 
Sensitizing Dye VII 2.6 .times. 10.sup.-4 
EX-6 0.180 
EX-8 0.010 
EX-1 0.008 
EX-7 0.012 
HBS-1 0.160 
HBS-4 0.008 
Gelatin 1.10 
Layer 9: 3rd Green-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion II 
silver 1.2 
EX-6 0.065 
EX-11 0.030 
EX-1 0.025 
HBS-1 0.25 
HBS-2 0.10 
Gelatin 1.74 
Layer 10: Yellow Filter Layer 
Yellow Colloid Silver silver 0.05 
EX-5 0.08 
HBS-3 0.03 
Gelatin 0.95 
Layer 11: 1st Blue-Sensitive Emulsion Layer 
Tabular Silver Iodobromide Emulsion (silver 
silver 0.24 
iodide = 6 mol %, average grain size = 0.6 .mu.m, 
average aspect ratio = 5.7, average thickness = 
0.15 .mu.m) 
Sensitizing Dye VIII 3.5 .times. 10.sup.-4 
EX-9 0.8 
EX-8 0.12 
HBS-1 0.28 
Gelatin 1.28 
Layer 12: 2nd Blue-Sensitive Emulsion Layer 
Monodisperse Silver Iodobromide Emulsion 
silver 0.45 
(silver iodide = 10 mol %, average grain size = 
0.8 .mu.m, variation coefficient of grain size = 
0.16) 
Sensitizing Dye VIII 2.1 .times. 10.sup.-4 
EX-9 0.20 
EX-10 0.015 
HBS-1 0.03 
Gelatin 0.46 
Layer 13: 3rd Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion III 
silver 0.77 
EX-9 0.20 
HBS-1 0.07 
Gelatin 0.69 
Layer 14: 1st Protective Layer 
Silver Iodobromide Emulsion (silver iodide = 
silver 0.5 
1 mol %, average grain size = 0.07 .mu.m) 
U-4 0.11 
U-5 0.17 
HBS-1 0.90 
Gelatin 1.00 
Layer 15: 2nd Protective Layer 
Polymethylacrylate Grains 
silver 0.54 
(diameter = about 1.5 .mu.m) 
S-1 0.15 
S-2 0.05 
Gelatin 0.72 
______________________________________ 
In addition to the above components, a gelatin hardener H-1 and/or a 
surfactant were added to each layer. 
Formulas of the used compounds are listed in Table B. 
Samples 401 to 403 were prepared following the same procedures as the above 
described sample except that the silver iodobromide emulsions I, II, and 
III in the layers 5, 9, and 13, respectively, were changed. 
These samples were subjected to sensitometry exposure to perform the 
following color development. 
The processed samples were subjected to density measurement by using red, 
green, and blue filters. The obtained results are shown in Table 4-1. 
The results of photographic properties are represented by relative 
sensitivities of the red-, green-, and blue-sensitive layers assuming that 
the sensitivity of the sample 401 is 100. Processing Method 
The color development process was performed at 38.degree. C. in accordance 
with the following process steps. 
______________________________________ 
Color Development 3 min. 15 sec. 
Bleaching 6 min. 30 sec. 
Washing 2 min. 10 sec. 
Fixing 4 min. 20 sec. 
Washing 3 min. 15 sec. 
Stabilizing 1 min. 05 sec. 
______________________________________ 
The processing solution compositions used in the respective steps were as 
follows. 
______________________________________ 
Color Development Solution 
Diethylenetriaminepentaacetic 
1.0 g 
Acid 
1-hydroxyethylidene-1,1- 
diphosphonic acid 2.0 g 
Sodium Sulfite 4.0 g 
Potassium Carbonate 30.0 g 
Potassium Bromide 1.4 g 
Potassium Iodide 1.3 mg 
Hydroxylamine Sulfate 2.4 g 
4-(N-ethyl-N-.beta.-hydroxyethylamino)- 
4.5 g 
2-methylanilinesulfate 
Water to make 1.0 l 
pH 10.0 
Bleaching Solution 
Ferric Ammonium 100.0 g 
Ethylenediaminetetraacetate 
Disodium 10.0 g 
Ethylenediaminetetraacetate 
Ammonium Bromide 150.0 g 
Ammonium Nitrate 10.0 g 
Water to make 1.0 
pH 6.0 
Fixing Solution 
Disodium 1.0 g 
Ethylenediaminetetraacetate 
Sodium Sulfite 4.0 g 
Ammonium Thiosulfate 175.0 ml 
Aqueous solution (70) 
Sodium Bisulfite 4.6 g 
Water to make 1.0 l 
pH 6.6 
Stabilizing Solution 
Formalin (40%) 2.0 ml 
Polyoxyethylene-p-monononyl- 
0.3 g 
phenylether (average poly- 
merization degree = 10) 
Water to make 1.0 l 
______________________________________ 
TABLE 4 - 1 
__________________________________________________________________________ 
Emulsion 
Emulsion 
Emulsion 
of layer 
of layer 
of layer 
1/100" 
10" Fogging 
Sample 
5 9 13 Sensitivity 
Sensitivity 
Density 
Remarks 
__________________________________________________________________________ 
401 Em - 25 
Em - 26 
Em - 27 
R 100 R 100 R 0.22 
Comparative 
G 100 G 100 G 0.23 
Example 
B 100 B 100 B 0.21 
402 Em - 28 
Em - 29 
Em - 30 
R 100 R 119 R 0.20 
Present 
G 114 G 121 G 0.20 
Invention 
B 121 B 128 B 0.19 
403 Em - 31 
Em - 32 
Em - 33 
R 116 R 119 R 0.19 
Present 
G 121 G 122 G 0.20 
Invention 
B 122 B 133 B 0.19 
__________________________________________________________________________ 
As is apparent from Table 4-1, the emulsions of the present invention have 
an effect of increasing the sensitivity with almost no increase in fogging 
density. 
When photographic properties were checked after aging following the same 
procedures as in Example 1, the samples using the emulsions of the present 
invention had good storage stability. 
EXAMPLE 5 
The samples 401 to 403 of the present invention and the comparative 
examples were exposed following the same procedures as in Example 4 and 
processed as follows by using an automatic developing machine. 
______________________________________ 
Processing Method 
Step Time Temperature 
______________________________________ 
Color Development 
3 min. 15 sec. 38.degree. C. 
Bleaching 1 min. 00 sec. 38.degree. C. 
Bleach-Fixing 3 min. 15 sec. 38.degree. C. 
Washing (1) 40 sec. 35.degree. C. 
Washing (2) 1 min. 00 sec. 35.degree. C. 
Stabilizing 40 sec. 38.degree. C. 
Drying 1 min. 15 sec. 55.degree. C. 
______________________________________ 
The processing solution compositions will be 
described below. 
Color Developing Solution 
(g) 
Diethylenetriaminepentaacetic 
1.0 
Acid 
1-hydroxyethylidene-1,1- 
3.0 
diphosphonic Acid 
Sodium Sulfite 4.0 
Potassium Carbonate 30.0 
Potassium Bromide 1.4 
Potassium Iodide 1.5 mg 
Hydroxylamine Sulfate 2.4 
4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]- 
4.5 
2-methylaniline Sulfate 
Water to make 1.0 l 
pH 10.05 
Bleaching Solution (g) 
Ferric Ammonium 120.0 
Ethylenediaminetetraacetate 
Dihydrate 
Disodium 10.0 
Ethylenediaminetetraacetate 
Ammonium Bromide 100.0 
Ammonium Nitrate 10.0 
Bleaching Accelerator 0.005 mol 
##STR5## 
Ammonia Water (27%) 15.0 ml 
Water to make 1.0 l 
pH 6.3 
Bleach-Fixing Solution (g) 
Ferric Ammonium 50.0 
Ethylenediaminetetraacetate 
Dihydrate 
Disodium 5.0 
Ethylenediaminetetraacetate 
Sodium Sulfite 12.0 
Ammonium Thiosulfate 240.0 ml 
Aqueous Solution (70%) 
Ammonia Water (27%) 6.0 ml 
Water to make 1.0 l 
pH 7.2 
Washing Solution 
Tap water was supplied to a mixed-bed column 
filled with an H type strongly acidic cation 
exchange resin (Amberlite IR-120B: available from 
Rohm & Haas Co.) and an OH type basic anion 
exchange resin (Amberlite IR-400) to set the con- 
centrations of calcium and magnesium to be 3 mg/l 
or less. Subsequently, 20 mg/l of sodium iso- 
cyanuric acid dichloride and 0.15 g/l of sodium 
sulfate were added. The pH of the solution fell 
within the range of 6.5 to 7.5. 
Stabilizing Solution (g) 
Formalin (37%) 2.0 ml 
Polyoxyethylene-p-monononyl- 
0.3 
phenylether (average poly- 
merization degree = 10) 
Disodium 0.05 
Ethylenediaminetetraacetate 
Water to make 1.0 l 
pH 5.0 to 8.0 
______________________________________ 
The samples 402 and 403 of the present invention provided the good results 
as in Example 4 after they were subjected to the above processing. 
EXAMPLE 6 
The samples 401 to 403 of the present invention and the comparative 
examples were exposed following the same procedures as in Example 4 and 
processed as follows by using an automatic developing machine. 
______________________________________ 
Processing Method 
Step Time Temperature 
______________________________________ 
Color development 
2 min. 30 sec. 40.degree. C. 
Bleach-Fixing 3 min. 00 sec. 40.degree. C. 
Washing (1) 20 sec. 35.degree. C. 
Washing (2) 20 sec. 35.degree. C. 
Stabilizing 20 sec. 35.degree. C. 
Drying 50 sec. 65.degree. C. 
______________________________________ 
The processing solution compositions will be described below. 
______________________________________ 
Color Developing Solution 
(g) 
Diethylenetriaminepentaacetic 
2.0 
Acid 
1-hydroxyethylidene-1,1- 
3.0 
diphosphonic Acid 
Sodium Sulfite 4.0 
Potassium Carbonate 30.0 
Potassium Bromide 1.4 
Potassium Iodide 1.5 mg 
Hydroxylamine Sulfate 2.4 
4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]- 
4.5 
2-methylaniline Sulfate 
Water to make 1.0 l 
pH 10.05 
Bleach-Fixing Solution (g) 
Ferric Ammonium 50.0 
Ethylenediaminetetraacetate 
Dihydrate 
Disodium 5.0 
Ethylenediaminetetraacetate 
Sodium Sulfite 12.0 
Ammonium Thiosulfate 260.0 ml 
Aqueous Solution (70%) 
Acetic Acid (98%) 5.0 ml 
Bleaching Accelerator 0.01 mol 
##STR6## 
Water to make 1.0 l 
pH 6.0 
Washing Solution 
Tap water was supplied to a mixed-bed column 
filled with an H type strongly acidic cation 
exchange resin (Amberlite IR-120B: available from 
Rohm & Haas Co.) and an OH type basic anion 
exchange resin (Amberlite IR-400) to set the con- 
centrations of calcium and magnesium to be 3 mg/l 
or less. Subsequently, 20 mg/l of sodium 
isocyanuric acid dichloride and 0.15 g/l of sodium 
sulfate were added. The pH of the solution fell 
within the range of 6.5 to 7.5. 
Stabilizing Solution (g) 
Formalin (37%) 2.0 ml 
Polyoxyethylene-p-monononyl- 
0.3 
phenylether (average poly- 
merization degree = 10) 
Disodium 0.05 
Ethylenediaminetetraacetate 
Water to make 1.0 l 
pH 5.0 to 8.0 
______________________________________ 
The samples 402 and 403 of the present invention provided the good results 
as in Example 4 after they were subjected to the above processing. 
EXAMPLE 7 
A plurality of layers having the following compositions were coated on an 
undercoated cellulose triacetate film support to prepare a sample as a 
multilatered color light-sensitive material. 
Compositions of Light-Sensitive Layers 
The amounts are represented in units of g/m.sup.2. The coated amounts of a 
silver halide and colloid silver are represented in units of g/m.sup.2 of 
silver, and that of sensitizing dyes is represented by the number of mols 
per mol of the silver halide in the same layer. 
______________________________________ 
Layer 1: Antihalation Layer 
Black Colloid Silver 0.2 
coated silver amount 
Gelatin 2.2 
UV-1 0.1 
UV-2 0.2 
Cpd-1 0.05 
Solv-1 0.01 
Solv-2 0.01 
Solv-3 0.08 
Layer 2: Interlayer 
Fine Silver Bromide Grain 0.15 
(sphere-equivalent 
diameter = 0.07 m) 
coated silver amount 
Gelatin 1.0 
Cpd-2 0.2 
Layer 3: 1st Red-Sensitive emulsion Layer 
Silver Iodobromide Emulsion (AgI = 10.0 mol %, 
0.26 
internally high AgI type, sphere-equivalent 
diameter = 0.7 .mu.m, variation coefficient of 
sphere-equivalent diameter = 14%, 
tetradecahedral grain) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 4.0 mol %, 
0.2 
internally high AgI type, sphere-ecui,valent 
diameter = 0.4 .mu.m, variation coefficient of 
sphere-equivalent diameter = 22%, 
tetradecahedral grain) 
coated silver amount 
Gelatin 1.0 
EXS-1 4.5 .times. 10.sup.-4 
EXS-2 1.5 .times. 10.sup.-4 
EXS-3 0.4 .times. 10.sup.-4 
ExS-4 0.3 .times. 10.sup.-4 
ExC-1 0.33 
ExC-2 0.009 
ExC-3 0.023 
ExC-6 0.14 
Layer 4: 2nd Red-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 16 mol%, 
0.55 
internally high AgI type, sphere-equivalent 
diameter = 1.0 .mu.m, variation coefficient of 
sphere-equivalent diameter = 25%, tabular 
grain, diameter/thickness ratio = 4.0) 
coated silver amount 
Gelatin 0.7 
ExS-1 3 .times. 10.sup.-4 
ExS-2 1 .times. 10.sup.-4 
ExS-3 0.3 .times. 10.sup.-4 
ExS-4 0.3 .times. 10.sup.-4 
ExC-3 0.05 
ExC-4 0.10 
ExC-6 0.08 
Layer 5: 3rd Red-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion I (internally 
high AgI type, sphere-equivalent diameter = 
1.2 .mu.m, variation coefficient of sphere- 
equivalent diameter = 28%) 
coated silver amount 0.9 
Gelatin 0.6 
ExS-1 2 .times. 10.sup.-4 
EXS-2 0.6 .times. 10.sup.-4 
EXS-3 0.2 .times. 10.sup.-4 
ExC-4 0.07 
ExC-5 0.06 
Solv-1 0.12 
Solv-2 0.12 
Layer 6: Interlayer 
Gelatin 1.0 
Cpd-4 0.1 
Layer 7: 1st Green-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 10.0 mol %, 
0.2 
internally high AgI type, sphere-equivalent 
diameter = 0.7 .mu.m, variation coefficient of 
sphere-equivalent diameter = 14%, tetra- 
decahedral grain) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 4.0 mol %, 
0.1 
internally high AgI type, sphere-equivalent 
diameter = 0.4 .mu.m, variation coefficient of 
sphere-equivalent diameter = 22%, tetra- 
decahedral grain) 
coated silver amount 
Gelatin 1.2 
ExS-5 5 .times. 10.sup.-4 
ExS-6 2 .times. 10.sup.-4 
ExS-7 1 .times. 10.sup.-4 
ExM-1 0.41 
ExM-2 0.10 
ExM-5 0.03 
Solv-1 0.2 
Solv-5 0.03 
Layer 8: 2nd Green-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 10 mol %, 
0.4 
internally high iodide type, sphere- 
equivalent diameter = 1.0 .mu.m, variation 
coefficient of sphere-equivalent diameter = 
25%, tabular grain, diameter/thickness ratio = 
3.0) 
coated silver amount 
Gelatin 0.35 
ExS-5 3.5 .times. 10.sup.-4 
ExS-6 1.4 .times. 10.sup.-4 
ExS-7 0.7 .times. 10.sup.-4 
ExM-1 0.09 
ExM-3 0.01 
Solv-1 0.15 
Solv-5 0.03 
Layer 9: Interlayer 
Gelatin 0.5 
Layer 10: 3rd Green-Sensitive Emulsion Layer 
Silver Iodobromide emulsion II (internally 
1.0 
high AgI type, sphere-equivalent diameter = 
1.2 .mu.m, variation coefficient of sphere- 
equivalent diameter = 28%) 
coated silver amount 
Gelatin 0.8 
ExS-5 2 .times. 10.sup.-4 
ExS-6 0.8 .times. 10.sup.-4 
ExS-7 0.8 .times. 10.sup.-4 
ExM-3 0.01 
ExM-4 0.04 
ExC-4 0.005 
Solv-1 0.2 
Layer 11: Yellow Filter Layer 
Cpd-3 0.05 
Gelatin 0.5 
Solv-1 0.1 
Layer 12: Interlayer 
Gelatin 0.5 
Cpd-2 0.1 
Layer 13: lst Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 10 mol %, 
0.1 
internally high iodide type, sphere-equivalent 
diameter = 0.7 .mu.m, variation coefficient of 
sphere-equivalent diameter = 14%, tetra- 
decahedral grain) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 4.0 mol .mu., 
0.05 
internally high iodide type, sphere-equivalent 
diameter = 0.4 .mu.m, variation coefficient of 
sphere-equivalent diameter = 22%, tetra- 
decahedral graih) 
coated silver amount 
Gelatin 1.0 
ExS-8 3 .times. 10.sup.-4 
ExY-1 0.53 
ExY-2 0.02 
Solv-1 0.15 
Layer 14: 2nd Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 19.0 mol %, 
0.19 
internally high AgI type, sphere-equivalent 
diameter = 1.0 .mu.m, variation coefficient of 
sphere-equivalent diameter = 16%, tetra- 
decahedral grain) 
coated silver amount 
Gelatin 0.3 
ExS-8 2 .times. 10.sup.-4 
ExY-1 0.22 
Solv-1 0.07 
Layer 15: Interlayer 
Fine Silver Iodobromide Grain (AgI = 2 mol %, 
0.2 
homogeneous type, sphere-equivalent diameter = 
0.13 .mu.m) 
coated silver amount 
Gelatin 
Layer 16: 3rd Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion III (internally 
1.0 
high AgI type, sphere-equivalent diameter = 
1.2 .mu.m, variation coefficient of sphere- 
equivalent diameter = 28%) 
coated silver amount 
Gelatin 0.5 
ExS-8 1.5 .times. 10.sup.-4 
ExY-1 0.2 
Solv-4 0.07 
Layer 17: 1st Protective Layer 
Gelatin 1.8 
UV-1 0.1 
UV-2 0.2 
Solv-1 0.01 
Solv-2 0.01 
Layer 18: 2nd Protective Layer 
Fine Silver Bromide Grain 0.18 
(sphere-equivalent diameter = 0.07 .mu.m) 
coating silver amount 
Gelatin 0.7 
Polymethylmethacrylate Grain 
0.2 
(diameter = 1.5 .mu.m) 
W-1 0.02 
H-1 0.4 
Cpd-5 1.0 
______________________________________ 
Formulas of the compounds used are listed in Table C. 
Samples 701 to 703 were prepared following the same procedures as for the 
above sample except that the silver iodobromide emulsions I, II, and III 
in the layers 5, 10, and 16, respectively, were changed. 
These samples were left under conditions of a temperature of 40.degree. C. 
and a relative humidity of 70% for 14 hours and then subjected to 
sensitometry exposure to perform color development following the same 
procedures as in Example 4. 
The processed samples were subjected to density measurement by using red, 
green, and blue filters. The results obtained are shown in Table 7-1. 
The results of photographic properties are represented by relative 
sensitivities of the red-, green-, and blue-sensitive layers assuming that 
the sensitivity of the sample 701 is 100. 
As is apparent from Table 7-1, the emulsions of the present invention have 
an effect of increasing the sensitivity with almost no increase in fogging 
density. 
When the samples were aged following the same procedures as in Example 1 
and their photographic properties were checked, the samples 702 and 703 
using the emulsions of the present invention provided good photographic 
properties. 
TABLE 7-1 
__________________________________________________________________________ 
Emulsion 
Emulsion 
Emulsion 
of layer 
of layer 
of layer 
1/100" 
10" Fogging 
Sample 
5 10 16 Sensitivity 
Sensitivity 
Density 
Remarks 
__________________________________________________________________________ 
701 Em - 1 
Em - 1 
Em - 1 
R 100 R 100 R 0.24 
Comparative 
G 100 G 100 G 0.23 
Example 
B 100 B 100 B 0.24 
702 Em - 5 
Em - 5 
Em - 7 
R 109 R 118 R 0.23 
Present 
G 116 G 122 G 0.21 
Invention 
B 122 B 130 B 0.22 
703 Em - 7 
Em - 8 
Em - 9 
R 112 R 115 R 0.22 
Present 
G 125 G 130 G 0.21 
Invention 
B 128 B 135 B 0.21 
__________________________________________________________________________ 
*R, G, and B represent red, green, and blue sensitivities, respectively. 
fogging density represents a value obtained by subtracting that of the 
same sample subjected only to the same fixing and stabilizing steps as 
described in the text. 
EXAMPLE 8 
A plurality of layers having the following compositions were coated on an 
undercoated triacetylcellulose film support to prepare a sample as a 
multilayered color light-sensitive material. 
Compositions of Light-Sensitive Layers 
The coated amount of a silver halide and colloid silver are represented in 
units of g/m.sup.2 of silver, that of couplers, additives, and gelatin is 
represented in units of g/m.sup.2, and that of sensitizing dye is 
represented by the number of mols per mol of the silver halide in the same 
layer. Symbols representing additives have the following meanings. Note 
that if an additive has a plurality of effects, only one of the effects is 
shown. 
UV: ultraviolet absorbent; Solv: high-boiling organic solvent; ExF: dye; 
ExS: sensitizing dye; ExC: cyan coupler; ExM: magenta coupler; ExY: yellow 
coupler; Cpd: additive. 
______________________________________ 
Layer 1: Antihalation Layer 
Black Colloid Silver 0.15 
Gelatin 2.9 
UV-1 0.03 
UV-2 0.06 
UV-3 0.07 
Solv-2 0.08 
ExF-1 0.01 
ExF-2 0.01 
Layer 2: Low-Sensitivity Red-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 4 mol %, 
0.4 
homogeneous type, sphere-equivalent diameter = 
0.4 .mu.m, variation coefficient of sphere- 
equivalent diameter = 37%, tabular grain, 
diameter/thickness ratio = 3.0) 
coated silver amount 
Gelatin 0.8 
ExS-1 2.3 .times. 10.sup.-4 
ExS-2 1.4 .times. 10.sup.-4 
ExS-5 2.3 .times. 10.sup.-4 
ExS-7 8.0 .times. 10.sup.-6 
ExC-1 0.17 
ExC-2 0.03 
ExC-3 0.13 
Layer 3: Intermediate-Sensitivity Red-Sensitive 
Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 6 mol %, 
0.65 
internally high AgI type having core/shell 
ratio of 2:1, sphere-equivalent diameter = 
0.65 .mu.m, variation coefficient of sphere- 
equivalent diameter = 25%, tabular grains, 
diameter/thickness ratio = 2.0) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 4 mol %, 
homogeneous AgI type, sphere-equivalent 
0.1 
diameter = 0.4 .mu.m, variation coefficient of 
sphere-equivalent diameter = 37%, tabular 
grain, diameter/thickness ratio = 3.0) 
coated silver amount 
Gelatin 1.0 
ExS-1 2 .times. 10.sup.-4 
ExS-2 1.2 .times. 10.sup.-4 
ExS-5 2 .times. 10.sup.-4 
ExS-7 7 .times. 10.sup.-6 
ExC-1 0.31 
ExC-2 0.01 
ExC-3 0.06 
Layer 4: High-Sensitivity Red-Sensitivity Emulsion Layer 
Silver Iodobromide Emulsion I (internally 
0.9 
high AgI type having core/shell ratio of 1: 
2, sphere-equivalent diameter = 0.75 .mu.m, 
variation coefficient of sphere-equivalent 
diameter = 25%) 
coated silver amount 
Gelatin 0.8 
ExS-1 1.6 .times. 10.sup.-4 
ExS-2 1.6 .times. 10.sup.-4 
ExS-5 1.6 .times. 10.sup.-4 
ExS-7 6 .times. 10.sup.-4 
ExC-1 0.07 
ExC-4 0.05 
Solv-1 0.07 
Solv-2 0.20 
Layer 5: Interlayer 
Gelatin 0.6 
UV-4 0.03 
UV-5 0.04 
Cpd-1 0.1 
Polyethylacrylate Latex 0.08 
Solv-1 0.05 
Layer 6: Low-Sensitivity Green-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 4 mol %, 
0.18 
homogeneous type, sphere-equivalent diameter = 
0.7 .mu.m, variation coefficient of sphere 
equivalent diameter = 37%, tabular grain, 
diameter/thickness ratio = 2.0) 
coated silver amount 
Gelatin 0.4 
ExS-3 2 .times. 10.sup.-4 
ExS-4 7 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
EXM-5 0.11 
ExM-7 0.03 
ExY-8 0.01 
Solv-1 0.09 
Solv-4 0.01 
Layer 7: Intermediate-Sensitivity Green-Sensitive 
Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 4 mol %, 
0.27 
surface high AgI type having core/shell ratio 
of 1:1, sphere-equivalent type, 
sphere-equivalent diameter = 0.5 .mu.m, 
variation coefficient of sphere-equivalent 
diameter = 20%, tabular grain, 
diameter/thickness ratio = 4.0) 
coated silver amount 
Gelatin 0.6 
ExS-3 2 .times. 10.sup.-4 
ExS-4 7 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
ExM-5 0.17 
ExM-7 0.04 
ExY-8 0.02 
Solv-1 0.14 
Solv-4 0.02 
Layer 8: High-Sensitivity Green-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion II (internally 
0.7 
high AgI type having core/shell ratio of 1: 
2, sphere-equivalent diameter = 0.75 .mu.m, 
variation coefficient of sphere-equivalent 
diameter = 25%) 
coated silver amount 
Gelatin 0.8 
ExS-4 5.2 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
ExS-8 0.3 .times. 10.sup.-4 
ExM-5 0.1 
ExM-6 0.03 
ExY-8 0.02 
ExC-1 0.02 
ExC-4 0.01 
Solv-1 0.25 
Solv-2 0.06 
Solv-4 0.01 
Layer 9: Interlayer 
Gelatin 0.6 
Cpd-1 0.04 
Polyethylacrylate Latex 0.12 
Solv-1 0.02 
Layer 10: Donor Layer having Interlayer Effect 
on Red-Sensitive Layer 
Silver Iodobromide Emulsion (AgI = 6 mol %, 
0.68 
internally high AgI type having core/shell 
ratio of 2:1, sphere-equivalent diameter = 
0.7 .mu.m, variation coefficient of sphere- 
equivalent diameter = 25%, tabular grain, 
diameter/thickness ratio = 2.0) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 4 mol %, 
0.19 
homogeneous type, variation coefficient of 
sphere-equivalent diameter = 37%, tabular 
grain, diameter/thickness ratio = 3.0) 
coated silver amount 
Gelatin 1.0 
ExS-3 6 .times. 10.sup.-4 
ExM-10 0.19 
Solv-1 0.20 
Layer 11: Yellow Filter Layer 
Yellow Colloid Silver 0.06 
Gelatin 0.8 
Cpd-2 0.13 
Solv-1 0.13 
Cpd-1 0.07 
H-1 0.13 
Layer 12: Low-Sensitivity Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion (AgI = 4.5 mol %, 
0.3 
homogeneous AgI type, sphere-equivalent 
diameter = 0.7 .mu.m, variation coefficient of 
sphere-equivalent diameter = 15%, tabular 
grain, diameter/thickness ratio = 7.0) 
coated silver amount 
Silver Iodobromide Emulsion (AgI = 3 mol %, 
0.15 
homogeneous AgI type, sphere-equivalent 
diameter = 0.3 .mu.m, variation coefficient of 
sphere-equivalent diameter = 30%, tabular 
grain, diameter/thickness ratio = 7.0) 
coated silver amount 
Gelatin 1.8 
ExS-6 9 .times. 10.sup.-4 
ExC-1 0.06 
ExC-4 0.03 
ExY-9 0.14 
ExY-11 0.89 
Solv-1 0.42 
Layer 13: Interlayer 
Gelatin 0.7 
ExY-12 0.20 
Solv-1 0.34 
Layer 14: High-Sensitivity Blue-Sensitive Emulsion Layer 
Silver Iodobromide Emulsion III (internally 
0.5 
high AgI type having core/shell ratio of 1: 
2, sphere-equivalent diameter = 0.75 .mu.m, 
variation coefficient of sphere-equivalent 
diameter = 25%) 
coated silver amount 
Gelatin 0.5 
ExS-6 1 .times. 10.sup.-4 
ExY-9 0.01 
ExY-11 0.20 
ExC-1 0.02 
Solv-1 0.10 
Layer 15: 1st Protective Layer 
Fine Grain Silver Bromide Emulsion (AgI = 2 
0.12 
mol %, homogeneous AgI type, sphere-equivalent 
diameter = 0.07 .mu.m) 
coated silver amount 
Gelatin 0.9 
UV-4 0.11 
UV-5 0.16 
Solv-5 0.02 
H-1 0.13 
Cpd-5 0.10 
Polyethylacrylate Latex 0.09 
Layer 16: 2nd Protective Layer 
Fine Grain Silver Bromide Emulsion (AgI = 
0.36 
2 mol %, homogeneous AgI type, sphere- 
equivalent diameter = 0.07 .mu.m) 
coating silver amount 
Gelatin 0.55 
Polymethylmethacrylate Grain 
0.2 
(diameter = 1.5 .mu.m) 
H-1 0.17 
______________________________________ 
In addition to the above components, a stabilizer Cpd-3 (0.07 g/m.sup.2) 
for an emulsion and a surfactant Cpd-4 (0.03 g/m.sup.2) were added as 
coating aids to each layer. 
Formulas of the used compounds are listed in Table D. 
An emulsion Em-201 was prepared following the same procedures as for Em-1 
in Example 1 except that the average sphere-equivalent diameter of a seed 
crystal was 0.5 .mu.m and therefore the average sphere-equivalent diameter 
of a final grain was 0.75 .mu.m. 
A thiosulfonic acid compound and a reduction sensitizer were added in 
amounts listed in Table 8-1 to Em-201 following the same procedures as in 
Example 1, thereby preparing emulsions 202 to 207. 
TABLE 8-1 
______________________________________ 
Thiosulfonic Acid 
Compound Addition 
Reduction Sensitizer 
Emulsion 
Amount/mol Ag Addition Amount/mol Ag 
______________________________________ 
202 No No Addition 
Tin 1.2 .times. 10.sup.-5 mol 
Addition Chloride 
203 1-2 2 .times. 10.sup.-5 mol 
Tin " 
Chloride 
204 No No Addition 
L-ascorbic 
2.1 .times. 10.sup.-3 mol 
Addition Acid 
205 1-2 2 .times. 10.sup.-5 mol 
L-ascorbic 
" 
Acid 
206 1-6 " L-ascorbic 
" 
Acid 
207 1-16 " L-ascorbic 
" 
Acid 
______________________________________ 
The emulsions 201 to 207 of the present invention and the comparative 
examples prepared as described above were optimally subjected to 
gold-plus-sulfur-sensitization by using a sodium thiosulfate and 
chloroauric acid. 
Samples 801 to 804 were prepared following the same procedures as for the 
above sample except that the silver iodobromide emulsions I, II, and III 
in the layers 4, 8, and 14, respectively, were changed. 
These samples were left under conditions of a temperature of 40.degree. C. 
and a relative humidity of 70% for 14 hours and then subjected to 
sensitometry exposure to perform color development following the same 
procedures as in Example 5. 
The processed samples were subjected to density measurement by using red, 
green, and blue filters. 
The results of photographic properties are compared by using relative 
sensitivities of the red-, green-, and blue-sensitive layers assuming that 
the sensitivity of the sample 801 is 100. 
The results showed that the samples 803 and 804 of the present invention 
had higher sensitivity and lower fogging density than the samples 801 and 
802 of the comparative example. When the samples were aged and stored 
following the same procedures as in Example 1 and their photographic 
properties were measured, a fogging density of the sample 802 was 
significantly increased while its sensitivity was decreased. However, the 
samples 803 and 804 of the present invention had photographic properties 
better than those of the comparative examples 801 and 802. 
EXAMPLE 9 
Samples 1101 to 1110 of multilayered color light-sensitive material having 
the same layer arrangement as that of Example 4 were prepared following 
the same procedures as in Example 4 except that the silver iodobromide 
emulsions I, II, and III of the layers 5, 9, and 13 were changed as shown 
in Table 9-2. Note that in addition to the emulsions listed in Table 9-2, 
the sensitizing dyes of the dye groups 1, 2, and 3 of Example 3 were added 
to the layers 5, 9, and 13, respectively, in the same amounts as those in 
Example 3. 
Methods of preparing tabular silver halide emulsions listed in the table 
9-2 will be described below. 
An aqueous solution obtained by dissolving 30 g of inactive gelatin and 6 g 
of potassium bromide in 1 liter of distilled water was stirred at 
75.degree. C., and 35 cc of an aqueous solution containing 5.0 g of silver 
nitrate and 35 cc of an aqueous solution containing 3.2 g of potassium 
bromide and 0.98 g of potassium iodide were added to the resultant 
solution each at a rate of 70 cc/min for 30 seconds. Thereafter, the pAg 
of resultant solution increased to 10 to perform ripening for 30 minutes, 
thereby preparing a seed emulsion. 
Equimolar amounts of a predetermined amount of 1 l of an aqueous solution 
containing 145 g of silver nitrate and a solution of a mixture of 
potassium bromide and potassium iodide were added at a predetermined 
temperature, a predetermined pAg, and an addition rate close to a critical 
growth rate, thereby preparing a tabular core emulsion. 
Subsequently, a thiosulfonic acid compound was added, and one minute after 
the addition, equimolar amounts of the remaining aqueous silver nitrate 
solution and an aqueous solution of a mixture of potassium bromide and 
potassium iodide having a different composition from that used in core 
emulsion preparation were added at an addition rate close to a critical 
growth rate to start shell formation. The ascorbic acid compound was added 
one minute after shell formation was started to continue shell formation, 
thereby finally preparing a core/shell type silver iodobromide tabular 
emulsions. An aspect ratio was adjusted by selecting the pAg upon core 
and/or shell formation. 85% or more of projected areas of all grains of 
the emulsions prepared as described above were occupied by tabular grains. 
The average sphere-equivalent diameter of the tabular grains was 1.2 
.mu.m, and its average iodide content was 7.6 mol %. 
The tabular emulsion grains used in the samples 1101 to 1110 are summarized 
in Table 9-1. 
TABLE 9-1 
__________________________________________________________________________ 
Aver- 
Aver- 
Aver- 
age age 
age Grain 
Grain 
Thiosulfonic Acid Compound 
Ascorbic Acid Compound 
Sample 
Emulsion 
Aspect 
Dia- 
Thick- 
Com- 
Addition Amount 
Com- 
Addition Amount 
No. No. Ratio 
meter 
ness 
pound 
(per mol of silver) 
pound 
(per mol of silver) 
__________________________________________________________________________ 
1101 
Em-101 
2.8 1.21 
0.55 
1-16 
3 .times. 10.sup.-5 mol 
A-1 1 .times. 10.sup.-2 mol 
1102 
Em-102 
6.7 1.74 
0.30 
" " " " 
1103 
Em-103 
9.8 2.10 
0.25 
" " " " 
1104 
Em-104 
17.4 
2.75 
0.18 
" " " " 
1105 
Em-105 
The same as Em-102 
1-2 3 .times. 10.sup.-5 mol 
" " 
1106 
Em-106 
The same as Em-103 
" " " " 
1107 
Em-107 
The same as Em-103 
-- -- -- -- 
1108 
Em-108 
The same as Em-102 
-- -- A-1 1 .times. 10.sup.-2 mol 
1109 
Em-109 
The same as Em-102 
-- -- -- -- 
1110 
Em-110 
The same as Em-102 
1-16 
3 .times. 10.sup.-5 mol 
-- -- 
__________________________________________________________________________ 
Average Aspect Ratio: A numberaveraged value of aspect ratios obtained by 
measuring an aspect ratio of each of 1,000 emulsion grains extracted at 
random, selecting grains corresponding to 50% of a total projected area 
from those having larger aspect ratios, and calculating a numberaveraged 
value of the aspect ratios of the selected grains. 
These samples were subjected to sensitometry exposure (1/100 sec) to 
perform the color development as described in Example 4. 
The processed samples were subjected to density measurement by using red, 
green, and blue filters. The obtained results are summarized in Table 9-2. 
The results of photographic properties are represented by relative 
sensitivities of the red-, green-, and blue-sensitive layers assuming that 
the sensitivity of the sample 1101 is 100. 
A response to pressure of each sample was evaluated as follows. That is, 
each sample was wound around a columnar rod having a diameter of 6 mm so 
that the emulsion surface of the sample faced inward, and held in this 
state for 10 seconds. Thereafter, wedge exposure was performed under the 
same conditions as described above for 1/100 seconds, development was 
performed following the same procedures as described above, and the 
density was measured by using a blue filter, thereby measuring fog and 
sensitivity of the blue-sensitive layer. The sensitivity is represented by 
a relative value assuming that the sensitivity of the sample 1101 was 100. 
The sharpness was evaluated by measuring the MTF of the red-sensitive 
layer. The MTF value was measured in accordance with a method described in 
"The Theory of Photographic Process", 3rd, ed., Macmillan. Exposure was 
performed by white light, and cyan color forming density was measured by a 
red filter. The MTF value with respect to a spatial frequency of 25 
cycle/mm at cyan color forming density of 1.0 is used as a typical value. 
Larger MTF values are more preferable. 
TABLE 9-2 
__________________________________________________________________________ 
Blue-Sensitive 
Red-Sensitive 
Green-Sensitive 
Blue-Sensitive 
Layer (After 
Layer Layer Layer Bending) 
M.T.F. (Red- 
Sample 
Sensi- Sensi- Sensi- Sensi- Sensitive- 
No. tivity 
Fog 
tivity 
Fog tivity 
Fog tivity 
Fog Layer) Remarks 
__________________________________________________________________________ 
1101 
100 0.15 
100 0.18 
100 0.26 
100 0.26 
0.52 Comparative 
Example 
1102 
105 0.15 
105 0.17 
105 0.26 
105 0.26 
0.59 Present 
Invention 
1103 
107 0.15 
105 0.18 
105 0.27 
105 0.28 
0.61 Present 
Invention 
1104 
107 0.16 
107 0.18 
105 0.27 
102 0.29 
0.63 Present 
Invention 
1105 
107 0.15 
107 0.18 
107 0.27 
107 0.27 
0.58 Present 
Invention 
1106 
110 0.15 
110 0.18 
107 0.27 
105 0.28 
0.60 Present 
Invention 
1107 
93 0.13 
93 0.16 
91 0.24 
83 0.28 
0.61 Comparative 
Example 
1108 
98 0.17 
98 0.19 
100 0.29 
98 0.30 
0.59 Present 
Intention 
1109 
91 0.13 
93 0.15 
91 0.24 
87 0.27 
0.58 Comparative 
Example 
1110 
85 0.10 
87 0.12 
85 0.21 
81 0.24 
0.59 Comparative 
Example 
__________________________________________________________________________ 
As is apparent from Table 9-2, the color photographic light-sensitive 
material of the present invention has good sharpness and response to 
pressure while maintaining high sensitivity. As is apparent from a 
comparison between the samples 1102 and 1108, an emulsion having higher 
sensitivity and producing lower fog can be obtained by additionally using 
a thiosulfonic acid compound. 
EXAMPLE 10 
Samples 1201 to 1210 having the same layer arrangement as that of Example 7 
were prepared using the emulsions prepared in Example 9 as silver bromide 
emulsions I, II, and III of layers 5, 10, and 16, respectively. 
These samples were exposed and color-developed following the same 
procedures as in Example 9, thereby obtaining the results summarized in 
Table 10-1. The MTF values were values at the cyan color forming density 
of 1.2. 
TABLE 10-1 
__________________________________________________________________________ 
Blue-Sensitive 
Red-Sensitive 
Green-Sensitive 
Blue-Sensitive 
Layer (After Silver 
Layer Layer Layer Bending) 
M.T.F. (Red- 
Iodo- 
Sample Sensi- Sensi- Sensi- Sensi- Sensitive- 
bromide 
No. tivity 
Fog 
tivity 
Fog tivity 
Fog tivity 
Fog Layer) Emulsion 
__________________________________________________________________________ 
1201 100 0.10 
100 0.13 
100 0.15 
100 0.16 
0.40 Em-101 
(Comparative 
Example) 
1202 105 0.11 
105 0.14 
102 0.15 
105 0.16 
0.46 Em-102 
(Present 
Invention) 
1203 107 0.11 
105 0.14 
105 0.16 
107 0.17 
0.48 Em-103 
(Present 
Invention) 
1204 107 0.12 
107 0.14 
105 0.16 
105 0.19 
0.50 Em-104 
(Present 
Invention) 
1205 107 0.11 
107 0.13 
105 0.15 
107 0.16 
0.46 Em-105 
(Present 
Invention) 
1206 110 0.10 
107 0.13 
107 0.15 
107 0.16 
0.48 Em-106 
(Present 
Invention) 
1207 93 0.10 
95 0.12 
93 0.14 
85 0.18 
0.48 Em-107 
(Comparative 
Example) 
1208 98 0.13 
98 0.16 
100 0.18 
98 0.20 
0.46 Em-108 
(Present 
Invention) 
1209 93 0.10 
93 0.12 
93 0.14 
89 
0.17 
0.47 Em-109 
(Comparative 
Example) 
1210 89 0.08 
87 0.11 
89 0.12 
85 0.15 
0.46 Em-110 
(Comparative 
Example) 
__________________________________________________________________________ 
As is apparent from Table 10-1, the color photographic light-sensitive 
material according to the present invention has high sensitivity and good 
sharpness and response to pressure. 
EXAMPLE 11 
Samples 1301 to 1310 having the same layer arrangement as that of Example 8 
were prepared using the emulsions 101 to 110 prepared in Example 9 as 
silver iodobromide emulsions I, II, and III of layers 4, 8, and 14, 
respectively. 
These samples were exposed and color-developed following the same 
procedures as in Example 9. Good results were obtained by samples using 
the emulsions of the present invention. 
TABLE A 
______________________________________ 
CH.sub.3 SO.sub.2 SNa (1-1) 
C.sub.2 H.sub.5 SO.sub.2 SNa (1-2) 
C.sub.3 H.sub.7 SO.sub.2 SK (1-3) 
C.sub.4 H.sub.9 SO.sub.2 SLi (1-4) 
C.sub.6 H.sub.13 SO.sub.2 SNa 
(1-5) 
C.sub.8 H.sub.17 SO.sub.2 SNa 
(1-6) 
##STR7## (1-7) 
C.sub.10 H.sub.21 SO.sub.2 SNa 
(1-8) 
C.sub.12 H.sub.25 SO.sub.2 SNa 
(1-9) 
C.sub.16 H.sub.33 SO.sub.2 SNa 
(1-10) 
##STR8## (1-11) 
t-C.sub.4 H.sub.9 SO.sub.2 SNa 
(1-12) 
CH.sub.3 OCH.sub.2 CH.sub.2 SO.sub.2 SNa 
(1-13) 
##STR9## (1-14) 
CH.sub.2CHCH.sub.2 SO.sub.2 Na 
(1-15) 
##STR10## (1-16) 
##STR11## (1-17) 
##STR12## (1-18) 
##STR13## (1-19) 
##STR14## (1-20) 
##STR15## (1-21) 
##STR16## (1-22) 
##STR17## (1-23) 
##STR18## (1-24) 
##STR19## (1-25) 
##STR20## (1-26) 
##STR21## (1-27) 
##STR22## (1-28) 
KSSO.sub.2 (CH.sub.2).sub.2 SO.sub.2 SK 
(1-29) 
NaSSO.sub.2 (CH.sub.2).sub.4 SO.sub.2 SNa 
(1-30) 
NaSSO.sub.2 (CH.sub.2).sub.4 S(CH.sub.2).sub.4 SO.sub.2 SNa 
(1-31) 
##STR23## (1-32) 
##STR24## (1-33) 
C.sub.2 H.sub.5 SO.sub.2 SCH.sub.3 
(2-1) 
C.sub.8 H.sub.17 SO.sub.2 SCH.sub.2 CH.sub.3 
(2-2) 
##STR25## (2-3) 
##STR26## (2-4) 
C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 CN 
(2-5) 
##STR27## (2-6) 
##STR28## (2-7) 
##STR29## (2-8) 
##STR30## (2-9) 
##STR31## (2-10) 
##STR32## (2-11) 
##STR33## (2-12) 
##STR34## (2-13) 
##STR35## (2-14) 
##STR36## (2-15) 
##STR37## (2-16) 
##STR38## (2-17) 
C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH 
(2-18) 
##STR39## (2-19) 
##STR40## (2-20) 
CH.sub.3 SSO.sub.2 (CH.sub.2).sub.4 SO.sub.2 SCH.sub.3 
(2-21) 
CH.sub.3 SSO.sub.2 (CH.sub.2).sub.2 SO.sub.2 SCH.sub.3 
(2-22) 
##STR41## (2-23) 
##STR42## (2-24) 
##STR43## (2-25) 
##STR44## (3-1) 
C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 
SSO.sub.2 C.sub.2 H.sub.5 (3-2) 
##STR45## (3-3) 
##STR46## (3-4) 
##STR47## (3-5) 
##STR48## (3-6) 
C.sub.2 H.sub.5 SO.sub.2 SSSO.sub.2 C.sub.2 H.sub.5 
(3-7) 
(n)C.sub.8 H.sub.17 SO.sub.2 SSSO.sub.2 C.sub.8 H.sub.17 (n) 
(3-8) 
##STR49## (3-9) 
______________________________________ 
##STR50## 
TABLE C 
__________________________________________________________________________ 
UV-1 
##STR51## UV-2 
##STR52## ExM-3 
##STR53## ExC-1 
##STR54## ExC-2 
##STR55## ExC-3 
##STR56## ExC-6 
##STR57## ExC-4 
##STR58## ExC-5 
##STR59## ExM-1 
##STR60## ExM-2 
##STR61## ExM-4 
##STR62## ExM-5 
##STR63## ExY-1 
##STR64## ExY-2 
##STR65## ExS-1 
##STR66## ExS-2 
##STR67## ExS-3 
##STR68## ExS-4 
##STR69## ExS-5 
##STR70## ExS-6 
##STR71## ExS-8 
##STR72## ExS-7 
##STR73## Solv-1 
##STR74## Solv-2 
##STR75## Solv-3 
##STR76## Solv-4 
##STR77## Solv-5 
##STR78## Cpd-1 
##STR79## Cpd-2 
##STR80## Cpd-3 
##STR81## Cpd-4 
##STR82## Cpd-5 
##STR83## W-1 
##STR84## H-1 
__________________________________________________________________________ 
TABLE D 
__________________________________________________________________________ 
##STR85## UV-1 
##STR86## UV-2 
##STR87## UV-3 
##STR88## UV-4 
##STR89## UV-5 
tricresyl phosphate Solv-1 
##STR90## Solv-2 
##STR91## Solv-4 
trihexyl phosphate Solv-5 
##STR92## ExF-1 
##STR93## ExF-2 
##STR94## ExS-1 
##STR95## ExS-2 
##STR96## ExS-3 
##STR97## ExS-4 
##STR98## ExS-5 
##STR99## ExS-6 
##STR100## ExS-7 
##STR101## ExS-8 
##STR102## ExC-1 
##STR103## ExC-2 
##STR104## ExC-3 
##STR105## ExC-4 
##STR106## ExM-5 
##STR107## ExM-6 
##STR108## ExM-7 
##STR109## ExM-10 
##STR110## ExY-8 
##STR111## ExY-9 
##STR112## ExY-11 
##STR113## ExY-12 
##STR114## Cpd-1 
##STR115## Cpd-2 
##STR116## H-1 
##STR117## Cpd-5 
##STR118## Cpd-3 
##STR119## Cpd-4 
__________________________________________________________________________