BACKGROUND OF THE INVENTION
[0001] This invention relates to a light-sensitive silver halide photographic material which
provides high contrast image, more particularly, to a light-sensitive silver halide
photographic material improved in problems in contrast increasing technique caused
by using a hydrazide compound.
[0002] In recent years, in the fields of printing and photomechanical process, colorination
or complication of the printing material has remarkably been progressed. Therefore,
demands for improvement in quality and stabilization of quality of a light-sensitive
silver halide photographic material for printing (hereinafter referred to as "light-sensitive
printing material") which is an intermediate medium of printing have been increased
year by year. Heretofore, the general light-sensitive printing material has been provided
the so-called "lith phenomenon" processing suitability in order to accomplish high
quality. However, in the "lith phenomenon", it has been well known for a person skilled
in the art that it is systematically impossible to contain high concentration sulfite
ion which is a preservative in a developing solution so that stability of the developing
solution is remarkably inferior.
[0003] As the technique for overcoming unstability of the "lith phenomenon" and obtaining
a high contrast image which is the same as the "lith phenomenon", attempts have been
done as disclosed in some patent documents. For example, there have been disclosed
the technique of obtaining a contrast increased image in Japanese Provisional Patent
Publications No. 16623/1978, No. 20921/1978, No. 20922/1978, No. 49429/1978, No. 66731/1978,
No. 66732/1978, No. 77616/1978,. No. 84714/1978, No. 137133/1978, No. 37732/1979,
No. 40629/1979, No. 52050/1980, No. 90940/1980 and No. 67843/1979, etc. In the processing
methods of the methods for forming an image using these hydrazide compounds, it is
necessary to be a pH value of the developing solution containing the hydrazide compounds
or a pH value of the processing developing solution of a light-sensitive photographic
material containing the hydrazide compounds to high level to obtain high contrast
image, but the technique involves the problem that high pH value decreases effective
lifetime of the developing solution.
[0004] To the contrary, in Japanese Provisional Patent Publication No. 106244/1981, there
is described that by containing a hydrazide compound and a development accelerating
amount of an amino compound during image formation, a high contract image can be formed
with a relatively low pH (11 to 11.5).
[0005] These image forming methods using the hydrazide compound can be obtained extremely
high contrast image. In general, unless suitable replenishment of a development replenishing
agent is supplied to a photographic processing solution, fog, etc. which are not preferred
for photographic performances will be caused. However, in the method of using the
hydrazide, even when exhaustion of the photographic processing solution is not so
remarkable, at an undeveloped portion, for example, generation of black dots (hereinafter
referred to as "pepper fog") such as black sesame between halftone dots during screen
photographying using a contact screen of the light-sensitive printing material can
be observed so that it sometimes causes serious defects on commercial values. In the
previously mentioned Japanese Provisional Patent Publications No. 16623/1978 and No.
20921/1978, generation of fog including the aforesaid pepper fog is restrained by
adding benzotriazole as a restrainer in a silver halide photographic emulsion, but
the effect is insufficient and yet high contrast property is sometimes lost, and thus
it cannot be said as a completed technique.
SUMMARY OF THE INVENTION
[0006] As the results earnest studies of the inventors of the present invention, they have
developed a light-sensitive silver halide photographic material which does not impair
high contrast while restraining fog including pepper fog which is a defect of the
contrast increasing technique using a hydrazide compound.
[0007] A first object of the present invention is to provide a light-sensitive silver halide
photographic material which can form a high contrast image stably using a hydrazide
compound.
[0008] A second object of the present invention is to provide a light-sensitive silver halide
photographic material which is high contrast without generation of fog including pepper
fog.
[0009] The above objects of the present invention can be accomplished by the light-sensitive
silver halide photographic material which comprises in a light-sensitive silver halide
photographic material provided by coating at least one layer of hydrophilic colloidal
layer including light-sensitive silver halide photographic emulsion layer on a support,
containing a hydrazide derivative in said light-sensitive silver halide emulsion layer
and containing, in said hydrophilic colloidal layer, at least one compound selected
from the groups A and B consisting of:
(Group A):
the compound represented by the formula (II):

wherein Y1 and Y2 may be the same or different and each represent -OH group or -CH20H group; and R represents an alkyl group having 1 to 3 carbon atoms;
the compound represented by the formula (III):

wherein R1, R2, R3 and R4 may be the same or different and each represent a hydrogen atom or a lower alkyl
group, and Z represents (CH2 )n (where n represents 0 or an integer of 1 to 5),

(where Rs and R6 each represent a hydrogen atom, a methyl group, an ethyl group or an isopropyl group
provided that the case where both of Rs and R6 are hydrogen atoms is excluded), -CH2-0-CH2 , -CH=CH-, -C≡C- or

the compound represented by the formula (IV):

wherein A represents a lower alkylene group,

or

B represents a polyalkylene ether group which does not bond with 0; A represents a
lower alkylene group or a polyalkylene ether group represented by the formula:

or

provided that A and A' cannot be the polyalkylene ether groups at the same time, p
represents 2 to 30, B and B each represents -NH- or -0-, but the case where both of
B and B are -O-'s is excluded, R7 represents a lower alkyl group, a phenyl group, an aralkyl group or (CH2)qCOOR' (where R represents a lower aralkyl group, q represents 1 to 3, and X represents
a divalent group represented by -S-, -0-, -CH2-,

(where R represents a lower alkyl group); and
the compound represented by the formula (V):

wherein A represents

(where Rs represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n represents
1 or 2, and m represents an average degree of polymerization of an integer of 1 to
50, and M represents a hydrogen atom or an alkaline metlal plate.
(Group B):
the compound represented by the formula (VI):

wherein R10 represents a tetrazaindenyl group or a pentazaindenyl group, n is 1 or 2, and M represents
a hydrogen atom or an alkali metal atom (for example, sodium, potassium, etc.);
the compound represented by the formula (VII):

wherein Q represents a substituted or unsubstituted straight aliphatic group having
a carbon atom of 1 or more which bonds pyrocatechol of both sides, or may be formed
a ring by bonding one end of an aliphatic group branched from the straight chain such
as siprohydrindene to one end of nucleus of pyrocatechol of both sides; and
the compound represented by the formula (VIII):

wherein R11, R12, R13 and R14 may be the same or different and each represent a hydrogen atom, a halogen atom,
a mercapto group, a hydroxy group, an alkyl group, a hydroxyalkyl group, a halogenated
alkyl group, an alkoxy group, an alkylthio group, a phenyl group, a benzyl group,
an amino group, an alkylamino group or a hydrazino group, provided that at least one
of R11, R12, R13 and R14 represents a mercapto group.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] In the following, the constitution of the present invention will be described in
more detail.
[0011] The hydrazide derivative to be used in the present invention may include the compounds
represented by the following formulae (I-a), (I-b) and (I-c).

wherein R
15 and R
16 each represent an aryl group or a heterocyclic group, R
17 represents an organic bonding group, n is 0 to 6 and m is 0 or 1, provided that n
is 2 or more, each R
17 may be the same or different with each other.

wherein R
2, represents an aliphatic group, an aromatic group or a heterocyclic group, R
22 represents a hydrogen atom, an alkoxy group, a heterocyclicoxy group, an amino group
or an aryloxy group, each of which may be substituted or unsubstituted, P
1 and P
2 each represent a hydrogen atom, an acyl group or a sulfinic acid group.

wherein Ar represents an aryl group containing at least one of a ballast group or
a silver halide adsorption accelerating group, and R
31 represents a substituted alkyl group.
[0012] In the following, the compounds of the formulae (I-a), (I-b) and (I-c) will be described
in more detail.

[0013] In the formula, R
15 and R
16 each represent an aryl group or a heterocyclic group, R
17 represents an organic bonding group, n is 0 to 6 and m is 0 or 1.
[0014] The aryl group represented by R
15 and R
16 may include a phenyl group, a naphthyl group, etc., and the heterocyclic group may
include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group,
etc., but preferred as R
15 and R
16 are an aryl group. To the aryl group or the heterocyclic group represented by R
15 and R
16 may be introduced various substituents. Such substituents may include, for example,
a halogen atom (e.g. chlorine, fluorine, etc.), an alkyl group (e.g. methyl, ethyl,
dodecyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, isopropoxy, butoxy, octyloxy,
dodecyloxy, etc.), an acylamino group, (e.g. acetylamino, pivalylamino, benzoylamino,
tetradecanoylamino, α-(2,4-di-t-amylphenoxy)butyryl amino, etc.), a sulfonylamino
group (e.g. methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino,
etc.), a urea group (e.g. phenylurea, ethylurea, etc.), a thiourea group (e.g. phenyl-
thiourea, ethylthiourea, etc.), a hydroxy group, an amino group, an alkylamino group
(e.g. methylamino, dimethylamino, etc.), a carboxy group, an alkoxycarbonyl group
(e.g. ethoxycarbonyl, etc.), a carbamoyl group, a sulfo group, etc. The divalent organic
group represented by R
17 may include, for example, an alkylene group (e.g. methylene, ethylene, trimethylene,
tetramethylene, etc.), an arylene group (e.g. phenylene, naphthylene, etc.), an aralkylene
group, etc., and the alkylene group may include in the bonding an oxy group, a thio
group, a seleno group, a carbonyl group,

group (where R
18 represents a hydrogen atom, an alkyl group or an aryl group), a sulfonyl group, etc.
Various substituents may be introduced in the group represented by R
17.
[0015] Such substituents may include, for example, -CONHNHR
19 (where R
19 has the same meaning as defined in the above R
15 and R
16), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group,
an acyl group, an aryl group, etc.
[0016] Preferred as R
1 7 is an alkylene group.
[0017] Among the compounds represented by the formula (I-a), preferred are the compounds
wherein R
15 and R
16 are substituted or unsubstituted phenyl group, n = m = 1 and R
17 represents an alkylene group.
[0018] Representative compounds represented by the above formula (I-a) are shown below.
[0020] Next, the compound of the formula (I-b) will be explained.

[0021] The aliphatic group represented by R
21 is those having 6 or more of carbon atoms, and particularly preferred is a straight,
branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group
may be cyclized to from a saturated heterocyclic group containing one or more of hetero
atoms therein. Also, the alkyl group may have a substituent(s) such as an aryl group,
an alkoxy group, a sulfoxy group, etc.
[0022] The aromatic group represented by R
21 is a monocyclic or bicyclic aryl group or a unsaturated heterocyclic group. The unsaturated
heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form
a heteroaryl group.
[0023] For example, there may be mentioned a benzene ring, a naphthalene ring, a pyridine
ring, a pyrimidine fing, an imidazole ring, a pyrazole ring, a quinoline ring, an
isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, etc.,
but those containing a benzene ring is preferred.
[0024] As R
21, particularly preferred is an aryl group.
[0025] The aryl group or the unsaturated heterocyclic group of R
21 may be substituted, and representative substituents may include a straight, branched
or cyclic alkyl group (preferably monocyclic or bicyclic one wherein carbon atoms
at the alkyl portion are 1 to 20), an alkoxy group (preferably those having 1 to 20
carbon atoms), a substituted amino group (preferably an amino group substituted by
an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably those
having 2 to 30 carbon atoms), a sulfonamide group (preferably those having 1 to 30
carbon atoms), a ureido group (preferably those having 1 to 30 carbon atoms), etc.
[0026] Among the groups represented by R
22 in the formula (I-b), the alkoxy group which may be substituted may be those having
1 to 20 carbon atoms and may be substituted by a halogen atom, an aryl group, etc.
[0027] Among the groups represented by R
22 in the formula (I-b), the aryloxy group or the heterocyclicoxy group, which may be
substituted, may preferably be monocyclic one, and also the substituents therefor
may include a halgen atom, an alkyl group, an alkoxy group, a cyano group, etc.
[0028] Among the groups represented by R
22, preferred are an alkoxy group or an amino group which may be substituted.
[0029] In the case of the amino group, it is

group, where A, and A
2 each may represent an alkyl group, an alkoxy group, which may be substituted, or
a cyclic structure containing -O-, -S- or -N- group bonding. Provided that the case
where R
22 is a hydrazino group is excluded.
[0030] R
21 or R
22 in the formula (I-b) may be those incorporated therein a ballast group which is conventionally
used as an immobilizing photographic additive such as a coupler, etc.
[0031] The ballast group is a relatively inactive group to photographic property having
8 or more carbon atoms, and it may be selected, for example, from an alkyl group,
an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy
group, etc.
[0032] R
21 or R
22 of the formula (I-b) may be those in which a group which enforces adsorption to the
surface of a silver halide grain is incorporated therein. Such adsorptive groups may
include the groups as disclosed in U.S. Patent No. 4,355,105 such as a thiourea group,
a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group, etc.
Among the compounds represented by the formula (I-b), particularly preferred compounds
are those represented by the following formula (2-a):

[0033] In the above formula (2-a),
R23 and R24. each represent a hydrogen atom, an alkyl group which may be substituted (e.g. a
methyl group, an ethyl group, a butyl group, a dodecyl group, a 2-hydroxypropyl group,
a 2-cyanoethyl group, a 2-chloroethyl group, etc.), a phenyl group, a naphthyl group,
a cyclohexyl group, a pyridyl group, a pyrrolidyl group, each of which may be susbtituted
(e.g. a phenyl group, a p-methylphenyl group, a naphthyl group, an a-hydroxynaphthyl
group, a cyclohexyl group, a p-methylcyclohexyl group, a pyridyl group, a 4-propyl-2-pyridyl
group, a pyrrolidyl group, a 4-methyl-2-pyrrolidyl group, etc.),
R2s represents a hydrogen atom, or a benzyl group, an alkoxy group or an alkyl group,
each of which may be substituted (e.g. a benzyl group, a p-methylbenzyl group, a methoxy
group, an ethoxy group, an ethyl group, a butyl group, etc.),
R26 and R27 each represent a divalent aromatic group (e.g. a phenylene group, a naphthylene group,
etc.), Y represents a sulfur atom or an oxygen atom, L represents a divalent bonding
group (e.g. -SO 2CH2CH2NH-SO2NH-, -OCH2SO2NH-, -0-, -CH=N-, etc.),
R28 represents -NR R or -OR29,
wherein R', R" and R29 eahc represents a hydrogen atom, an alkyl group (e.g. a methyl group, an ethyl group,
a dodecyl group, etc.), a phenyl group (e.g. a phenyl group, a p-methylphenyl group,
a p-methoxyphenyl group, etc.) or a naphthyl group (e.g. an a-naphthyl group, a β-naphthyl
group, etc.), each of which may be substituted, and m and n each represent 0 or 1.
When R28 represents OR29, Y is preferably a sulfur atom.
[0035] Next, among the above specific compounds, synthetic methods of the compounds (I-b-45)
and (I-b-47) are exemplified.
[0036] Reaction scheme

[0037] 153 g of the compound 4-nitrophenylhydrazide and 500 ml of diethyloxalate were mixed
and the mixture was stirred for one hour under reflux. While proceeding the reaction,
ethanol was removed and then the mixture was cooled to precipitate crystals. The resulting
crystals were filtered, washed with several times with peteroleum ether, and recrystallized.
Next, among the resulting crystals (A), 50 g was dissolved in 1000 ml of methanol
under heating and reduced under the pressure of 50 Psi of H
2 atmosphere in the presence of a Pd/C (palladium-carbon) catalyst to obtain the compound
(B).
[0038] 22 g of the compound (B) was dissolved in a solution of 200 ml of acetonitrile and
16 g of pyridine, and to the solution was added dropwise 24 g of the compound (C)
in acetonitrile solution at room temperature. After insolubles were filtered off,
the filtrate was condensed and purified by recrystallization to obtain 31 g of the
compound (D).
[0039] 30 g of the compound (D) was hydrogenated in the above manner as mentioned above
to obtain 20 g of the compound (E).
[0040] 10 g of the compound (E) was dissolved in 100 ml of acetonitrile, then 3.0 g of ethylisothiocyanate
was added thereto and the mixture was refluxed for one hour. After the solvent was
removed, crude material was purified by recrystallization to obtain 7.0 g of the compound
(F). 5.0 g of the compound (F) was dissolved in 50 ml of methan ol, methyl amine (8
ml, 40 % aqueous solution) was added thereto and the mixture was stirred. After a
part of methanol was removed, the precipitated solid was taken out and purified by
recrystallization to obtain the compound i-b-45.
Synthesis of the compound l-b-47
[0041] Reaction scheme

[0042] 22 g of the compound (B) was dissolved in 200 ml of pyridine and under stirring,
22 g of p-nitrobenzenesulfonyl chloride was added to the solution. The reaction mixture
was poured into water, and precipitated crystals were taken out to obtain the compound
(C). The compound (C) was treated in the same manner as in the compound l-b-45 to
obtain the compound I-b-47.
[0043] Next, the compounds of the formula (1-c) will be explained.

[0044] In the formula (I-c), Ar represents an aryl group containing at least one of a ballast
group or a silver halide adsorption accelerating group. As the ballast group, those
conventionally used in additives for immobilized photography such as a coupler are
preferred. Such a ballast group is a group having 8 or more carbon atoms and is relatively
inactive to photographic performance. It can be selected from, for example, an alkyl
group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an
alkylphenoxy group, etc.
[0045] The silver halide adsorption accelerating group may include the groups as disclosed
in U.S. Patent No. 4,385,108 such as a thiourea group, a thiourethane group, a heterocyclic
thioamide group, a mercapto heterocyclic group, a triazole group, etc.
[0046] R
31 represents a substituted alkyl group. The alkyl group may include a straight, branched
or cyclic alkyl group, and more specifically, there may be mentioned, for example,
each group of methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, etc.
[0047] As the substituents which may be incorporated into these alkyl group, there may be
mentioned each group of alkoxy (e.g. methoxy, ethoxy, etc.), aryloxy (e.g. phenoxy,
p-chlorophenoxy, etc.), heterocyclicoxy (e.g. pyridyloxy, etc.), mercapto, alkylthio
(e.g. methylthio, ethylthio, etc.), arylthio (e.g. phenylthio, p-chlorophenylthio,
etc.), heterocyclicthio (e.g. pyridylthio, pyrimidylthio, thiadiazolylthio, etc.),
alkylsulfonyl (e.g. methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl (e.g. benzenesulfonyl,
etc.), heterocyclicsulfonyl (e.g. pyridylsulfonyl, morpholinosulfonyl, etc.), acyl
(e.g. acetyl, benzoyl, etc.), cyano, chloro, bromo, alkoxycarbonyl (e.g. ethoxycarbonyl,
methoxycarbonyl, etc.), aryloxycarbonyl (e.g. phenoxycarbonyl, etc.), carboxy, carbamoyl,
alkylcarbamoyl (e.g. N-methylcarbamoyl, N,N-dimethylcarbamoyl, etc.), arylcarbamoyl
(e.g. N-phenylcarbamoyl, etc.), amino, alkylamino (e.g. methylamino, N,N-dimethylamino,
etc.), arylamino (e.g. phenylamino, naphthylamino, etc.), acylamino (e.g. acetylamino,
benzoylamino, etc.), alkoxycarbonylamino (e.g. ethoxycarbonylamino, etc.), aryloxycarbonylamino
(e.g. phenoxycarbonylamino, etc.), acyloxy (e.g. acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy
(e.g. methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g. phenylaminocarbonyloxy,
etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g. methylsulfamoyl, etc.), arylsulfamoyl
(e.g. phenylsulfamoyl, etc.), and the like.
[0048] The hydrogen atom(s) of the hydrazine may be substituted by any of substituents such
as a sulfonyl group (e.g. methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g.
acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g. ethoxalyl, etc.), and the like.
[0050] Next, synthesis example of the compound I-c-5 will be explained.
Synthesis of the compound I-c-5.
[0051] Reaction scheme

[0052] In accordance with the synthesis method of the compound I-b-45, the compound I-c-5
was obtained. As the hydrazide derivative to be used in the present invention, the
compound of the formula (I-c), and (I-c-3) is particularly preferred.
[0053] Amounts of the compounds of the formulae (I-a), (I-b) and I-c) to be contained in
the light-sensitive silver halide photographic material are each preferably in the
range of 5 x 10-
7 to 5 x 10
-1 mole, more preferably 5 x 10-
5 to 1 x 10-
2 per one mole of silver halide contained in the light-sensitive silver halide photographic
material of the present invention.

[0054] In the formula, Y
1 and Y
2 each represent -OH group or -CH
20H group, which may be the same or different from each other. R represents an alkyl
group having 1 to 3 carbon atoms.
[0056] In the formula, R
1, R
2, R
3 and R
4 may be the same or different and each represent a hydrogen atom or a lower alkyl
group, and Z represents -(CH
2)
n, (where n represents 0 or an integer of 1 to 5),

(where R
s and R
6 each represent a hydrogen atom, a methyl group, an ethyl group or an isopropyl group
provided that the case where both of R
s and R
6 are hydrogen atoms is excluded), -CH
2-0-CH
2-, -CH=CH-, -C≡C- or

[0058] In the formula, A represents a lower alkylene group,

represents a polyalkylene ether group which does not bond with 0; A represents a lower
alkylene group or a poly alkylene ether group represented by the formula:

provided that A and A cannot be the polyalkylene ether groups at the same time. p
represents 2 to 30.
[0059] B and B each represent -NH- or -0- but the case where both of B and B are -O-'s is
excluded.
[0060] R
7 represents a lower alkyl group, a phenyl group, an aralkyl group or (CH
2)
qCOOR' (where R' represents a lower aralkyl group, q represents 1 to 3, and X represents
a divalent group represented by -S-, -0-,

(where R represents a lower alkyl group).
[0062] In the formula, A represents

R
8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
[0063] n represents 1 or 2, and m represents an average degree of polymerization of an integer
of 1 to 50.
[0064] M represents a hydrogen atom or an alkaline metlal plate.
[0066] The above compounds of the formulae (II), (III), (IV) and (V) are each known compound
and can be obtained by the synthetic methods in accordance with the method as des
cribed in the following patent documents, etc.
[0067] For example, the cyclohexane derivative represented by the formula (II) can be easily
obtianed in accordance with the method as described in Journal of Aerican Chemical
Society, vol. 76, p. 771 (1954).
[0068] Also, the diol derivative represented by the formula (III) can be obtained by, for
example, the methods as disclosed in U.S. Patents No. 2,960,404 and No. 3,650,759,
the thioether derivative represented by the formula (IV) can be easily obtained by,
for example, the method as disclosed in Japanese Patent Publication No. 11116/1972,
and the phenol or naphthol type aldehyde resin represented by the formula (V) can
be easily obtained by, for example, the method as disclosed in Japanese Patent Publication
No. 16765/1960.
[0069] Amounts of the compounds of the above formulae (II), (III), (IV) and (V) to be used
in the light-sensitive silver halide photographic material of the present invention
may differ depending on the kinds of the silver halide emulsion, but they may be each
in the range of 1 x 10
-6 to 1 x 10
-1 mole/mole Ag, more preferably 5 x 10-
5 to 1 x 10-
2 mole/mole Ag.
[0070] These compounds may be preferably added after dissolving them in water or an organic
solvent (such as methanol, etc.) which is miscible with water, but they may be added
in the form of dispersion dispersed in a coating solution.
[0071] The position to which the hydrazide derivative and the compounds represented by the
formulae (II), (III), (IV) and (V) of the present invention are added may be anywhere
of a silver halide emulsion layer or non-light-sensitive layer, but preferably a silver
halide emulsion layer.
[0072] The time at which these compounds are added may be any time in the case of a silver
halide emulsion layer between the chemical ripenning step and immediately before coating,
but preferably at the completion of the chemical ripenning.
[0073] When these compounds are added to a non-light-sensitive hydrophilic colloidal solution,
it may be added at an optional stage to adjust the coating solution
[0074] Next, the compounds of the group B will be explained.
[0076] Regarding the heterocyclic compounds represented by the above formula (VI), they
are disclosed in, for example, U.S. Patents No. 2,743,181, No. 2,543,333, No. 2,566,
659 and No. 2,956,876, and British Patent No. 701, 054, etc.
[0078] The method for preparing the bispyrocatechol to be used in the present invention
is not uniform but is different from each other depending on the kinds of the compounds.
The exemplary compounds 1 and 2 can be synthesized by using the mehtod as described
in Saburo Tamura and Kazuhiko Ohkuma (Journal of Nippon Agricultural Chemistry Association,
vol. 27, pp. 877 to 881). The exemplary compound 3 was synthesized according to the
method as described in Gisvolt Bureau Calson (J. Am. Pharm. Assoc., vol 35, pp. 186
to 191), the examplary compound 4 was Keiichi Shishido, Hitoshi Nozaki and Hiroshi
Kuyama (J. Ary. Chem., vol. 14, pp. 1124, 9), the examplary compound 6 was Ralph B.
Tompson (U.S. Patent No. 2,542,972, issued on February 27, 1955), and the examplary
compound 7 was Wilson and Baker (J. Chem. Soc., pp. 1678 to 1681 (1934)), respectively.
[0079] Next, specific examples of the compounds represented by the above formula (VIII)
to be used in the present invention are shown in the following Table 1. In order to
show each exemplary compound, in the table, only each of substituents R
11, R
12, R
13 and R
14 in the above formula (VIII) is described.

[0080] These only show examples of the present invention and the present invention is needless
to say limited by these.

[0081] The mercaptpyridine compounds to be used in the present invention can be synthesized
according to various methods. For example, they can be synthesized as'disclosed in
Japanese Patent Publication Open to Public Inspection (hereinafter referred to as
Japanese Patent O.P.I. Publication) No. 1948/1975.
[0082] Amounts of the compounds of the above formulae (VI), (VII) and (VIII) to be used
in the light-sensitive silver halide photographic material of the present invention
may differ depending on the kinds of the silver halide emulsion, but they may be each
in the range of 1 x 10-
6 to 1 x 10
-1 mole/mole Ag, more preferably 5 x 10-
5 to 1 x 10-
2 mole/mole Ag.
[0083] The silver halide to be used in the silver halide emulsion layer of the present invention
may be any of silver chlorobromide, silver chloroiodobromide and silver iodobromide.
[0084] The particle size of the silver halide is not particularly limited, but those having
an average particle size of smaller than 0.5 u.m are preferred, and more preferably
those so-called monodispersed grains in which 90 % or more of the total grains belong
within ± 40 % of the average particle size as the center.
[0085] Crystal habit of the silver halide grain may be any of cubic, tetradecahedral and
octahedral, and also it may be a tablet type grain as disclosed in Japanese Patent
O.P.I. Publication No. 108525/1983.
[0086] The method for preparing the silver halide grains of the silver halide emulsion layer
of the present invention may be any of the single jet method such as normal precipitation
method, reverse precipitation method, etc. or the double-jet method by the simultaneous
precipitation method, but more preferably the simultaneous precipitation method. Also,
any of the ammoniacal methodd, neutral method, acidic method, or the irregular ammoniacal
method as disclosed in Japanese Patent Publication No. 3232/1983 may be employed and
more preferably the acidic method or the neutral method.
[0087] Also, in these silver halide grains, a metal atom such as irridium, rhodium, osmium,
bismuth, cobalt, nickel, ruthenium, iron, copper, zinc, lead, cadmium, etc. may be
contained.
[0088] When these metal atoms are contained, they may be preferably contained in an amount
in the range of 10-
8 to 10-
5 mole per one mole of silver halide. Also, the silver halide grain may preferably
a surface latent image type one.
[0089] The silver halide photographic emulsion of the silver halide emulsion layer according
to the present invention (hereinafter referred to "the silver halide photographic
emulsion of the present invention") may be subjected to chemical sensitization. For
chemical sensitization, there may be included sulfur sensitization, reduction sensitization
and noble metal sensitization, but in the present invention, it is preferred to effect
chemical sensitization only with sulfur sensitization. As the sulfur sensitizer, there
may be employed, in addition to sulfur compounds contained in gelatin, various sulfur
compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. and more specifically
the sulfur sensitizer as disclosed in U.S. Patents No. 1,574,944, No. 2,410,689 and
No. 2,728,668, and Japanese Patent Publication No. 11892/1984, etc. may be employed.
[0090] The silver halide photographic emulsion of the present invention may be provided
sensitivity to desired light-sensitive wavelength region. Here, spectral sensitization
may be carried out by using one or more sensitizing dyes. As the sensitizing dyes,
various ones may be used but sensitizing dyes advantageously used in the present invention
may include cyanines, carbocyanines, merocyanines, trinuclear or tetranuclear merocyanines,
trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols,
hemioxonols, etc. These spectral sensitizing dyes may preferably have, at a part thereof
as a nitrogen- containing heterocyclic nucleus, a basic group such as thiazoline,
thiazole, etc., or nucleus such as rhodanine, thiohidantoin, oxazolidindione, barbituric
acid, thiobarbituric acid, pyrazolone, etc., and these groups may be substituted by
alkyl, hydroxyalkyl halogen, phenyl, cyano, alkoxy, etc. These spectal sensitizing
dyes may also be condensed with a carbon ring or a hetero ring.
[0091] In the silver halide photographic emulsion of the present invention, it may be added
tetrazaindenes, etc. as a stabilizer, triazoles, tetrazoles, etc. as an antifoggant,
oxanole dyes, dialkylaminobenzilidene dyes, etc. as a covering powder increasing agent
or irradiation preventive, polymer latexes as a wetting agent, and other additives
used for general photographic emulsion such as a spreading agent, a hardener other
than the present invention for combination use, etc.
[0092] As a substate of the light-sensitive silver halide photographic material of the present
invention, there may be employed those generally used such as a polyester base, TAC
base, baryta paper, laminated converted paper, glass plate, etc.
[0093] As a developing solution to be used in the light-sensitive silver halide photographic
material of the present invention, any of the developing solutions which are used
in usual light-sensitive silver halide photographic material and the lith developing
solution may be employed. As the developing agent for the developing solution, there
may be mentioned dihydroxybenzenes such as hydroquinone, chlorohydroquinone, catechol,
etc., 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,
etc., and further paraaminophenols such as N-methyl-p-aminophenol, N-(4-hydroxyphenyl)-glycine,
etc., p-phenylenediamines such as S-methanesulfonamide ester, ethylaminotoluidine,
N,N-diethyl-p-phenylenediamine, etc., and ascorbic acids, etc. and the developing
solution may be used as an aqueous solution containing at least one of the above developing
agents.
[0094] In addition to the above, in the developing solution, there may be added a preservative
such as sodium sulfite, potassium sulfite, formaldehyde, sodium hydrogen sulfite,
hydroxylamine, ethylene urea, etc., a development inhibitor of inorganic salts such
as sodium bromide, potassium bromide, potassium iodide, etc., at least one of organic
inhibitor such as 1-phenyl-5-mercaptotetrazole, 5-nitrobenzimidazole, 5-nitrobenztriazole,
5-nitroindazole, 5-methyl-benzotriazole, 4-thiazolin-2-thione, etc., an alkaline agent
such as sodium hydroxide, potassium hydroxide, an alkanol amine having a development
accelerating effect such as diethanolamine, triethanolamine, 3-diethylamine-1-propanol,
2-methylamino-1-ethanol, 3-diethy)amino1,2-propanediol, diisopropylamine, 5-amino-1-pentanol,
6-amino-1-hexanol, etc., a buffering agent having a buffer effect in the developing
solution such as sodium carbonate, sodium phosphate, carbonic acid aqueous solution,
phosphoric acid aqueous solution, etc., a salt such as sodium sulfate, sodium acetate,
sodium succinate, etc., a water softening agent by a chelating effect such as sodium
ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxydiaminetriacetate,
etc., a development hardening agent such as glutaraldehyde, etc., a solvent for the
developing agent or the organic inhibitor such as diethylene glycol, dimethylformaldehyde,
ethyl alcohol, benzyl alcohol, etc., a development compensating agent such as methylimidazoline,
methylimidazole, polyethylene glycol, dodecylpyridinium bromide, etc. to constitute
the developing solution.
[0095] A pH of the developing solution is not particularly limited but it is preferably
in the range of 9 to 13.
[0096] One preferred example to constitute the developing solution for developing the light-sensitive
silver halide photographic material of the present invention is as shown below. That
is, the developing solution which comprises 20 to 60 gil of hydroquinone and 0.1 to
2 g/l of 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone or 0.1 to 2 g/I of 1-phenyl-4,4-dimethyl-3-pyrazolidone
as developing agents, 10 to 200 g/I of sodium sulfite or 10 to 200 g
/l of potassium sulfite as a preservative for the developing solution, 1 to 10 g/I
of sodium bromide or potassium bromide as a development inhibitor of an inorganic
salt, 1 to 50 g/I of an alkanol amine having a development accelerating effect, 0.05
to 2 g/I of 5-methylbenzotriazole or 0.01 to 2 gil of 5-nitroindazole as an organic
inhibitor, 1 to 50 g/I of sodium carbonate or 10 to 800 ml/I of phosphate aqueous
solution (1 mole/liter) as a buffering agent, 0.1 to 10 g/I of ethylenediaminetetraacetate
disodium salt, and adjusted to its pH to 11.0 to 12.5 by using a suitable alkali agent
(e.g. potassium hydroxide).
[0097] The light-sensitive silver halide photographic material of the present invention
is developed with the above develop ing solution, and then through the processes of
fixing, washing and drying to fix an image thereon. At this time, with regard to the
temperature and time of the development, there is no specific limitation, but the
development temperature may preferably be 20 to 45 ° C and the development time may
preferably be 15 to 200 seconds.
EXAMPLES
[0098] In the following, the present invention will be explained in more detail, but the
present invention is not limited thereby.
Example 1
[0099] In a gelatin aqueous solution maintained at 40 °C were added a silver nitride aqueous
solution and a halide aqueous solution (KBr 40 mole % and NaCI 60 mole %) simultaneously
by the controlled double-jet method over 60 minutes while maintaining pH to 3.0 and
pAg to 7.7 to prepare monodispersed silver chlorobromide emulsion having an average
particle size of 0.30 µm. The emulsion was subjected to desalting and washing by the
conventional manner, and then chemical ripenning was carried out by adding 15 mg of
sodium thiosulfate per one mole of silver chlorobromide at 60 °C for 60 minutes.
[0100] Subsequently, to the emulsion was added 1 g/I of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene.
The following compound (M) as the sensitizing dye (300 mg/one mole of Ag), 250 mg/one
mole of Ag of polyethylene glycol having a molecular weight of about 4000, a hydrazide
compound and the compound of the formula (II) according to the present invention were
added as shown in Table 2. Further, 1 x 10-
3 mole/one mole of Ag of 5-nitroindazole, 5 x 10-
3 mole/one mole of Ag of hydroquinone, butylacrylate latex polymer and a saponine aqueous
solution as spreading agent were added thereto to prepare an emulsion coating solution.
Moreover, in the gelatin aqueous solution were added an aqueous sodium 1-decyl-2-(3-isopentyl)succinate2-sulfonate
solution as a spreading agent, a methyl methacrylate polymer having an average particle
diameter of 3.0 µm as a matting agent and 2-hydroxy-4,6-dichloro1,3,5-triazine sodium
salt as a hardening agent to prepare a coating solution for a protective layer. This
coating solution and the above emulsion coating solution were subjected to simultaneous
multi-layer coating on a PET base followed by drying. At this time, provided amounts
of gelatin were 2.5 g/m
2 for the emulsion layers and 1.0 g/m
2 for the protective layer, a provided amount of AgX grains was 3.5 g/m
2 in terms of Ag, a provided amount of the butylacrylate latex polymer was 2 g/m
2, a provided amount of the matting agent was 30 g
/m
2, and a provided amount of a hardening agent was 2 g/100 g per total amount of gelating
including both of the emulsion layer and the protective layer.

[0101] At the time using a fixing solution, in 500 ml of water were dissolved the following
composition A and the above composition B in this order to adjust to 1 liter for use.
A pH of this fixing solution was adjusted to 6 with acetic acid.
[0102] It can be understood that the resulting sample can remarkably restrain generation
of pepper fog without imparing sensitivity and contrast. In Table 2, sensitivity was
shown as a relative sensitivity.

[0103] By using the above samples No. 1 to No. 8, stepwise expo sure was provided by using
a tungsten light source through a film wedge in accordance with the conventional method,
then development was carried out by the developing solution shown below at 38 °C for
30 seconds, followed by fixing, washing and drying, and then sensitivity, contract
and pepper' fog of the samples were evaluated. Contrast was shown with gradation at
the linear portion of the characteristic curve (tan θ value), and generation degree
of pepper fog was ranked with four steps of (5) no generation, (4) one or two in a
visual field, (3) a little but low quality and (2) remarkably generated. The results
thus obtained are shown in the following Table 2.

Comparative compounds

Example 2
[0104] In the same manner as in Example 1, in a gelatin aqueous solution maintained at 40
°C were added a silver nitride aqueous solution and a halide aqueous solution (KBr
40 mole % and NaCI 60 mole %) simultaneously by the controlled double-jet method over
60 minutes while maintaining pAg to 7.7 and pH to 3.0. This emulsion was subjected
to desalting and washing according to the conventional method and then subjecting
to redispersion by adding gelatin to prepare monodispersed silver chlorobromide emulsion
Em - 1 having an average particle size of 0.30 u.m. Subsequently, in the same manner
as in Em - 1 except for adding 1 x 10-
6 mole/one mole of AgX of potassium hexachloroiridium (IV) acid which is an aqueous
iridium compound to a halide aqueous solution to prepare monodispersed silver chlorobromide
emulsion Em - 2 having an average particle size of 0.30 µm.
[0105] Subsequently, in the same manner as in Em - 1 except for adding 2.28 x 10-
7 mole/one mole of AgX of rhodium trichloride trihydrate which is an aqueous rhodium
salt to a halide aqueous solution to prepare monodispersed silver chlorobromide emulsion
Em - 3 having an average particle size of 0.30 um. Each emulsion of these Em - 1,
2 and 3 were subjected to the same operations as in Example 1 from chemical rippening
to simultaneous multi-layer coating and drying to obtain Samples No. 9 to No. 14.
[0106] Thereafter, exposure, development and evaluation were carried out in the methods
as in Example 1. Contents of the compounds of the present invention to be used in
the experiments and the results of the evaluations are shown in Table 3.

[0107] As clearly seen from Table 3, it can be confirmed that Samples No. 9, No. 11 and
No. 13 in which the compound of the present invention is used show remarkable pepper
fog inhibiting effect in the emulsion which is metal doped by using iridium and rhodium.
Example 3
[0108] In the same manner as in Example 1, coating and drying were carried out except for
using the compound (III) in place of the compound (II) to prepare Samples. Then, these
samples were subjected to exposure treatment in the same manner as in Example 1 and
then evaluated. Contents of the samples and the results of evaluation are shown in
Table 4.
Example 4
[0109] In the same manner as in Example 1, coating and drying were carried out except for
using the compound (IV) in place of the compound (II) to prepare Samples. Then, these
samples were subjected to exposure treatment in the same manner as in Example 1 and
then evaluated. Contents of the samples and the results of evaluation are shown in
Table 5.
Example 5
Example 6
[0111] In a gelatin aqueous solution maintained at 40 °C were added a silver nitride aqueous
solution and a halide aqueous solution (KBr 40 mole % and NaCl 60 mole %) simultaneously
by the controlled double-jet method over 60 minutes while maintaining pH to 3.0 and
pAg to 7.7 to prepare monodispersed silver chlorobromide emulsion having an average
particle size of 0.25 µm. The emulsion was subjected to desalting and washing by the
conventional manner, and then chemical ripenning was carried out by adding 15 mg of
sodium thiosulfate per one mole of silver chlorobromide at 60 °C for 60 minutes.
[0112] Subsequently, to the emulsion was added 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene
and as the sensitizing dye, 150 mg/one mole of Ag of 1-(β-hydroxyethyl)-3-phenyl-5-[(3-y-sulfopropyl-αa-benzox-
azoliridene)ethylidene]thiohydantoin was added to effect optical sensitization.
[0113] Then, a hydrazide compound represented by the formula (I) of the present invention
and the compound of the formula (VI) were added as shown in Table 7. Further, 400
mg of sodium p-dodecylbenzenesulfonate, 3.5 g of saponin and 2 g of styrene-maleic
acid copolymer were added thereto per one mole of Ag and the mixture was coated on
a base so as to become the Ag amount of 4.0 g/m
2 and the gelatin amount of 2.0 gim
2. At this time, a protective layer containing 30 mg/m
2 of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a spreading agent and 25
mg/m
2 of formalin as a hardening agent with 1.2 gim
2 of gelatin was multilayer coated to prepare Samples 38 to 55.
[0114] To the resulting samples were exposed by using an optical wedge with use of a tungsten
light source.
[0115] The above test samples were processed by using the developing solution with the following
prescription and the commercially available fixing solution according to an automatic
developer having a development tank volume of 40 liters.

[0116] In the above table, the comparative compounds (a) and (b) added to the silver halide
emulsion layer are the same with those as used in Example 1.
[0117] After the above samples were processed, sensitivity, sharpness at the leg portion
of the characteristic curve and pepper fog were evaluated. The sensitivity was shown
by a relative sensitivity obtained by a reverse value of the exposed dose necessary
for forming 2.5 with an optical density. Also, sharpness at the leg portion was shown
by the exposure range of from 0.1 to 0.5 of the optical density. This value shows
that smaller value is preferred characteristic wherein sharpness at the leg portion
is good. Generation degree of the pepper fog is employed as the same rating system
in Example 1. These results are shown in Table 8.

[0118] When using the developing solution, the above compositions A and B were successively
dissolved in 500 ml of pure water in this order to make up to one liter for use.

[0119] As clearly seen from the results in Table 8, it can be understood that the samples
obtained by the present invention remarkably inhibit generation of pepper fog without
impairing sensitivity and contract.
Example 7
[0120] In the same manner as in Example 6, samples were obtained except for replacing the
compound of the formula (VI) with the compound of the formula (VII) and then the samples
were subjected to the developing processing and evaluated as in Example 6. Contents
of the samples and the results are shown in Table 9.

[0121] An added amound of the compound represented by the formula (I) is 2 x 10-
5 mole/one mole of Ag and that of the compound of the formula (VII) is 3 x 10-
5 mole/one mole of Ag.
[0122] As clearly seen from Table 9, it can be understood that the samples No. 59 to 65
using the compounds of the present invention have pepper fog inhibiting effect without
impairing sensitivity and contract as compared with the comparative samples No. 56
to 58.
Example 8
[0123] In the same manner as in Example 6, samples were obtained except for replacing the
compound of the formula (VI) with the compound of the formula (VIII) and then the
samples were subjected to the developing processing and evaluated as in Example 6.
Contents of the samples and the results are shown in Table 10.

[0124] An added amound of the compound represented by the formula (I) is 2 x 10-
5 mole/one mole of Ag and that of the compound of the formula (VIII) is 3 x 10-
5 mole/one mole of Ag.
[0125] As clearly seen from Table 10, it can be understood that the samples No. 69 to 75
using the compounds of the present invention have pepper fog inhibiting effect without
impairing sensitivity and contract as compared with the comparative samples No. 66
to 68.
[0126] According to formation of high contrast image due to the light-sensitive silver halide
photographic material using the hydrazine compound of the present invention, generation
of pepper fog can be inhibited without impairing high contract.
[0127] In other word, according to the present invention, the light-sensitive silver halide
photographic material which is extremely high contract and inhibited in generation
of pepper fog can be provided without impairing high contrast.