Silver halide photographic material

A silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer, wherein at least one layer contains at least one metallocene compound.

FIELD OF THE INVENTION 
The present invention relates to a high-sensitivity silver halide 
photographic material. 
BACKGROUND OF THE INVENTION 
Heretofore, provision of high-sensitivity silver halide photographic 
materials has been desired. In particular, provision of color-sensitized 
high-sensitivity silver halide photographic materials has especially been 
desired. 
Color sensitization technology is extremely important and is indispensable 
for producing high-sensitivity photographic materials with excellent color 
reproducibility. A color sensitizer inherently has a function of absorbing 
light with a long wavelength range which is not substantially absorbed by 
silver halide photographic emulsions and of transmitting the energy of the 
absorbed light to the silver halide. Therefore, increasing the amount of 
light to be captured by a color sensitizer is advantageous for elevating 
the photographic sensitivity of a photographic material. Accordingly, 
attempts have heretofore been made to elevate the amount of light to be 
captured by a color sensitizer by increasing the amount of the color 
sensitizer to be added to the silver halide emulsion. However, if the 
amount of the color sensitizer to be added to the silver halide is greater 
than an optimum amount, the result is severe desensitization. This is 
generally called dye desensitization, which is a phenomenon resulting in 
desensitization in the light-sensitive range intrinsic to a silver halide 
substantially free from color absorption by a sensitizing dye. If dye 
desensitization of a photographic material is great, then the total 
sensitivity of the photographic material will be low even though the 
material may be heavily color-sensitized. In other words, decreasing dye 
desensitization causes a proportional elevation of the sensitivity of the 
light-absorbing range by a color sensitizer (namely, the color sensitivity 
of a color sensitizer itself). Therefore, the solution of the problem of 
dye desensitization is an important theme in color sensitization 
technology. In general, a sensitizing dye having a light-sensitivity in a 
longer wavelength range involves greater dye desensitization. These 
matters are described in T. H. James, The Theory of the Photographic 
Process, Forth Edition, pages 265 to 268 (published by Macmillan 
Publishing Co., Inc. 1977). 
Methods of elevating the sensitivity of a photographic material by 
decreasing the dye desensitization thereof are known, as described in 
JP-A-47-28916, JP-A-49-46738, JP-A-54-118236 and U.S. Pat. No. 4,011,083. 
(The term "JP-A" as used herein means an "unexamined published Japanese 
patent application".) However, these proposed methods are limited to 
specific sensitizing dyes and the effects thereof are still 
unsatisfactory. The most effective means of eliminating dye 
desensitization presently known is a method of using bisaminostilbene 
compounds substituted by pyrimidine derivatives or triazine derivatives, 
for example, as described in JP-B-45-22189, JP-A-54-18726, JP-A-52-4822, 
JP-A-52-151026 and U.S. Pat. No. 2,945,762. (The term "JP-B" as used 
herein means an "examined Japanese patent publication".) However, the 
proposed compounds are only effective with a limited class of sensitizing 
dyes: the so-called M-band sensitizing dyes which show a gently-sloping 
sensitization peak in a relatively long wavelength range, such as 
dicarbocyanines, tricarbocyanines, rhodacyanines and merocyanines. 
U.S. Pat. No. 3,695,888 discloses combination of a tricarbocyanine and an 
ascorbic acid to yield infrared sensitization of a photographic material; 
British Patent 1,255,084 discloses combination of a particular dye and an 
ascorbic acid to yield elevation of the minus-blue sensitivity of a 
photographic material; British Patent 1,064,193 discloses combination of a 
particular dye and an ascorbic acid to yield elevation of the sensitivity 
of a photographic material; and U.S. Pat. No. 3,809,561 discloses 
combination of a desensitizing nucleus-containing cyanine dye and a 
supercolor sensitizer such as an ascorbic acid. 
However, the preceding technology often displays an unsatisfactory 
sensitizing effect of the dyes used, and even if a high sensitizing effect 
is attained, it often causes an increase of fog of the photographic 
material. 
It is known that sensitizing dyes having a reduction potential of -1.25 V 
or more are low in a relative quantum yield of spectral sensitization as 
described in T. Tani et al., Journal of the Physical Chemistry, vol. 94, 
page 1298 (1990). It is proposed in the aforesaid The Theory of the 
Photographic Process, Forth Edition, pages 259-265 (1977) that 
super-sensitization is conducted by positive hole capture to increase the 
relative quantum yield of spectral sensitization. However, it is highly 
demanded to provide more effective supersensitizing agents. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a silver halide 
photographic material, particularly a spectral-sensitized silver halide 
photographic material, which has high sensitivity and which does not tend 
to fog. 
Another object of the present invention is to provide a silver halide 
photographic material which has high storage stability. 
These and other objects of the present invention have been achieved by 
providing a silver halide photographic material, particularly preferably 
spectral-sensitized silver halide photographic material, comprising a 
support having thereon at least one silver halide emulsion layer, wherein 
at least one layer contains at least one metallocene compound. 
DETAILED DESCRIPTION OF THE INVENTION 
The metallocene is a general term for biscyclopentadienyl metal compounds 
[described in Iwanami Rikagaku Jiten, the third edition an enlarged 
edition, page 1335 edited by Bunichi Tamamushi et al., (published by 
Iwanami Shoten 1986) (written in Japanese)]. 
Preferably, the metallocene compound is selected from the compounds 
represented by the following formula (I): 
##STR1## 
wherein M represents Fe, Ti, V, Cr, Co, Ni, Ru, Os or Pd; and V.sub.1, 
V.sub.2, V.sub.3, V.sub.4, V.sub.5, V.sub.6, V.sub.7, V.sub.8, V.sub.9 and 
V.sub.10 are the same or different and each represents a hydrogen atom or 
a monovalent substituent, provided that two of V.sub.1, V.sub.2, V.sub.3, 
V.sub.4, V.sub.5, V.sub.6, V.sub.7, V.sub.8, V.sub.9 and V.sub.10 may be 
combined with each other to form a ring; or two or more of the metallocene 
compounds may be combined together. 
The compounds where M is Fe are more preferred and are called ferrocene 
compounds. 
Now, the compounds represented by formula (I) are explained in more detail 
below. 
V.sub.1, V.sub.2, V.sub.3, V.sub.4, V.sub.5, V.sub.6, V.sub.7, V.sub.8, 
V.sub.9 and V.sub.10 ( V.sub.1 to V.sub.10) are the same or different and 
each represents a hydrogen atom or a monovalent substituent. 
Any of substituents may be used. However, the following substituents are 
preferred. 
Examples of preferred substituents represented by V.sub.1 to V.sub.10 
include an unsubstituted alkyl group (e.g., methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, cyclopentyl, 
cyclopropyl, cyclohexyl); a substituted alkyl group (when the substituent 
attaching to the alkyl group is referred to as V, examples of the 
substituent represented by V include, but are not limited to, a carboxyl 
group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, 
chlorine, bromine, iodine), a hydroxyl group, an alkoxycarbonyl group 
(e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an 
aryloxycarbonyl group (e.g., phenoxymethoxy, an alkoxy group (e.g., 
methoxy, ethoxy, benzyloxy, phenethyloxy), an aryloxy group having from 6 
to 18 carbon atoms (e.g., phenoxy, 4-methylphenoxy, 1-napthoxy), an 
acyloxy group (e.g., acetyloxy, propionyloxy), an acyl group (e.g., 
acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (e.g., carbamoyl, 
N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a 
sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, 
morpholinosulfonyl, piperidinosulfonyl), an aryl group (e.g., phenyl, 
4-chlorophenyl, 4-methylphenyl, 1-naphthyl), a heterocyclic group (e.g., 
2-pyridyl, tetrahydrofurfuryl, morpholino, 2-thiopheno), an amino group 
(e.g., amino, dimethylamino, anilino, diphenylamino), an alkylthio group 
(e.g., methylthio, ethylthio), an alkylsulfonyl group (e.g., 
methylsulfonyl, propylsulfonyl), an alkylsulfinyl group (e.g., 
methylsulfinyl), a nitro group, a phosphoric acid group, an acylamino 
group (e.g., acetylamino), an ammonium group (e.g., trimethylammonium, 
tributylammonium), a mercapto group, a hydrazino group (e.g., 
trimethylhydrazino), a ureido group (e.g., ureido, N,N-dimethylureido), an 
imido group and an unsaturated hydrocarbon group (e.g., vinyl, ethynyl, 
1-cyclohexenyl); the substituent V has preferably from 0 to 18 carbon 
atoms, and these substituents may be further substituted by one or more of 
the substituents represented by V}; an unsubstituted aryl group (e.g., 
phenyl, 1-naththyl); a substituted aryl group (examples of the substituent 
include those already described above in the definition of V); an 
unsubstituted heterocyclic group (e. g., 2-pyridyl, 2-thiazolyl, 
morpholino, 2-thiopheno); a substituted heterocyclic group ( examples of 
the substituent include those already described above in the definition of 
V); and a substituent represented by V. 
More specifically, the examples of preferred substituent represented by V 
include a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, 
carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 
sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 
2-hydroxy-3-sulfopropyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl, 
2-hydroxyethyl, 3-hydroxypropyl, hydroxymethyl, 2-hydroxyethyl, 
4-hydroxybutyl, 2,4-dihydroxybutyl, 2-methoxyethyl, 2-ethoxyethyl, 
methoxymethyl, 2-ethoxycarbonylethyl, methoxycarbonylmethyl, 
2-methoxyethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2-acetyloxyethyl, 
2-propionyloxyethyl, 2-acetylethyl, 3-benzoylpropyl, 2-carbamoylethyl, 
2-morpholinocarbonylethyl, sulfamoylmethyl, 
2-(N,N-dimethylsulfamoyl)ethyl, benzyl, 2-naphthylethyl, 
2-(2-pyridyl)ethyl, allyl, 3-aminopropyl, dimethylaminomethyl, 
3-methylaminopropyl, methylthiomethyl, 2-methylsulfonylethyl, 
methylsulfinylmethyl, 2-acetylaminoethyl, acetylaminomethyl, 
trimethylammoniummethyl, 2-mercaptoethyl, 2-trimethylhydrazinoethyl, 
methylsulfonylcarbamoylmethyl, (2-methoxy)ethoxymethyl), a substituted or 
unsubstituted aryl group (e.g., phenyl, 1-naphthyl, p-chlorophenyl), a 
substituted or unsubstituted heterocyclic group (e.g., 2-pyridyl, 
2-thiazolyl, 4-phenyl-2-thiazolyl) and a substituent represented by V 
(e.g., a carboxyl group, a formyl group, an acetyl group, a benzoyl group, 
a 3-carboxypropanoyl group, a 3-hydroxypropanoyl group, a chlorine atom, 
an N-phenylcarbamoyl group, an N-butylcarbamoyl group, a boric acid group, 
a sulfo group, a hydroxyl group, a methoxy group, a methoxycarbonyl group, 
an acetyloxy group, a dimethylamino group). 
The substituents represented by V.sub.1 to V.sub.10 have more preferably 
from 1 to 18 carbon atoms. 
Any two of V.sub.1 to V.sub.10 may be combined with each other to form a 
ring. The ring may be any of an aliphatic ring and an aromatic ring. The 
ring amy be substituted by one or more of the substituents represented by 
V. 
Further, two or more compounds represented by formula (I) may be combined 
together. 
Specific examples of the compounds represnted by formula (I) include, but 
are not limited to, the following compounds. 
______________________________________ 
##STR2## 
Compound No. 
V.sub.1 
______________________________________ 
(I-1) H 
(I-2) CO.sub.2 H 
(I-3) (CH.sub.2).sub.11 N.sup..sym. (CH.sub.3).sub.3 I.sup..crclbar. 
(I-4) CHO 
(I-5) SO.sub.3 H 
(I-6) 
##STR3## 
(I-7) 
##STR4## 
(I-8) B(OH).sub.2 
(I-9) (CH.sub.2)N.sup..sym. (CH.sub.3).sub.3 I.sup..crclbar. 
(I-10) CH.sub.2 N(CH.sub.3).sub.2 
(I-11) CO(CH.sub.2).sub.2 CO.sub.2 H 
(I-12) COCH.sub.3 
(I-13) 
##STR5## 
(I-14) CONH(CH.sub.2).sub.3 CH.sub.3 
(I-15) CH.sub.2 OH 
(I-16) Cl 
(I-17) 
##STR6## 
(I-18) CO(CH.sub.2).sub. 3 Br 
(I-19) CO(CH.sub.2).sub.3 OH 
(I-20) CO(CH.sub.2).sub.2 OH 
(I-21) CHNOH 
(I-22) CHN.sup..sym.O.sup..crclbar. 
(I-23) CH.sub.2 SO.sub.3.sup..crclbar. Na.sup..sym. 
(I-24) CH.sub.2 OCH.sub.3 
(I-25) CH.sub.2 NHCOCH.sub.3 
(I-26) C.sub.2 H.sub.5 
(I-27) CH(OH)CH.sub.3 
(I-28) C(OH)(CH.sub.3).sub.2 
(I-29) (CH.sub.2).sub.4 OH 
(I-30) CH(OH)(CH.sub.2).sub.2 CH.sub.2 OH 
(I-31) 
##STR7## 
(I-32) 
##STR8## 
(I-33) 
##STR9## 
(I-34) 
##STR10## 
(I-35) 
##STR11## 
(I-36) and (I-37) 
##STR12## 
(I-36) R = H 
(I-37) 
##STR13## 
(I-38) 
##STR14## 
(I-39) 
##STR15## 
(I-40) 
##STR16## 
(I-41) 
##STR17## 
(I-42) 
##STR18## 
(I-43) 
##STR19## 
(I-44) 
##STR20## 
(I-45) 
##STR21## 
(I-46) 
##STR22## 
(I-47) 
##STR23## 
(I-48) 
##STR24## 
(I-49) 
##STR25## 
(I-50) 
##STR26## 
(I-51) 
##STR27## 
(I-52) 
##STR28## 
______________________________________ 
The metallocene compounds used in the present invention can be synthesized 
by referring to the method described in D. E. Bublitz et al., Organic 
Reactions, vol. 17, pp 1-154 (1969). 
The metallocene compounds and the ferrocene compounds are conveniently 
expressed by formula (I) in the present invention. However, these 
compounds can be expressed by other formulae and refer to the same 
compounds, though these compounds are expressed by different formulae. 
Expression in the present invention 
##STR29## 
Other expressions 
##STR30## 
The effect obtained by the metallocene compounds of the present invention 
is particularly remarkable when the metallocene compounds are contained in 
the silver halide photographic materials spectral-sensitized by spectral 
sensitizing dyes. 
The spectral sensitizing dyes which can be used in the present invention 
include any of conventional dyes such as cyanine dyes, merocyanine dyes, 
rhodacyanine dyes, oxonol dyes, hemicyanine dyes, benzylidene dyes and 
xanthene dyes. Examples of these dyes are described in T. H. James, The 
Theory of the Photographic Process, the third edition, pp. 198-228 (1966) 
(Macmillan Co.). 
Firstly, sensitizing dyes having an oxidation potential of 0.95 (V .sub.VS 
SCE) or less are preferred (the term "SCE" as used herein means a 
"saturated calomel electrode"). It is known that these dyes generally 
cause greatly dye desensitization. Secondly, sensitizing dyes having a 
reduction potential of -1.3 (V .sub.VS SCE) or more are preferred. It is 
known that these dyes are generally low in the relative quantum yield of 
spectral sensitization. 
The measurement of oxidation and reduction potentials was carried out by a 
phase discrimination second higher frequency alternating current 
polargraphy. The detail of the measurement is described below. 
Acetonitrile (spectral grade) dried in 4A-1/16 molecular sieves was used 
as the solvent. n-Tetrapropylammonium perchlorate (special reagent for a 
polargraphy) was used as the supporting electrolyte. A sample solution was 
prepared by dissolving from 10.sup.-3 to 10.sup.-5 mol of a sensitizing 
dye per liter in acetonitrile containing 0.1M supporting electrolyte. 
Before measurement, the sample solution was deoxidized for at least 15 
minutes by using ultra-high-purity argon gas (99.999%) passed through a 
highly alkaline aqueous solution of pyrogallol and a tube packed with 
calcium chloride. A rotating platinum electrode was used as the working 
electrode in the measurement of oxidation potential, and a dropping 
mercury electrode was used as the working electrode in the measurement of 
reduction potential. Saturated calomel electrode (SCE) was used as a 
reference electrode, and platinum was used as an opposite electrode. The 
reference electrode was connected with the sample solution by means of a 
Luggin tube filled with acetonitrile containing 0.1M supporting 
electrolyte, and Vycor glass was used for a liquid junction part. The top 
of the Luggin tube was from 5 to 8 mm away from the top of the rotating 
platinum electrode, and the measurement was carried out at 25.degree. C. 
The above measurement of oxidation and reduction potentials by the phase 
discrimination second higher frequency alternating current voltmmetry is 
described in Journal of Imaging Science, vol. 30, pp. 27-35 (1986). When 
the measurement was carried out under the above conditions, the dye 
(XIV-9) described hereinafter had an oxidation potential of 0.915 (V 
.sub.VS SCE) and a reduction potential of -1.22 (V .sub.VS SCE). 
Sensitizing dyes represented by the following formulae (XI), (XII) and 
(XIII) can be particularly preferably used: 
##STR31## 
In formulae (XI), (XII) and (XIII), Z.sub.11, Z.sub.12, Z.sub.13, Z.sub.14, 
Z.sub.15 and Z.sub.16 are the same or different each represents an atomic 
group necessary for forming a five-membered or six-membered 
nitrogen-containing heterocyclic ring. 
D and D' are the same or different and each represents an atomic group 
necessary for forming a non-cyclic or cyclic acid nucleus. 
R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.16 are the same or 
different and each represents a substituted or unsubstituted alkyl group. 
R.sub.15 represents a substituted or unsubstituted alkyl group, a 
substituted or unsubstituted aryl group or a substituted or unsubstituted 
heterocyclic group. 
L.sub.11, L.sub.12, L.sub.13, L.sub.14, L.sub.15, L.sub.16, L.sub.17, 
L.sub.18, L.sub.19, L.sub.20, L.sub.21, L.sub.22, L.sub.23, L.sub.24, 
L.sub.25, L.sub.26, L.sub.27, L.sub.28, L.sub.29 and L.sub.30 are the same 
or different and each represents a substituted or unsubstituted methine 
group. 
M.sub.11, M.sub.12 and M.sub.13 are the same or different and each 
represents a counter ion for neutralizing charge; m.sub.11, m.sub.12 and 
m.sub.13 are the same or different and each represents a number of 0 or 
more necessary for neutralizing the molecular charge; n.sub.11, n.sub.13, 
n.sub.14, n.sub.16 and n.sub.19 are the same or different and each 
represents 0 or 1; and n.sub.12, n.sub.15, n.sub.17 and n.sub.18 are the 
same or different and each represents an integer of 0 or more. 
The sensitizing dyes represented by formula (XI) called cyanine dyes are 
more preferred. 
The compounds represented by formulae (XI), (XII) and (XIII) are explained 
in more detail below. 
Preferably, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.16 are each an 
unsubstituted alkyl group having from 1 to 18 carbon atoms (for example, 
methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or 
a substituted alkyl group {for example, an alkyl group having from 1 to 18 
carbon atoms substituted by one or more of substituents such as a carboxyl 
group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, 
chlorine, bromine), a hydroxyl group, an alkoxycarbonyl group having from 
2 to 8 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, 
phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having from 1 to 8 
carbon atoms (e.g., methoxy, ethoxy, benzyloxy, phenethyloxy), a 
monocyclic aryloxy group having from 6 to 10 carbon atoms (e.g., phenoxy, 
p-tolyloxy), an acyloxy group having 2 or 3 carbon atoms (e.g., acetyloxy, 
propionyloxy), an acyl group having from 2 to 8 carbon atoms (e.g., 
acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (e.g., carbamoyl, 
N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a 
sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, 
morpholinosulfonyl, piperidinosulfonyl) and an aryl group having from 6 to 
10 carbon atoms (e.g., phenyl, 4-chlorophenyl, 4-methylphenyl, 
1-naphthyl)}. More preferably, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and 
R.sub.16 are each an unsubstituted alkyl group (e.g., methyl, ethyl, 
n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (e.g., 
2-carboxyethyl, carboxymethyl), a sulfoalkyl group (e.g., 2-sulfoethyl, 
3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl) or a 
methanesulfonylcarbamoylmethyl group. 
M.sub.11 m.sub.11, M.sub.12 m.sub.12 and M.sub.13 m.sub.13 are each 
included in the formulae to show the presence or absence of a cation or an 
anion when it is necessary for neutralizing the ionic charge of the dye. 
Whether a certain dye is cationic, anionic or neutral depends on the 
auxochrome and the substituents in the dye. Typical examples of the cation 
include inorganic or organic ammonium ions (e.g., ammonium ion, tetraalkyl 
ammonium ion, pyridinium ion), an alkali metal ion (e.g., sodium ion, 
potassium ion) and an alkaline earth metal ion (e.g., calcium ion). The 
anion may be any of an inorganic ion and an organic ion. Specific examples 
of the anion include a halide ion (e.g., fluoride ion, chloride ion, 
bromide ion, iodide ion), a substituted arylsulfonate ion (e.g., 
p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), an aryldisulfonate 
ion (e.g., 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 
2,6-naphthalenedisulfonate ion), an alkylsulfate ion (e.g., methylsulfate 
ion, ethylsulfate ion), a sulfate ion, a thiocyanate ion, a perchlorate 
ion, a tetrafluoroborate ion, a picrate ion, an acetate ion and a 
trifluoromethanesulfonate ion. 
Further, an ionic polymer or other dyes having an opposite charge to that 
of the sensitizing dye may be used as a counter ion for neutralizing 
charge. For example, a metal complex ion (e.g., 
bisbenzene-1,2-dithiolatonickel (III)) can be used. 
Preferred ions are an ammonium ion, an iodide ion and a p-toluenesulfonate 
ion. 
Preferably, m.sub.11, m.sub.12 and m.sub.13 are each 0, 1 or 2. 
Examples of the nucleus formed by Z.sub.11, Z.sub.12, Z.sub.13, Z.sub.14 or 
Z.sub.16 include a thiazole nucleus [for example, a thiazole nucleus 
(e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 
4,5-diphenylthiazole), a benzothiazole nucleus (e.g., benzothiazole, 
4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 
5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 
6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 
5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 
6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenzothiazole, 
5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 
5-phenethylbenzothiazole, 5-fluorobenzothiazole, 
5-chloro-6-methylbenzothiazole, 5,6-di-methylbenzothiazole, 
5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 
tetrahydrobenzothiazole, 4-phenylbenzothiazole), a naphthothiazole nucleus 
(e.g., naphtho[2,1-d]thiazole, naphtho[1,2-d]thiazole, 
naphtho[2,3-d]thiazole, 5-methoxynaphtho[1,2-d]thiazole, 
7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 
5-methoxynaphtho[2,3-d]thiazole)]; a thiazoline nucleus (for example, 
thiazoline, 4-methylthiazoline, 4-nitrothiazoline); an oxazole nucleus 
[for example, an oxazole nucleus (e.g., oxazole, 4-methyloxazole, 
4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 
4-ethyloxazole), a benzoxazole nucleus (e.g., benzoxazole, 
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 
5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 
5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 
5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 
6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 
5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), a 
naphthoxazole nucleus (e.g., naphtho[2,1-d ]oxazole, 
naphtho[1,2-d]oxazole, naphtho[2,3-d]oxazole, 
5-nitronaphtho[2,1-d]oxazole)]; an oxazoline nucleus (for example, 
4,4-dimethyloxazoline); a selenazole nucleus [for example, a selenazole 
nucleus (e.g., 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), 
a benzoselenazole nucleus (e.g., benzoselenazole, 5-chlorobenzoselenazole, 
5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 
5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 
5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), a 
naphthoselenazole nucleus (e.g., naphtho[2,1-d ]selenazole, naphtho[1,2-d 
]selenazole)]; a selenazoline nucleus (for example, selenazoline, 
4-methylselenazoline); a tellurazole nucleus [for example, a tellurazole 
nucleus (e.g., tellurazole, 4-methyltellurazole, 4-phenyltellurazole), a 
benzotellurazole nucleus (e.g., benzotellurazole, 
5-chlorobenzotellurazole, 5-methylbenzotellurazole, 
5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), a 
naphthotellurazole nucleus (e.g., naphtho[2,1-d]tellurazole, 
naphtho[1,2-d]tellurazole)]; a tellurazoline nucleus (for example, 
tellurazoline, 4-methyltellurazoline); 3,3-dialkylindolenine nucleus (for 
example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 
3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 
3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 
3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine); an imidazole 
nucleus [for example, an imidazole nucleus (e.g., 1-alkylimidazole, 
1-alkyl-4-phenylimidazole, 1-arylimidazole), a benzimidazole nucleus 
(e.g., 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 
1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 
1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 
1-alkyl-5-trifluoromethylbenzimidazole, 
1-alkyl-6-chloro-5-cyanobenzimidazole, 
1-alkyl-6-chloro-5-trifloromethylbenzimidazole, 
1-allyl-5,6-dichorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 
1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 
1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 
1-aryl-5-cyanobenzimidazole), a naphthoimidazole nucleus (e.g., 
1-alkylnaphtho[1,2-d]imidazole, 1-arylnaphtho[1,2-d]imidazole); wherein 
the above-described alkyl group has preferably from 1 to 8 carbon atoms; 
and the alkyl group is preferably an unsubstituted alkyl group such as 
methyl, ethyl, propyl, isopropyl and butyl or a hydroxyalkyl group such as 
2-hydroxyethyl and 3-hydroxypropyl, and more preferably a methyl group or 
an ethyl group; and wherein examples of the above-described aryl group 
include a phenyl group, a halogen-substituted phenyl group such as 
chlorophenyl, an alkyl-substituted phenyl group such as methylphenyl and 
an alkoxy-substituted phenyl group such as methoxyphenyl]; a pyridine 
nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 
3-methyl-4-pyridine); a quinoline nucleus [for example, a quinoline 
nucleus (e.g., 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 
6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 
6-methoxy-2-quinoline, 6-hydroxy-2quinoline, 8-chloro-2-quinoline, 
4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 
8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 
8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-5-quinoline, 
6-chloro-4-quinoline, 5,6-dimethyl-4-quinoline), an isoquinoline nucleus 
(e.g., 6-nitro-l-isoquinoline, 3,4-dihydro-1-isoquinoline, 
6-nitro-3-isoquinoline)]; an imidazo[4,5-b]quinoxaline nucleus (e.g., 
1,3-diethylimidazo[4,5-b]quinoxaline, 
6-chloro-1,3-diallylimidazo[4,5-b]quinoxaline); an oxadiazole nucleus; a 
thiadiazole nucleus; a tetrazole nucleus; and a pyrimidine nucleus. 
Preferred examples of the nucleus formed by Z.sub.11, Z.sub.12, Z.sub.13, 
Z.sub.14 or Z.sub.16 include a benzthiazole nucleus, a naphthothiazole 
nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole 
nucleus, a 2-quinoline nucleus and a 4-quinoline nucleus. 
D and D' each represents an atomic group necessary for forming an acid 
nucleus and may be in any form of the acid nuclei of conventional 
merocyanine dyes. The term "acid nucleus" as used herein refers to the 
nucleus defined, for example, by T .H. James, The Theory of the 
Photographic Process, the fourth edition, page 198 (Macmillan Co. 1977). 
In a preferred form, examples of substituent groups which participate in 
the resonance of D include a carbonyl group, a cyano group, a sulfonyl 
group and a phenyl group. D' is the residual moiety of the atomic group 
necessary for forming the acid nucleus. 
Specific examples thereof include those described in U.S. Pat. Nos. 
3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480 and 4,925,777 and 
JP-A-3-167546. 
When the acid nucleus is a non-cyclic nucleus, the terminal of the methine 
bond is such a group as derived from a malononitrile group, an 
alkanesulfonylacetonitrile group, a cyanomethylbenzofuranylketone group or 
a cyanomethylphenylketone group. 
When the acid nucleus formed by D and D' is a cyclic nucleus, a 
five-membered or six-membered heterocyclic ring comprising carbon, 
nitrogen or chalcogen (typically, oxygen, sulfur, selenium, tellurium) 
atoms is formed. 
Preferred examples of the acid nucleus include 2-pyrazoline-5-one, 
pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2- or 
4-thiohydantoin, 2-iminoxazolidine-4-one, 2-oxazoline-5-one, 
2-thioxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazoline-4-one, 
thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, 
thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, 
thiophene-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 
indazoline-3-one, 2-oxoindazolium, 3-oxoindazolium, 
5,7-dioxo-6,7-dihydrothiazolo[3,2-a]pyrimidine, cyclohexane-1,3-dione, 
3,4-dihydroisoquinoline 4 -one, 1,3-dioxane-4,4-dione, barbituric acid, 
2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, 
pyrido[1,2-a]pyrimidine-1,3-dione, pyrazolo[1,5-b]quinazolone, 
pyrazolo[1,5-a]benzimidazole, pyrazolopyridone, 
1,2,3,4-tetrahydroquinoline-2,4-dione, 
3-oxo-2,3-dihydrobenzo[d]thiophene-1,1-dioxide and 
3,3-dicyanomethine-2,3-dihydrobenzo[d]thiophene-1,1-dioxide. 
The nuclei of 3-alkylrhodanine, 3-alkyl-2-thioxazolidine-2,4-dione and 
3-alkyl-2-thiohydantoin are more preferred. 
R.sub.15 and the substituents attached to the nitrogen atom in the acid 
nucleus each represents a hydrogen atom, an alkyl group having from 1 to 
18 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 
hexyl, octyl, dodecyl, octadecyl), an aryl group having from 6 to 18 
carbon atoms (e.g., phenyl, 2-naphthyl, 1-naphthyl) or a heterocyclic 
group having from 1 to 18 carbon atoms (e.g., 2-pyridyl, 2-thiazolyl, 
2-furyl). These groups may be further substituted. Examples of the 
substituent include a carboxyl group, a sulfo group, a cyano group, a 
nitro group, a halogen atom (e.g., fluorine, chlorine, iodine, bromine), a 
hydroxyl group, an alkoxy group having from 1 to 8 carbon atoms (e.g., 
methoxy, ethoxy, benzyloxy, phenethyl), an aryloxy group having from 6 to 
15 carbon atoms (e.g., phenoxy), an acyloxy group having from 2 to 8 
carbon atoms (e.g., acetyloxy), an alkoxycarbonyl group having from 2 to 8 
carbon atoms, an acyl group having from 2 to 8 carbon atoms, a sulfamoyl 
group, a carbamoyl group, an alkanesulfonylaminocarbonyl group having from 
2 to 8 carbon atoms (e.g., methanesulfonylaminocarbonyl), an 
acylaminosulfonyl group having from 2 to 8 carbon atoms (e.g., 
acetylaminosulfonyl), an aryl group having from 6 to 15 carbon atoms 
(e.g., phenyl, 4-methylphenyl, 4-chlorophenyl, naphthyl) and a 
heterocyclic group having from 1 to 15 carbon atoms (e.g., 
pyrrolidine-2-one-1-yl, tetrahydrofurfuryl, 2-morpholino). These 
substituents may be further substituted by one or more of these 
substituents. 
Of these groups, an unsubstituted alkyl group (e.g., methyl, ethyl, 
n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (e.g., 
carboxymethyl, 2-carboxyethyl) and a sulfoalkyl group (e.g., 2-sulfoethyl) 
are preferred. 
The five-membered or six-membered nitrogen-containing heterocyclic ring 
formed by Z.sub.15 is a ring formed by removing oxo group or thioxo group 
at an appropriate position from a heterocyclic ring formed by D and D', 
preferably a ring formed by removing a thioxo group from a rhodanine 
nucleus. 
L.sub.11, L.sub.12, L.sub.13, L.sub.14, L.sub.15, L.sub.16, L.sub.17, 
L.sub.18, L.sub.19, L.sub.20, L.sub.21, L.sub.22, L.sub.23, L.sub.24, 
L.sub.25, L.sub.26, L.sub.27, L.sub.28, L.sub.29 and L.sub.30 each 
represents a methine group or a substituted methine group [for example, a 
methine group substituted by one or more of a substituted or unsubstituted 
alkyl group (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or 
unsubstituted aryl group (e.g., phenyl, o-carboxyphenyl), a halogen atom 
(e.g., chlorine, bromine), an alkoxy group (e.g., methoxy, ethoxy), an 
amino group (e.g., N,N-diphenylamino, N-methyl-N-phenylamino, 
N-methylpiperazine) and an alkylthio group (e.g., methylthio, ethylthio), 
or each may be combined with other methine group or an auxochrome to form 
a ring. 
Preferably, L.sub.11, L.sub.12, L.sub.16, L.sub.17, L.sub.18, L.sub.19, 
L.sub.22, L.sub.23, L.sub.29 and L.sub.30 are each an unsubstituted 
methine group. 
Preferably, h.sub.12 is 0, 1, 2 or 3. 
Methine dyes such as monomethine, trimethine, pentamethine and heptamethine 
dyes can be formed by L.sub.13, L.sub.14 and L.sub.15. When n.sub.12 is 2 
or more, an L.sub.13 -L.sub.14 unit is repeated, but the repeating units 
may be different. 
Preferred examples of L.sub.13, L.sub.14 and L.sub.15 include the following 
groups: 
##STR32## 
Preferably, n.sub.15 is 0, 1, 2 or 3. 
Methine dyes such as zeromethine, dimethine, tetramethine and hexamethine 
dyes can be formed by L.sub.20 and L.sub.21. When n.sub.15 is 2 or more, 
an L.sub.20 -L.sub.21 unit is repeated, and the repeating units may be 
different. 
Preferred examples of L.sub.20 and L.sub.21 include the following groups: 
##STR33## 
Preferably, n17 is 0, 1, 2 or 3. 
Methine dyes such as zeromethine, dimethine, tetramethine and hexamethine 
dyes can be formed by L24 and L.sub.25. When n.sub.17 is 2 or more, an 
L.sub.24 -L.sub.25 unit is repeated, and the repeating units may be 
different. 
Preferred examples of L.sub.24 and L.sub.25 are the same as those of 
L.sub.20 and L.sub.21. 
Preferably, h.sub.18 is 0, 1, 2 or 3. 
Methine dyes such as monomethine, trimethine, pentamethine and heptamethine 
dyes can be formed by L.sub.26, L.sub.27 and L.sub.28. When n.sub.18 is 2 
or more, an L.sub.26 -L.sub.27 unit is repeated, and the repeating units 
may be different. 
Preferred examples of L.sub.26, L.sub.27 and L.sub.28 include the following 
groups: 
##STR34## 
In addition to the above-described groups, the groups represented by 
L.sub.13, L.sub.14 and L.sub.15 are also preferred. 
The compound represented by formula (XI) is more preferably represented by 
the compound represented by the following formula (XIV): 
##STR35## 
wherein Z.sub.17 and Z.sub.18 are the same or different and each 
represents a sulfur atom or a selenium atom. 
R.sub.17 and R.sub.18 are the same or different and each represents a 
substituted or unsubstituted alkyl group. R.sub.19, V.sub.11, V.sub.12, 
V.sub.13, V.sub.14, V.sub.15, V.sub.16, V.sub.17 and V.sub.18 are the same 
or different and each represents a hydrogen atom or a monovalent 
substituent. 
M.sub.14 represents a counter ion fro neutralizing charge; and m.sub.14 
represents a number of 0 or more necessary for neutralizing the molecular 
charge. 
The compound represented by formula (XIV) will be explained in greater 
detail below. 
R.sub.17 an R.sub.18 have the same meaning as R.sub.11, R.sub.12, R.sub.13, 
R.sub.14 and R.sub.16. 
Examples of te substituent represented by R.sub.19, V.sub.11, V.sub.12, 
V.sub.13, V.sub.14, V.sub.15, V.sub.16, V.sub.17 or V.sub.18 include, but 
are not limited to, those already described above in the definition of the 
substituent group represented by V.sub.1 to V.sub.10. 
Adjacent two of V.sub.11, V.sub.12, V.sub.13, V.sub.14, V.sub.15, V.sub.16, 
V.sub.17 and V.sub.18 may be combined with each other to form a condensed 
ring. 
Examples of the condensed ring include those comprising a benzene ring and 
a heterocyclic ring (e.g., pyrrole, thiophene, furan, pyridine, imidazole, 
triazole, thiazole). 
R.sub.19 is preferably a methyl group, an ethyl group, a propyl group or a 
cyclopropyl group, and more preferably an ethyl group. 
Preferably, V.sub.11, V.sub.12, V.sub.14, V.sub.15, V.sub.16 and V.sub.18 
are each a hydrogen atom. 
Preferably, V.sub.13 and V.sub.17 are each a chlorine atom, a methyl group, 
a methoxy group, a phenyl group or a carboxyl group. 
It is also preferred that V.sub.13 and V.sub.14 or V.sub.17 and V.sub.18 
are combined together to form a benzene ring. 
M.sub.14 m.sub.14 has the same meaning as M.sub.11 m.sub.11, M.sub.12 
m.sub.12 and M.sub.13 m.sub.13. 
Typical examples of the sensitizing dyes which can be used in the present 
invention include, but are not limited to, the following compounds. 
The sensitizing dyes are described in order of higher conception, and more 
preferred sensitizing dyes included in lower conception are excluded. 
Examples of the sensitizing dyes represented by formula (XI) [exclusive of 
the dyes represented by formula (XTV)]: 
##STR36## 
Examples of the sensitizing dyes represented by formula (XII): 
##STR37## 
Examples of the sensitizing dyes represented by formula (XIII): 
##STR38## 
Examples of the sensitizing dyes represented by formula (XIV): 
##STR39## 
The sensitizing dyes used in the present invention can be synthesized by 
the methods described in F. M. Hamer, Heterocyclic Compounds-Cyanine Dyes 
and Related Compounds (John & Sons New York London 1964), D. M. Sturmer, 
Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry-, chapter 
18, paragraph 14, pp. 482-515 (John Wiley & Sons New York London 1977), 
and Rodd's Chemistry of Carbon Compounds, 2nd ed., vol. IV, part B (1977), 
chapter 15, pp. 369-422 and 2nd ed., vol. IV, part B (1985), chapter 15, 
pp. 267-296 (Elsvier Science Publishing Company Inc., New York). 
The metallocene compounds of the present invention and the sensitizing dyes 
used in the present invention may be directly dispersed in the silver 
halide emulsions used in the present invention. Alternatively, the 
metallocene compounds and the sensitizing dyes may be dissolved in a 
solvent such as water, methanol, ethanol, propanol, acetone, methyl 
cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 
3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol or 
N,N-dimethylformamide alone or a mixture thereof, and the resulting 
solution may be added to the emulsions. 
Further, there can be used a method wherein the dye and the metallocene 
compound represented by formula (I) are dissolved in a volatile organic 
solvent, the resulting solution is dispersed in water or hydrophilic 
colloid, and the resulting dispersion is added to the emulsion as 
described in U.S. Pat. No. 3,469,987; a method wherein a water-insoluble 
dye and the metallocene compound represented by formula (I) are dispersed 
in a watersoluble solvent without dissolving the dye and the metallocene 
compound, and the resulting dispersion is added to the emulsion as 
described in JP-B-46-24185; a method wherein the dye and the metallocene 
compound represented by formula (I) are dissolved in an acid, and the 
resulting solution is added to the emulsion, or an aqueous solution of the 
dye and the metallocene compound is prepared in the presence of an acid or 
a base, and the aqueous solution is added to the emulsion as described in 
JP-B-44-23389, JP-B-44-27555 and JP-B-57-22091; a method wherein an 
aqueous solution or a colloid dispersion is prepared in the presence of a 
surfactant and added to the emulsion as described in U.S. Pat. Nos. 
3,822,135 and 4,006,026; a method wherein the dye and the metallocene 
compound represented by (I) are directly dispersed in hydrophilic colloid, 
and the resulting dispersion is added to the emulsion as described in 
JP-A-58-105141; and a method wherein the dye and the metallocene compound 
represented by formula (I) are dissolved by using a compound to be 
red-shifted, and the resulting solution is added to the emulsion as 
described in JP-A-51-74624. 
Furthermore, ultrasonic wave can be used to dissolve the dye and the 
metallocene compound represented by formula (I). 
The sensitizing dyes used in the present invention and the metallocene 
compounds may be added to the emulsions during the preparation of the 
emulsions at any stage conventionally considered to be advantageous. For 
example, they may be added during the formation of silver halide grains 
and/or before desalting, or during desalting and/or before chemical 
sensitization after desalting as described in U.S. Pat. Nos. 2,735,766, 
3,628,960, 4,183,756 and 4,225,666, JP-A-58-184142 and JP-A-60-196749. 
They may be added immediately before or during chemical ripening or at any 
stage before coating after chemical ripening as described in 
JP-A-58-113920. Further, the same compound alone or a combination of 
compounds having different structures may be divided into two or more 
portions and added. For example, a part thereof is added during the 
formation of the grains, and the remainder is added during or after 
chemical ripening. A part thereof is added before chemical ripening, and 
the remainder is added after completion of chemical ripening. The types of 
compounds to be divided or the combinations of compounds may be changed 
and added. 
The amounts of the sensitizing dyes to be added vary depending on the form 
and size of the silver halide grains, but are preferably used in an amount 
of from 4.times.10.sup.-8 to 8.times.10.sup.-2 mol per mol of silver 
halide. 
The metallocene compounds of the present invention may be added before or 
after the addition of the sensitizing dyes and are used in an amount of 
preferably from 1.times.10.sup.-6 to 5.times.10.sup.-5 mol, more 
preferably from 1.times.10.sup.-5 to 2.times.10.sup.-2 mol, and most 
preferably from 1.times.10.sup.-4 to 1.6.times.10.sup.-2 mol, per mol of 
silver halide in the silver halide emulsion. 
The ratio (by mol) of the sensitizing dye to the metallocene compound is 
not particularly limited. However, the ratio of the sensitizing dye/the 
metallocene compound is preferably from 100/1 to 1/1000, more preferably 
from 10/1 to 1/100. 
The silver halide used in the present invention may be any of silver 
chloride, silver bromide, silver iodide, silver chlorobromide, silver 
chloroiodide, silver chloroiodobromide and silver iodobromide. The silver 
halide emulsions used in the present invention may contain one kind of 
silver halide grains or a mixture of two or more kinds of silver halide 
grains. Silver halide grains may be different in phase between the 
interior of the grain and the surface layer thereof. The silver halide 
grains may have a polyphase structure having a joint structure. The silver 
halide grains may have localized phases on the surface of the grain. The 
silver halide grains may comprise a uniform phase throughout the entire 
grain or may be in the mixed form of a uniform phase and other phases. 
The silver halide grains used in the present invention may be a 
monodisperse type or a polydisperse type, and may have a regular crystal 
form such as a cubic, octahedral or tetradecahedral form, an irregular 
crystal form or a composite form of these crystal forms. There may be used 
tabular emulsions comprising grains having such a grain size distribution 
that AgX grains having an aspect ratio (a ratio of the diameter of the 
grain in terms of the diameter of the corresponding circle to the 
thickness of the grain) of 3 or more account for 50% or more of the entire 
projected areas of the entire grains. An aspect ratio of from 5 to 8 is 
more preferred. Emulsions may comprise a mixture of grains having various 
crystal forms. The emulsions may be a surface latent image type wherein a 
latent image is predominantly formed on the surface of the grain or an 
internal latent image type wherein a latent image is predominantly formed 
in the interior of the grain. 
The photographic emulsions used in the present invention can be prepared by 
the methods described in the literature such as P. Glafkides, Chemie et 
Physique Photographique (Paul Montel 1967), G. F. Daffin, Photographic 
Emulsion Chemistry (Focal Press 1966), V. L. Zelikman et al., Making and 
Coating Photographic Emulsion (Focal Press 1964), F. H. Claes et al., The 
Journal of Photographic Science, (21) pages 39 to 50 (1973) and (21) pages 
85-92 (1973) and in the patent specifications of JP-B-55-42737, U.S. Pat. 
Nos. 4,400,463 and 4,801,523, JP-A-62-218959, JP-A-63-213836, 
JP-A-63-218938 and JP-A-2-32. Namely, any of the acid process, the neutral 
process and the ammonia process can be used. A soluble silver salt and a 
soluble halide can be reacted by the single jet process, the double jet 
process or a combination thereof. A method wherein grains are formed in 
the presence of an excess of silver (called a reverse mixing method) can 
be used. As a type of the double jet process, a method wherein the pAg in 
a liquid phase in which silver halide is formed is kept constant, that is, 
the controlled double jet process can also be used. According to this 
process, a silver halide emulsion wherein the grain form is regular and 
the grain size is nearly uniform can be obtained. 
Further, the present invention can use emulsions prepared by a conversion 
method including the step of converting silver halide already formed 
during the course of the formation of silver halide grains and emulsions 
prepared by a conversion method including the step of converting silver 
halide grains after completion of the formation of the silver halide 
grains. 
Solvents for silver halide may be used during the preparation of the silver 
halide grains used in the present invention. Examples of the solvents for 
silver halide which are often used include thioether compounds (e.g., 
those described in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130 and 
4,276,347), thione compounds and thiourea compounds (e.g., those described 
in JP-A-53-144319, JP-A-53-82408, JP-A-55-77737) and amine compounds 
(e.g., those described in JP-A-54-100717). Further, ammonia can be used in 
an amount which does not provide any adverse effect. 
It is preferred that the addition rates of the silver salt solution (e.g., 
an aqueous solution of silver nitrate) and the halide solution (e.g., an 
aqueous solution of sodium chloride) and the amounts and concentrations 
thereof are increased with time to expedite the growth of the grains 
during the preparation of the silver halide grains. The methods are 
described in, for example, British Patent 1,335,925, U.S. Pat. Nos. 
3,672,900, 3,650,757 and 4,242,445, JP-A-55-142329, JP-A-55-158124, 
JP-A-55-113927, JP-A-58-113928, JP-A-58-111934 and JP-A-58-111936. 
A cadmium salt, a zinc salt, a potassium salt, a rhenium salt, a ruthenium 
salt, an iridium salt or a complex salt thereof, a rhodium salt or a 
complex salt thereof, or an iron salt or a complex salt thereof may be 
allowed to coexist during the course of the formation of the silver halide 
grains or during the physical ripening thereof. Particularly, the use of a 
rhenium salt, an iridium salt, a rhodium salt or an iron salt is 
preferred. 
The amounts of these salts to be added may be arbitrarily determined. 
However, the iridium salt (e.g., Na.sub.3 IrCl.sub.6, Na.sub.2 IrCl.sub.6, 
Na.sub.3 Ir(CN).sub.6) is used in an amount of preferably from 
1.times.10.sup.-8 to 1.times.10.sup.-5 mol per mol of silver. The rhodium 
salt (e.g., RhCl.sub.3, K.sub.3 Rh(CN).sub.6) is used in an amount of 
preferably from 1.times.10.sup.-8 to 1.times.10.sup.-5 mol per mol of 
silver. 
The silver halide emulsions used in the present invention may be used 
without chemical sensitization. If desired, the silver halide emulsions 
may be chemical-sensitized. 
Examples of chemical sensitization methods include gold sensitization 
method using gold compounds (described in, for example, U.S. Pat. Nos. 
2,448,060 and 3,320,069), sensitization method using metal such as 
iridium, platinum, rhodium or palladium (described in, for example, U.S. 
Pat. Nos. 2,448,060, 2,566,246 and 2,566,263), sulfur sensitization method 
using sulfur-containing compounds (described in, for example, U.S. Pat. 
No. 2,222,264), selenium sensitization method using selenium compounds and 
reduction sensitization method using tin salts, thiourea dioxide or 
polyamides (described in, for example, U.S. Pat. Nos. 2,487,850, 2,518,698 
and 2,521,925). These sensitization methods may be used either alone or in 
a combination of two or more of them. 
It is preferred that the silver halide emulsions used in the present 
invention are subjected to gold sensitization, sulfur sensitization or a 
combination thereof. Gold sensitizing agents and sulfur sensitizing agents 
are used in an amount of preferably from 1.times.10.sup.-7 to 
1.times.10.sup.-2 mol, more preferably 5.times.10.sup.-6 to 
1.times.10.sup.-3 mol, per mol of silver. When gold sensitization and 
sulfur sensitization are carried out in combination, the gold sensitizing 
agent and the sulfur sensitizing agent are used in a ratio by mol of 
preferably from 1:3 to 3:1, more preferably from 1:2 to 2:1. 
In the present invention, chemical sensitization is carried out at a 
temperature of from 30.degree. to 90.degree. C. The pH thereof is from 4.5 
to 9.0, preferably from 5.0 to 7.0. The time of chemical sensitization 
varies depending on the temperature, the pH and the types and amounts of 
the chemical sensitizing agents used, and may be over a period of several 
minutes to several hours, but is usually from 10 to 200 minutes. 
It is preferred in the present invention that the sensitizing dyes are used 
together with water-soluble iodides such as typically potassium iodide, 
water-soluble bromides such as typically potassium bromide and 
water-soluble thiocyanates such as typically potassium thiocyanate to 
enhance adsorptivity to silver halide or the formation of J-aggregate or 
to obtain more higher spectral sensitivity. When the silver chloride or 
silver chlorobromide having a high silver chloride content is used, the 
effects obtained by using water-soluble bromides or water-soluble 
thiocyanates are particularly remarkable. 
High silver chloride emulsions having a silver chloride content of 50 mol % 
or more are preferred to conduct ultra-high rapid processing where 
development time is 30 seconds or less. For this purpose, it is preferred 
that the concentration of iodide ion including the above-described 
water-soluble iodides is 0.05 mol % or less because the iodide ion 
possesses a high development inhibiting effect. 
High silver chloride emulsions having a silver chloride content of 80 mol % 
or more are more preferred to prepare ultra-high rapid processable silver 
halide photographic materials. When the emulsions are to be prepared, the 
use of the sensitizing dyes together with the water-soluble bromides 
and/or the water-soluble thiocyanates is preferred as described above 
because the formation of J-aggregate can be enhanced and higher spectral 
sensitivity can be obtained. The amounts of these compounds to be added 
are preferably from 0.03 to 3 mol %, particularly preferably from 0.08 to 
1 mol %, per mol of silver. 
High silver chloride grains having a silver chloride content of 80 mol % or 
more have such a characteristic that when the grains are 
spectral-sensitized to infrared region, high sensitivity can be obtained, 
and a latent image having excellent stability can be obtained. High silver 
chloride grains having localized phases described in JP-A-2-248945 are 
more preferred. It is preferred that the localized phases have a silver 
bromide content of 15 mol % or more as described in the above patent 
specification. A silver bromide content of from 20 to 60 mol % is more 
preferred. It is most preferred that the silver bromide content is from 30 
to 50 mol %, and the remainder is silver chloride. The localized phases 
may exist on the surface of the grain or in the interior thereof, or may 
be distributed so that a portion of the localized phases exists in the 
interior of the grain, a portion thereof exists on the surface thereof, 
and a portion thereof exists in the subsurface thereof. The localized 
phases may exist in a laminar structure so that the silver halide grain is 
surrounded with the localized phases in the interior of the grain or on 
the surface thereof. The localized phases may exist in a discontinuous 
independent form. In a preferred embodiment of the arrangement of the 
localized phase having a higher silver bromide content than that of the 
circumference, the localized phase having a silver bromide content of more 
than 15 mol % is formed on the surface of the silver halide grain by 
epitaxial growth. 
The silver bromide content of the localized phase can be analyzed by X-ray 
diffractometry (e.g., described in New Experimental Chemical Lecture 6, 
"Structural Analysis", edited by Chemical Society of Japan, published by 
Maruzen, Japan) or XPS method (e.g., Surface Analysis, IPA, Application of 
Auger Electron Photoelectron Spectroscopy, published by Kodan-sha, Japan). 
The localized phases are preferably from 0.1 to 20%, more preferably 0.5 
to 7%, of silver based on the total amount of silver in the silver halide 
grain. 
The interface between the localized phase having a high silver bromide 
content and other phase may be a clear phase boundary or may have a short 
transition zone where the halogen composition is gradually changed. 
The localized phase having a high silver bromide content can be formed by 
various methods. For example, the localized phases can be formed by 
reacting a soluble silver salt with a soluble halide according to the 
single jet process or the double jet process or by a conversion method 
including a stage where an already formed silver halide is converted to 
silver halide having a smaller solubility product. Alternatively, the 
localized phases can be formed by adding fine silver bromide grains to 
silver halide grains to recrystallize the fine silver bromide grains on 
the surfaces of the silver halide grains. 
The silver halide emulsions prepared according to the present invention can 
be applied to any of color photographic materials and black and white 
photographic materials. 
Examples of the color photographic materials include color paper, color 
films for photographing and reversal color films. Examples of the black 
and white photographic materials include X-ray films, general-purpose 
films for photographing and films for printing photographic materials. 
Additives described in Research Disclosure vol. 176, No. 17643 (RD 17643) 
and ibid. vol. 187, No. 18716 (RD 18716) can be applied to the emulsions 
of the photographic materials used in the present invention without 
particular limitation. 
Places where additives are described in RD 17643 and RD 18716 are listed in 
Table 1 below. 
TABLE 1 
______________________________________ 
Additive RD 17643 RD18716 
______________________________________ 
1 Chemical Sensitizing 
page 23 right column 
Agent of page 648 
2 Sensitivity Increaser 
-- right column 
of page 648 
3 Spectral Sensitizing 
pages 23-24 
right column 
Agent, Supersensitizing of page 648 to 
Agent right column 
of page 649 
4 Brightener page 24 
5 Anti-fogging Agent, 
pages 24-25 
right column 
Stabilizer of page 649 
6 Light Absorber, Filter 
pages 25-26 
right column 
Dye, UV Absorber of page 649 to 
left column of 
page 650 
7 Anti-staining Agent 
right column 
left column to 
of page 25 right column 
of page 650 
8 Dye Image Stabilizer 
page 25 
9 Hardening Agent page 26 left column 
of page 651 
10 Binder page 26 left column 
of page 651 
11 Plasticizer, Lubricant 
page 27 right column 
of page 650 
12 Coating Aid, Surfactant 
pages 26-27 
right column 
of page 650 
13 Antistatic Agent page 27 right column 
of page 650 
______________________________________ 
Dyes other than sensitizing dye suitable for use in the photographic 
material of the present invention will be described in detail below. 
The photographic material of the present invention may contain colloidal 
silver and other dyes for the purpose of anti-irradiation and 
anti-halation, and especially for separation of the spectral sensitivity 
distribution of each light-sensitive layer and for ensuring safety to a 
safelight. Such dyes include, for example, oxonole dyes having pyrazolone 
nuclei, barbituric nuclei or barbituric acid nuclei, such as those 
described in U.S. Pat. Nos. 506,385, 1,177,429, 1,131,884, 1,338,799, 
1,385,371, 1,467,214, 1,438,102 and 1,553,516, JP-A-48-85130, 
JP-A-49-114420, JP-A-52-117123, JP-A-55-161233, JP-A-59-111640, 
JP-B-39-22069, JP-B-43-13168, JP-B-62-273527, and U.S. Pat. Nos. 
3,247,127, 3,469,985 and 4,078,933; other oxonole dyes, such as those 
described in U.S. Pat. Nos. 2,533,472 and 3,379,533, British Patent 
1,278,621, JP-A-1-134447, and JP-A-1-183652; azo dyes such as those 
described in British Patents 575,691, 680,631, 599,623, 786,907, 907,125 
and 1,045,609, U.S. Pat. No. 4,255,326, and JP-A-59-211043; azomethine 
dyes such as those described in JP-A-50-100116, JP-A-54-118247 and British 
Patents 2,014,598 and 750,031; anthraquinone dyes such as those described 
in U.S. Pat. No. 2,865,752; arylidene dyes such as those described in U.S. 
Pat. Nos. 2,538,009, 2,688,541 and 2,538,008, British Patents 584,609 and 
1,210,252, JP-A-50-40625, JP-A-51-3623, JP-A-51-10927, JP-A-54-118247, 
JP-B-48-3286 and JP-B-59-37303; styryl dyes such as those described in 
JP-B-28-3082, JP-B-44-16594, and JP-B-59-28898; triarylmethane dyes such 
as those described in British Patents 446,538, and 1,335,422, and 
JP-A-59-228250; merocyanine dyes such as those described in British 
Patents 1,075,653, 1,153,341, 1,284,730, 1,475,228 and 1,542,807; and 
cyanine dyes such as those described in U.S. Pat. Nos. 2,843,486 and 
3,294,539, and JP-A-1-291247. 
For the purpose of preventing diffusion of these dyes in the photographic 
material of the present invention, various means may be employed. For 
instance, a ballast group may be introduced into the dyes so as to make 
them non-diffusive. 
A hydrophilic polymer charged oppositely to the dissociated anion dye may 
be incorporated into a layer along with the dye as a mordant, whereby the 
dye is localized and fixed in the particular layer due to the interaction 
of the polymer and the dye molecule, as described in U.S. Pat. Nos. 
2,548,564, 4,124,386 and 3,625,694. 
A water-insoluble solid dye may be used for coloring a particular layer, as 
so described in JP-A-56-12639, JP-A-55-155350, JP-A-55-155351, 
JP-A-63-278838, JP-A-63-197943, and European Patent 15,601. 
Fine grains of a metal salt to which dyes have been adsorbed may be used 
for coloring a particular layer, as described in U.S. Pat. Nos. 2,719,088, 
2,496,841 and 2,496,842, and JP-A-60-45237. 
The photographic material of the present invention may contain an 
antifoggant or stabilizer selected from, for example, azoles (e.g., 
benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, 
chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, 
aminotriazoles); mercapto compounds (e.g., mercaptothiazoles, 
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, 
mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), 
mercaptopyrimidines, mercaptotriazines); thioketo compounds (e.g., 
oxazolinethiones); azaindenes (e.g., triazaindenes, tetrazaindenes 
(especially 4-hydroxy-substituted (1,3,3a,7)tetrazaindenes), 
pentazaindenes); benzenethiosulfonic acids; benzenesulfinic acids; and 
benzenesulfonic acid amides. 
The photographic material of the present invention may contain color 
couplers, preferably non-diffusive couplers having a hydrophobic group 
called a ballast group in the molecule or polymerized couplers. The 
couplers may be either 4-equivalent or 2-equivalent with respect to silver 
ions. The photographic material of the present invention may also contain 
colored couplers having a color-correcting effect, or couplers capable of 
releasing a development inhibitor during development of the photographic 
material (so-called DIR couplers). The photographic material may also 
contain colorless DIR coupling compounds capable of producing a colorless 
product by a coupling reaction and releasing a development inhibitor. 
Preferred examples of such couplers for use in the present invention are 
described in JP-A-62-215272, from page 91, right top column, line 4 to 
page 121, left top column, line 6; and JP-A-2-33144, from page 3, right 
top column, line 14 to page 18, left top column, last line, and from page 
30, right top column, line 6 to page 35, right bottom column, line 11. 
Specifically, suitable magenta couplers include 5-pyrazolone couplers, 
pyrazolobenzimidazole couplers, pyrazolotriazole couplers, 
pyrazolotetrazole couplers, cyanoacetylchroman couplers, and open-chain 
acylacetonitrile couplers; suitable yellow couplers include acylacetamide 
couplers (e.g., benzoylacetanilides, pivaloylacetanilides); and suitable 
cyan couplers include naphthol couplers and phenol couplers. Preferred 
cyan couplers include phenol couplers having an ethyl group at the 
meta-position of the phenol nucleus, 2,5-diacylamino-substitued phenol 
couplers, phenol couplers having a phenylureido group at the 2-position 
and having an acylamino group at the 5-position, and naphthol couplers 
having a sulfonamido or amido group at the 5-position of the naphthol 
nucleus, such as those described in U.S. Pat. Nos. 3,772,002, 2,772,162, 
3,758,308, 4,126,396, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 
4,451,559 and 4,427,767, as they form fast images. 
Two or more different kinds of the above-mentioned couplers may be 
incorporated into one and the same layer, or one and the same compound of 
the couplers may be added to two or more layers, for the purpose of 
satisfying the intended characteristics of the photographic material of 
the present invention. 
The photographic material of the present invention may contain an 
anti-fading agent selected from, for example, hindered phenols such as 
hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, 
p-alkoxyphenols and hisphenols; and gallic acid derivatives, 
methylenedioxybenzenes, aminophenols, hindered amines and ether or ester 
derivatives of them formed by silylating or alkylating the phenolic 
hydroxyl group of the compounds. In addition, metal complexes such as 
bis(salicylaldoximato)nickel complexes and 
bis(N,N-dialkyldithiocarbamato)nickel complexes may also be used as an 
anti-fading agent. 
For photographic processing of the photographic material of the present 
invention, any known method and any known processing solution may be 
employed. The processing temperature may be selected generally from the 
range between 18.degree. C. and 50.degree. C. However, it may be lower 
than 18.degree. C. or higher than 50.degree. C. In accordance with the 
object of the photographic material, either black-and-white development 
for forming a silver image or color development for forming a color image 
may be employed. 
As a black-and-white developer for the former black-and-white development, 
any known developing agent, such as dihydroxybenzenes (e.g., 
hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone) and 
aminophenols (e.g., N-methyl-p-aminophenol) may be employed singly or in 
combinations of them. 
The color developer for the latter color development is generally an 
alkaline aqueous solution containing a color developing agent. The color 
developing agent in it may be a known primary aromatic amine developing 
agent, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 
3-methyl-4-amino-N,N-diethylaniline, 
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, 
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline). 
In addition, the color developing agents described in F .A. Meson, 
Photographic Processing Chemistry. (published by Focal Press Co., 1966), 
pp. 226-229 and in U.S. Pat. Nos. 2,193,015 and 2,592,364, and 
JP-A-48-64933 may also be used. 
The developer may additionally contain a pH buffer such as alkali metal 
sulfites, carbonates, borates or phosphates, as well as a development 
inhibitor or anti-foggant such as bromides, iodides or organic 
antifoggants. If desired, it may also contain a water softener; a 
preservative such as hydroxylamine; an organic solvent such as benzyl 
alcohol or diethylene glycol; a development accelerator such as 
polyethylene glycol, quaternary ammonium salts or amines; a dye forming 
coupler; a competing coupler; a foggant such as sodium boronhydride; a 
developing aid such as 1-phenyl-3-pyrazolidone; a thickener; a 
polycarboxylic acid chelating agent such as those described in U.S. Pat. 
No. 4,083,723; and an antioxidant such as those described in German Patent 
OLS No. 2,622,950. 
After being color-developed, the color photographic material is generally 
bleached. Bleaching of the material may be carried out simultaneously with 
or separately from fixation. Suitable bleaching agents to be used for 
bleaching the material include, for example, compounds of polyvalent 
metals such as iron(III), cobalt(III), chromium(VI) and copper(II), as 
well as peracids, quinones and nitroso compounds. Specific examples of 
suitable bleaching agents include ferricyanides; bichromates; organic 
complexes of iron(III) or cobalt(III), such as complexes with 
aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, 
nitrilotriacetic acid, 1,3-diamino-2-propanol-tetraacetic acid) or with 
organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates; 
permanganates; and nitrosophenols. Of them, especially advantageous are 
potassium ferricyanide, sodium ethylenediaminetetraacetato/iron(III) and 
ammonium ethylenediaminetetraacetato/iron(III). 
Ethylenediaminetetraacetato/iron(II) complexes are useful both in an 
independent bleaching solution and in a one-bath bleach-fixing solution. 
The bleaching solution or bleach-fixing solution to be used for processing 
the photographic material of the present invention may contain various 
additives, for example, a bleaching accelerator such as those described in 
U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-B-45-8506, and JP-B-45-8836; 
and a thiol compound such as those described in JP-A-53-65732. After being 
bleached or bleach-fixed, the photographic material may be rinsed in water 
or may be directly stabilized in a stabilizing bath without rinsing in 
water. 
The support of the photographic material of the present invention may be 
any ordinary transparent film support such as a cellulose nitrate film or 
polyethylene terephthalate film support, or a reflective support, which is 
used in forming ordinary photographic materials. 
The "reflective support" of the photographic material of the present 
invention is one which elevates the reflectivity of the support itself to 
make the color image formed in the silver halide emulsion layer clear and 
sharp. Reflective supports of this kind include a support coated with a 
hydrophobic resin containing a dispersion of a photo-reflective substance, 
such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, 
so as to elevate the reflectivity of the support to light within the 
visible ray wavelength range, and a support made of a hydrophobic resin 
containing a dispersion of such a photo-reflective substance. Examples of 
suitable reflective supports include a baryta paper, a polyethylene-coated 
paper, a polypropylene synthetic paper, and a transparent support coated 
with a reflective layer thereon or containing a reflective substance 
therein. Suitable transparent supports include, for example, a glass 
sheet, a polyester film such as polyethylene terephthalate, cellulose 
triacetate or cellulose nitrate film, as well as a polyamide film, a 
polycarbonate film, a polystyrene film, and a polyvinyl chloride resin 
film. These supports are suitably selected in accordance with the use and 
object of the photographic material. 
Exposure of the photographic material of the present invention for forming 
a photographic image thereon may be effected by any ordinary means. For 
instance, any one of various known light sources, such as natural light 
(sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a 
xenon-arc lamp, a carbon-arc lamp, a xenon-flash lamp, lasers, an LED and 
a CRT can be used for exposure. The exposing time may be any ordinary one 
for ordinary cameras of from 1/1000 second to one second. As the case may 
be, shorter exposures of less than 1/1000 second, for example from 
1/10.sup.6 to 1/10.sup.4 second, may be applied to the photographic 
material of the present invention by the use of a xenon-flash lamp; or 
longer exposures of more than one second may be applied thereto. If 
desired, a color filter may be used for exposure of the photographic 
material of the present invention for adjusting the spectral composition 
of the light to be applied thereto. Laser rays may be used for exposure of 
the material. If desired, the material may also be exposed with a light to 
be emitted from phosphors as excited with electron rays, X rays, .gamma. 
rays or .alpha. rays.

The present invention will be described in more detail by way of the 
following examples, but it should be understood that the present invention 
is not to be deemed to be limited thereto. 
EXAMPLE 1 
To a reaction vessel were added 1000 ml of water, 25 g of deionized ossein 
gelatin, 15 ml of a 50% aqueous solution of NH.sub.4 NO.sub.3 and 7.5 ml 
of a 25% aqueous solution of NH.sub.3. The temperature of the mixture was 
kept at 50.degree. C. with vigorous stirring. To the mixture were added 
750 ml of an aqueous solution of 1N silver nitrate and an aqueous solution 
of 1N potassium bromide over a period of 50 minutes while the silver 
potential was kept at +60 mV versus saturated calomel electrode during the 
reaction. The aqueous solution of 1N potassium bromide was added in an 
amount necessary for keeping the silver potential at 60 mV. 
The resulting silver bromide grains were cubic and had a side length of 
0.76.+-.0.06 .mu.m. The temperature of the resulting emulsion was lowered. 
A copolymer of isobutene and monosodium maleate as a flocculating agent 
was added thereto, and the emulsion was washed with water and desalted by 
a precipitation method. Subsequently, 95 g of deionized ossein gelatin and 
430 ml of water were added thereto. The pH of the emulsion was adjusted to 
6.5, and the pAg was adjusted to 8.3 at 50.degree. C. Sodium thiosulfate 
was added thereto at 40.degree. C., and the emulsion was ripened at 
55.degree. C. for 45 minutes so as to provide the optimum sensitivity. The 
emulsion contained 0.74 mol of silver bromide per kg. 
Sensitizing dyes shown in Tables 2 and 3 below were added to 55 g of the 
emulsion at 35.degree. C., and the emulsion was ripened at 55.degree. C. 
for 30 minutes. The temperature of the emulsion was lowered to 40.degree. 
C., and the metallocene compounds shown in Tables 2 and 3 were added 
thereto. Further, 10 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 15 g 
of a 10% gel of deionized gelatin and 55 ml of water were added thereto. 
The resulting coating solution was coated on a cellulose triacetate film 
base in such an amount as to provide the following coating weights. 
The amount of the coating solution was set so as to provide 2.5 g/m.sup.2 
of silver and 3.8 g/m.sup.2 of gelatin. An aqueous solution comprising 
mainly 0.22 g of sodium dodecylbenzenesulfonate per liter, 0.50 g of 
p-sulfostyrene sodium homopolymer per liter, 3.9 g of 
1,3-bis-(vinylsulfonyl)-2-propanol per liter and 50 g of gelatin per liter 
was simultaneously coated as the upper layer in such an amount as to 
provide 1.0 g/m.sup.2 of gelatin. 
Each of the coated samples prepared above was exposed to light through a 
continuous wedge for one second by using a tungsten lamp (2856.degree. 
K.), a blue color filter V40 (a band pass filter which transmits light in 
the range of 370 to 440 nm, a product of Toshiba Glass Co., Ltd.) and an 
orange color filter SC 54 (which transmits light having a wavelength of 
520 nm more, a product of Fuji Photo Film Co., Ltd.). Each of the exposed 
samples was developed with a developing solution (prepared by three times 
diluting D-72 developing solution and then adjusting the pH thereof to 
10.4), stopped, fixed, rinsed and dried. The density of each sample was 
measured by using a densitometer (a product of Fuji Photo Film Co., Ltd.) 
to determine the blue filter sensitivity (S.sub.B), the orange filter 
sensitivity (S.sub.O) and fog. The reciprocal of an exposure amount 
providing an optical density of (fog+0.2) is referred to as the 
sensitivity. The sensitivity in terms of the relative sensitivity is shown 
in Tables when each of the blue filter sensitivity and the orange filter 
sensitivity of each sample containing no metallocene compound in each 
group of the samples containing the same spectral sensitizing dye is 
referred to as 100. 
TABLE 2 
__________________________________________________________________________ 
Sensitizing Dye 
Metallocene Compound 
Sample 
and Amount Added 
and Amount Added 
Relative Sensitivity 
No. (10.sup.-4 mol/molAg) 
(10.sup.-3 mol/molAg) 
S.sub.B S.sub.O Fog 
Remarks 
__________________________________________________________________________ 
1-1 XII-1 1.5 -- -- 100 (standard) 
100 (standard) 
0.03 
1-2 " " I-1 3.0 100 105 0.03 
Invention 
1-3 " " " 15.0 110 112 0.03 
Invention 
1-4 " " I-26 3.0 100 110 0.03 
Invention 
1-5 " " " 15.0 105 117 0.02 
Invention 
1-6 XII-19 
2.5 -- -- 100 (standard) 
100 (standard) 
0.04 
1-7 " " I-27 4.5 112 145 0.04 
Invention 
1-8 " " " 15.0 120 155 0.03 
Invention 
1-9 " " I-31 2.0 115 151 0.04 
Invention 
1-10 
" " " 10.0 117 166 0.04 
Invention 
1-11 
XIV-5 3.0 -- -- 100 (standard) 
100 (standard) 
0.03 
1-12 
" " I-1 3.0 105 123 0.04 
Invention 
1-13 
" " " 15.0 112 174 0.03 
Invention 
1-14 
" " I-23 3.0 123 132 0.04 
Invention 
1-15 
" " " 15.0 120 234 0.03 
Invention 
1-16 
XIVI-7 
3.0 -- -- 100 (standard) 
100 (standard) 
0.03 
1-17 
" " I-1 3.0 105 126 0.03 
Invention 
1-18 
" " " 15.0 120 195 0.03 
Invention 
1-19 
" " I-2 0.3 123 155 0.03 
Invention 
I-20 
" " " 3.0 135 295 0.03 
Invention 
1-21 
" " " 15.0 87 186 0.03 
Invention 
1-22 
" " I-5 3.0 126 195 0.03 
Invention 
1-23 
" " " 15.0 120 251 0.02 
Invention 
1-24 
" " I-12 0.03 120 195 0.03 
Invention 
1-25 
" " " 0.3 123 282 0.03 
Invention 
1-26 
" " " 3.0 71 117 0.03 
Invention 
1-27 
" " I-14 0.03 93 126 0.03 
Invention 
1-28 
" " " 0.3 129 209 0.03 
Invention 
1-29 
" " " 3.0 110 166 0.03 
Invention 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
Sensitizing Dye 
Metallocene Compound 
Sample 
and Amount Added 
and Amount Added 
Relative Sensitivity 
No. (10.sup.-4 mol/molAg) 
(10.sup.-3 mol/molAg) 
S.sub.B S.sub.O Fog 
Remarks 
__________________________________________________________________________ 
1-16 
XIV-7 3.0 -- -- 100 (standard) 
100 (standard) 
0.03 
1-30 
" " I-15 0.03 145 195 0.03 
Invention 
1-31 
" " " 0.3 110 331 0.03 
Invention 
1-32 
" " " 15.0 110 112 0.03 
Invention 
1-33 
" " I-31 0.3 107 129 0.03 
Invention 
1-34 
" " " 3.0 117 162 0.02 
Invention 
1-35 
" " " 15.0 138 240 0.03 
Invention 
1-36 
XIV-7 4.5 -- -- 100 (standard) 
100 (standard) 
0.03 
1-37 
" " I-1 4.5 105 224 0.03 
Invention 
1-38 
" " " 22.5 102 331 0.03 
Invention 
1-39 
" " I-27 4.5 107 245 0.03 
Invention 
1-40 
" " " 22.5 105 371 0.03 
Invention 
1-41 
XII-8 3.0 -- -- 100 (standard) 
100 (standard) 
0.04 
1-42 
" " I-1 0.3 100 117 0.03 
Invention 
1-43 
" " " 3.0 95 117 0.04 
Invention 
1-44 
" " I-7 0.3 100 178 0.04 
Invention 
1-45 
" " " 3.0 95 174 0.04 
Invention 
1-46 
" " I-24 0.6 100 162 0.03 
Invention 
__________________________________________________________________________ 
It is apparent from the results shown in Tables 2 and 3 that when the 
sensitizing dyes are used together with the metallocene compounds, the 
spectral sensitivity (S.sub.O) can be increased. 
EXAMPLE 2 
The silver halide emulsion used in Example 2 was prepared in the following 
manner. 
______________________________________ 
Solution (1) 
Water 1000 ml 
NaCl 4.65 g 
Gelatin 22 g 
Citric Acid 0.80 g 
Solution (2) 
KBr 25.3 g 
NaCl 32.3 g 
K.sub.2 IrCl.sub.6 (0.005%) 
11.2 ml 
Na.sub.3 RhCl.sub.6.2H.sub.2 O (10.sup.-5 mol/liter) 
18.9 ml 
Add Water to make 348 ml 
Solution (3) 
AgNO.sub.3 120.6 g 
Add Water to make 348 ml 
Solution (4) 
KBr 30.0 g 
NaCl 48.7 g 
Add Water to make 552 ml 
Solution (5) 
AgNO.sub.3 176.3 g 
Add Water to make 552 ml 
______________________________________ 
Solution (1) was heated to 50.degree. C., and 262 ml of Solution (2) and 
262 ml of Solution (3) were simultaneously added thereto at a given flow 
rate over a period of 12 minutes. Subsequently, Solution (4) and Solution 
(5) were simultaneously added thereto over a period of 20 minutes. The 
temperature of the mixture was lowered, and a copolymer of isobutene and 
monosodium maleate as a flocculating agent was added thereto, and the 
resulting emulsion was washed with water and desalted by a precipitation 
method. Water and ossein gelatin were then added thereto. The pH of the 
emulsion was adjusted to 6.1, and the pAg thereof was adjusted to 7.5. The 
thus prepared silver chlorobromide emulsion comprised monodisperse cubic 
grains having an average side length of 0.28 .mu.m, a coefficient of 
variation (a value s/d obtained by dividing standard deviation by average 
side length) of 0.08 and a silver bromide content of 30 mol %. 
Sodium thiosulfate, chloroauric acid and potassium thiocyanate were added 
to the emulsion. The emulsion was ripened at 55.degree. C. to carry out 
chemical sensitization so as to obtain the optimum sensitivity. The 
emulsion was divided into portions. The sensitizing dyes shown in Table 4 
below were added to these portions at 50.degree. C. as shown in Table 4 
below. After 20 minutes, the metallocene compounds according to the 
present invention and 7.5.times.10.sup.-4 mol of 
4-hydroxy-5,6-propanol-1,3,3a,7-tetrazaindene per mol of silver 
chlorobromide were added as shown in Table 4 below. 
To each of these emulsions were added 280 g of a 10% gel of deionized 
gelatin and 1.04 liters of water, each amount being kg of the emulsion. 
Subsequently, 7 g of 1,2-bis(vinylsulfonylacetylamino)ethane per kg of the 
emulsion was added. The resulting emulsion was coated on a polyethylene 
terephthalate film base in such an amount as to provide a coating weight 
of 1.2 g/m.sup.2 in terms of silver in the same manner as in Example 1. 
These samples were exposed to light an developed in the same manner as in 
Example 1 except that development was carried out at 38.degree. C. for 20 
seconds by using a developing solution LD-835 (a product of Fuji Photo 
Film Co., Ltd.). The density of each sample was measured in the same 
manner as in Example 1. The sensitivity and fog were determined. The 
results obtained are shown in Table 4 below. The reciprocal of an exposure 
amount providing an optical density of (fog+0.5) is referred to as the 
sensitivity. The sensitivity in terms of the relative sensitivity is shown 
in Table 4 below when each of the blue filter sensitivity (S.sub.B) and 
the orange filter sensitivity (S.sub.O) of each sample containing no 
metallocene compound in each group of the samples containing the same 
spectral sensitizing dyes is referred to as 100. 
Further, a change in the sensitivity was examined after the samples were 
stored at 25.degree. C. under oxygen partial pressure of 10 arms for 4 
days. The change in the sensitivity is referred to as raw preservability 
with time, and the results obtained are shown in Table 4 below. Namely, 
after the samples are stored at 25.degree. C. under oxygen partial 
pressure of 10 arms for 4 days, the samples are exposed to light and 
developed as described above. The orange filter sensitivity of each of the 
exposed and developed samples in terms of the relative sensitivity is 
shown in Table 4 below when the orange filter sensitivity of the 
corresponding sample which is not stored is referred to as 100. 
TABLE 4 
__________________________________________________________________________ 
Raw Pre- 
Sensitizing Dye 
Metallocene Compound servability 
Sample 
and Amount Added 
and Amount Added 
Relative Sensitivity 
with Time 
No. (10.sup.-4 mol/molAg) 
(10.sup.-3 mol/molAg) 
S.sub.B S.sub.O Fog 
.DELTA.S.sub.O 
Remarks 
__________________________________________________________________________ 
2-1 XI-5 8.0 -- -- 100 (standard) 
100 (standard) 
0.02 
85 
2-2 " " I-1 2.6 120 123 0.02 
93 Invention 
2-3 " " " 13.0 129 141 0.02 
95 Invention 
2-4 XI-14 2.5 -- -- 100 (standard) 
100 (standard) 
0.02 
91 
2-5 " " I-23 5.2 169 214 0.02 
95 Invention 
2-6 " " " 20.8 191 309 0.02 
100 Invention 
2-7 XI-16 2.5 -- -- 100 (standard) 
100 (standard) 
0.02 
91 
2-8 " " I-26 2.6 148 269 0.02 
98 Invention 
2-9 " " " 13.0 162 302 0.02 
100 Invention 
2-10 
XI-40 5.0 -- -- 100 (standard) 
100 (standard) 
0.02 
69 
2-11 
" " I-1 2.6 114 123 0.02 
87 Invention 
2-12 
" " " 13.0 117 126 0.02 
91 Invention 
2-13 
" " I-31 2.6 135 138 0.02 
89 Invention 
2-14 
" " " 13.0 132 148 0.02 
95 Invention 
2-15 
XI-44 6.8 -- -- 100 (standard) 
100 (standard) 
0.02 
74 
2-16 
" " I-1 2.6 125 125 0.02 
89 Invention 
2-17 
" " " 13.0 125 120 0.02 
93 Invention 
2-16 
" " I-7 2.6 132 129 0.02 
87 Invention 
2-17 
" " " 13.0 123 132 0.02 
87 Invention 
2-18 
" " I-31 2.6 135 145 0.02 
89 Invention 
2-19 
" " " 13.0 135 155 0.02 
95 Invention 
2-20 
XIII-1 
1.0 -- -- 100 (standard) 
100 (standard) 
0.02 
89 
2-21 
" " II-31 0.1 115 120 0.02 
89 Invention 
2-22 
" " " 1.0 135 162 0.02 
93 Invention 
2-23 
" " " 10.0 129 209 0.02 
95 Invention 
__________________________________________________________________________ 
It will be understood from the results shown in Table 4 that the 
combinations according to the present invention are low in fog and provide 
high sensitivity and at the same time, the problem of a lowering in the 
sensitivity caused by oxygen can be effectively improved. 
EXAMPLE 3 
To one liter of a 2% aqueous solution of gelatin were added 6.5 g of 
potassium bromide, 1.2 g of potassium iodide and 4.9 g of potassium 
thiocyanate. While the mixture was stirred at 70.degree. C., 0.4 liters of 
an aqueous solution containing 57.5 g of potassium bromide and 2.5 g of 
potassium iodide and 0.4 liters of an aqueous solution containing 85 g of 
silver nitrate were added thereto at an equal flow rate over a period of 
45 minutes by the double jet process. A copolymer of isobutene and 
monosodium maleate was then added thereto at 35.degree. C. The pH of the 
resulting emulsion was adjusted to 3.8. The emulsion was washed with water 
and desalted by a precipitation method. Subsequently, gelatin, water and 
phenol were added thereto. The pH of the emulsion was adjusted to 6.8, and 
the pAg thereof was adjusted to 8.7. The thus obtained silver halide 
grains had an average diameter of 1.74 .mu.m and an average thickness of 
0.23 .mu.m (an average ratio of the diameter/the thickness was 7.57). The 
emulsion was divided into portions. The sensitizing dye shown in Table 5 
below was added to each portion at 35.degree. C. After the emulsion was 
ripened with stirring for 15 minutes, sodium thiosulfate pentahydrate, 
potassium tetraaurate and potassium thiocyanate were added thereto. The 
temperature was rapidly raised to 60.degree. C., and the emulsion was 
ripened so as to obtain the optimum sensitivity. 
The metallocene compounds shown in Table 5 below were added to the thus 
prepared silver iodobromide emulsions at 40.degree. C. Further, a 14% gel 
of deionized gelatin and 2.times.10.sup.-3 mol of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mol of silver iodobromide 
were added thereto. After the mixture was mixed with stirring, each of the 
emulsions was coated on an antistatic-processed polyethylene terephthalate 
film base in the same manner as in Example 1. 
The coated samples were exposed to light and developed, and density was 
measured in the same manner as in Example 1. The results of the 
sensitivity and fog obtained are shown in Table 5 below. The reciprocal of 
an exposure amount providing an optical density of (fog+0.2) is referred 
to as the sensitivity. The sensitivity in terms of the relative 
sensitivity is shown in Table 5 below when each of the blue filter 
sensitivity (S.sub.B) and the orange filter sensitivity (S.sub.O) of each 
sample containing no metallocene compound in each group of the samples 
containing the same spectral sensitizing dyes is referred to as 100. 
Further, the latent image stability was examined when exposure to light was 
conducted through the orange filter. The results obtained are shown in 
Table 5 below. 
Namely, after the exposed samples were stored at 50.degree. C. and 30% RH 
for 5 days, the samples were developed. The orange filter sensitivity of 
each of the developed samples in terms of the relative sensitivity 
(.DELTA.R.sub.O) is shown in Table 5 below when the orange filter 
sensitivity of the corresponding sample which is not stored is referred to 
as 100. 
TABLE 5 
__________________________________________________________________________ 
Sensitizing Dye 
Metallocene Compound Latent Image 
Sample 
and Amount Added 
and Amount Added 
Relative Sensitivity 
Stability 
No. (10.sup.-4 mol/molAg) 
(10.sup.-3 mol/molAg) 
S.sub.B S.sub.O Fog 
.DELTA.S.sub.O 
Remarks 
__________________________________________________________________________ 
3-1 XI-35 7.1 -- -- 100 (standard) 
100 (standard) 
0.03 
87 
3-2 " " I-1 0.3 100 123 0.03 
93 Invention 
3-3 " " " 3.0 100 117 0.03 
98 Invention 
3-4 " " I-13 0.3 100 145 0.03 
91 Invention 
3-5 " " " 3.0 100 162 0.03 
98 Invention 
3-6 " " " 15.0 95 148 0.03 
102 Invention 
3-7 XIV-3 4.7 -- -- 100 (standard) 
100 (standard) 
0.03 
91 
3-8 " " I-26 2.6 148 269 0.03 
98 Invention 
3-9 " " " 13.0 162 302 0.03 
100 Invention 
3-10 
XIV-7 4.7 -- -- 100 (standard) 
100 (standard) 
0.03 
89 
3-11 
" " I-1 3.0 100 115 0.03 
95 Invention 
3-12 
" " " 15.0 105 134 0.03 
98 Invention 
3-13 
" " I-23 0.6 100 138 0.03 
91 Invention 
3-14 
" " " 3.0 115 155 0.03 
95 Invention 
3-15 
" " " 15.0 120 170 0.03 
95 Invention 
3-16 
" " I-32 0.6 100 120 0.03 
93 Invention 
3-17 
" " " 3.0 110 138 0.03 
100 Invention 
3-18 
" " " 10.0 95 132 0.04 
100 Invention 
__________________________________________________________________________ 
It will be understood from the results shown in Table 5 that when the 
silver iodobromide emulsion is used, the combinations of the present 
invention have such an effect that fog is also low, and the sensitivity 
can be greatly increased as in the use of other silver halide emulsions, 
and further the stability of the latent image can be increased. 
EXAMPLE 4 
The following layers having the following compositions were coated on an 
undercoated cellulose triacetate film base to prepare a multi-layer color 
photographic material as Sample 4-1. All sensitizing dyes used were added 
before the commencement of the chemical ripening of the silver halide 
emulsions, namely, before the addition of the chemical sensitizing agents. 
Layer Structure 
Each layer had the following composition. Numerals represent coating 
weights (g/m.sup.2). The amounts of the silver halide emulsions are 
represented by coating weights in terms of silver. 
Sample 4-1 
______________________________________ 
First Layer (antihalation layer) 
Black Colloidal Silver 
0.18 
(in terms of silver) 
Gelatin 1.40 
Second Layer (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 
Third Layer (first red-sensitive emulsion layer) 
Emulsion A (in terms of silver) 
0.25 
Emulsion B (in terms of silver) 
0.25 
Sensitizing Dye (XI-1) 
6.9 .times. 10.sup.-5 
Sensitizing Dye (XIV-15) 
1.8 .times. 10.sup.-5 
Sensitizing Dye (XIV-7) 
3.1 .times. 10.sup.-5 
EX-2 0.34 
EX-10 0.02 
U-1 0.07 
U-2 0.05 
U-3 0.07 
HBS-1 0.06 
Gelatin 0.87 
Fourth Layer (second red-sensitive emulsion layer) 
Emulsion G (in terms of silver) 
1.00 
Sensitizing Dye (XI-1) 
5.1 .times. 10.sup.-5 
Sensitizing Dye (XIV-15) 
1.4 .times. 10.sup.-5 
Sensitizing Dye (XIV-7) 
2.3 .times. 10.sup.-5 
EX-2 0.40 
EX-3 0.05 
EX-10 0.015 
U-1 0.07 
U-2 0.05 
U-3 0.07 
Gelatin 1.30 
Fifth Layer (third red-sensitive emulsion layer) 
Emulsion D (in terms of silver) 
1.60 
Sensitizing Dye (XI-1) 
5.4 .times. 10.sup.-5 
Sensitizing Dye (XIV-15) 
1.4 .times. 10.sup.-5 
Sensitizing Dye (XIV-7) 
2.4 .times. 10.sup.-5 
EX-2 0.097 
EX-3 0.01 
EX-4 0.08 
HBS-1 0.22 
HBS-2 0.10 
Gelatin 1.63 
Sixth Layer (interlayer) 
EX-5 0.04 
HBS-1 0.02 
Gelatin 0.80 
Seventh Layer (first green-sensitive emulsion layer) 
Emulsion A (in terms of silver) 
0.15 
Emulsion B (in terms of silver) 
0.15 
Sensitizing Dye (XI-45) 
3.0 .times. 10.sup.-5 
Sensitizing Dye (XI-48) 
1.0 .times. 10.sup.-4 
Sensitizing Dye (XI-38) 
3.8 .times. 10.sup.-4 
EX-1 0.021 
EX-6 0.26 
EX-7 0.03 
EX-8 0.025 
HBS-1 0.10 
HBS-3 0.01 
Gelatin 0.63 
Eighth Layer (second green-sensitive emulsion layer) 
Emulsion C (in terms of silver) 
0.45 
Sensitizing Dye (XI-45) 
2.1 .times. 10.sup.-5 
Sensitizing Dye (XI-48) 
7.0 .times. 10.sup.-5 
Sensitizing Dye (XI-38) 
2.6 .times. 10.sup.-4 
EX-6 0.094 
EX-7 0.026 
EX-8 0.018 
HBS-1 0.16 
HBS-3 0.008 
Gelatin 0.50 
Ninth Layer (third green-sensitive emulsion layer) 
Emulsion E (in terms of silver) 
1.20 
Sensitizing Dye (XI-45) 
3.5 .times. 10.sup.-5 
Sensitizing Dye (XI-48) 
8.0 .times. 10.sup.-5 
Sensitizing Dye (XI-38) 
3.0 .times. 10.sup.-4 
EX-1 0.025 
EX-11 0.10 
EX-13 0.015 
HBS-1 0.25 
HBS-2 0.10 
Gelatin 1.54 
Tenth Layer (yellow filter layer) 
Yellow Colloidal Silver 
0.05 
(in terms of silver) 
EX-5 0.08 
HBS-1 0.03 
Gelatin 0.95 
Eleventh Layer (first blue-sensitive emulsion layer) 
Emulsion A (in terms of silver) 
0.08 
Emulsion B (in terms of silver) 
0.07 
Emulsion F (in terms of silver) 
0.07 
Sensitizing Dye (XI-28) 
3.5 .times. 10.sup.-4 
EX-8 0.042 
EX-9 0.72 
HBS-1 0.28 
Gelatin 1.10 
Twelfth Layer (second blue-sensitive emulsion layer) 
Emulsion G (in terms of silver) 
0.45 
Sensitizing Dye (XI-28) 
2.1 .times. 10.sup.-4 
EX-9 0.15 
EX-10 0.007 
HBS-1 0.05 
Gelatin 0.78 
Thirteenth Layer (third blue-sensitive emulsion layer) 
Emulsion H (in terms of silver) 
0.77 
Sensitizing Dye (XI-28) 
2.2 .times. 10.sup.-4 
EX-9 0.20 
HBS-1 0.07 
Gelatin 0.69 
Fourteenth Layer (first protective layer) 
Emulsion I (in terms of silver) 
0.20 
U-4 0.11 
U-5 0.17 
HBS-1 0.05 
Gelatin 1.00 
Fifteenth Layer (second protective layer) 
HA-1 0.40 
BP-1 (diameter: 1.7 .mu.m) 
0.05 
BP-2 (diameter: 1.7 .mu.m) 
0.10 
BP-3 0.10 
S-1 0.20 
Gelatin 1.20 
______________________________________ 
Further, all layer contained W-1, W-2, W-3, BP-4, BP-5, 
5-methylthio-2-mercapto-1,3,4-thiadiazole, 
1-p-carboxyphenyl-5-mercaptotetrazole, 1-m-sulfophenyl-5mercaptotetrazole, 
5-nitro-1H-indazole, 5-methyl-1H-benzotriazole, 2-mercaptobenzothiazole, 
6-(2-ethylhexanoylamino)-2-mercaptobenzimidazole, 1-m-(3-methylureido) 
phenyl-5-mercaptotetrazole, .alpha.-lipoic acid, 
2-hydroxyamino-4,6-bis(hexylamino)-1,3,5-triazole, 
2-hydroxyamino-4,6-bis(ethylamino)-1,3,5-triazole, 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, sodium p-toluenesulfinate, an 
iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt and 
a rhodium salt to improve preservability, processability, pressure 
resistance, antifungal and anti-microbial properties, antistatic 
properties and coatability. 
TABLE 6 
__________________________________________________________________________ 
Coefficient 
Average 
Mean 
of Variation 
AgI Grain 
in Grain Size 
Ratio of 
Content 
Size 
Distribution 
Diameter/ 
Emulsion 
(%) (.mu.m) 
(%) Thickness 
Ratio of Amount of Silver (AgI content 
__________________________________________________________________________ 
%) 
A 4.0 0.45 
27 1 core/shell = 1/3(13/1), double structural 
grains 
B 8.9 0.70 
14 1 core/shell = 3/7(25/2), double structural 
grains 
C 10 0.75 
30 2 core/shell = 1/2(24/3), double structural 
grains 
D 16 1.05 
35 2 core/shell = 4/6(40/0), double structural 
grains 
E 10 1.05 
35 3 core/shell = 1/2(24/3), double structural 
grains 
F 4.0 0.25 
28 1 core/shell = 1/3(13/1), double structural 
grains 
G 14.0 0.75 
25 2 core/shell = 1/2(42/0), double structural 
grains 
H 14.5 1.30 
25 3 core/shell = 37/63(34/3), double structural 
grains 
I 1 0.07 
15 1 uniform structural grains 
__________________________________________________________________________ 
##STR40## 
Sample 4-2 was prepared in the same manner as the preparation of Sample 4-1 
except that 8.0.times.10.sup.-3 mol of Metallocene Compound (I-1) 
according to the present invention was added to the first red-sensitive 
emulsion layer, 6.0.times.10.sup.-3 mol of Metallocene Compound (I-1) was 
added to the second red-sensitive emulsion layer, and 7.5.times.10.sup.-3 
mol of Metallocene Compound (I-1) was added to the third red-sensitive 
emulsion layer before the coating of the emulsion, each amount being per 
mol of silver halide. Further, Sample 4-3 was prepared in the same manner 
as in the preparation of Sample 4-2 except that an equal amount of 
Metallocene Compound (I-23) was used in place of Metallocene Compound 
(I-1). Sample 4-4 was prepared in the same manner as in the preparation of 
Sample 4-2 except that an equal amount of Metallocene Compound (I-26) was 
used in place of Metallocene Compound (I-1). Sample 4-5 was prepared in 
the same manner as in the preparation of Sample 4-2 except that 
Metallocene Compound (I-32) was used in place of Metallocene Compound 
(I-1). 
These samples were exposed to light through a continuous wedge and a red 
color filter (which transmits light having a longer wavelength than 600 
nm) for 1/100 sec, and processed with the following processing solutions 
in the following stages. The density of each sample was measured. The 
reciprocal of an exposure amount providing an optical density of (fog+0.2) 
is referred to as the sensitivity. The sensitivity in terms of the 
relative sensitivity is shown in Table 7 below when the sensitivity of 
Sample 4-1 is referred to as 100. The description of an increase or 
decrease in fog in Table 7 is shown by an increase or decrease in fog 
density in comparison with the fog density of Sample 4-1. 
Development Method 
______________________________________ 
Process- 
ing 
Processing Temper- Tank 
Stage Time ature Replenisher 
Capacity 
______________________________________ 
Color 2 min 45 sec 
38.degree. C. 
33 ml 20 liters 
Develop- 
ment 
Bleaching 
6 min 30 sec 
38.degree. C. 
25 ml 40 liters 
Rinsing 2 min 10 sec 
24.degree. C. 
1200 ml 20 liters 
Fixing 4 min 20 sec 
38.degree. C. 
25 ml 30 liters 
Rinsing (1) 
1 min 05 sec 
24.degree. C. 
counter-current 
10 liters 
system of from 
(2) to (1) 
Rinsing (2) 
1 min 00 sec 
24.degree. C. 
1200 ml 10 liters 
Stabiliza- 
1 min 05 sec 
38.degree. C. 
25 ml 10 liters 
tion 
Drying 4 min 20 sec 
55.degree. C. 
______________________________________ 
Replenisher being per 1 m long by 35 mm wide 
The processing solutions had the following compositions. 
______________________________________ 
Mother 
Solution 
Replenisher 
(g) (g) 
______________________________________ 
Color developing Solution 
Diethylenetriamine- 
1.0 1.1 
pentaacetic Acid 
1-Hydroxyethylidene-1,1- 
3.0 3.2 
diphosphonic Acid 
Sodium Sulfite 4.0 4.4 
Potassium Carbonate 
30.0 37.0 
Potassium Bromide 1.4 0.7 
Potassium Iodide 1.5 mg -- 
Hydroxylamine Sulfate 
2.4 2.8 
4-[N-Ethyl-N-.beta.-hydroxy- 
4.5 5.5 
ethylamino]-2-methylaniline 
Sulfate 
Add Water to make 1.0 liter 1.0 liter 
pH 10.05 10.10 
Bleaching Solution 
Sodium Ethylenediamine- 
100.0 120.0 
tetraacetato Ferrate 
Trihydrate 
Disodium Ethylenediamine- 
10.0 11.0 
tetraacetate 
Ammonium Bromide 140.0 160.0 
Ammonium Nitrate 30.0 35.0 
Ammonia Water (27%) 
6.5 ml 4.0 ml 
Add Water to make 1.0 liter 1.0 liter 
pH 6.0 5.7 
Fixing Solution 
Disodium Ethylenediamine- 
0.5 0.7 
tetraacetate 
Sodium Sulfite 7.0 8.0 
Sodium Bisulfite 5.0 5.5 
Aqueous Solution of 
170.0 ml 200.0 
ml 
Ammonium Thiosulfate (70%) 
Add Water to make 1.0 liter 1.0 liter 
pH 6.7 6.6 
Stabilizing Solution 
Formalin (37%) 2.0 ml 3.0 ml 
Polyoxyethylene p-Monononyl- 
0.3 0.45 
phenyl Ether (an average 
degree of polymerization: 10) 
Disodium Ethylenediamine- 
0.05 0.08 
tetraacetate 
Add Water to make 1.0 liter 1.0 liter 
pH 5.0 to 8.0 
5.8 to 8.0 
______________________________________ 
TABLE 7 
______________________________________ 
Relative Red Increase or 
Sample 
Metallocene 
Sensitivity Decrease 
No. Compound S.sub.R in Fog Remarks 
______________________________________ 
4-1 -- 100 (standard) 
(standard) 
4-2 I-1 112 -0.01 Invention 
4-3 I-23 123 0.02 Invention 
4-4 I-26 129 0.02 Invention 
4-5 I-32 123 0.01 Invention 
______________________________________ 
It is apparent from the results shown in Table 7 that when the combinations 
according to the present invention are applied to the multi-layer color 
photographic material, fog is not so much increased and high sensitivity 
can be obtained. 
EXAMPLE 5 
After the coated Samples 4-1, 4-2, 4-3 and 4-4 prepared in Example 4 were 
left to stand at room temperature for one year, the samples were exposed 
to light and developed in the same manner as in Example 4. The red filter 
sensitivity and fog were determined. The results obtained are shown in 
Table 8 below. 
The sensitivity in terms of the relative sensitivity is shown in Table 8 
when the sensitivity of the corresponding sample stored in a refrigerator 
at -30.degree. C. in an argon atmosphere during the corresponding period 
is referred to as 100. An increase or decrease in fog is also shown in 
comparison with the corresponding sample stored in a refrigerator at 
-30.degree. C. in an argon atmosphere. 
TABLE 8 
______________________________________ 
Relative Red Increase or 
Sample 
Metallocene 
Sensitivity Decrease 
No. Compound S.sub.R in Fog Remarks 
______________________________________ 
4-1 -- 87 -0.01 
4-2 I-1 93 -0.01 Invention 
4-3 I-23 98 0.02 Invention 
4-4 I-26 100 0.02 Invention 
4-5 I-32 95 0.01 Invention 
______________________________________ 
It will be understood from the results shown in Table 8 that when the 
metallocene compounds according to the present invention are applied to 
the silver halide photographic materials, particularly spectral-sensitized 
silver halide photographic materials, sensitivity can be increased without 
increasing fog, and storage stability can be improved. 
Accordingly, the metallocene compounds according to the present invention 
are useful compounds for increasing sensitivity. 
While the present invention has been described in detail and with reference 
to specific embodiments thereof, it is apparent to one skilled in the art 
that various changes and modifications can be made therein without 
departing from the spirit and the scope of the present invention.