Developer for silver halide photographic photosensitive material

A developer for a silver halide photographic photosensitive material containing at least one of monocyclic dimercaptotriazine compounds, bis-type dimercaptotriazine compounds, mercapto-1,2,4-triazine compounds and dimercaptopyrimidine compounds, and a process for developing a silver halide photographic photosensitive material using the developer. The compounds of the present invention provides excellent effect in preventing silver stains without affecting the photographic properties of the photographic material.

FIELD OF THE INVENTION 
The present invention relates to a development processing method for use in 
the processing of a silver halide photographic photosensitive material 
(hereinafter sometimes referred to as "photosensitive material"). More 
specifically, the present invention relates to a method of, in the 
development processing of a black-and-white photographic photosensitive 
material for general use, a black-and-white photographic photosensitive 
material for printing or an X-ray photographic photosensitive material for 
medical or industrial use, reducing silver stains (also called silver 
sludge) adhering to or precipitating in the development tank, development 
rack or rollers in an automatic developing machine to thereby facilitates 
daily maintenance of instruments and machines. 
BACKGROUND OF THE INVENTION 
Generally speaking, in the development processing of a silver halide 
photosensitive material, use of an automatic developing machine 
(hereinafter referred to as "automatic processor") increases in view of 
rapidity, simpleness and handleability. When the processing is performed 
using an automatic processor, development-fixing-water washing-drying 
steps are usually provided. In recent years, a demand for expediting the 
development processing is more and more increasing. To intensify activity 
of the developer is one means for achieving rapid processing. In the rapid 
processing of a black-and-white photosensitive material, the activity may 
be intensified by increasing concentration of the developing agent or 
elevating pH of the developer, however, the developer conspicuously 
deteriorates due to air oxidation and it is difficult to maintain the 
activity. Further, approach from the photosensitive material to the rapid 
processing is aggressively investigated. Reduction in the layer thickness 
(for example, protective layer) of the photosensitive material is 
effective in achieving rapid processing. 
It is known from of old to use a sulfite for preventing deterioration of 
the developer, however, since a compound having an action of dissolving 
silver halide, such as sulfite, is added to the developer, silver is 
dissolved out from the photosensitive material into the developer as a 
sulfite silver complex. The silver complex is reduced in the developer and 
the silver gradually adheres to and accumulates in the development tank or 
the development roller. This is called silver stain or silver sludge. The 
silver stain or silver sludge adheres to the photosensitive material to be 
processed to soil the image and therefore, the instruments must be 
periodically washed and maintained. If the addition amount of the sulfite 
is increased, the amount of the sulfite complex dissolved out increases 
and as a result, the degree of silver stain becomes higher and advantages 
in the rapid processing cannot be used successfully. 
On the other hand, as a method for reducing the silver stain, a method of 
adding a compound capable of decreasing silver ions to dissolve out into 
the developer and/or restraining reduction of silver ions to silver as 
described in JP-A-56-24347 (the term "JP-A" as used herein means an 
"unexamined published Japanese patent application") is known. However, 
according to this method, the development itself is inevitably restrained, 
and the method is disadvantageous in that lowering of sensitivity is 
involved. For the photosensitive material/development processing system 
intended to achieve sensitivity as high as possible, the above-described 
lowering of sensitivity is a serious problem. Further, to reduce the layer 
thickness (for example, protective layer) of the photosensitive material 
is very effective in performing rapid processing, however, if such a 
photosensitive material is subjected to running processing in an automatic 
processor, silver ions dissolved out into the developer increase and the 
silver stain is worsened. 
The compound which reduces silver stains include various compounds hitherto 
disclosed. Mercaptotriazines are one example thereof. 
JP-A-49-5334 has succeeded in removing tailing of a high-contrast 
photographic photosensitive material by adding a heterocyclic mercapto 
compound to a lith-type developer and discloses 
2,4,6-trimercapto-1,3,5-triazine as a specific example. JP-A-59-204037 
uses a heterocyclic mercapto compound in combination so as to prevent 
silver sludge (silver stain) of a black-and-white developer having a pH of 
11.5 or more and discloses 2,4-dimercapto-6-hydroxy-1,3,5-triazine as a 
specific example. JP-A-3-53244 uses mercapto-1,3,5-triazine so as to 
prevent silver sludge of a developer. Further, JP-A-3-282457, 
JP-A-4-11249, JP-A-4-31852, JP-A-4-299337, JP-A-4-299338, JP-A-4-322248, 
JP-A-4-175178, JP-A-5-61159 and JP-A-5-303179 disclose that 
mercapto-1,3,5-triazine is effective. 
However, these compounds adversely affect the photographic properties to a 
large extent, such as reduction in the sensitivity. 
JP-A-6-230525 also discloses a mercaptotriazine compound and states that 
when processing is performed with a developer containing no alkanolamine, 
an effect of preventing black peppers is obtained without causing 
softening. However, it has no disclosure of the excellent effect obtained 
by the mercaptotriazine compound having a specific functional group as in 
the present invention, and this effect cannot be expected. 
Mercapto 1,2,4-triazines are one example of the compounds which reduces 
silver stains. 
JP-A-5-303179, JP-A-5-61159 and JP-A-6-324435 disclose that a mercapto 
1,2,4-triazine compound having a hydroxy group is useful in preventing 
silver stains. The present inventors actually evaluated this compound and 
verified that the compound has a silver stain prevention effect, however, 
the effect is yet insufficient and a further improvement is demanded. 
Furthermore, mercaptopyrimidines are one example of the compounds which 
reduces silver stains. 
JP-A-59-204037 describes use of a heterocyclic mercapto compound in 
combination in a black-and-white developer having a pH of 11.5 or more for 
the purpose of inhibiting silver sludge and discloses 
2-mercapto-4-hydroxypyrimidine as a specific example thereof. 
JP-A-4-362942 discloses an improved hydroxypyrimidine compound. However, 
these patent publications have no specific disclosure of the 
dimercaptopyrimidine compound as in the present invention. Further, on 
evaluating the above-described compounds, a prevention effect of silver 
sludge is verified, however, it is not necessarily satisfactory and in 
need of more improvement. 
JP-A-49-11333 discloses that a dimercaptopyrimidine compound provides an 
effect to improve color tone of a silver image in a silver salt diffusion 
transfer viscous developer. JP-B-46-11630 (the term "JP-B" as used herein 
means an "examined Japanese patent publication") uses a 
2,4-dimercaptopyrimidine compound as an inhibitor of sludge in an alkaline 
processing solution in an activator system diffusion transfer method. 
However, on evaluating these compounds, they showed not necessarily 
satisfactory prevention effect against silver sludge. 
JP-A-53-141623 discloses that after development processing, a dimer of a 
nitrogen-containing heterocyclic compound having a mercapto group provides 
a bleaching acceleration effect. However, this patent publication does not 
refer at all to the effect of the dimercaptopyrimidine compound in the 
developer as in the present invention. 
SUMMARY OF THE INVENTION 
Accordingly, a first object of the present invention is, in the processing 
of a silver halide photosensitive material capable of rapid processing, to 
reduce silver stains generated in the development tank and/or the 
development rack and roller. A second object of the present invention is 
to facilitate maintenance of the automatic processor and the development 
instrument. A third object of the present invention is to reduce silver 
stains completely without affecting the photographic properties. A fourth 
object of the present invention to reduce silver stains without impairing 
stability of the developer. 
The above-described objects of the present invention can be attained by the 
following developers for silver halide photographic photosensitive 
material. 
(1) A developer for a silver halide photographic photosensitive material 
comprising at least one compound represented by the following formula 
(1-I) or (1-II): 
##STR1## 
wherein L.sub.1 represents a divalent group, R.sub.11 represents an amino 
group, an ammonio group, an alkoxy group, and M represents a hydrogen atom 
or a cation; 
##STR2## 
wherein L.sub.3 represents a linking group, M represents a hydrogen atom 
or a cation, and X.sub.1 and X.sub.2 each represents a group capable of 
substituting to the triazine ring. 
(2) A developer for a silver halide photographic photosensitive material 
comprising at least one compound represented by the following formula 
(2-I): 
##STR3## 
wherein R.sub.21, R.sub.22 and R.sub.23 each represents a hydrogen atom, 
an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a 
heterocyclic group, a halogen atom, a cyano group, a nitro group, a 
carboxy group, a sulfo group, a sulfino group, a phosphono group, an amino 
group, an ammonio group, a phosphonio group, a mercapto group, an oxy 
group, a thio group, an acyl group, a carbamoyl group, an acylamino group, 
a sulfamoyl group, a sulfonamido group, a sulfonyl group, a sulfinyl 
group, an oxycarbonyl group, a urethane group or a ureido group, provided 
that at least one of R.sub.21, R.sub.22 and R.sub.23 represents a mercapto 
group. 
(3) A developer for a silver halide photographic photosensitive material 
comprising at least one compound represented by the following formula 
(3-I) and/or (3-II): 
##STR4## 
wherein R.sub.311 and R.sub.312 each represents a mercapto group or a 
group capable of substituting to the pyrimidine ring; 
##STR5## 
wherein R.sub.321 represents an aromatic hydrocarbon group, a heterocyclic 
group, a halogen atom, a cyano group, a nitro group, a sulfo group, a 
sulfino group, a carboxy group, a phosphono group, an amino group, an 
ammonio group, a phosphonio group, a mercapto group, an oxy group, a thio 
group, an acyl group, a carbamoyl group, an acylamino group, a sulfamoyl 
group, a sulfonamido group, a sulfonyl group, a sulfinyl group, an 
oxycarbonyl group, a urethane group or a ureido group, and R.sub.322 
represents a mercapto group or a group capable of substituting to the 
pyrimidine ring. 
(4) A developer for a silver halide photographic photosensitive material 
comprising at least one compound represented by the following formula (4): 
##STR6## 
wherein R.sub.41 represents a hydrogen atom or an aliphatic group, 
R.sub.42 represents a hydrogen atom or a substituent, with the proviso 
that when R.sub.42 represents a hydrogen atom, R.sub.41 represents an 
aliphatic group substituted with at least one water-soluble group. 
Formula (1-I) is described in detail below. 
Examples of the amino group represented by R.sub.11 in formula (1-I) 
include an unsubstituted amino group, a methylamino group, an ethylamino 
group, a dimethylamino group, a diethylamino group, an anilino group, an 
o-toluidino group and a 2,4-xylidino group. 
Examples of the ammonio group represented by R.sub.11 in formula (1-I) 
include a trimethylammonio group, a triethylammonio group, a 
diethylmethylammonio group and a tri-n-butylammonio group, and the counter 
anion for neutralizing the positive electric charge of the ammonio group 
is an inorganic anion (e.g., halogen ion (e.g., chloride ion, bromide 
ion)) or an organic anion (e.g., acetate ion, CH.sub.3 OSO.sub.3.sup.- 
ion). 
Examples of the alkoxy group represented by R.sub.11 in formula (1-I) 
include a methoxy group, an ethoxy group, an isopropyl group, an n-butoxy 
group, a cyclohexyloxy group and a metoxyethoxy group. 
Examples of the cation represented by M in formula (1-I) include alkali 
metal ions such as lithium ion, sodium ion, potassium ion and cesium ion, 
and ammonio ions such as ammonio ion and tetramethylammonio ion. 
Examples of the divalent group represented by L.sub.1 in formula (1-I) 
include an alkylene group having from 1 to 10 carbon atoms (preferably 
from 1 to 6 carbon atoms) (e.g., methylene, ethylene, propylene), 
--N(R.sub.110)L.sub.2 -- (wherein R.sub.110 represents a hydrogen atom or 
an aliphatic hydrocarbon group having from 1 to 6 carbon atoms), 
--O--L.sub.2 --, --S--L.sub.2 --, --C(O)--L.sub.2 --, --SO.sub.2 --L.sub.2 
--, --C(O)O--L.sub.2 --, a methylenedioxy group, a ureylene group and a 
composite group thereof. 
L.sub.2 is a divalent and examples thereof include an alkylene group having 
from 1 to 10 carbon atoms (preferably from 1 to 6 carbon atoms) (e.g., 
methylene, ethylene, propylene). 
The groups represented by R.sub.11 and L.sub.1 in formula (1-I) each may be 
substituted. Examples of the substituent include the followings: 
a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., 
methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, 
cyclohexyl), an alkenyl group (e.g., allyl, 2-butenyl, 3-pentenyl), an 
alkynyl group (e.g., propargyl, 3-pentenyl), an aralkyl group (e.g., 
benzyl, phenethyl), an aryl group (e.g., phenyl, naphthyl, 
4-methylphenyl), a heterocyclic group (e.g., pyridyl, furyl, imidazolyl, 
piperidyl, morpholino), an alkoxy group (e.g., methoxy, ethoxy, butoxy), 
an aryloxy group (e.g., phenoxy, 2-naphthyloxy), an amino group (e.g., 
unsubstituted amino, dimethylamino, ethylamino, anilino), a ureido group 
(e.g., unsubstituted ureido, N-methylureido, N-phenylureido), a urethane 
group (e.g., methoxycarbonylamino, phenoxycarbonylamino), a sulfonyl group 
(e.g., mesyl, tosyl), a sulfinyl group (e.g., methylsulfinyl, 
phenylsulfinyl), an alkyloxycarbonyl group (e.g., methoxycarbonyl, 
ethoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an acyl 
group (e.g., acetyl, benzoyl, formyl, pivaloyl), an acyloxy group (e.g., 
acetoxy, benzoyloxy), a phosphoramide group (e.g., 
N,N-diethylphosphoramide), an alkylthio group (e.g., methylthio, 
ethylthio), an arylthio group (e.g., phenylthio), a cyano group, a 
mercapto group, a phosphono group, a nitro group, a sulfino group, an 
ammonio group (e.g., trimethylammonio), a phosphonio group and a silyl 
group (e.g., trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, 
t-butyldiphenylsilyl). These groups each may be further substituted. When 
two or more substituents are present, they may be the same or different. 
Formula (1-II) is described in detail below. 
Examples of the linking group represented by L.sub.3 in formula (1-II) 
include an alkylene group (e.g., methylene, ethylene, propylene), an 
arylene group (e.g., o-phenylene, p-phenylene), a mere bond, 
--N(R.sub.111)-- (wherein R.sub.111 represents a hydrogen atom, an 
aliphatic hydrocarbon group, an aromatic hydrocarbon group or a 
heterocyclic group), --O--, --S--, --SS--, --C(O)--, --SO--, --SO.sub.2 
--, --OC(O)O--, --SC(O)S--, a methylenedioxy group, a ureylene group and a 
composite group thereof. 
Examples of the group capable of substituting to the triazine ring 
represented by X.sub.1 or X.sub.2 in formula (1-II) include substituents 
of R.sub.11 and L.sub.1 in formula (I) and additionally, an acylamino 
group (e.g., acetylamino, benzoylamino), a sulfonylamino group (e.g., 
methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (e.g., 
unsubstituted sulfamoyl, N,N-dimethylsulfamoyl, N-phenylsulfamoyl group), 
a carbamoyl group (e.g., unsubstituted carbamoyl, N,N-diethylcarbamoyl, 
N-phenylcarbamoyl), a sulfo group, a carboxy group and a hydroxy group. 
The cation represented by M in formula (1-II) has the same meaning as the 
cation represented by M in formula (1-I). 
In a preferred embodiment of formula (1-I), the divalent group represented 
by L.sub.1 is an alkylene group, --N(R.sub.110)--L.sub.2 --, --O--L.sub.2 
-- or --C(O)--L.sub.2 --, R.sub.11 is an amino group or an ammonio group 
and M is a hydrogen atom or a cation. 
In a more preferred embodiment of formula (1-I), the divalent group 
represented by L.sub.1 is an alkylene group or --N(R.sub.110)--L.sub.2 --, 
R.sub.11 is an amino group or an ammonio group and M is a hydrogen atom or 
a cation. 
In a most preferred embodiment of formula (1-I), the divalent group 
represented by L.sub.1 is an alkylene group or --N(R.sub.110)--L.sub.2 --, 
R.sub.11 is an amino group and M is a hydrogen atom or a cation. 
In a preferred embodiment of formula (1-II), L.sub.3 is an alkylene group, 
--N(R.sub.111)--, --O-- or --S--, and M is a hydrogen atom or a cation. 
In a more preferred embodiment of formula (1-II), L.sub.3 is 
--N(R.sub.111)-- (wherein R.sub.111 represents a hydrogen atom or an 
aliphatic hydrocarbon group) or --O--, and M is a hydrogen atom or a 
cation. 
Specific examples of the compounds represented by formula (1-I) or (1-II) 
are set forth below, however, the compounds of the present invention are 
by no means limited thereto. 
##STR7## 
The compounds represented by formulae (1-I) and (1-II) can be synthesized 
according to the method described in E. M. Smolin and L. Lapoport, 
s-Triazine and Derivatives (The Chemistry of Heterocyclic Compounds 
Series), Interscience Publishers. 
Formula (2-I) is described in detail below. 
The aliphatic hydrocarbon group represented by R.sub.21, R.sub.22 or 
R.sub.23 in formula (I) is preferably an aliphatic hydrocarbon group 
having from 1 to 15 carbon atoms, more preferably a linear, branched or 
cyclic alkyl, alkenyl, alkynyl or aralkyl group having from 1 to 8 carbon 
atoms. Out of these groups, branched groups each may be cyclized to form a 
saturated heterocyclic ring containing one or more hetero atoms. Examples 
of the alkyl group include a methyl group, an ethyl group, an isopropyl 
group, a t-butyl group, an n-octyl group, a cyclopropyl group, a 
cyclopentyl group and a cyclohexyl group. Examples of the alkenyl group 
include an allyl group, a 2-butenyl group and a 3-pentenyl group. Examples 
of the alkynyl group include a propargyl group and a 3-pentenyl group. 
Examples of the aralkyl group include a benzyl group. 
The aromatic hydrocarbon group represented by R.sub.21, R.sub.22 or 
R.sub.23 in formula (2-I) is preferably an aromatic hydrocarbon group 
having from 5 to 15 carbon atoms, more preferably a monocyclic or 
condensed ring aryl group having from 6 to 10 carbon atoms, and examples 
thereof include a phenyl group and a naphthyl group. 
The heterocyclic group represented by R.sub.21, R.sub.22 or R.sub.23 in 
formula (2-I) is a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated or 
unsaturated heterocyclic group containing at least one of a nitrogen atom, 
an oxygen atom and a sulfur atom. The heterocyclic group may be monocyclic 
or may form a condensed ring with other aromatic ring. The heterocyclic 
group is preferably a 5- or 6-membered aromatic heterocyclic group and 
examples thereof include a pyridyl group, an imidazolyl group, a quinolyl 
group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an 
isoquinolinyl group, a thiazolyl group, a thienyl group, a furyl group and 
a benzothiazolyl group. 
Examples of the halogen atom represented by R.sub.21, R.sub.22 or R.sub.23 
in formula (2-I) include a fluorine atom, a chlorine atom, a bromine atom 
and an iodine atom. 
Examples of the amino group represented by R.sub.21, R.sub.22 or R.sub.23 
in formula (2-I) include an unsubstituted amino group, a methylamino 
group, an ethylamino group, a dimethylamino group, a diethylamino group, 
an anilino group, an o-toluidino group and a 2,4-xylidino group. Examples 
of the ammonio group include a trimethylammonio group, a triethylammonio 
group and an unsubstituted ammonio group. Examples of the phosphonio group 
include a trimethylphosphonio group and a triethylphosphonio group. 
Examples of the oxy group represented by R.sub.21, R.sub.22 or R.sub.23 in 
formula (2-I) include an alkoxy group (e.g., methoxy, ethoxy, isopropoxy, 
n-butoxy, cyclohexyloxy), an aryloxy group (e.g., phenoxy, 
p-methylphenoxy), an oxy group resulting from bonding of an oxygen atom to 
a heterocyclic ring (e.g., 2-pyridyloxy, 2-imidazolyloxy), an allyloxy 
group and a benzyloxy group. 
Examples of the thio group represented by R.sub.21, R.sub.22 or R.sub.23 in 
formula (2-I) include an alkylthio group (e.g., methylthio, ethylthio, 
isopropylthio, n-butylthio, cyclohexylthio), an arylthio group (e.g., 
phenylthio, p-methylphenylthio), a thio group resulting from bonding of a 
sulfur atom to a heterocyclic ring (e.g., 2-pyridylthio, 
2-imidazolylthio), an allylthio group and a benzylthio group. 
Examples of the acyl group represented by R.sub.21, R.sub.23 or R.sub.23 in 
formula (2-I) include a formyl group, an acetyl group, a propionyl group, 
an isobutyryl group, a valeryl group, a pivaloyl group, an octanoyl group, 
an acryloyl group, a pyruvoyl group, a benzoyl group, a 1-naphthoyl group, 
an m-toluoyl group and a cynnamoyl group. Examples of the carbamoyl group 
include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, an 
N-ethylcarbamoyl group, an N,N-dimethylcarbamoyl group, an 
N,N-diethylcarbamoyl group and an N-phenylcarbamoyl group. Examples of the 
acylamino group include an acetylamino group, a benzamido group, a 
propionylamino group and a pivaloylamino group. Examples of the sulfamoyl 
group include an unsubstituted sulfamoyl group, a methylsulfamoyl group, 
an ethylsulfamoyl group, a dimethylsulfamoyl group, a diethylsulfamoyl 
group and a phenylsulfamoyl group. Examples of the sulfonamido group 
include a benzenesulfonamido group and a methylsulfonylamino group. 
Examples of the sulfonyl group include a mesyl group, a tosyl group and a 
tauryl group. Examples of the sulfinyl group include a methylsulfinyl 
group and a phenylsulfinyl group. 
Examples of the oxycarbonyl group represented by R.sub.21, R.sub.22 or 
R.sub.23 in formula (2-I) include an alkoxycarbonyl group (e.g., 
methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl) and an 
aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthyloxycarbonyl). 
Examples of the ureido group represented by R.sub.21, R.sub.22 or R.sub.23 
in formula (2-I) include an N'-methylureido group, an N',N'-dimethylureido 
group, an N,N',N'-trimethylureido group, an N'-ethylureido group and an 
N'-phenylureido group. Examples of the urethane group include a 
methoxycarbonylamino group and a phenoxycarbonylamino group. 
The groups represented by R.sub.21, R.sub.22 or R.sub.23 in formula (2-I) 
each may be substituted. Examples of the substituent include the 
following: 
a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., 
methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, 
cyclohexyl), an alkenyl group (e.g., allyl, 2-butenyl, 3-pentenyl), an 
alkynyl group (e.g., propargyl, 3-pentenyl), an aralkyl group (e.g., 
benzyl, phenethyl), an aryl group (e.g., phenyl, naphthyl, 
4-methylphenyl), a heterocyclic group (e.g., pyridyl, furyl, imidazolyl, 
piperidyl, morpholino), an alkoxy group (e.g., methoxy, ethoxy, butoxy), 
an aryloxy group (e.g., phenoxy, 2-naphthyloxy), an amino group (e.g., 
unsubstituted amino, dimethylamino, ethylamino, anilino), a ureido group 
(e.g., unsubstituted ureido, N-methylureido, N-phenylureido), a urethane 
group (e.g., methoxycarbonylamino, phenoxycarbonylamino), a sulfonyl group 
(e.g., mesyl, tosyl), a sulfinyl group (e.g., methylsulfinyl, 
phenylsulfinyl), an alkyloxycarbonyl group (e.g., methoxycarbonyl, 
ethoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an acyl 
group (e.g., acetyl, benzoyl, formyl, pivaloyl), an acyloxy group (e.g., 
acetoxy, benzoyloxy), a phosphoramide group (e.g., 
N,N-diethylphosphoramide), an alkylthio group (e.g., methylthio, 
ethylthio), an arylthio group (e.g., phenylthio), a cyano group, a 
mercapto group, a carboxy group, a sulfo group, a phosphono group, a nitro 
group, a sulfino group, an ammonio group (e.g., trimethylammonio), a 
phosphonio group and a silyl group (e.g., trimethylsilyl, triethylsilyl, 
t-butyldimethylsilyl, t-butyldiphenylsilyl). These groups each may be 
further substituted. When two or more substituents are present, they may 
be the same or different. 
R.sub.21, R.sub.22 and R.sub.23 in formula (2-I) each is preferably a 
hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon 
group, a heterocyclic group, a carboxy group, a sulfo group, an amino 
group, a mercapto group, an oxy group, a thio group, an acylamino group or 
a sulfonamido group, provided that at least one of R.sub.21, R.sub.22 and 
R.sub.23 is a mercapto group. 
R.sub.21, R.sub.22 and R.sub.23 in formula (2-I) each is more preferably a 
hydrogen atom, an aliphatic hydrocarbon group, a heterocyclic group, a 
carboxy group, a sulfo group, an amino group, a mercapto group, an oxy 
group or an acylamino group, provided that at least one of R.sub.21, 
R.sub.22 and R.sub.23 is a mercapto group. 
R.sub.21, R.sub.22 and R.sub.23 in formula (2-I) are most preferably all a 
mercapto group. 
Specific examples of the compounds represented by formula (2-I) are set 
forth below, however, the compounds of the present invention are by no 
means limited thereto. 
##STR8## 
The compounds represented by formulae (2-I) can be synthesized according to 
the method described in J. G. Erickson, P. F. Wiley, and V. P. Wystrack, 
The 1,2,3- and 1,2,4-Triazines, Tetrazines and Pentazines (The Chemistry 
of Heterocyclic Compounds Series), Interscience Publishers. 
Formula (3-I) is described in detail below. 
Examples of the group capable of substituting to the pyrimidine ring, 
represented by R.sub.311 or R.sub.312 in formula (3-I) includes a hydrogen 
atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a 
heterocyclic group, a halogen atom, a cyano group, a nitro group, a sulfo 
group, a sulfino group, a carboxy group, a phosphono group, an amino 
group, an ammonio group, a phosphonio group, a mercapto group, an oxy 
group, a thio group, an acyl group, a carbamoyl group, an acylamino group, 
a sulfamoyl group, a sulfonamido group, a sulfonyl group, a sulfinyl 
group, an oxycarbonyl group, an acyloxy group, a urethane group and a 
ureido group. 
The aliphatic hydrocarbon group represented by R.sub.311 or R.sub.312 in 
formula (3-I) is preferably an aliphatic hydrocarbon having from 1 to 15 
carbon atoms, more preferably a linear, branched or cyclic alkyl, alkenyl, 
alkynyl or aralkyl group having from 1 to 8 carbon atoms. Among these, the 
branched group may be cyclized to form a saturated heterocyclic ring 
containing one or more hetero atoms therein. Examples of the alkyl group 
include a methyl group, an ethyl group, an isopropyl group, a t-butyl 
group, an n-octyl group, a cyclopropyl group, a cyclopentyl group and a 
cyclohexyl group. Examples of the alkenyl group include an allyl group, a 
2-butenyl group and a 3-pentenyl group. Examples of the alkynyl group 
include a propargyl group and a 3-pentenyl group. Examples of the aralkyl 
group include a benzyl group. 
The aromatic hydrocarbon group represented by R.sub.311 or R.sub.312 in 
formula (3-I) is preferably an aromatic hydrocarbon group having from 5 to 
15 carbon atoms, more preferably a monocyclic or condensed ring aryl group 
having from 6 to 10 carbon atoms, and examples thereof include a phenyl 
group and a naphthyl group. 
The heterocyclic group represented by R.sub.311 or R.sub.312 in formula 
(3-I) is a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated or 
unsaturated heterocyclic group containing at least one of a nitrogen atom, 
an oxygen atom and a sulfur atom. The group may be monocyclic or may form 
a condensed ring with other aromatic ring. The heterocyclic group is 
preferably a 5- or 6-membered aromatic heterocyclic group and examples 
thereof include a pyridyl group, an imidazolyl group, a quinolyl group, a 
benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolyl 
group, a thiazolyl group, a thienyl group, a furyl group and a 
benzothiazolyl group. 
Examples of the halogen atom represented by R.sub.311 or R.sub.312 in 
formula (3-I) include a fluorine atom, a chlorine atom, a bromine atom and 
an iodine atom. 
Examples of the amino group represented by R.sub.311 or R.sub.312 in 
formula (3-I) include an unsubstituted amino group, a methylamino group, 
an ethylamino group, a dimethylamino group, a diethylamino group, an 
anilino group, an o-toluidino group and a 2,4-xylydino group. Examples of 
the ammonio group include a trimethylammonio group, a triethylammonio 
group and an unsubstituted ammonio group. Examples of the phosphonio group 
include a trimethylphosphonio group and a triethylphosphonio group. 
Examples of the oxy group represented by R.sub.311 or R.sub.312 in formula 
(3-I) include an alkoxy group (e.g., methoxy, ethoxy, isopropoxy, 
n-butoxy, cyclohexyloxy), an aryloxy group (e.g., phenoxy, 
p-methylphenoxy), an oxy group resulting from bonding of an oxygen atom to 
a heterocyclic ring (e.g., 2-pyridyloxy, 2-imidazolyloxy), an allyloxy 
group and a benzyloxy group. 
Examples of the thio group represented by R.sub.311 or R.sub.312 in formula 
(3-I) include an alkylthio group (e.g., methylthio, ethylthio, 
isopropylthio, n-butylthio, cyclohexylthio), an arylthio group (e.g., 
phenylthio, p-methylphenylthio), a thio group resulting from bonding of a 
sulfur atom to a heterocyclic ring (e.g., 2-pyridylthio, 
2-imidazolylthio), an allylthio group and a benzylthio group. 
Examples of the acyl group represented by R.sub.311 or R.sub.312 in formula 
(3-I) include a formyl group, an acetyl group, a propionyl group, an 
isobutyryl group, a valeryl group, a pivaloyl group, an octanoyl group, an 
acryloyl group, a pyruvoyl group, a benzoyl group, a l-naphthoyl group, an 
m-toluoyl group and a cynnamoyl group. Examples of the carbamoyl group 
include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, an 
N-ethylcarbamoyl group, an N,N-dimethylcarbamoyl group, an 
N,N-diethylcarbamoyl group and an N-phenylcarbamoyl group. Examples of the 
acylamino group include an acetylamino group, a benzamido group, a 
propionylamino group and a pivaloylamino group. Examples of the sulfamoyl 
group include an unsubstituted sulfamoyl group, a methylsulfamoyl group, 
an ethylsulfamoyl group, an N,N-diemthylsulfamoyl group, a 
diethylsulfamoyl group and a phenylsulfamoyl group. Examples of the 
sulfonamido group include a benzenesulfonamido group and a 
methylsulfonylamino group. Examples of the sulfonyl group include a mesyl 
group, a tosyl group and a tauryl group. Examples of the sulfinyl group 
include a methylsulfinyl group and a phenylsulfinyl group. 
Examples of the oxycarbonyl group represented by R.sub.311 or R.sub.312 in 
formula (3-I) include an alkoxycarbonyl group (e.g., methoxycarbonyl, 
ethoxycarbonyl, isopropoxycarbonyl) and an aryloxycarbonyl group (e.g., 
phenoxycarbonyl, naphthyloxycarbonyl). 
Examples of the ureido group represented by R.sub.311 or R.sub.312 in 
formula (3-I) include an N'-methylureido group, an N',N'-dimethylureido 
group, an N,N',N'-trimethylureido group, an N'-ethylureido group and an 
N'-phenylureido group. Examples of the urethane group include a 
methoxycarbonylamino group and a phenoxycarbonylamino group. 
The groups represented by R.sub.311 or R.sub.312 in formula (3-I) each may 
be substituted. Examples of the substituent include the following: 
a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., 
methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, 
cyclohexyl), an alkenyl group (e.g., allyl, 2-butenyl, 3-pentenyl), an 
alkynyl group (e.g., propargyl, 3-pentynyl), an aralkyl group (e.g., 
benzyl, phenethyl), an aryl group (e.g., phenyl, naphthyl, 
4-methylphenyl), a heterocyclic group (e.g., pyridyl, furyl, imidazolyl, 
piperidyl, morpholino), an alkoxy group (e.g., methoxy, ethoxy, butoxy), 
an aryloxy group (e.g., phenoxy, 2-naphthyloxy), an amino group (e.g., 
unsubstituted amino, dimethylamino, ethylamino, anilino), a ureido group 
(e.g., unsubstituted ureido, N-methylureido, N-phenylureido), a urethane 
group (e.g., methoxycarbonylamino, phenoxycarbonylamino), a sulfonyl group 
(e.g., mesyl, tosyl), a sulfinyl group (e.g., methylsulfinyl, 
phenylsulfinyl), an alkyloxycarbonyl group (e.g., methoxycarbonyl, 
ethoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an acyl 
group (e.g., acetyl, benzoyl, formyl, pivaloyl), an acyloxy group (e.g., 
acetoxy, benzoyloxy), a phosphoric amido group (e.g., 
N,N-diethylphosphoric amido), an alkylthio group (e.g., methylthio, 
ethylthio), an arylthio group (e.g., phenylthio), a cyano group, a 
mercapto group, a carboxy group, a phosphono group, a nitro group, a 
sulfino group, an ammonio group (e.g., trimethylammonio), a phosphonio 
group and a silyl group (e.g., trimethylsilyl, triethylsilyl, 
t-butyldimethylsilyl, t-butyldiphenylsilyl). These groups each may be 
further substituted. When two or more substituents are present, they may 
be the same or different. 
R.sub.311 and R.sub.312 in formula (3-I) each is preferably a hydrogen 
atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a 
heterocyclic group, a sulfo group, a carboxy group, an amino group, a 
mercapto group, an oxy group, a thio group, an acylamino group or a 
sulfonamido group. 
R.sub.311 and R.sub.312 in formula (3-I) each is more preferably an 
aliphatic hydrocarbon group, a sulfo group, a carboxy group, an amino 
group, a mercapto group, an oxy group or a thio group. 
R.sub.311 and R.sub.312 in formula (3-I) each is most preferably an 
aliphatic hydrocarbon group, a sulfo group, a carboxy group, an amino 
group or a mercapto group. 
Formula (3-II) is described in detail below. 
The aromatic hydrocarbon group, the heterocyclic group, the halogen atom, 
the amino group, the ammonio group, the phosphonio group, the oxy group, 
the thio group, the acyl group, the carbamoyl group, the acylamino group, 
the sulfamoyl group, the sulfonamido group, the sulfonyl group, the 
sulfinyl group, the oxycarbonyl group, the acyloxy group, the urethane 
group and the ureido group represented by R.sub.321 in formula (3-II) have 
the same meanings as the aromatic hydrocarbon group, the heterocyclic 
group, the halogen atom, the amino group, the ammonio group, the 
phosphonio group, the oxy group, the thio group, the acyl group, the 
carbamoyl group, the acylamino group, the sulfamoyl group, the sulfonamido 
group, the sulfonyl group, the sulfinyl group, the oxycarbonyl group, the 
acyloxy group, the urethane group and the ureido group represented by 
R.sub.311 or R.sub.312 in formula (3-I), respectively. 
The group capable of substituting to the pyrimidine ring represented by 
R.sub.322 in formula (3-II) has the same meaning as the group capable of 
substituting to the pyrimidine ring, represented by R.sub.311 or R.sub.312 
in formula (3-I). 
In formula (3-II), R.sub.321 is preferably an aromatic hydrocarbon group, a 
heterocyclic group, a sulfo group, a carboxy group, an amino group, a 
mercapto group, an oxy group, a thio group, an acylamino group or a 
sulfonamido group, and R.sub.322 is preferably a hydrogen atom, an 
aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic 
group, a sulfo group, a carboxy group, an amino group, a mercapto group, 
an oxy group, a thio group, an acylamino group or a sulfonamido group. 
In formula (3-II), R.sub.321 is more preferably a heterocyclic group, a 
sulfo group, a carboxy group, an amino group, a mercapto group, an oxy 
group, a thio group, an acylamino group, a sulfonamido group, and 
R.sub.322 is more preferably a hydrogen atom, an aliphatic hydrocarbon 
group, a sulfo group, a carboxy group, an amino group, a mercapto group, 
an oxy group or a thio group. 
In formula (3-II), R.sub.321 is most preferably a sulfo group, a carboxy 
group, an amino group, a mercapto group or an oxy group, and R.sub.322 is 
most preferably an aliphatic hydrocarbon group, a sulfo group, a carboxy 
group or an amino group. 
Particularly preferred compounds among the compounds represented by formula 
(3-I) or (3-II) are described below. 
Among the compounds represented by formula (3-I), particularly preferred 
are compounds in which R.sub.311 represents a group substituted with a 
water-soluble group. Examples of the group substituted with a 
water-soluble group include an alkyl group, an aryl group, an alkylthio 
group, an arylthio group, an alkoxy group, an alkylamino group or an 
arylamino group. The water-soluble group herein represents a carboxy group 
(or a salt thereof), a hydroxy group, an amino group, an ammonio group, a 
sulfo group (or a salt thereof) or a group containing at least one of 
these groups. 
R.sub.311 in formula (3-I) is more preferably an alkyl group, an aryl 
group, an alkylthio group, an alkoxy group, an alkylamino group or an 
arylamino group, each being substituted with a water-soluble group. Most 
preferred are an alkyl group, an alkylamino group or an arylamino group, 
each being substituted with a water-soluble group. As a water-soluble 
group, more preferred are a carboxy group (or a salt thereof), a hydroxy 
group or a sulfo group (a salt thereof). R.sub.312 in formula (3-I) 
represents particularly preferably a hydrogen atom. 
One of the particularly preferred compounds among the compounds represented 
by formula (3-II) is a compound in which R.sub.321 represents an alkylthio 
group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino 
group or an arylamino group, each being substituted with a water-soluble 
group. The water-soluble group herein represents a carboxy group (or a 
salt thereof), a hydroxy group, an amino group, an ammonio group, a sulfo 
group (or a salt thereof) or a group containing at least one of these 
groups. 
R.sub.321 in formula (3-II) is more preferably an alkylthio group, an 
alkoxy group, an alkylamino group or an arylamino group, each being 
substituted with a water-soluble group. Most preferred are an alkylamino 
group or an arylamino group, each being substituted with a water-soluble 
group. As a water-soluble group, more preferred are a carboxy group (or a 
salt thereof), a hydroxy group or a sulfo group (a salt thereof). 
R.sub.322 in formula (3-II) represents particularly preferably a hydrogen 
atom. 
The other of the particularly preferred compounds among the compounds 
represented by formula (3-II) is a compound in which R.sub.321 represents 
a mercapto group and R.sub.322 represents an alkyl group, an alkylthio 
group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino 
group or an arylamino group, each being substituted with a water-soluble 
group. The water-soluble group herein represents a carboxy group (or a 
salt thereof), a hydroxy group, an amino group, an ammonio group, a sulfo 
group (or a salt thereof) or a group containing at least one of these 
groups. 
R.sub.322 in formula (3-II) is more preferably an alkyl group, an alkylthio 
group, an alkoxy group, an alkylamino group or an arylamino group, each 
being substituted with a water-soluble group. An alkyl group substituted 
with a water-soluble group is most preferred. As a water-soluble group, 
more preferred are a carboxy group (or a salt thereof), a hydroxy group or 
a sulfo group (a salt thereof). R.sub.322 in formula (3-II) represents 
particularly preferably a hydrogen atom. 
Specific examples of the compounds represented by formula (3-I) or (3-II) 
are set forth below, however, the compounds of the present invention are 
by no means limited thereto. 
##STR9## 
The compounds represented by formulae (3-I) and (3-II) can be synthesized 
according to the methods described in already known literatures, for 
example, D. J. Brown, The Pyrimidines (The Chemistry of Heterocyclic 
Compounds Series), Interscience Publishers. 
Pyrimidine derivatives represented by formula (4) are described below. 
R.sub.41 in formula (4) represents a hydrogen atom or an aliphatic group. 
The aliphatic group herein represents a linear, branched or cyclic alkyl 
group, alkenyl group or alkynyl group, which may be substituted or 
unsubstituted. 
When the aliphatic group has a substituent, examples of the substituent 
include a halogen atom (e.g., fluorine, chlorine, bromine or iodine), an 
alkyl group (including an aralkyl group, a cycloalkyl group and active 
methine group), an alkenyl group, an alkynyl group, an aryl group, a 
heterocyclic group, a quarternized nitrogen-containing heterocyclic ring 
(e.g., pyridinio group), an acyl group, an alkoxycarbonyl group, an 
aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt 
thereof, a sulfonylcarbamoyl group, an acylcarbamoyl group, a 
sulfamoylcarbamoyl group, a carbazoyl group, an oxalyl group, an oxamoyl 
group, a cyano group, a thiocarbamoyl group, a hydroxy group, an alkoxy 
group (including groups having an ethyleneoxy group or a propyleneoxy 
group as a repeating unit), an aryloxy group, a heterocyclic oxy group, an 
acyloxy group, an alkoxyoxycarbonyloxy group, an aryloxycarbonyloxy group, 
a carbamoyloxy group, a sulfonyloxy group, an amino group, an alkylamino 
group, an arylamino group, a heterocyclic amino group, a hydroxyamino 
group, a saturated or unsaturated N-substituted nitrogen-containing 
heterocyclic group, an acylamino group, a sulfonamide group, an ureido 
group, a thioureido group, an imido group, an alkoxycarbonylamino group, 
an aryloxycarbonylamino group, a sulfamoylamino group, a semicarbazide 
group, a thiosemicarbazide group, a hydrazino group, a quaternary ammonio 
group, an oxamoylamino group, an alkylsulfonylureido group, an 
arylsulfonylureido group, an acylureido group, an acylsulfamoylamino 
group, a nitro group, a mercapto group, an alkylthio group, an arylthio 
group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl 
group, an alkylsulfinyl group, an arylsulfinyl group, a sulfo group or 
salt thereof, a sulfamoyl group, an acylsulfamoyl group, a 
sulfonylsulfamoyl group or salt thereof, a group containing a phosphoric 
amido or phosphoric ester structure. 
These groups each may be further substituted with at least one of these 
groups. 
The alkyl group represented by R.sub.41 in formula (4) is an alkyl group 
having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, cyclopropyl, 
2-hydroxyethyl, cyanocarboxymethyl, phenylcarboxymethyl, 
tri(hydroxymethyl)methyl, methylthiomethyl and phenoxymethyl group. The 
alkyl group represented by R.sub.41 may be an active methine group. The 
alkenyl group represented by R.sub.41 is an alkenyl group having 1 to 10 
carbon atoms, such as vinyl, 2-propenyl and styryl group. The alkynyl 
group represented by R.sub.41 is an alkynyl group having 1 to 10 carbon 
atoms, such as ethynyl, 2-propynyl and 2-ethoxycarbonylethynyl group. 
When R.sub.42 in formula (4) represents a hydrogen atom, R.sub.41 
represents an aliphatic group substituted with at least one water-soluble 
group. The water-soluble group herein represents a sulfonic acid or salt 
thereof, a carboxylic acid or salt thereof, a salt comprising an ammonio 
group or a group containing a dissociative group capable of partly or 
completely dissociating by an alkaline developer. Specific examples of the 
water-soluble group include a sulfo group (or a salt thereof), a carboxy 
group (or a salt thereof), a hydroxy group, a mercapto group, an amino 
group, an ammonio group, a sulfonamido group, an acylsulfamoyl group, a 
sulfonylsulfamoyl group, an active methine group or a substituent 
containing at least one of these groups. The active methine group herein 
means a methyl group substituted with two electron-withdrawing groups, 
such as dicyanomethyl group, .alpha.-cyano-.alpha.-ethoxycarbonylmethyl 
group and .alpha.-acetyl-.alpha.-ethoxycarbonylmethyl group. 
R.sub.41 in formula (4) is preferably a hydrogen atom or an alkyl group. 
The alkyl group represented by R.sub.41 in formula (4) is preferably an 
unsubstituted alkyl group having 1 to 4 carbon atoms in total, an active 
methine group having 3 to 8 carbon atoms in total or a substituted alkyl 
group having 1 to 8 carbon atoms in total. The substituent of the 
substituted alkyl group is preferably a water-soluble group or a 
substituent containing a water-soluble group. The water-soluble group for 
the alkyl group represented by R.sub.41 is preferably a sulfo group (or a 
salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a 
mercapto group or an amino group, particularly preferably a sulfo group 
(or a salt thereof), a carboxy group (or a salt thereof) or a hydroxy 
group. 
R.sub.42 in formula (4) is preferably a hydrogen atom or a substituent. 
Specific examples of the substituent represented by R.sub.42 include the 
same as the substituents described above which the aliphatic group 
represented by R.sub.41 may have. 
The substituent represented by R.sub.42 is preferably a substituent having 
0 to 15 carbon atoms in total, such as a halogen atom (especially chlorine 
atom), an alkyl group, an aryl group, a heterocyclic group, a carboxy 
group or salt thereof, a cyano group, a hydroxy group, an alkoxy group, an 
aryloxy group, a heterocyclic oxy group, an acyloxy group, an amino group, 
an alkylamino group, an arylamino group, a heterocyclic amino group, a 
hydroxyamino group, a saturated or unsaturated N-substituted 
nitrogen-containing heterocyclic group, an acylamino group, a sulfonamido 
group, an ureido group, a thioureido group, an imido group, a 
sulfamoylamino group, a quaternary ammonio group, a nitro group, a 
mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio 
group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group or 
salt thereof, or a sulfamoyl group, more preferably a chlorine atom, an 
alkyl group (especially a methyl group substituted with an amino group), 
an aryl group, an aryloxy group, an amino group, a mercapto group, an 
alkylthio group, an arylthio group or a heterocyclic thio group. 
R.sub.42 in formula (4) is preferably a hydrogen atom or a substituent 
substituted with a water-soluble group and having 1 to 15 carbon atoms in 
total, such as an alkyl group (especially a methyl group substituted with 
an amino group), an aryl group, an aryloxy group or an alkylthio group. 
The water-soluble group herein has the same meaning as the water-soluble 
group which the aliphatic group represented by R.sub.41 when R.sub.42 in 
formula (4) represents a hydrogen atom may have. The water-soluble group 
which the substituent represented by R.sub.42 may have is preferably a 
sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a 
hydroxy group, a mercapto group, an amino group, an ammonio group or a 
sulfonamido group. 
Among the pyrimidine derivatives represented by formula (4), most preferred 
are pyrimidine derivatives represented by the following formula (4-2): 
##STR10## 
In the above formula, R.sub.411 has the same meaning as R.sub.41 in formula 
(4). Preferred examples of the group represented by R.sub.411 also have 
the same meaning. 
R.sub.401 and R.sub.402 may be same or different, and each represents a 
hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, with 
the proviso that at least one of the substituents represented by R.sub.401 
and R.sub.402 contains at least one water-soluble group. The water-soluble 
group herein has the same meaning as the water-soluble group which the 
aliphatic group represented by R.sub.41 when R.sub.42 in formula (4) 
represents a hydrogen atom may have. The water-soluble group is preferably 
a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a 
hydroxy group or an amino group. 
R.sub.401 and R.sub.402 is preferably an alkyl group or an aryl group. When 
R.sub.401 and R.sub.402 each represents an alkyl group, the alkyl group is 
preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon 
atoms in total. The substituent of the substituted alkyl group is 
preferably a water-soluble group, especially preferably a sulfo group (or 
a salt thereof), a carboxy group (or a salt thereof), a hydroxy group or 
an amino group. When R.sub.401 and R.sub.402 each represents an aryl 
group, the aryl group is preferably a substituted or unsubstituted phenyl 
group having 6 to 8 carbon atoms in total. The substituent of the 
substituted phenyl group is preferably a water-soluble group, especially 
preferably a sulfo group (or a salt thereof), a carboxy group (or a salt 
thereof), a hydroxy group or an amino group. 
When R.sub.401 and R.sub.402 each represents an alkyl group or an aryl 
group, the substituents represented by R.sub.401 and R.sub.402 may bond to 
each other to form a ring structure. 
Specific examples of the compounds represented by formula (4) are set forth 
below, however, the compounds of the present invention are by no means 
limited thereto. 
##STR11## 
The compounds represented by formula (4) can be readily synthesized 
according to known methods described in already known literatures. 
Synthesis examples of the compounds represented by formula (4) are 
described below. 
1. Synthesis of Compound 4-I-1 
A mixture containing 28.8 g (0.2 mol) of 2,4-dimercaptopyrimidine, 17.9 g 
of 37% formalin aqueous solution, 18.2 ml (0.22 mol) of pyrrolidine and 
300 ml of ethanol was heated and refluxed for 3 hours to give a 
precipitate. The precipitate was filtered off, washed with 100 ml of 
methanol and air-dried to obtain 40 g of crude crystals. The crude 
crystals were dissolved in 200 ml of 1N NaOH and acidified with 3N HCl to 
obtain 28 g of Compound 4-I-1 (yield: 62%). 
2. Synthesis of Compound 4-I-2 
Compound 4-I-2 was synthesized in the same manner as in Synthesis of 
Compound 4-I-1, except for using N-methylglycine instead of pyrrolidine. 
3. Synthesis of Compound 4-I-3 
Compound 4-I-3 was synthesized in the same manner as in Synthesis of 
Compound 4-I-1, except for using N-phenylglycine instead of pyrrolidine. 
4. Synthesis of Compound 4-I-12 
Compound 4-I-12 was synthesized in the same manner as in Synthesis of 
Compound 4-I-3, except for using 2,4-dimercapto-6-methylpyrimidine instead 
of 2,4-dimercaptopyrimidine. 
The compound represented by formula (1-I), (1-II), (2-I), (3-I), (3-II) or 
(4) of the present invention is added to the developer preferably in an 
amount of from 0.01 to 10 mmol, more preferably from 0.1 to 5 mmol, per 
liter of the developer. 
The processing agents such as developer and fixing solution, and the 
processing method for use in the present invention are described below, 
however, the present invention is by no means limited to the following 
description and specific examples. 
In the development processing of the present invention, any known method 
may be used and known development processing solutions may be used. 
The developing agent used in the developer (the development initiating 
solution and the development replenisher are collectively called a 
developer, hereinafter the same) for use in the present invention is not 
particularly restricted, however, it preferably contains a 
dihydroxybenzene, an ascorbic acid derivative or a hydroquinone 
monosulfonate, and these may be used individually or in combination. 
Further, in view of developing capability, a combination of a 
dihydroxybenzene or an ascorbic acid derivative with a 
1-phenyl-3-pyrazolidone and a combination of a dihydroxybenzene or an 
ascorbic acid with a p-aminophenol are preferred. 
Examples of the dihydroxybenzene developing agent for use in the present 
invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone 
and methylhydroquinone, with hydroquinone being particularly preferred. 
Examples of the ascorbic acid derivative developing agent include an 
ascorbic acid, an isoascorbic acid and a salt thereof, and sodium 
erythorbate is particularly preferred in view of the cost for materials. 
An auxiliary developing agent is preferably used in the present invention. 
Examples of the 1-phenyl-3-pyrazolidone or a derivative thereof as the 
auxiliary developing agent for use in the present invention include 
1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. 
Examples of the p-aminophenol-base auxiliary developing agent for use in 
the present invention include N-methyl-p-aminophenol, p-aminophenol, 
N-(.beta.-hydroxyphenyl)-p-aminophenol and N-(4-hydroxyphenyl)glycine, 
with N-methyl-p-aminophenol being particularly preferred. 
The dihydroxybenzene-base developing agent is usually used preferably in an 
amount of from 0.05 to 0.8 mol/l. In the case when a dihydroxybenzene and 
a 1-phenyl-3-pyrazolidone or a p-aminophenol are used in combination, the 
former is preferably used in an amount of from 0.05 to 0.6 mol/l, more 
preferably from 0.23 to 0.5 mol/l, and the latter is preferably used in an 
amount of 0.06 mol/l or less, more preferably from 0.03 to 0.003 mol/l. 
The ascorbic acid derivative developing agent is usually used preferably in 
an amount of from 0.01 to 0.5 mol/l, more preferably from 0.05 to 0.3 
mol/l. In the case when an ascorbic acid derivative and a 
1-phenyl-3-pyrazolidone or a p-aminophenol are used in combination, the 
ascorbic acid is preferably used in an amount of from 0.01 to 0.5 mol/l, 
and the 1-phenyl-3-pyrazolidone or p-aminophenol is preferably used in an 
amount of from 0.005 to 0.2 mol/l. 
The developer for use in processing the photosensitive material of the 
present invention may contain additives (e.g., developing agent, alkali 
agent, pH buffer, preservative, chelating agent) which are commonly used. 
Specific examples thereof are described below, however, the present 
invention is by no means limited thereto. 
Examples of the buffer for use in the developer used in processing the 
photosensitive material of the present invention include a carbonate, a 
boric acid described in JP-A-62-186259, saccharides (e.g., saccarose) 
described in JP-A-60-93433, oximes (e.g., acetoxime), phenols (e.g., 
5-sulfosalicylic acid) and a tertiary phosphate (e.g., sodium salt, 
potassium salt), and a carbonate and a boric acid are preferably used. The 
buffer, particularly carbonate, is used preferably in an amount of 0.5 
mol/l or more, more preferably from 0.5 to 1.5 mol/l. 
Examples of the preservative for use in the present invention include 
sodium sulfite, potassium sulfite, lithium sulfite, ammonio sulfite, 
sodium bisulfite, potassium metabisulfite and sodium formaldehyde 
bisulfite. The sulfite is used in an amount of 0.2 mol/l or more, 
preferably 0.3 mol/l or more, however, if it is added in excess, silver 
stains are caused in the developer and therefore, the upper limit is 
preferably 1.2 mol/l. The sulfite is more preferably used in an amount of 
from 0.35 to 0.7 mol/l. 
As the preservative of the dihydroxybenzene-base developing agent, a small 
amount of an ascorbic acid derivative may be used in combination with the 
sulfite. In particular, sodium erythorbate is preferred in view of the 
cost for materials. The addition amount thereof is, in terms of a molar 
ratio to the dihydroxybenzene-base developing agent, preferably from 0.03 
to 0.12, more preferably from 0.05 to 0.10. In the case where an ascorbic 
acid derivative is used as the preservative, the developer preferably 
contains no boron compound. 
Examples of additives other than those described above include a 
development inhibitor such as sodium bromide and potassium bromide; an 
organic solvent such as ethylene glycol, diethylene glycol, triethylene 
glycol and dimethylformamide; a development accelerator such as 
alkanolamine (e.g., diethanolamine, triethanolamine), imidazole and a 
derivative thereof, and a physical development unevenness inhibitor such 
as heterocyclic mercapto compound (e.g., sodium 
3-(5-mercaptotetrazol-1-yl)benzenesulfonate, 1-phenyl-5-mercaptotetrazole) 
and the compounds described in JP-A-62-212651. 
Further, the developer may contain an antifoggant or a black pepper 
inhibitor such as a mercapto-base compound, an indazole-base compound, a 
benzotriazole-base compound and a benzimidazole-base compound. Specific 
examples thereof include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 
1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 
5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 
5-nitrobenzotriazole, sodium 
4-((2-mercapto-1,3,4-thiadiazol-2-yl)thio)butanesulfonate, 
5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 
5-methylbenzotriazole and 2-mercaptobenzotriazole. These additives are 
each usually used in an amount of from 0.01 to 10 mmol, preferably from 
0.1 to 2 mmol, per liter of the developer. 
The developer of the present invention can further use various organic or 
inorganic chelating agents individually or in combination. 
Examples of the inorganic chelating agent include sodium tetrapolyphosphate 
and sodium hexametaphosphate. 
Examples of the organic chelating agent which is predominantly used, 
include an organic carboxylic acid, an aminopolycarboxylic acid, an 
organic phosphonic acid, an aminophosphonic acid and an organic 
phosphonocarboxylic acid. 
Examples of the organic carboxylic acid include an acrylic acid, an oxalic 
acid, a malonic acid, a succinic acid, a glutaric acid, a gluconic acid, 
an adipic acid, a pimelic acid, an azelaic acid, a sebacic acid, a 
nonanedicarboxylic acid, a decanedicarboxylic acid, an 
undecanedicarboxylic acid, a maleic acid, an itaconic acid, a malic acid, 
a citric acid and a tartaric acid. 
Examples of the aminopolycarboxylic acid include di(carboxymethyl)aspartic 
acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, 
ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic 
acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, 
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 
1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic 
acid, and the compounds described in JP-A-52-25632, JP-A-55-67747, 
JP-A-57-102624 and JP-B-53-40900. 
Examples of the organic phosphonic acid include hydroxyalkylidene 
diphosphonic acid described in U.S. Pat. Nos. 3,214,454 and 3,794,591 and 
German Patent Application (OLS) No. 2,227,396, and the compounds described 
in Research Disclosure, Vol. 181, Item 18170 (May 1979). 
Examples of the aminophosphonic acid include aminotris(methylenephosphonic 
acid), ethylenediaminetetramethylenephosphonic acid, 
aminotrimethylenephosphonic acid, and the compounds described in Research 
Disclosure (supra), No. 18170, JP-A-57-208554, JP-A-54-61125, 
JP-A-55-29883 and JP-A-56-97347. 
Examples of the organic phosphonocarboxylic acid include the compounds 
described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-4024, 
JP-A-55-4025, JP-A-55-126241, JP-A-55-65955, JP-A-55-65956 and Research 
Disclosure (supra), No. 18170. 
The organic and/or inorganic chelating agents are not limited to those 
described above. Further, they may be used in the form of an alkali metal 
salt or an ammonio salt. The chelating agent is preferably added in an 
amount of from 1.times.10.sup.-4 to 1.times.10-.sup.1 mol, more preferably 
from 1.times.10.sup.-3 to 1.times.10.sup.-2 mol, per liter of the 
developer. 
The compounds of the present invention as a silver stain inhibitor may be 
used individually or may be used in combination with a compound described 
in JP-B-56-24347, JP-B-56-46585, JP-B-62-2849 and JP-A-4-362942 or a 
polyoxyalkyl phosphate described in U.S. Pat. No. 5,457,011. The silver 
stain inhibitor is added in an amount of preferably from 0.05 to 10 mmol, 
more preferably from 0.1 to 5 mmol, per liter of the developer. 
Further, the developer may use the compound described in JP-A-62-212651 as 
an uneven development inhibitor and the compound described in 
JP-A-61-267759 as a dissolution aid. 
The developer may also contain a color toner, a surface active agent, a 
defoaming agent and a hardening agent, if desired. 
The developer preferably has a pH of from 9.0 to 12.0, more preferably from 
9.5 to 11.0, particularly preferably from 9.5 to 10.7. The pH of the 
development replenisher and the pH of the developer in a developer tank in 
continuous processing are also in the same range as described above. The 
alkali agent used for adjusting the pH may be a usual water-soluble 
inorganic alkali metal salt (e.g., sodium hydroxide, potassium hydroxide, 
sodium carbonate, potassium carbonate). 
The replenishing amount of the developer is 390 ml or less, preferably from 
30 to 325 ml, most preferably from 120 to 180 ml, per 1 m.sup.2 of the 
photosensitive material. The development replenisher may have the same 
composition and/or concentration as the development initiating solution or 
may have a composition and/or a concentration different from the 
initiating solution. 
Examples of the fixing agent in the fixing processing agent for use in the 
present invention includes ammonio thiosulfate, sodium thiosulfate and 
ammonio sodium thiosulfate. The use amount of the fixing agent may be 
varied appropriately, however, it is generally from about 0.7 to about 3.0 
mol/l. 
The fixing solution for use in the present invention may contain a 
water-soluble aluminum salt or a water-soluble chromium salt which acts as 
a hardening agent, and of these, a water-soluble aluminum salt is 
preferred. Examples thereof include aluminum chloride, aluminum sulfate, 
potassium alum, ammonio aluminum sulfate, aluminum nitrate and aluminum 
lactate. These are each preferably contained, in terms of an aluminum ion 
concentration in the solution used, in an amount of from 0.01 to 0.15 
mol/l. 
When the fixing solution is stored as a concentrated solution or a solid 
agent, it may be constituted by a plurality of portions preparing a 
hardening agent or the like as a separate portion or may be constituted as 
a one-part agent containing all components. 
The fixing processing agent may contain, if desired, a preservative (e.g., 
sulfite, bisulfite, metabisulfite, in an amount of 0.015 mol/l or more, 
preferably from 0.02 to 0.3 mol/l), a pH buffer (e.g., acetic acid, sodium 
acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, 
succinic acid, adipic acid, in an amount of from 0.1 to 1 mol/l, 
preferably from 0.2 to 0.7 mol/l), or a compound having aluminum 
stabilizing ability or hard water softening ability (e.g., gluconic acid, 
iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic 
acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, 
benzoic acid, salicylic acid, tylon, ascorbic acid, glutaric acid, 
aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, 
nitrilotriacetic acid, a derivative and a salt thereof, saccharides, boric 
acid, in an amount of from 0.001 to 0.5 mol/l, preferably from 0.005 to 
0.3 mol/l). 
0058! 
In addition, the developer may contain a compound described in 
JP-A-62-78551, a pH adjusting agent (e.g., sodium hydroxide, ammonia, 
sulfuric acid), a surface active agent, a wetting agent or a fixing 
accelerator. Examples of the surface active agent include anionic surface 
active agents such as sulfated product and sulfonated product, 
polyethylene-base surface active agents, and amphoteric surface active 
agents described in JP-A-57-6840. A known defoaming agent may also be 
used. Examples of the wetting agent include alkanolamine and alkylene 
glycol. Examples of the fixing accelerator include alkyl- or 
aryl-substituted thiosulfonic acids and salts thereof described in 
JP-A-6-308681, thiourea derivatives described in JP-B-45-35754, 
JP-B-58-122535 and JP-B-58-122536, alcohols having a triple bond within a 
molecule, thioether compounds described in U.S. Pat. No. 4,126,459, 
mercapto compounds described in JP-A-1-4739, JP-A-1-159645 and 
JP-A-3-101728, meso-ionic compounds described in JP-A-4-170539 and 
thiocyanates. 
The fixing solution for use in the present invention has a pH of 4.0 or 
more, preferably from 4.5 to 6.0, and more preferably from 4.7 to 5.0. 
The replenishing amount of the fixing solution is 500 ml or less, 
preferably 390 ml or less, more preferably from 80 to 320 ml, per 1 
m.sup.2 of the photosensitive material. The replenisher may have the same 
composition and/or concentration as the initiating solution or may have a 
composition and/or a concentration different from the initiating solution. 
The fixing solution may be reused using a known fixing solution 
regeneration method such as electrolytic silver recovery. Examples of the 
regeneration apparatus include Reclaim R-60 manufactured by Fuji Hunt 
Electronics Technology Co., Ltd. 
When the developer or the fixing processing solution for use in the present 
invention is stored in the liquid form, it is preferably stored in a 
packaging material having a low oxygen permeability described, for 
example, in JP-A-61-73147. And, when these solutions each is supplied as a 
concentrated solution, it is diluted with water to have a predetermined 
concentration on use and the water for dilution is used in an amount of 
from 0.2 to 3 parts per 1 part of the concentrated solution. 
When the development processing agent or the fixing processing agent for 
use in the present invention is used as a solid, the same effects as 
provided by the liquid agent can be obtained. The solid processing agent 
is described below. 
The solid processing agent for use in the present invention may be used in 
a known shape (e.g., powder, grain, granule, lump, tablet, compactor, 
briquette, plate, cracked product, stick, paste). The solid agent may be 
prepared by coating respective components with a water-soluble coating 
agent or coating film so as to separate components which react with each 
other on contacting or may have a plural layer structure so as to separate 
components which react with each other. These techniques may also be used 
in combination. 
The coating may be performed using a known compound and polyvinyl 
pyrrolidone, polyethylene glycol, sulfonated polystyrene and a vinyl-base 
compound are preferred. In addition, gelatin, pectin, polyacrylic acid, 
polyvinyl alcohol, vinyl acetate copolymer, polyethylene oxide, sodium 
carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl 
cellulose, alginic acid, xanthane gum, gum arabic, tragacanth gum, 
carrageenan, methyl vinyl ether, maleic anhydride copolymer, a 
polyoxyethylene alkyl ether such as polyoxyethylene stearyl ether and 
polyoxyethylene ethyl ether, a polyoxyethylene alkylphenol ether such as 
polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, 
or a water-soluble binder described in EP 469,877A may be used 
individually or in combination of two or more thereof. These each may also 
be used as a granulating aid. 
In the case of a plural layer structure, a component which does not react 
on contacting may be interposed between components which react with each 
other and the layer structure may be processed into a tablet or a 
briquette. Or, components in a known shape may also be constituted into 
the same layer structure and then packaged. These methods are described, 
for example, in JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, 
JP-A-4-78848 and JP-A-5-93991. 
The solid processing agent has a bulk density of preferably from 0.5 to 6.0 
g/cm.sup.3, particularly in the case of a tablet, it is preferably from 
1.0 to 5.0 g/cm.sup.3 and in the case of a granule, from 0.5 to 1.5 
g/cm.sup.3. 
The solid processing agent for use in the present invention may be prepared 
by any known method. For example, the packaging method is described in 
JP-A-61-259921, JP-A-4-16841 and JP-A-4-78848 and the compression method 
is described in JP-A-4-85533, JP-A-4-85534, JP-A-4-85535, JP-A-5-134362, 
JP-A-5-197070, JP-A-5-204098, JP-A-5-224361, JP-A-6-138604 and 
JP-A-6-138605. 
More specifically, a rolling granulation method, an extrusion granulation 
method, a compressive granulation method, a cracking granulation method, 
an agitating granulation method, a spray dry method, a dissolving 
coagulation method, a briquetting method or a roller compacting method may 
be used. 
The grain size and the shape of the granulated product suitable for the 
present invention vary depending on the characteristics desired, however, 
in general, taking account of solubility of the photographic processing 
agent requested and the residual powder amount in the waste package after 
preparation of the solution or durability against rupture of the 
granulated product due to vibration upon transportation, in the case of 
granule, the sphere conversion grain size is approximately from 0.5 to 50 
mm, preferably approximately from 1 to 15 mm, and the shape is a 
cylindrical, sphere, cubic or rectangular parallelopiped form, preferably 
a spherical or cylindrical form. 
The solid processing agent prepared by a roller compacting process may be 
cracked and further may be sieved to have a size of approximately from 2 
mm to 1 cm. 
In the case of a briquette or a tablet, the grain size and the shape 
similarly vary depending on the characteristics desired, however, the size 
is preferably on the order of from 2 mm to 5 cm, and the shape is 
preferably a cylindrical, spherical, cubic or rectangular parallelopiped 
form, more preferably a spherical or cylindrical form. When improvement in 
the solubility is desired, a platy form reduced in the thickness or 
further reduced in the thickness in the central portion, or a hollow 
doughnut form is useful. On the contrary, the size or the thickness may 
further be increased so as to perform dissolution gradually. Thus, the 
size and the shape can be selected as needed. In order to control the 
solubility, the surface condition (e.g., smooth, porous) may be changed. 
It is also possible to impart different solubilities to a plurality of 
granulated products or to have a plurality of shapes so as to harmonize 
the solubility of materials different in the solubility. Further, a 
granulated product comprising a plurality of layers different in the 
composition between the surface and the inside may be used. 
The packaging material for the solid processing agent is preferably a 
material having low permeability to oxygen and water. The shape of the 
packaging material may be a known form such as a bag, a cylinder or a box. 
Further, a shape capable of folding as disclosed in JP-A-6-242585 to 
JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-7-5664, JP-A-7-5666 to 
JP-A-7-5669 is also preferred so as to save the space for storing waste 
packaging materials. The packaging material may be fixed at the takeout 
port for the processing agent by a screw cap, a pull-top or an aluminum 
seal or may be heat sealed, and in addition, a known means may be used, 
however, the present invention is by no means limited thereto. The waste 
packaging material is preferably recycled or reused in view of 
environmental conservation. 
The method for dissolving or replenishing the solid processing agent of the 
present invention is not particularly restricted and known methods may be 
used. Examples of the method include a method of dissolving a constant 
amount of solid processing agent in a dissolving apparatus having an 
agitation function and replenishing it, a method of dissolving a solid 
processing agent in a dissolving apparatus having a dissolving portion and 
a portion for stocking the finished solution and replenishing the solution 
from the stock portion as described in Japanese Patent Application No. 
Hei. 7-235499, a method of charging a processing agent into a circulation 
system of an automatic developing machine and dissolving and replenishing 
it in the system as described in JP-A-5-119454, JP-A-6-19102 and 
JP-A-7-261357, and a method of charging and dissolving a processing agent 
according to the processing of a photosensitive material in an automatic 
developing machine containing a dissolution tank. Other than these, any 
known method may be used. The charging of the processing agent may be 
performed by manually unsealing the package and charging the processing 
agent or by means of automatic unsealing and automatic charging in a 
dissolving apparatus or automatic developing machine having an unsealing 
mechanism as described in Japanese Patent Application No. Hei. 7-235498. 
In view of working environment, the latter is preferred. Specific examples 
of the method include a method of bursting, peeling off, cutting out or 
pushing away the takeout port and methods described in JP-A-6-19102 and 
JP-A-6-95331. 
The photosensitive material processed through development and fixing is 
then subjected to water washing or stabilization (hereinafter, unless 
otherwise specified, water washing includes stabilization and the solution 
for use therein is called water or washing water). The water for use in 
water washing may be tap water, ion exchanged water, distilled water or a 
stabilizing solution. The replenishing amount of the washing water is 
generally from about 8 l to about 17 l per m.sup.2 of the photosensitive 
material, however, a replenishing amount lower than the above-described 
range may also be used. In particular, when the replenishing amount is 3 l 
or less (including 0, namely, standing water washing), not only processing 
with water saving can be performed but also the processing can dispense 
with piping for installation of an automatic developing machine. When 
water washing is performed with a small replenishing amount of water, a 
rinsing tank such as squeeze roller or cross-over roller described in 
JP-A-63-18350 and JP-A-62-287252 is preferably provided. Or, addition of 
various oxidizing agents (e.g., ozone, hydrogen peroxide, sodium 
hypochloride, active halogen, chlorine dioxide, sodium carbonate hydrogen 
peroxide salt) or filter filtration may be combined so as to reduce the 
pollution load which is a problem encountered in water washing with a 
small amount of water or for preventing water scale. 
As a method for reducing the replenishing amount of washing water, a 
multi-stage countercurrent system (for example, two stages or three 
stages) has been known from of old, and the replenishing amount of washing 
water is preferably from 50 to 200 ml per m.sup.2 of the photosensitive 
material. This effect can be also obtained similarly in the case of an 
independent multi-stage system (a method of not using a countercurrent 
system but supplying a new solution individually to the multi-stage water 
washing tanks). 
In the method of the present invention, a means for preventing water scale 
may be provided in the water washing step. The water scale preventing 
means is not particularly restricted and a known means may be used. 
Examples thereof include a method of adding a fungicide (so-called water 
scale inhibitor), a method of applying electricity, a method of 
irradiating ultraviolet rays, infrared rays or far infrared rays, a method 
of applying magnetic field, a method of performing ultrasonic wave 
treatment, a method of applying heat, and a method of evacuating the tank 
on standing. The water scale preventing means may be performed according 
to the processing of the photosensitive material, may be performed at a 
predetermined interval irrespective of the use state, or may be performed 
only in the period of non-processing time such as night time. Or, the 
washing water may be previously treated with a water scale preventing 
means and then replenished. Also, in view of preventing generation of 
resistance microbes, it is preferred to perform different water scale 
preventing means every a predetermined period. 
The fungicide is not particularly restricted and a known fungicide may be 
used. Examples thereof include, in addition to the above-described 
oxidizing agents, glutaraldehyde, a chelating agent such as 
aminopolycarboxylic acid, a cationic surface active agent and 
mercaptopyridine oxide (e.g., 2-mercaptopyridine-N-oxide), and a sole 
fungicide may be used or a plurality of fungicides may be used in 
combination. 
The electricity may be applied according to the method described in 
JP-A-3-224685, JP-A-3-224687, JP-A-4-16280 or JP-A-4-18980. 
A known water-soluble surface active agent or defoaming agent may be added 
so as to prevent uneven processing due to bubbling or to prevent transfer 
of stains. Further, a dye adsorbent described in JP-A-63-163456 may be 
provided in the water washing system so as to prevent stains due to a dye 
dissolved out from the photosensitive material. 
The overflow solution from water washing step may be partly or wholly used 
by mixing it with the processing solution having fixing ability as 
described in JP-A-60-235133. It is also preferred in view of conservation 
of natural environment to reduce the biochemical oxygen demand (BOD), 
chemical oxygen demand (COD) or iodine consumption before discharge by 
subjecting the solution to microorganism treatment (a treatment with a 
filter comprising a porous carrier such as activated carbon or ceramic, 
having carried thereon sulfur oxidation bacteria, activated sludge process 
or microorganisms) or oxidation treatment by electrification or with an 
oxidizing agent, or to reduce silver concentration in waste water by 
passing the solution through a filter using a polymer having affinity for 
silver or by adding a compound which forms a sparingly soluble silver 
complex, such as trimercaptotriazine to precipitate silver and then 
passing the solution through a filter. 
In some cases, stabilization may be performed subsequent to the water 
washing and as one example, a bath containing the compound described in 
JP-A-2-201357, JP-A-2-132435, JP-A-1-102553 and JP-A-46-44446 may be used 
as a final bath of the photosensitive material. This stabilization bath 
may also contain, if desired, an ammonium compound, a metal compound such 
as Bi or Al, a fluorescent brightening agent, various chelating agents, a 
layer pH adjusting agent, a layer hardening agent, a bactericide, a 
fungicide, an alkanolamine or a surface active agent. 
The additives and the stabilizing agents, such as a fungicide, added to the 
water washing or stabilization bath may be formed into a solid agent 
similarly to the above-described development and fixing processing agents. 
Waste water of the developer, the fixing solution, the washing water or the 
stabilizing solution for use in the present invention is preferably burned 
for disposal. The waste water may also be formed into a concentrated 
solution or a solid by a concentration apparatus as described, for 
example, in JP-B-7-83867 and U.S. Pat. No. 5,439,560 and then disposed. 
In the case when the replenishing amount of the processing agent is 
reduced, it is preferred to prevent evaporation or air oxidation of the 
solution by reducing the contact area of the processing tank with air. A 
roller transportation-type automatic developing machine is described in 
U.S. Pat. Nos. 3,025,779 and 3,545,971, and in the present invention, it 
is referred to simply as a roller transportation-type automatic processor. 
This automatic processor comprises four steps of development, fixing, 
water washing and drying, and it is most preferred to follow this 
four-step processing also in the present invention, though other steps 
(e.g., stopping step) are not excluded. Further, a rinsing bath may be 
provided between development and fixing and/or between fixing and water 
washing. 
In the development of the present invention, the dry-to-dry time is 
preferably from 25 to 160 seconds, the development time and the fixing 
time each is 40 seconds or less, preferably from 6 to 35 seconds, and the 
temperature of each solution is preferably from 25.degree. to 50.degree. 
C., more preferably from 30.degree. to 40.degree. C. The temperature and 
the time of water washing are preferably from 0.degree. to 50.degree. C. 
and 40 seconds or less, respectively. According to the method of the 
present invention, the photosensitive material after development, fixing 
and water washing may be passed through squeeze rollers for squeezing 
washing water and then dried. The drying is performed at a temperature of 
from about 40.degree. C. to about 100.degree. C. The drying time may be 
appropriately varied depending upon the ambient condition. The drying 
method is not particularly restricted and any of known methods may be 
used, however, hot air drying, drying by a heat roller as disclosed in 
JP-A-4-15534, JP-A-5-2256 and JP-A-5-289294, and drying by far infrared 
rays may be used, and a plurality of drying methods may be used in 
combination. 
In the silver halide emulsion for use in the photosensitive material of the 
present invention, the silver halide may be any commonly used in the 
silver halide emulsion, such as silver bromide, silver iodobromide, silver 
chloride, silver chlorobromide and silver chloroiodobromide, and it is 
preferably, for the negative silver halide emulsion, silver chlorobromide 
having a silver chloride content of 60 mol % or more, and for the positive 
silver halide emulsion, silver chlorobromide, silver bromide or silver 
iodobromide each having a silver bromide content of 60 mol % or more. The 
silver halide grain may be obtained by any of an acid process, a neutral 
process and an ammonia process. The silver halide grain may be either a 
grain having a uniform silver halide composition distribution within the 
grain or a core/shell grain different in the silver halide composition 
between the inside and the surface layer of the grain. Further, the silver 
halide grain may be either a grain where a latent image is formed mainly 
on the surface or a grain where the latent image is formed mainly in the 
inside of the grain. The surface of the grain may be previously fogged. 
The silver halide grain for use in the present invention may have any 
shape. One preferred example is a cubic form having a crystal surface of 
{100} face. Further, a grain having an octahedral, tetradecahedral or 
dodecahedral form may be prepared according to the methods described in 
U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, J. 
Photogr. Sci., 21-39 (1973), and used. Furthermore, a grain having a twin 
plane may be used. The silver halide grains for use in the present 
invention may have a uniform form or a mixture of grains having various 
shapes may be used. In the present invention, a monodisperse emulsion is 
preferred. In the monodisperse silver halide grains in the monodisperse 
emulsion, the weight of silver halide grains having a grain size of an 
average grain size .gamma..+-.10% preferably accounts for 60% or more of 
the weight of all silver halide grains. 
The silver halide emulsion for use in the present invention is not 
particularly limited on the halogen composition, however, in order to 
achieve the objects of the present invention more effectively, silver 
chloride, silver chlorobromide and silver chloroiodobromide each having a 
silver chloride content of 50 mol % or more are preferred. The silver 
iodide content is preferably less than 5 mol %, more preferably less than 
2 mol %. 
In the present invention, a photosensitive material suitable for high 
illuminance exposure such as scanner exposure or a photosensitive material 
for line work photographing contains a rhodium compound so as to achieve 
high contrast and low fog. 
A water-soluble rhodium compound may be used as the rhodium compound for 
use in the present invention. Examples thereof include rhodium(III) 
halogenide compounds and rhodium complex salts having a halogen, an amine 
or an oxalate as a ligand, such as hexachlororhodium(III) complex salt, 
hexabromorhodium(III) complex salt, hexaaminerhodium(III) complex salt and 
trioxalaterhodium(III) complex salt. The rhodium compound is dissolved in 
water or an appropriate solvent before use, however, a method commonly 
well used for stabilizing the rhodium compound solution, that is, a method 
of adding an aqueous solution of hydrogen halogenide (e.g., hydrochloric 
acid, bromic acid, fluoric acid) or halogenated alkali (e.g., KCl, NaCl, 
KBr, NaBr) may be used. In place of using water-soluble rhodium, separate 
silver halide grains previously doped with rhodium may be added and 
dissolved at the time of preparation of silver halide. 
The amount of the rhodium compound added is from 1.times.10.sup.-8 to 
5.times.10.sup.-6 mol, preferably from 5.times.10.sup.-8 to 
1.times.10.sup.-6, per mol of silver in the silver halide emulsion. 
The rhodium compound may be appropriately added at the time of production 
of silver halide emulsion grains or at respective stages before coating of 
the emulsion, however, it is preferably added at the time of formation of 
the emulsion and integrated into the silver halide grain. 
The photographic emulsion for use in the present invention can be prepared 
according to the methods described in P. Glafkides, Chimie et Physique 
Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion 
Chemistry, The Focal Press (1966), and V. L. Zelikman et al, Making and 
Coating Photographic Emulsion, The Focal Press (1964). 
A soluble silver salt and a soluble halogen salt may be reacted by any of a 
single jet method, a double jet method and a combination thereof. 
A method of forming grains in the presence of excessive silver ions 
(so-called reverse mixing method) may also be used. Further, a method of 
maintaining constant the pAg in the liquid phase where the silver halide 
is formed, a so-called controlled double jet method as one form of the 
double jet method, may be used. The grains are preferably formed using a 
so-called silver halide solvent such as ammonia, thioether or 
tetra-substituted thiourea. The tetra-substituted thiourea compound is 
more preferred and this is described in JP-A-53-82408 and JP-A-55-77737. 
Preferred examples of the thiourea compound include tetramethylthiourea 
and 1,3-dimethyl-2-imidazolidinethione. 
In the controlled double jet method and the grain formation method using a 
silver halide solvent, a silver halide emulsion having a regular crystal 
form and a narrow grain size distribution can be easily prepared, and 
these are a useful means for preparing a silver halide emulsion for use in 
the present invention. 
The silver halide for use in the present invention is not particularly 
limited on the shape of grain and any of cubic, octahedral and spherical 
silver halide grains and in addition, tabular silver halide grains having 
a high aspect ratio described in Research Disclosure, 22534 (January 
1983), may be used. 
In order to achieve a uniform grain size, it is preferred to rapidly grow 
grains within the range of not exceeding the critical saturation degree, 
using a method of changing the addition rate of silver nitrate or 
halogenated alkali according to the grain growth rate as described in 
British Patent 1,535,016, JP-B-48-36890 and JP-B-52-16364, or a method of 
changing the concentration of the aqueous solution as described in British 
Patent 4,242,445 and JP-A-55-158124. 
The emulsion of the present invention is preferably a monodisperse emulsion 
having a coefficient of variation of 20% or less, more preferably 15% or 
less. 
The grains in the monodisperse silver halide emulsion have an average grain 
size of 0.5 .mu.m or less, more preferably from 0.1 to 0.4 .mu.m. 
The silver halide emulsion of the present invention is preferably subjected 
to chemical sensitization. The chemical sensitization may be performed 
using a known method such as sulfur sensitization, selenium sensitization, 
tellurium sensitization or noble metal sensitization, and these 
sensitization methods may be used individually or in combination. When 
these sensitization methods are used in combination, a combination of 
sulfur sensitization and gold sensitization, a combination of sulfur 
sensitization, selenium sensitization and gold sensitization, and a 
combination of sulfur sensitization, tellurium sensitization and gold 
sensitization are preferred. 
The sulfur sensitization for use in the present invention is usually 
performed by adding a sulfur sensitizer and stirring the emulsion at a 
high temperature of 40.degree. C. or higher for a predetermined time. The 
sulfur sensitizer may be a known compound and examples thereof include, in 
addition to the sulfur compound contained in gelatin, various sulfur 
compounds such as thiosulfates, thioureas, thiazoles and rhodanines. 
Preferred sulfur compounds are a thiosulfate and a thiourea compound. The 
addition amount of the sulfur sensitizer varies depending upon various 
conditions such as the pH and the temperature at the time of chemical 
ripening and the size of silver halide grains, however, it is generally 
from 10.sup.-7 to 10.sup.-2 mol, preferably from 10.sup.-5 to 10.sup.-3 
mol, per mol of silver halide. 
Examples of the sulfur sensitizer include, in addition to the sulfur 
compound contained in gelatin, various sulfur compounds such as 
thiosulfates, thioureas, thiazoles and rhodanines. Specific examples 
thereof include those described in U.S. Pat. Nos. 1,574,944, 2,278,947, 
2,410,689, 2,728,668, 3,501,313 and 3,656,955. Preferred sulfur compounds 
are a thiosulfate and a thiourea compound. The pAg at the chemical 
sensitization is preferably 8.3 or less, more preferably from 7.3 to 8.0. 
Further, good results may be obtained also by a method of using 
polyvinylpyrrolidone and a thiosulfate in combination as reported in 
Moisar, Klein Gelationc. Proc. Symp. 2nd, 301-309 (1970). 
The selenium sensitizer for use in the present invention may be a known 
selenium compound. The selenium sensitization is usually performed by 
adding a labile and/or non-labile selenium compound and stirring the 
emulsion at a high temperature of 40.degree. C. or higher for a 
predetermined time. Examples of the labile selenium compound include the 
compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-4-109240 and 
JP-A-4-324855, and among these, particularly preferred are the compounds 
represented by formulae (VIII) and (IX) of JP-A-4-324855. 
The tellurium sensitizer for use in the present invention is a compound of 
forming silver telluride presumed to be a sensitization speck, on the 
surface or in the inside of a silver halide grain. The formation rate of 
silver telluride in a silver halide emulsion can be examined by a method 
described in JP-A-5-313284. 
Specific examples of the tellurium sensitizer include the compounds 
described in U.S. Pat. Nos. 1,623,499, 3,320,069 and 3,772,031, British 
Patents 235,211, 1,121,496, 1,295,462 and 1,396,696, Canadian Patent 
800,958, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043, JP-A-5-303157, J. 
Chem. Soc. Chem. Commun., 635 (1980), ibid., 1102 (1979), ibid., 645 
(1979), J. Chem. Soc. Perkin. Trans., 1, 2191 (1980), S. Patai (compiler), 
The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1 (1986), 
and ibid., Vol. 2 (1987). The compounds represented by formulae (II), 
(III) and (IV) of JP-A-5-313284 are particularly preferred. 
The use amount of the selenium sensitizer or the tellurium sensitizer for 
use in the present invention varies depending upon silver halide grains 
used or chemical ripening conditions, however, it is generally on the 
order of from 10.sup.-8 to 10.sup.-2 mol, preferably from 10.sup.-7 to 
10.sup.-3 mol, per mol of silver halide. The conditions for chemical 
sensitization in the present invention are not particularly restricted, 
however, the pH is from 5 to 8, the pAg is from 6 to 11, preferably from 7 
to 10, and the, temperature is from 40.degree. to 95.degree. C., 
preferably from 45.degree. to 85.degree. C. 
Examples of the noble metal sensitizer for use in the present invention 
include gold, platinum, palladium and iridium, and gold sensitization is 
particularly preferred. Specific examples of the gold sensitizer for use 
in the present invention include chloroauric acid, potassium chlorate, 
potassium aurithiocyanate and gold sulfide, and the gold sensitizer is 
used in an amount of approximately from 10.sup.-7 to 10.sup.-2 mol per mol 
of silver halide. 
In the silver halide emulsion for use in the present invention, a cadmium 
salt, a sulfite, a lead salt or a thallium salt may be present together 
during formation or physical ripening of silver halide grains. 
In the present invention, reduction sensitization may be used. Examples of 
the reduction sensitizer which can be used include stannous salt, amines, 
formamidinesulfinic acid and silane compounds. 
To the silver halide emulsion of the present invention, a thiosulfonic acid 
compound may be added according to the method described in European 
Unexamined Patent Publication (EP) 293917. 
In the photosensitive material for use in the present invention, one kind 
of silver halide emulsion may be used or two or more kinds of silver 
halide emulsions (for example, different in the average grain size, 
different in the halogen composition, different in the crystal habit, or 
different in chemical sensitization conditions) may be used in 
combination. 
In the present invention, the silver halide emulsion particularly suitable 
for a dot-to-dot work photosensitive material comprises silver halide 
having a silver chloride content of 90 mol % or more, preferably 95 mol % 
or more, more specifically, silver chlorobromide or silver 
chloroiodobromide containing from 0 to 10 mol % of silver bromide. If the 
proportion of silver bromide or silver iodide increases, the safelight 
safety in a bright room may be worsened or the .gamma. value may be 
disadvantageously lowered. 
The silver halide emulsion for use in the dot-to-dot work photosensitive 
material of the present invention preferably contains a transition metal 
complex and examples of the transition metal include Rh, Ru, Re, Os, Ir 
and Cr. 
Examples of the ligand include a nitrosyl cross-linked ligand, a 
thionitrosyl cross-linked ligand, a halide ligand (e.g., fluoride, 
chloride, bromide, iodide), a cyanide ligand, a cyanate ligand, a 
thiocyanate ligand, a selenocyanate ligand, a tellurocyanate ligand, an 
acid ligand and an aquo ligand. When an aquo ligand is present, it 
preferably occupies one or more of the ligands. 
More specifically, the rhodium atom may be incorporated by forming it into 
a metal salt in any form, such as a single salt or a complex salt, and 
adding the salt at the time of preparation of grains. 
Examples of the rhodium salt include rhodium mono-chloride, rhodium 
dichloride, rhodium trichloride and ammonium hexachlororhodate, and 
preferred are a halogen complex compound of water-soluble trivalent 
rhodium, such as hexachlororhodium(III) acid and a salt thereof (e.g., 
ammonium salt, sodium salt, potassium salt). 
The addition amount of the water-soluble rhodate is from 
1.0.times.10.sup.-6 to 1.0.times.10.sup.-3, preferably 1.0.times.10.sup.-5 
to 1.0.times.10.sup.-3, more preferably from 5.0.times.10.sup.-5 to 
5.0.times.10.sup.-4 mol, per mol of silver halide. 
The following transition metal complexes are also preferred. 
1. Ru(NO)Cl.sub.5 !.sup.-2 
2. Ru(NO).sub.2 Cl.sub.4 !.sup.-1 
3. Ru(NO)(H.sub.2 O)Cl.sub.4 !.sup.-1 
4. Rh(NO)CN.sub.5 !.sup.-2 
5. Re(NO)CN.sub.5 !.sup.-2 
6. Re(NO)ClCN.sub.4 !.sup.-2 
7. Rh(NO).sub.2 Cl.sub.4 !.sup.-1 
8. Rh(NO)(H.sub.2 O)Cl.sub.4 !.sup.-1 
9. Ru(NO)CN.sub.5 !.sup.-2 
10. Ru(NO)Br.sub.5 !.sup.-2 
11. Rh(NS)Cl.sub.5 !.sup.-2 
12. Os(NO)Cl.sub.5 !.sup.-2 
13. Cr(NO)Cl.sub.5 !.sup.-3 
14. Re(NO)Cl.sub.5 !.sup.-1 
15. Os(NS)Cl.sub.4 (TeCN)!.sup.-2 
16. Ru(NS)I.sub.5 !.sup.-2 
17. Re(NS)Cl.sub.4 (SeCN)!.sup.-2 
18. Os(NS)Cl(SCN).sub.4 !.sup.-2 
19. Ir(NO)Cl.sub.5 !.sup.-2 
The spectral sensitizing dye for use in the present invention is not 
particularly restricted. 
The addition amount of the sensitizing dye for use in the present invention 
varies depending upon the shape or size of silver halide grains, however, 
it is generally from 4.times.10.sup.-6 to 8.times.10.sup.-3 mol per mol of 
silver halide. For example, when the silver halide grain size is from 0.2 
to 1.3 .mu.m, the addition amount is preferably from 2.times.10.sup.-7 to 
3.5.times.10.sup.-6 mol, more preferably from 6.5.times.10.sup.-7 to 
2.0.times.10.sup.-6 mol, per 1 m.sup.2 of the surface area of silver 
halide grains. 
0099! 
The photosensitive silver halide emulsion of the present invention may be 
spectrally sensitized by a sensitizing dye to blue light, green light, red 
light or infrared light, each having a relatively long wavelength. 
Examples of the sensitizing dye which can be used include a cyanine dye, a 
merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a 
holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye and 
a hemioxonol dye. 
Useful sensitizing dyes for use in the present invention are described, for 
example, in Research Disclosure, Item 17643, IV-A, page 23 (December 
1978), ibid., Item 18341-X, page 437 (August 1979), U.S. Pat. Nos. 
4,425,425 and 4,425,426, and publications cited therein. 
In particular, sensitizing dyes having spectral sensitivity suitable for 
spectral characteristics of various scanner light sources can be 
advantageously selected. 
For example, A) for an argon laser light source, simple merocyanines 
described in JP-A-60-162247, JP-A-2-48653, U.S. Pat. No. 2,161,331, West 
German Patent 936,071 and JP-A-5-11389, B) for a helium-neon laser light 
source, trinuclear cyanine dyes described in JP-A-50-62425, JP-A-54-18726 
and JP-A-59-102229, C) for an LED light source and a red semiconductor 
laser, thiacarbocyanines described in JP-B-48-42172, JP-B-51-9609, 
JP-B-55-39818, JP-A-62-284343 and JP-A-2-105135, and D) for an infrared 
semiconductor laser light source, tricarbocyanines described in 
JP-A-59-191032 and JP-A-60-80841, and dicarbocyanines containing a 
4-quinoline nucleus described in JP-A-59-192242 and JP-A-3-67242, formulae 
(IIIa) and (IIIb), may be advantageously selected. 
These sensitizing dyes may be used individually or in combination, and the 
combination of sensitizing dyes is often used for the purpose of 
supersensitization. In combination with the sensitizing dye, a dye which 
itself has no spectral sensitization effect or a material which absorbs 
substantially no visible light, but exhibits supersensitization may be 
incorporated into the emulsion. 
Useful sensitizing dyes, combinations of dyes which exhibit 
supersensitization, and materials which show super-sensitization are 
described in Research Disclosure, Vol. 176, 17643, page 23, Item IV-J 
(December 1978). Specific examples thereof are described below. 
##STR12## 
For the helium-neon light source, the sensitizing dyes represented by 
formula (I) of JP-A-6-75322 are particularly preferred as well as the 
compounds as described above. Specific examples thereof are described 
below. 
##STR13## 
For the LED light source and the infrared semiconductor laser, the dyes 
described below are particularly preferred. 
##STR14## 
For the infrared semiconductor laser light source, the dyes described below 
are particularly preferred. 
##STR15## 
For the white light source in camera work, the sensitizing dyes represented 
by formula (IV) of JP-A-7-36139 are preferably used. Specific examples 
thereof are described below. 
##STR16## 
In the case of an X-ray photosensitive material, tabular silver halide 
emulsion is preferably used. In this case, silver bromide or silver 
iodobromide is preferred and the silver iodide content is preferably 10 
mol % or less, more preferably from 0 to 5 mol %. This emulsion can 
achieve high sensitivity and is suitable for rapid processing. 
In the preferred grain form of the tabular silver halide emulsion, the 
aspect ratio is from 4 to less than 20, more preferably from 5 to less 
than 10. The grain thickness if preferably 0.3 .mu.m or less, more 
preferably 0.2 .mu.m or less. The aspect ratio of the tabular silver 
halide emulsion is the ratio of an average of diameters of circles each 
having an area equal to the area of individual tabular grains, to an 
average of thicknesses of individual tabular grains. 
The tabular grains are preferably present at a proportion of 80 wt %, more 
preferably 90 wt % or more, of all grains in the tabular silver halide 
emulsion. 
By using the tabular silver halide emulsion, stability of photographic 
properties can be further increased in the running processing according to 
the present invention. Further, the coated silver amount can be reduced 
and accordingly, the load in the fixing step and the drying step is 
lightened, whereby rapid processing can be achieved. 
The tabular silver halide emulsion is described in Cugnac and Chateau, 
Evolution of the Morphology of Silver Bromide Crystals during Physical 
Ripening, Vol. 33, No. 2, pp. 121-125, Science et Industrie Photography 
(1962), Duffin, Photographic Emulsion Chemistry, The Focal Press, New 
York, pp. 66-72 (1966), A. P. H. Tribvlli and W. F. Smith, Photographic 
Journal, Vol. 80, page 285 (1940), and can be easily prepared by referring 
to the methods described in JP-A-58-127921, JP-A-58-113927 and 
JP-A-58-113928. 
The tabular silver halide emulsion can also be obtained by forming seed 
crystals where tabular grains are present at a proportion of 40 wt % or 
more in an atmosphere of relatively low pBr value of 1.3 or less and 
growing the seed crystals by simultaneously adding silver and a halogen 
solution while keeping the pBr value on the order of the same value. 
In the process of grain formation, silver and a halogen solution are 
preferably added so that new crystal nuclei are not generated. 
The size of tabular silver halide grains can be adjusted by controlling the 
temperature, selecting the kind and the amount of solvent or controlling 
the addition rate of silver salt and halide used in the growth of grains. 
In the present invention, a tetrazolium compound, a hydrazine compound or a 
nucleation accelerator may be added. 
As the hydrazine derivative for use in the present invention, the compound 
represented by formula (I) of JP-A-7-287335 (corresponding to EP 670516A) 
is preferred and specifically, Compounds I-1 to I-53 may be used. 
In addition, the following hydrazine derivatives may be preferably used. 
The compound represented by (Chem. 1) of JP-B-6-77138, specifically, 
compounds described at pages 3 and 4; the compound represented by formula 
(I) of JP-B-6-93082, specifically, Compounds 1 to 38 described at pages 8 
to 18; the compounds represented by formulae (4), (5) and (6) of 
JP-A-6-230497, specifically, Compounds 4-1 to 4-10 described at pages 25 
and 26, Compounds 5-1 to 5-42 described at pages 28 to 36 and Compounds 
6-1 to 6-7 described at pages 39 and 40; the compounds represented by 
formulae (1) and (2) of JP-A-6-289520, specifically, Compounds 1-1) to 
1-17) and 2-1) described at pages 5 to 7; the compounds represented by 
(Chem. 2) and (Chem. 3) of JP-A-6-313936, specifically, compounds 
described at pages 6 to 19; the compound represented by (Chem. 1) of 
JP-A-6-313951, specifically, compounds described at pages 3 to 5; the 
compound represented by formula (I) of JP-A-7-5610, specifically, 
Compounds I-1 to I-38 described at pages 5 to 10; the compound represented 
by formula (II) of JP-A-7-77783, specifically, Compounds II-1 to II-102 
described at pages 10 to 27; and the compounds represented by formulae (H) 
and (Ha) of JP-A-7-104426, specifically, Compounds H-1 to H-44 described 
at pages 8 to 15. 
With respect to the addition method and the addition amount of the 
hydrazine derivative, and the layer where the hydrazine derivative is 
added, JP-A-7-287335 (corresponding to EP 670516A) (supra) may be referred 
to. 
The photographic emulsion of the present invention may contain various 
compounds so as to prevent reduction in the sensitivity or generation of 
fogging, during preparation, storage or processing of the silver halide 
photographic photosensitive material. More specifically, a compound known 
as an antifoggant or a stabilizer may be added and examples thereof 
include a large number of compounds such as azoles (e.g., benzothiazolium 
salt), nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, 
mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, 
mercaptothiadiazoles, aminotriazoles, benzothiazoles and 
nitrobenzotriazoles; mercaptotriazines; thioketo compounds (e.g., 
oxazolinethione); azaindenes (e.g., triazaindenes, tetrazaindenes (in 
particular, 4-hydroxy-substituted (1,3,3a,7)-tetrazaindenes) and 
pentazaindenes); benzenethiosulfonic acids; benzenesulfinic acids; and 
benzenesulfonic acid amides. Among these, preferred are benzotriazoles 
(e.g., 5-methylbenzotriazole) and nitroindazoles (e.g., 5-nitroindazole). 
This compound may also be incorporated into a processing solution. 
Further, the photographic emulsion may contain a compound which releases a 
inhibitor into the developer described in JP-A-62-30243, as a stabilizer 
or for the purpose of preventing black peppers. 
A technique for incorporating a polymer latex into the silver halide 
emulsion or the backing layer to improve dimensional stability may also be 
used. This technique is described, for example, in JP-B-39-4272, 
JP-B-39-17702 and JP-B-43-13482. For the purpose of achieving dimensional 
stability, in addition, the photographic emulsion may contain a 
water-insoluble or difficultly soluble synthetic polymer dispersion. For 
example, polymers comprising as a monomer component alkyl (meth)acrylate, 
alkoxyacryl (meth)acrylate, glycidyl (meth)acrylate, individually or in 
combination, or a mixture thereof with an acrylic acid or a methacrylic 
acid may be used. 
The photographic photosensitive material of the present invention may 
contain in the emulsion layer a polymer or an emulsified product such as 
alkyl acrylate latex or a plasticizer such as polyols (e.g., 
trimethylpropane) so as to improve pressure property. 
The photosensitive material prepared according to the present invention may 
contain in the photographic emulsion layer or other hydrophilic colloid 
layer various surface active agents as a coating aid or for the purposes 
of electrification inhibition, improvement of slipperiness, emulsion 
dispersion, prevention of adhesion or improvement of photographic 
characteristics (e.g., development acceleration, high contrast, 
sensitization). 
Examples thereof include nonionic surface active agents such as saponin 
(steroid-base), alkylene oxide derivatives (e.g., polyethylene glycol, 
polyethylene glycol/polypropylene glycol condensate, polyethylene glycol 
alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol 
esters, polyethylene glycol sorbitan esters, polyalkylene glycol 
alkylamines, polyalkylene glycol alkylamides, polyethylene oxide adducts 
of silicone), glycidol derivatives (e.g., alkenylsuccinic polyglyceride, 
alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and 
alkyl esters of saccharide; anionic surface active agents containing an 
acidic group such as a carboxy group, a sulfo group, a phospho group, a 
sulfuric ester group or a phosphoric ester group, such as alkyl 
carboxylate, alkyl sulfonate, alkylbenzenesulfonate, 
alkylnaphthalenesulfonate, alkylsulfuric esters, alkylphosphoric esters, 
N-acyl-N-alkyltaurines, sulfosuccinic esters, sulfoalkylpolyoxyethylene 
alkylphenyl ethers and polyoxyethylene alkylphosphoric esters; amphoteric 
surface active agents such as amino acids, aminoalkylsulfonic acids, 
aminoalkylsulfuric esters, aminoalkylphosphoric esters, alkylbetaines and 
aminoxides; and cationic surface active agents such as alkylamine salts, 
aliphatic and aromatic quaternary ammonium salts, heterocyclic quaternary 
ammonium salts such as pyridinium and imidazolium, aliphatic or 
heterocyclic ring-containing phosphonium salts, and aliphatic or 
heterocyclic ring-containing sulfonium salts. 
The silver halide photographic photosensitive material for use in the 
present invention comprises a support having thereon at least one silver 
halide emulsion layer, however, in the case of a direct medical X-ray 
photosensitive material, as described in JP-A-58-127921, JP-A-59-90841, 
JP-A-58-111934 and JP-A-61-201235, at least one silver halide emulsion 
layer is preferably provided on both surfaces of the support. 
In addition, the photographic material of the present invention may have, 
if desired, an interlayer, a filter layer, an antihalation layer and the 
like. 
The silver amount of the photosensitive material for use in the present 
invention is preferably from 0.5 to 5 g/m.sup.2 (per one surface), more 
preferably from 1 to 4 g/m.sup.2 (per one surface). 
In view of suitability for rapid processing, the silver amount preferably 
does not exceed 5 g/m.sup.2 and in order to obtain constant image density 
and contrast, the silver amount is preferably 0.5 g/m.sup.2 or more. 
Gelatin is used as a binder in the photosensitive material for use in the 
present invention, however, hydrophilic colloid such as a gelatin 
derivative, a cellulose derivative, a graft polymer of gelatin to other 
polymer, a protein other than these, a saccharide derivative and a 
synthetic hydrophilic polymer material such as a homopolymer or a 
copolymer, may be used in combination. 
As the bonder or protective colloid of the photographic emulsion, gelatin 
is advantageously used, however, other hydrophilic colloid may be used and 
examples thereof include gelatin derivatives, graft polymers of gelatin to 
other polymer, proteins such as albumin and casein, cellulose derivatives 
such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose 
sulfuric esters, saccharide derivatives such as sodium alginate and starch 
derivative, and various synthetic hydrophilic polymer materials such as 
homopolymers and copolymers of polyvinyl alcohol, polyvinyl alcohol 
partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic 
acid, polyacrylamide, polyvinyl imidazole or polyvinyl pyrazole. 
The gelatin may be a lime-processed gelatin or an acid-processed gelatin, 
and a hydrolyzate or an enzymolyzate of gelatin may also be used. 
The X-ray photosensitive material preferably contains in the emulsion layer 
or other hydrophilic colloid layer an organic substance which dissolves 
out during development processing. When the substance which dissolves out 
is gelatin, the gelatin is preferably such a type as not to participate in 
the cross-linking reaction of gelatin by a hardening agent, and examples 
thereof include acetylated gelatin and phthalated gelatin. This gelatin 
preferably has a small molecular weight. Effective examples of the polymer 
material other than gelatin include hydrophilic polymers such as 
polyacrylamide described in U.S. Pat. No. 3,271,158, polyvinyl alcohol and 
polyvinyl pyrrolidone, and saccharides such as dextran, saccharose, 
pullurane are also effective. Among these, polyacrylamide and dextran are 
preferred and polyacrylamide is more preferred. This polymer material has 
an average molecular weight of preferably 20,000 or less, more preferably 
10,000 or less. The effective outflow on processing is from 10 to 50%, 
preferably from 15 to 30%, of the total weight of organic materials coated 
other than silver halide grains. 
The organic material to be dissolved out on processing may be added to 
either an emulsion layer or a surface protective layer, however, if the 
total coated weight of the above-described organic material is the same, 
it is preferably incorporated into both a surface protective layer and an 
emulsion layer rather than into only an emulsion layer, more preferably 
incorporated into only a surface protective layer. In the case of a 
photosensitive material comprising multi-layer structure emulsion layers, 
if the coated total amount of the above-described organic material is the 
same, it is preferably added in a larger amount to the emulsion layer 
closer to the surface protective layer. 
As the matting agent, fine particles of an organic compound such as a 
polymethyl methacrylate homopolymer, a methyl methacrylate/methacrylic 
acid copolymer or starch as described in U.S. Pat. Nos. 2,992,101, 
2,701,245, 4,142,894 and 4,396,706, or of an inorganic compound such as 
silica, titanium dioxide, ballium strontium sulfate may be used. The 
particle size is preferably from 1.0 to 10 .mu.m, more preferably from 2 
to 5 .mu.m. 
In the silver halide photographic photosensitive material of the present 
invention, a photographic layer or other layer may be colored by a dye for 
the purpose of absorbing light in a specific wavelength region, in other 
words, for preventing halation or irradiation, or to provide a filter 
layer for controlling spectral composition of light entering into the 
photographic emulsion layer. In the case of a double emulsion film such as 
direct, medical Roentgen film, a layer for the purpose of crossover cut 
may be provided under an emulsion layer. Examples of the dye used to this 
effect include an oxonol dye having a pyrazolone nucleus or a barbituric 
acid nucleus, a hemioxonol dye, an azo dye, an azomethine dye, an 
anthraquinone dye, an arylidene dye, a styryl dye, a triarylmethane dye, a 
merocyanine dye and a cyanine dye. 
Among these, a oxonol dye, a hemioxonol dye and a merocyanine dye are 
useful. Specific example thereof are described in West German Patent 
616,007, British Patents 584,609 and 1,117,429, JP-B-26-7777, 
JP-B-39-22069, JP-B-54-38129, JP-A-48-85130, JP-A-49-99620, 
JP-A-49-114420, JP-A-49-129537, PB Report 74175 and Photo. Abst. 128 
('21). These dyes are suitably used particularly in the photosensitive 
material for dot-to-dot work in a bright room. Further, solid fine 
particle dispersion of dyes described in JP-A-7-168311 may be used. In the 
silver halide photographic photosensitive material according to the 
present invention, when a dye or an ultraviolet absorbent is incorporated 
into a hydrophilic colloid layer, it may be mordanted by a cationic 
polymer or the like. 
In using the above-described dye, to mordant an anionic dye to a specific 
layer of the photosensitive material using a polymer having a cationic 
site is an effective technique. In this case, it is preferred to use a dye 
which is irreversibly decolored in the development-fixing-water washing 
process. The layer to be mordanted by a dye using a polymer having a 
cation site may be in an emulsion layer or on the surface of a surface 
protective layer opposite to the emulsion layer through a support, 
however, it is preferably between an emulsion layer and a support. In 
particular, for the purpose of crossover cut of a medical X-ray double 
emulsion film, the dye is ideally mordanted to an undercoat layer. 
As the coating aid of the undercoat layer, a polyethylene oxide-base 
nonionic surface active agent is preferably used in combination with the 
polymer having a cation site. 
The polymer which offers a cation site is preferably an anion conversion 
polymer. 
Examples of the anion conversion polymer include various known quaternary 
ammonium salt (or phosphonium salt) polymers. The quaternary ammonium salt 
(or phosphonium salt) polymer is broadly known as a mordant polymer or an 
antistatic agent polymer. 
Examples thereof include water dispersion latexes described in 
JP-A-59-166940, U.S. Pat. No. 3,958,995, JP-A-55-142339, JP-A-54-126027, 
JP-A-54-155835, JP-A-53-30328 and JP-A-54-92274; polyvinyl pyridinium 
salts described in U.S. Pat. Nos. 2,548,564, 3,148,061 and 3,756,814; 
water-soluble quaternary ammonium salt polymers described in U.S. Pat. No. 
3,709,690; and water-insoluble quaternary ammonium salt polymers described 
in U.S. Pat. No. 3,898,088. 
Further, in order to prevent transfer of the dye from a desired layer to 
other layer or the processing solution to adversely affect the 
photographic properties, a cross-linked aqueous polymer latex obtained by 
copolymerizing a monomer having at least two or more (preferably from 2 to 
4) ethylenically unsaturated groups, is preferably used. 
To immobilize the dye, a solid dispersion method described in 
JP-A-55-155350 or WO88/04794 is also effective. 
The photographic photosensitive material of the present invention may 
contain a developing agent such as a hydroquinone derivative or a 
phenidone derivative for various purposes, for example, as a stabilizer or 
an accelerator. 
The photographic photosensitive material of the present invention may 
contain in the photographic emulsion layer or other hydrophilic colloid 
layer an inorganic or organic hardening agent. Examples thereof include 
chromium salts (e.g., chromium alum, chromium acetate), aldehydes (e.g., 
formaldehyde, glutaraldehyde), N-methylol compounds (e.g., 
dimethylolurea), dioxane derivatives, active vinyl compounds (e.g., 
1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), 
active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) and 
mucohalogen acids (e.g., mucochloric acid), and these may be used either 
individually or in combination. 
The photographic photosensitive material of the present invention may 
contain in a photographic emulsion layer or other hydrophilic colloid 
layer, a hydroquinone derivative which releases a development inhibitor 
(so-called DIR-hydroquinone) in correspondence with the density of an 
image at the time of development. 
Specific examples thereof include the compounds described in U.S. Pat. Nos. 
3,379,529, 3,620,746, 4,377,634 and 4,332,878, JP-A-49-129536, 
JP-A-54-67419, JP-A-56-153336, JP-A-56-153342, JP-A-59-278853, 
JP-A-59-90435, JP-A-59-90436 and JP-A-59-138808. 
The photographic photosensitive material of the present invention 
preferably contains in a silver halide emulsion layer or other layer a 
compound having an acid radical. Examples of the compound having an acid 
radical include organic acids such as salicylic acid, acetic acid and 
ascorbic acid, and homopolymers and copolymers having a repeating unit of 
an acid monomer such as acrylic acid, maleic acid or phthalic acid. These 
compounds are described in JP-A-61-223834, JP-A-61-228437, JP-A-62-25745 
and JP-A-62-55642. Among these compounds, more preferred are, as a low 
molecular compound, an ascorbic acid, and as a high molecular compound, a 
water dispersing latex of a copolymer comprising an acid monomer such as 
acrylic acid and a cross-linking monomer having two or more unsaturated 
groups, such as divinylbenzene. 
The thus produced silver halide emulsion is coated on a support such as 
cellulose acetate film or polyethylene terephthalate film, by a dip 
coating method, an air knife coating method, a bead coating method, an 
extrusion doctor coating method or a double-side coating method, and then 
dried. 
The present invention can be applied also to a color photosensitive 
material. In this case, various color couplers may be used. The term 
"color coupler" as used herein means a compound capable of forming a dye 
upon coupling reaction with an oxidation product of an aromatic primary 
amine developing agent. Typical examples of useful color couplers include 
naphthol- and phenol-base compounds, pyrazolone- and pyrazoloazole-base 
compounds, and open chain or heterocyclic ketomethylene compounds. 
Specific examples of the cyan, magenta and yellow couplers which can be 
used in the present invention are described in the patents cited in 
Research Disclosure (RD), 17643, Item VII-D (December 1978) and ibid., 
18717 (November 1979). 
Various additives for use in the photosensitive material of the present 
invention are not particularly limited and, for example, those described 
below may be preferably used: 
______________________________________ 
Items Pertinent Portions 
______________________________________ 
1) Nucleation Compounds represented by formulae 
accelerator (I), (II), (III), (IV), (V) and 
(VI) of JP-A-6-82943; compounds 
represented by formulae (II-m) to 
(II-p) of JP-A-2-103536, from page 
9, right upper column, line 13 to 
page 16, left upper column, line 
10, and Compounds II-1 to II-22; 
and compounds described in JP-A-1- 
179939. 
2) Spectral Spectral sensitizing dyes described 
sensitizing dye 
in JP-A-2-12236, page 8, from left 
lower column, line 13 to right 
lower column, line 4, JP-A-2- 
103536, from page 16, right lower 
column, line 3 to page 17, left 
lower column, line 20, JP-A-1- 
112235, JP-A-2-124560 and JP-A-3- 
7928, JP-A-5-11389. 
3) Surface Active Compounds described in JP-A-2- 
agent 12236, page 9, right upper column, 
line 7 to right lower column, line 
7, and JP-A-2-18542, from page 2, 
left lower column, line 13 to page 
4, right lower column, line 18. 
4) Antifoggant Compounds described in JP-A-2- 
103536, from page 17, right lower 
column, line 19 to page 18, right 
upper column, line 4 and right 
lower column lines 1 to 5; and 
thiosulfinic acid compounds 
described in JP-A-1-237538. 
5) Polymer latex Compounds described in JP-A-2- 
103536, page 18, left lower column, 
lines 12 to 20. 
6) Compound having 
Compounds described in JP-A-2- 
acid radical 103536, from page 18, right lower 
column, line 6 to page 19, left 
upper column, line 1. 
7) Matting agent, Compounds described in JP-A-2- 
slipping agent and 
103536, page 19, from left upper 
plasticizer column, line 15 to right upper 
column, line 15. 
8) Hardening agent 
Compounds described in JP-A-2- 
103536, page 18, right upper 
column, lines 5 to 17. 
9) Dye Dyes described in JP-A-2-103536, 
page 17, right lower column, lines 
1 to 18; and solid dyes described 
in JP-A-2-294638 and JP-A-5-11382. 
10) Binder Compounds described in JP-A-2- 
18542, page 3, right lower column, 
lines 1 to 20. 
11) Black pepper Compounds described in U.S. Pat. 
inhibitor 4,956,257 and JP-A-1-118832. 
12) Redox compound Compounds represented by formula 
(I) of JP-A-2-301743 (particularly 
Compounds 1 to 50); compounds 
represented by formulae (R-1), (R- 
2) and (R-3) of JP-A-3-174143, 
pages 3 to 20, and Compounds 1 to 
75; compounds described in JP-A-5- 
257239 and JP-A-4-278939. 
13) Monomethine Compounds represented by formula 
compounds (II) of JP-A-2-287532 (Compounds 
II-1 to II-26). 
14) Dihydroxybenzenes 
Compounds described in JP-A-3- 
39948, from page 11, left upper 
column to page 12, left lower 
column, and EP 452772A. 
______________________________________

EXAMPLES 
Photosensitive Materials (1-1) to (1-4) used in Examples were prepared as 
follows. 
Production of Photosensitive Material (1-1): 
Emulsion A was prepared as follows. 
To Solution 1 shown in Table 1 kept at 38.degree. C. and having a pH of 
4.5, Solution 2 and Solution 3 were simultaneously added while stirring 
over 24 minutes to form grains having a size of 0.18 .mu.m. Subsequently, 
Solution 4 and Solution 5 shown in Table 1 were added over 8 minutes and 
then 0.15 g of potassium iodide was added to complete grain formation. 
Thereafter, the grains were washed with water by flocculation in a usual 
manner, gelatin was added, the pH and the pAg were adjusted to 5.2 and 
7.5, respectively, and thereto 4 mg of sodium thiosulfate, 2 mg of 
N,N-dimethylselenourea, 10 mg of chloroauric acid, 4 mg of sodium 
benzenethiosulfonate and 1 mg of sodium benzenethiosulfinate were added to 
perform chemical sensitization so as to have an optimal sensitivity at 
55.degree. C. 
Further, 50 mg of 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene as a 
stabilizer and phenoxy ethanol as an antiseptic in an amount of giving a 
coverage of 100 ppm were added. The grains finally obtained were silver 
iodochlorobromide cubic grains having a silver chloride content of 80 mol 
% and an average grain size of 0.20 .mu.m (coefficient of variation: 9%). 
______________________________________ 
Solution 1: 
Water 1.0 l 
Gelatin 20 g 
Sodium chloride 2 g 
1,3-Dimethylimidazolidine-2-thione 
20 mg 
Sodium benzenethiosulfonate 
3 mg 
Solution 2: 
Water 600 ml 
Silver nitrate 150 g 
Solution 3: 
Water 600 ml 
Sodium chloride 45 g 
Potassium bromide 21 g 
Potassium hexachloroiridate (III) 
15 ml 
(0.001% aq. soln.) 
Ammonium hexabromorhodate (III) 
1.5 ml 
(0.001% aq. soln.) 
Solution 4: 
Water 200 ml 
Silver nitrate 50 g 
Solution 5: 
Water 200 ml 
Sodium chloride 15 g 
Potassium bromide 7 g 
K.sub.4 Fe(CN).sub.6 30 mg 
______________________________________ 
Preparation of Silver Halide Photographic Photosensitive Material: 
On a polyethylene terephthalate film having a moisture-proofing undercoat 
layer containing vinylidene chloride, the UL, EM, PC and OC layers were 
coated to prepare a sample having a layer structure of UL, EM, PC and OC 
in this order from the support side. 
The preparation method and the coating amount of each layer are described 
below. 
UL Layer: 
To an aqueous gelatin solution, 30 wt %, based on gelatin, of 
polyethylacrylate dispersion was added and the resulting solution was 
coated to have a gelatin coverage of 0.5 g/m.sup.2. 
EM Layer: 
To Emulsion A prepared above, 2.5.times.10.sup.-4 mol/mol-Ag of Compound 
(S-1) shown below as a sensitizing dye was added and further, 
3.times.10.sup.-4 mol/mol-Ag of a mercapto compound shown below as 
Compound (a), 3.times.10.sup.-3 mol/mol-Ag of KBr, 7.0.times.10.sup.-4 
mol/mol-Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 4.times.10-4 
mol/mol-Ag of a mercapto compound shown below as Compound (b), 
4.times.10.sup.-4 mol of a triazine compound shown below as Compound (c), 
2.times.10.sup.-3 mol/mol-Ag of 5-chloro-8-hydroxyquinoline, 
7.0.times.10.sup.-5 mol/mol-Ag of Nucleating Agent (HZ-1) (hydrazine 
derivative), 4.2.times.10.sup.-4 mol/mol-Ag of Nucleation Accelerator 
(AC-1), 9.times.10.sup.-3 mol/mol-Ag of sodium p-dodecylbenzenesulfonate 
and 3.times.10.sup.-2 mol/mol-Ag of hydroquinone were added. Furthermore, 
200 mg/m.sup.2 of a polyethyl acrylate dispersion, 200 mg/m.sup.2 of a 
latex copolymer of methyl acrylate, sodium 
2-acrylamide-2-methylpropanesulfonate and 2-acetoacetoxyethyl methacrylate 
(weight ratio: 88:5:7), 200 mg/m.sup.2 of colloidal silica having an 
average particle size of 0.02 .mu.m and 200 mg/m.sup.2 of compound (d) as 
a hardening agent were added. The resulting mixed solution was coated to 
have a coated silver amount of 3.5 g/m.sup.2. The finished solution had a 
pH of 5.7. 
PC Layer: 
To an aqueous gelatin solution, 50 wt %, based on gelatin, of an ethyl 
acrylate dispersion, Surface Active Agent (e) shown below in an amount of 
giving a coverage of 5 mg/m.sup.2 and 1,5-dihydroxy-2-benzaldoxime in an 
amount of giving a coverage of 10 mg/m.sup.2 were added, and the resulting 
solution was coated to have a gelatin coverage of 0.5 g/m.sup.2. 
OC Layer: 
Gelatin (0.5 g/m.sup.2), 40 mg/m.sup.2 of an amorphous SiO.sub.2 matting 
agent having an average particle size of about 3.5 .mu.m, 0.1 g/m.sup.2 of 
methanol silica, 100 mg/m.sup.2 of polyacrylamide, 20 mg/m.sup.2 of 
silicone oil, and as coating aids, 5 mg/m.sup.2 of a fluorine surface 
active agent shown below by structural formula (f), 10 mg/m.sup.2 of 
sodium dodecylbenzenesulfonate and 20 mg/m.sup.2 of a compound shown below 
by structural formula (g) were coated. 
##STR17## 
The thus-obtained coated sample had a back layer and a back protective 
layer having the following compositions. 
__________________________________________________________________________ 
Formulation of Back Layer: 
Gelatin 3 g/m.sup.2 
Latex: polyethyl acrylate 2 g/m.sup.2 
Surface active agent: 40 mg/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
Hardening agent: Compound (d) shown below 
200 
mg/m.sup.2 
SnO.sub.2 /Sb 200 
mg/m.sup.2 
(weight ratio: 90/10, average particle size: 0.20 .mu.m) 
Dye: Mixture of Dye a!, Dye b! and Dye c! 
Dye a! 
##STR18## 70 mg/m.sup.2 
Dye b! 
##STR19## 70 mg/m.sup.2 
Dye c! 
##STR20## 90 mg/m.sup.2 
Back Protective Layer: 
Gelatin 0.8 
g/m.sup.2 
Polymethyl methacrylate fine particles 
30 mg/m.sup.2 
(average particle size: 4.5 .mu.m) 
Sodium dihexyl-.alpha.-sulfosuccinate 
15 mg/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
15 mg/m.sup.2 
Sodium acetate 40 mg/m.sup.2 
__________________________________________________________________________ 
The swelling ratio ((swollen layer thickness/dry layer 
thickness).times.100) on the side having an emulsion layer was 100. 
Preparation of Photosensitive Material (1-2): 
Emulsion B: 
Emulsion B was prepared in the same manner as Emulsion A except for 
changing the amount of sodium thiosulfate added to 2 mg per mol of silver 
and using no selenium sensitizer. 
A sample was prepared in the same manner as Photosensitive Material (1-1) 
except for replacing the sensitizing dyes of Photosensitive Material (1-1) 
by the following Sensitizing Dyes S-2 (5.times.10.sup.-4 mol/mol-Ag) and 
S-3 (5.times.10.sup.-4 mol/mol-Ag) and using Emulsion B as the emulsion in 
EM layer. 
##STR21## 
The swelling ratio on the side having an emulsion layer was the same as in 
Photosensitive Material (1-1). 
Preparation of Photosensitive Material (1-3): 
Emulsion C: 
An aqueous 1.5% gelatin solution kept at 40.degree. C., containing sodium 
chloride, 3.times.10.sup.-5 mol/mol-Ag of sodium benzenesulfonate and 
5.times.10.sup.-3 mol/mol-Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene 
and having a pH of 2.0 and an aqueous sodium chloride solution containing 
2.0.times.10.sup.-6 mol/mol-Ag of K.sub.2 Ru(NO)Cl.sub.5 were added 
simultaneously by a double jet method at a potential of 95 mV over 3 
minutes and 30 seconds to consume a half of the silver amount of the final 
grain, thereby preparing core grains having a size of 0.12 .mu.m. 
Thereafter, an aqueous silver nitrate solution and an aqueous sodium 
chloride solution containing 6.0.times.10.sup.-6 mol/mol-Ag of K.sub.2 
Ru(NO)Cl.sub.5 were added in the same manner as above over 7 minutes to 
prepare silver chloride cubic grains having an average grain size of 0.15 
.mu.m (coefficient of variation: 12%). 
The grains were washed with water by a flocculation method well known in 
the art to remove soluble salts, then gelatin was added, 60 mg/mol-Ag of 
Compound A and 60 mg/mol-Ag of phenoxy ethanol as antiseptics were added, 
the pH and the pAg were adjusted to 5.7 and 7.5, respectively, 
4.times.10.sup.-5 mol/mol-Ag of chloroauric acid and 4.times.10.sup.-5 
mol/mol-Ag of Compound Z were added, and then 1.times.10.sup.-5 mol/mol-Ag 
of sodium thiosulfate and 1.times.10.sup.-5 mol/mol-Ag of potassium 
selenocyanide were added to perform chemical sensitization under heating 
at 60.degree. C. for 60 minutes. Thereafter, 1.times.10.sup.-3 mol/mol-Ag 
of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene as a stabilizer was added. 
(The grains finally obtained had a pH of 5.7, a pAg of 7.5 and an Ru 
content of 4.0.times.10.sup.-6 mol/mol-Ag.) 
On the support described below, EM, PC and OC were coated in this order. 
EM: 
The following compounds were added to Emulsion C prepared above and a 
silver halide emulsion layer was coated to have a gelatin coated amount of 
0.9 g/m.sup.2 and a coated silver amount of 2.7 g/m.sup.2. 
______________________________________ 
1-Phenyl-5-mercaptotetrazole 
1 mg/m.sup.2 
Nucleation Accelerator (AC-2) 
3.6 .times. 10.sup.-3 
mol/mol-Ag 
N-Oleyl-N-methyltaurin sodium salt 
10 mg/m.sup.2 
Compound B 10 mg/m.sup.2 
Compound C 10 mg/m.sup.2 
Compound D 10 mg/m.sup.2 
n-Butyl acrylate/2-acetoacetoxyethyl 
760 mg/m.sup.2 
methacrylate/acrylic acid copolymer 
(89/8/3) 
Compound E (hardening agent) 
105 mg/m.sup.2 
Sodium polystyrenesulfonate 
57 mg/m.sup.2 
Nucleating Agent (HZ-3) 
1.2 .times. 10.sup.-3 
mol/mol-Ag 
______________________________________ 
PC: 
The following compounds were added to an aqueous gelatin solution and the 
resulting solution was coated to give a gelatin coated amount of 0.6 
g/m.sup.2. 
______________________________________ 
Gelatin (Ca.sup.++ content: 2,700 ppm) 
0.6 g/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
10 mg/m.sup.2 
Sodium polystyrenesulfonate 
6 mg/m.sup.2 
Compound A 1 mg/m.sup.2 
Compound F 14 mg/m.sup.2 
n-Butyl acrylate/2-acetoacetoxyethyl 
250 mg/m.sup.2 
methacrylate/acrylic acid copolymer (89/8/3) 
______________________________________ 
OC: 
The following compounds were added to an aqueous gelatin solution and the 
resulting solution was coated to give a gelatin coated amount of 0.45 
g/m.sup.2. 
______________________________________ 
Gelatin (Ca.sup.++ content: 2,700 ppm) 
0.45 g/m.sup.2 
Amorphous silica matting agent (average 
40 mg/m.sup.2 
particle size: 3.5 .mu.m, pore diameter: 
25 .ANG., surface area: 700 m.sup.2 /g) 
Amorphous silica matting agent (average 
10 mg/m.sup.2 
particle size: 2.5 .mu.m, pore diameter: 
170 .ANG., surface area: 300 m.sup.2 /g) 
Potassium N-perfluorooctanesulfonyl-N- 
5 mg/m.sup.2 
propylglycine 
Sodium p-dodecylbenzenesulfonate 
30 mg/m.sup.2 
Compound A 1 mg/m.sup.2 
Liquid paraffin 40 mg/m.sup.2 
Solid Disperse Dye G.sub.1 
30 mg/m.sup.2 
Solid Disperse Dye G.sub.2 
150 mg/m.sup.2 
Sodium polystyrenesulfonate 
4 mg/m.sup.2 
______________________________________ 
Then, on the opposite surface of the support, the following electrically 
conductive layer and back layer were simultaneously coated. 
Preparation of Coating Solution for Electrically Conductive Layer and 
Coating: 
The following compounds were added to an aqueous gelatin solution and the 
resulting solution was coated to give a gelatin coated amount of 0.06 
g/m.sup.2. 
______________________________________ 
SnO.sub.2 /Sb (9/1 by weight, average particle 
186 mg/m.sup.2 
size: 0.25 .mu.m) 
Gelatin (Ca.sup.++ content: 3,000 ppm) 
60 mg/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
13 mg/m.sup.2 
Sodium dihexyl-.alpha.-sulfosuccinate 
12 mg/m.sup.2 
Sodium polystyrenesulfonate 
10 mg/m.sup.2 
Compound A 1 mg/m.sup.2 
______________________________________ 
Preparation of Coating Solution for Back Layer and Coating: 
The following compounds were added to an aqueous gelatin solution and the 
resulting solution was coated to give a gelatin coated amount of 1.94 
g/m.sup.2. 
______________________________________ 
Gelatin (Ca++ content: 30 ppm) 
1.94 g/m.sup.2 
Polymethyl methacrylate fine particles 
15 mg/m.sup.2 
(average particle size: 3.4 .mu.m) 
Compound H 140 mg/m.sup.2 
Compound I 140 mg/m.sup.2 
Compound J 30 mg/m.sup.2 
Compound K 40 mg/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
7 mg/m.sup.2 
Sodium dihexyl-.alpha.-sulfosuccinate 
29 mg/m.sup.2 
Compound L 5 mg/m.sup.2 
Potassium N-perfluorooctanesulfonyl-N- 
5 mg/m.sup.2 
propylglycine 
Sodium sulfate 150 mg/m.sup.2 
Sodium acetate 40 mg/m.sup.2 
Compound E (hardening agent) 
105 mg/m.sup.2 
______________________________________ 
Support and Undercoat Layer: 
An undercoat first layer and an undercoat second layer each having the 
following composition were coated on both surfaces of a biaxially 
stretched polyethylene terephthalate support (thickness: 100 .mu.m). 
______________________________________ 
Undercoat First Layer: 
Core-shell type vinylidene chloride 
15 g 
copolymer (1) 
2,4-Dichloro-6-hydroxy-s-triazine 
0.25 g 
Polystyrene fine particles 
0.05 g 
(average particle size: 3 .mu.m) 
Compound M 0.20 g 
Colloidal silica (Snowtex ZL, produced by 
0.12 g 
Nissan Chemical KK, particle size: 
70 to 100 .mu.m) 
Water to make 100 g 
______________________________________ 
The resulting coating solution was adjusted to have a pH of 6 by adding 10 
wt % of KOH and coated at a drying temperature of 180.degree. C. within 2 
minutes to give a dry thickness of 0.9 .mu.m. 
______________________________________ 
Undercoat Second Layer: 
Gelatin 1 g 
Methyl cellulose 0.05 g 
Compound N 0.02 g 
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 H 
0.03 g 
Compound A 3.5 .times. 10.sup.-3 
g 
Acetic acid 0.2 g 
Water to make 100 g 
______________________________________ 
The resulting coating solution was coated at a drying temperature of 
170.degree. C. within 2 minutes to give a dry thickness of 0.1 .mu.m, 
thereby preparing a sample. 
The swelling ratio on the side having an emulsion layer was 100. 
##STR22## 
Preparation of Photosensitive Material (1-4): Emulsion D: 
An aqueous silver nitrate solution (250 ml) having dissolved therein 64 g 
of silver nitrate and 250 ml of an aqueous halogen salt solution 
containing K.sub.2 Rh(H.sub.2 O)Cl.sub.5 corresponding to 
1.times.10.sup.-7 mol per mol of silver in the entire emulsion, K.sub.3 
IrCl.sub.6 corresponding to 2.times.10.sup.-7 mol per mol of silver in the 
entire emulsion, 20 g of potassium bromide and 14 g of sodium chloride 
were added to a 2% aqueous gelatin solution containing sodium chloride 
(0.3%), 1,3-dimethyl-2-imidazolithione (0.002%) and a citric acid (0.05%), 
while stirring at 38.degree. C. by a double jet method over 12 minutes to 
obtain silver chlorobromide grains having an average grain size of 0.16 
.mu.m and a silver chloride content of 55 mol %, thereby performing 
nucleation. Subsequently, 300 ml of an aqueous silver nitrate solution 
having dissolved therein 106 g of silver nitrate and 300 ml of an aqueous 
halogen salt solution having dissolved therein 28 g of potassium bromide 
and 26 g of sodium chloride were added by a double jet method over 20 
minutes to perform grain formation. 
Thereafter, 1.times.10.sup.-3 mol/mol-Ag of a KI solution was added to 
perform conversion and the grains were washed with water by flocculation 
in a usual manner. Thereto, 40 g/mol-Ag of gelatin was added, the pH and 
the pAg were adjusted to 5.9 and 7.5, respectively, and then 3 mg/mol-Ag 
of sodium benzenethiosulfonate, 1 mg/mol-Ag of sodium benzenesulfinate, 2 
mg of sodium thiosulfate, 2 mg of a compound shown below by structural 
formula (h) and 8 mg of chloroauric acid were added to perform chemical 
sensitization under heating at 60.degree. C. for 70 minutes. Then, 150 mg 
of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene as a stabilizer and 100 mg 
of proxel as an antiseptic were added. Thereafter, 400 mg of a dye shown 
below by structural formula (i) was added and after 10 minutes, the 
temperature was lowered. The grains obtained were silver iodochlorobromide 
cubic grains having an average grain size of 0.22 .mu.m and a silver 
chloride content of 60 mol % (coefficient of variation: 10%). 
Preparation of Coating Solution for Emulsion Layer: 
To the thus-obtained emulsion, 2.times.10.sup.-4 mol/mol-Ag of a short wave 
cyanine dye shown below by structural formula (j), 5.times.10.sup.-3 
mol/mol-Ag of potassium bromide, 2.times.10.sup.-4 mol/mol-Ag of 
1-phenyl-5-mercaptotetrazole, 2.times.10.sup.-4 mol/mol-Ag of a mercapto 
compound shown below by structural formula (k), 3.times.10.sup.-4 
mol/mol-Ag of a triazine compound shown below by structural formula (1), 
6.times.10.sup.-4 mol/mol-Ag of Nucleation Accelerator (AC-1) and 
2.times.10.sup.-4 mol/mol-Ag of Nucleating Agent (HZ-2) were added, and 
further hydroquinone, sodium p-dodecylbenzenesulfonate, colloidal silica 
(Snowtex C, produced by Nissan Chemical KK), a polyethyl acrylate 
dispersion and 1,2-bis(vinylsulfonylacetamido)ethane were added to give a 
coated amount of 100 mg/m.sup.2, 10 mg/m.sup.2, 150 mg/m.sup.2, 500 
mg/M.sup.2 and 80 mg/M.sup.2, respectively, to prepare a coating solution 
for the emulsion layer. The coating solution was adjusted to have a pH of 
5.6. 
##STR23## 
Preparation of Coating Solutions for PC and OC: 
To an aqueous gelatin solution containing proxel as an antiseptic, Compound 
(n), Compound (o) and a polyethyl acrylate dispersion were added to give a 
coated amount of 10 mg/m.sup.2, 100 mg/m.sup.2 and 300 mg/m.sup.2, 
respectively, thereby preparing a PC solution. 
Further, to a gelatin solution containing proxel as an antiseptic, an 
amorphous SiO.sub.2 matting agent having an average particle size of about 
3.5 .mu.m, colloidal silica (Snowtex C, produced by Nissan Chemical KK), 
liquid paraffin, and as coating aids, a fluorine surface active agent 
shown below by structural formula (p) and sodium p-dodecylbenzenesulfonate 
were added to give a coated amount of 50 mg/m.sup.2, 100 mg/m.sup.2, 30 
mg/m.sup.2, 5 mg/m.sup.2 and 30 mg/m.sup.2, respectively, thereby 
preparing an OC solution. 
##STR24## 
These coating solutions were coated on a polyethylene terephthalate film 
having on both surfaces thereof a moisture-proofing undercoat containing 
vinylidene chloride, to have a layer structure of an emulsion layer 
(silver amount: 3.0 g/m.sup.2, gelatin: 1.5 g/m.sup.2) as a lowermost 
layer, PC (gelatin: 0.5 g/m.sup.2) and OC (gelatin: 0.4 g/m.sup.2). The 
sample obtained had a layer surface pH on the emulsion surface of 5.8. 
A back layer having the following formulation was coated. 
______________________________________ 
Back Layer: 
______________________________________ 
Gelatin 1.5 g/m.sup.2 
Surface active agent: 30 mg/m.sup.2 
Sodium p-dodecylbenzenesulfonate 
Gelatin hardening agent: 100 mg/m.sup.2 
1,2-bis(vinylsulfonylacetamido)ethane 
Dye: Mixture of the following Dyes (q), (r), (s) and (t) 
Dye (q) 50 mg/m.sup.2 
Dye (r) 100 mg/m.sup.2 
Dye (s) 30 mg/m.sup.2 
Dye (t) 50 mg/m.sup.2 
Proxel 1 mg/m.sup.2 
______________________________________ 
(q) 
##STR25## 
(r) 
##STR26## 
(s) 
##STR27## 
(t) 
##STR28## 
The swelling ratio on the side having an emulsion layer was 150. 
Developer (1-1) had the following composition per 1 l of the use solution. 
______________________________________ 
Potassium hydroxide (100%) 
35.0 g 
Diethylenetriaminepentaacetic acid 
2.0 g 
Potassium carbonate 40.0 g 
Sodium metabisulfite 40.0 g 
Potassium bromide 3.0 g 
Diethylene glycol 20.0 g 
Hydroquinone 25.0 g 
5-Methylbenzotriazole 0.08 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3- 
0.45 g 
pyrazolidone 
2,3,5,6,7,8-Hexahydro-2-thioxo-4-(1H)- 
0.04 g 
quinazoline 
Sodium 2-mercaptobenzimidazole-5-sulfonate 
0.15 g 
Sodium erythorbate 3.0 g 
Compound shown in Table 1-1 
shown in Table 1-1 
pH 10.5 
______________________________________ 
Developer (1-2) had the following composition. 
______________________________________ 
Sodium hydroxide (100%) 40.0 g 
Diethylenetriaminepentaacetic acid 
2.0 g 
Potassium carbonate 60.0 g 
Sodium metabisulfite 70.0 g 
Potassium bromide 7.0 g 
Diethylene glycol 5.0 g 
Hydroquinone 40.0 g 
5-Methylbenzotriazole 0.35 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3 
1.50 g 
pyrazolidone 
Sodium 2-mercaptobenzimidazole-5-sulfonate 
0.30 g 
Sodium 3-(5-Mercaptotetrazole-1-yl)- 
0.10 g 
benzenesulfonate 
Sodium erythorbate 6.0 g 
Compound shown in Table 1-2 
shown in Table 1-2 
pH 10.5 
______________________________________ 
Fixing solution (1-1) had the following formulation per 1 l of the use 
solution. 
______________________________________ 
Ammonium thiosulfate 119.7 g 
Disodium ethylenediaminetetraacetate 
0.03 g 
dihydrate 
Sodium thiosulfate pentahydrate 
10.9 g 
Sodium metasulfite 25.0 g 
Sodium hydroxide (100%) 
12.4 g 
Glacial acetic acid 29.1 g 
Tartaric acid 2.9 g 
Sodium gluconate 1.7 g 
Aluminum sulfate 8.4 g 
pH 4.8 
______________________________________ 
Example 1-1 
After dipping 16 sheets of contact film RU-100 (3.6 cm.times.12 cm) 
produced by Fuji Photo Film Co., Ltd. in 250 ml of a developer at 
38.degree. C. for 20 seconds while stirring by nitrogen bubbling, the 
silver concentration in the developer was measured. 
The results in Developer (1-1) are shown in Table 1-1 and the results in 
Developer (1-2) are shown in Table 1-2. The compounds of the present 
invention exhibited excellent capability to inhibit dissolving out of 
silver. 
Example 1-2 
In an automatic developing machine FG-460A (manufactured by Fuji Photo Film 
Co., Ltd.) filled with a developer and a fixing solution, Photosensitive 
Materials (1-1) to (1-4), output photosensitive material LS-5500 produced 
by the same company, dupe paper photosensitive material DU-150WP each was 
subjected to sensitometry. The exposure and processing conditions were as 
follows. 
Photosensitive Material (1-1): 
exposed to xenon flash light through an interference filter of 633 nm and a 
step wedge for an emission time of 10.sup.-6 second 
Photosensitive Material (1-2): 
exposed to xenon flash light through an interference filter having a peak 
at 488 nm and a step wedge for an emission time of 10.sup.-5 second 
Photosensitive Material (1-3): 
exposed by P-627FM Printer manufactured by Dainippon Screen Mfg. Co., Ltd. 
through a step wedge 
Photosensitive Material (1-4): 
exposed to tungsten light of 3200.degree. K through a step wedge 
LS-5500: 
exposed to xenon flash light through an interference filter having a peak 
at 488 nm and a step wedge for an emission time of 10.sup.-4 second 
DU-150WP: 
exposed by P-627FM Printer manufactured by Dainippon Screen Mfg. Co., Ltd. 
through a step wedge 
Processing Conditions: 
Photosensitive Materials (1-1), (1-2) and (1-4) were processed at a 
development temperature of 35.degree. C. and a fixing temperature of 
34.degree. C. for a development time of 30 seconds; 
the other photosensitive material was processed at a development 
temperature of 38.degree. C. and a fixing temperature of 37.degree. C. for 
a development time of 20 seconds 
In Tables 1-1 and 1-2, difference of the minimum density (Dmin) from blank 
and difference of sensitivity at a density of 3.0 (S3.0) from blank are 
shown. The smaller the difference, the smaller the influence on 
photographic properties and the more preferred. It is seen that the 
compounds of the present invention little affect the photographic 
properties. In particular, even when the addition amount is large, 
excellent result is obtained that the Dmin of dupe photosensitive material 
is not affected. The tolerance in practice is 0.03 or less for Dmin 
difference and within .+-.0.02 for S3.0 difference. 
Example 1-3 
After unexposed contact film RU-100 produced by the same company was 
processed at a rate of 100 m.sup.2 per day for 5 days in Example 1-2, 
unexposed contact paper photosensitive material KU-150WP (10.times.12 
inches) produced by the same company was processed and stains were 
observed. Developer (1-1) was replenished in an amount of 320 ml/m.sup.2, 
Developer (1-2) was replenished in an amount of 160 ml/m.sup.2 and the 
fixing solutions each was replenished in an amount of 260 ml/m.sup.2. The 
results obtained are shown in Tables 1-1 and 1-2. Samples on the level of 
4 or higher have no problem in practice. 
By using the compounds of the present invention, an excellent effect in 
preventing silver stains can be achieved without affecting the 
photographic properties at all. 
TABLE 1-1 
__________________________________________________________________________ 
(results in Developer (1-1)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Difference 
Material 
Material 
Material 
Material 
Compound 
(m/M) 
Out (ppm) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
1-I-1 0.5 0.11 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.06 .+-.0 +0.01 
.+-.0 
+0.01 
.+-.0.01 
.+-.0 
5 
1-I-3 0.5 0.20 .+-.0.01 
.+-.0 
-0.01 
.+-.0 
-0.01 
.+-.0 
4 
Invention 
1.0 0.13 +0.02 -0.01 
-0.02 
-0.02 
-0.02 
-0.01 
5 
1-I-5 0.5 0.1 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.05 +0.01 +0.01 
+0.01 
-0.01 
+0.01 
+0.01 
5 
1-I-6 0.5 0.15 .+-.0 .+-.0 
.+-.0 
+0.01 
-0.01 
.+-.0 
4 
Invention 
1.0 0.11 +0.01 +0.02 
+0.02 
+0.02 
-0.02 
+0.01 
5 
1-I-7 0.5 0.21 +0.01 +0.01 
.+-.0 
+0.01 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.12 +0.02 +0.02 
+0.01 
+0.02 
+0.01 
+0.01 
5 
1-I-9 0.5 0.19 .+-.0 .+-.0 
+0.01 
-0.01 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.1 +0.01 +0.02 
+0.02 
-0.02 
+0.01 
+0.02 
5 
1-II-1 
0.5 0.1 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.05 .+-.0 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
1-II-3 
0.5 0.17 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
-0.01 
4 
Invention 
1.0 0.1 +0.01 +0.01 
+0.01 
-0.02 
-0.02 
-0.02 
5 
1-II-8 
0.5 0.1 .+-.0 .+-.0 
.+-.0 
-0.01 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.08 +0.01 .+-.0 
-0.01 
-0.01 
-0.01 
.+-.0 
5 
1-C-1 0.5 0.5 +0.02 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
2 
Comparison 
1.0 0.35 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
3 
1-C-2 0.5 0.45 +0.03 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
3 
Comparison 
1.0 0.32 +0.06 +0.02 
+0.02 
+0.02 
+0.02 
+0.02 
3 
1-C-3 0.5 0.4 +0.03 -0.01 
-0.02 
.+-.0 
-0.02 
-0.02 
3 
Comparison 
1.0 0.31 +0.08 -0.04 
-0.04 
-0.03 
-0.04 
-0.04 
3 
1-C-4 0.5 1.8 +0.01 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
1 
Comparison 
1.0 1.0 +0.03 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
2 
Blank -- 3.4 -- -- -- -- -- -- 1 
Comparison 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
TABLE 1-2 
__________________________________________________________________________ 
(results in Developer (1-2)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Difference 
Material 
Material 
Material 
Material 
Compound 
(m/M) 
Out (ppm) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
1-I-1 0.5 0.10 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.05 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
+0.01 
5 
1-I-3 0.5 0.18 +0.01 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
4 
Invention 
1.0 0.15 +0.01 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
5 
1-I-5 0.5 0.10 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.04 +0.01 .+-.0 
+0.01 
-0.01 
+0.01 
.+-.0 
5 
1-I-6 0.5 0.13 .+-.0 .+-.0 
.+-.0 
+0.01 
-0.01 
.+-.0 
4 
Invention 
1.0 0.09 +0.01 +0.0 +0.0 +0.02 
-0.02 
+0.01 
5 
1-I-7 0.5 0.17 +0.01 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
4 
Invention 
1.0 0.11 +0.02 +0.02 
+0.01 
+0.02 
+0.02 
+0.01 
5 
1-I-9 0.5 0.16 +0.01 +0.01 
+0.01 
-0.01 
+0.01 
.+-.0 
4 
Invention 
1.0 0.12 +0.02 +0.02 
+0.02 
-0.02 
+0.02 
+0.02 
5 
1-II-1 
0.5 0.10 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.05 +0.01 +0.01 
.+-.0 
+0.01 
.+-.0 
.+-.0 
5 
1-II-3 
0.5 0.14 .+-.0 .+-.0 
.+-.0 
-0 .+-.0 
-0.01 
4 
Invention 
1.0 0.09 +0.01 +0.01 
+0.01 
-0.02 
-0.02 
-0.02 
5 
1-II-8 
0.5 0.08 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.06 .+-.0 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
5 
1-C-1 0.5 0.45 +0.02 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
3 
Comparison 
1.0 0.3 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
4 
1-C-2 0.5 0.4 +0.03 +0.01 
.+-.0.01 
+0.01 
+0.01 
+0.01 
3 
Comparison 
1.0 0.3 +0.06 +0.02 
+0.02 
+0.02 
+0.02 
+0.02 
4 
1-C-3 0.5 0.32 +0.03 -0.01 
-0.02 
-0.01 
-0.02 
.+-.0 
3 
Comparison 
1.0 0.25 +0.08 -0.04 
-0.04 
-0.03 
-0.04 
-0.03 
3 
1-C-4 0.5 1.7 +0.03 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
2 
Comparison 
1.0 1.0 +0.08 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
3 
Blank -- 2.8 -- -- -- -- -- -- 1 
Comparison 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
Comparative Compounds 1-C-1, 1-C-2, 1-C-3 and 1-C-4 in Tables 1-1 and 1-2 
had the following structural formulae: 
Comparative Compound 1-C-1: 
Compound described in JP-A-3-53244 
##STR29## 
Comparative Compound 1-C-2: 
Compound described in JP-A-3-53244 
##STR30## 
Comparative Compound 1-C-3: 
Compound described in JP-A-6-230525 
##STR31## 
Comparative Compound 1-C-4: 
Compound described in JP-A-56-24347, etc. 
##STR32## 
Example 2 
Developer (2-1) had the following composition per 1 l of the use solution. 
______________________________________ 
Potassium hydroxide 35.0 g 
Diethylenetriaminepentaacetic acid 
2.0 g 
Potassium carbonate 40.0 g 
Sodium metabisulfite 40.0 g 
Potassium bromide 3.0 g 
Hydroquinone 25.0 g 
5-Methylbenzotriazole 0.08 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3- 
0.45 g 
pyrazolidone 
Compound shown in Table 2-1 
shown in Table 2-1 
Sodium erythorbate 3.0 g 
Diethylene glycol 20.0 g 
pH 10.5 
______________________________________ 
Developer (2) had the following composition. 
______________________________________ 
Sodium hydroxide (beads, 99.5%) 
11.5 g 
Potassium sulfite (raw powder) 
63.0 g 
Sodium sulfite (raw powder) 
46.0 g 
Potassium carbonate 62.0 g 
Hydroquinone (briquette) 
40.0 g 
The following components were collectively 
briquetted. 
Diethylenetriaminepentaacetic acid 
2.0 g 
5-Methylbenzotriazole 0.35 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3 
1.5 g 
pyrazolidone 
Compound shown in Table 2-2 
shown in Table 2-2 
Sodium 3-(5-mercaptotetrazol-1-yl) 
0.1 g 
benzenesulfonate 
Sodium erythorbate 6.0 g 
Potassium bromide 6.6 g 
Dissolved in water to make 1l 
pH 10.65 
______________________________________ 
With respect to the shape of raw materials, the raw powder was a general 
industrial product used as it was and the beads of alkali metal salt were 
a commercially available product. 
The raw materials in the shape of a briquette each was compressed under 
pressure using a briquetting machine to have an undefined Rugby ball form 
having a length of approximately from 4 to 6 mm, and the briquette was 
crushed on use. With respect to the components in a small amount, 
respective components were blended and then briquetted. 
The thus-obtained processing agents (10 l portion) were each packed into a 
high density polyethylene-made container capable of folding and the 
takeout port was sealed with aluminum seal. On dissolving and replenishing 
the processing agent, a dissolving/replenishing apparatus having an 
automatic unsealing mechanism was used. 
Fixing solution (2-1) had the following formulation per 1 l of the use 
solution. 
______________________________________ 
Ammonium thiosulfate 120 g 
Disodium ethylenediaminetetraacetate 
0.03 g 
dihydrate 
Sodium thiosulfate pentahydrate 
11.0 g 
Sodium metasulfite 19.0 g 
Sodium hydroxide 12.4 g 
Acetic acid (100%) 30.0 g 
Tartaric acid 2.9 g 
Sodium gluconate 1.7 g 
Aluminum sulfate 8.4 g 
pH 4.8 
______________________________________ 
Fixing agent (2-2) had the following composition. 
______________________________________ 
Agent A: (solid) 
Ammonium thiosulfate (compact) 
125.0 g 
Sodium thiosulfate anhydride (raw powder) 
19.0 g 
Sodium metabisulfite (raw powder) 
18.0 g 
Sodium acetate anhydride (raw powder) 
42.0 g 
Agent B: (liquid) 
Disodium ethylenediaminetetraacetate 
0.03 g 
dihydrate 
Citric anhydride 3.7 g 
Sodium gluconate 1.7 g 
Aluminum sulfate 8.4 g 
Sulfuric acid 2.1 g 
Dissolved in water to make 50 ml. 
Agent A and Agent B were dissolved in water to make 1l. 
pH 4.8 
______________________________________ 
Ammonium thiosulfate (compact) used was obtained by compressing flakes 
prepared by a spray drying method under pressure in a roller compactor 
into undefined form chips having a size of approximately from 4 to 6 mm 
and blending with sodium thiosulfate anhydride. Other raw powders used 
were a general industrial product. 
Agent A and Agent B each in a 10 l portion were separately packed in a high 
density polyethylene-made container capable of folding. The takeout port 
of Agent A was sealed with an aluminum seal and the port of Agent B 
container was sealed with a screw cap. On dissolving and replenishing the 
processing agent, a dissolving/replenishing apparatus having an automatic 
unsealing mechanism was used. 
Example 2-1 
After dipping 16 sheets of contact film RU-100 (3.6 cm.times.12 cm) 
produced by Fuji Photo Film Co., Ltd. in 250 ml of a developer at 
38.degree. C. for 20 seconds while stirring by nitrogen bubbling, the 
silver concentration in the developer was measured. 
The results in Developer (2-1) are shown in Table 2-1 and the results in 
Developer (2-2) are shown in Table 2-2. The compounds of the present 
invention exhibited excellent capability to inhibit dissolving out of 
silver. 
Example 2 
In an automatic developing machine FG-460A (manufactured by Fuji Photo Film 
Co., Ltd.) filled with a developer and a fixing solution, Photosensitive 
Materials (1-1) to (1-4), output photosensitive material LS-5500 produced 
by the same company, dupe paper photosensitive material DU-150WP each was 
subjected to sensitometry. Developer (2-1) was used in combination with 
Fixing Solution (2-1) and Developer (2-2) was used in combination with 
Fixing Solution (2-2). The exposure and processing conditions were the 
same as in Example 1-2 
In Tables 2-1 and 2-2, difference of the minimum density (Dmin) from blank 
and difference of sensitivity at a density of 3.0 (S3.0) from blank are 
shown. The smaller the difference, the smaller the influence on 
photographic properties and the more preferred. It is seen that the 
compounds of the present invention little affect the photographic 
properties. In particular, even when the addition amount is large, 
excellent result is obtained that the Dmin of dupe photosensitive material 
is not affected. The tolerance in practice is 0.03 or less for Dmin 
difference and within .+-.0.02 for S3.0 difference. 
Example 2-3 
After unexposed contact film RU-100 produced by the same company was 
processed at a rate of 100 m.sup.2 per day for 5 days in Example 2-2, 
unexposed contact paper photosensitive material KU-150WP (10.times.12 
inches) produced by the same company was processed and stains were 
observed. Developer (2-1) was replenished in an amount of 320 ml/m.sup.2, 
Developer (2-2) was replenished in an amount of 160 ml/m.sup.2 and the 
fixing solutions each was replenished in an amount of 260 ml/m.sup.2. The 
results obtained are shown in Tables 2-1 and 2-2. Samples on the level of 
4 or higher have no problem in practice. 
By using the compounds of the present invention, an excellent effect in 
preventing silver stains can be achieved without affecting the 
photographic properties at all. 
TABLE 2-1 
__________________________________________________________________________ 
(results in Developer (2-1)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Difference 
Material 
Material 
Material 
Material 
Compound 
(mg/l) 
Out (ppm) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
2-I-1 73 0.20 .+-.0.00 
.+-.0.00 
.+-.0.00 
+0.01 
-0.01 
.+-.0.00 
4 
Invention 
145 0.15 +0.01 +0.02 
+0.02 
+0.02 
-0.02 
+0.01 
5 
2-I-2 87 0.18 +0.01 .+-.0.00 
.+-.0.00 
+0.02 
.+-.0.00 
.+-.0.00 
4 
Invention 
173 0.12 +0.02 +0.01 
+0.01 
.+-.0.00 
+0.01 
+0.01 
5 
2-I-3 133 0.17 .+-.0.00 
.+-.0.00 
+0.00 
+0.01 
.+-.0.00 
.+-.0.00 
5 
Invention 
265 0.10 +0.01 +0.02 
+0.02 
-0.01 
+0.01 
+0.02 
5 
2-I-10 
64 0.20 +0.01 .+-.0.00 
.+-.0.00 
-0.02 
.+-.0.00 
.+-.0.00 
4 
Invention 
128 0.15 +0.02 +0.01 
+0.01 
.+-.0.00 
+0.01 
+0.01 
5 
2-I-24 
88 0.20 .+-.0.00 
.+-.0.00 
.+-.0.00 
+0.01 
.+-.0.00 
-0.01 
4 
Invention 
177 0.16 +0.01 +0.01 
+0.01 
.+-.0.00 
-0.02 
-0.02 
5 
2-I-25 
102 0.21 .+-.0.00 
.+-.0.00 
.+-.0.00 
-0.02 
.+-.0.00 
.+-.0.00 
4 
Invention 
203 0.16 +0.01 -0.02 
-0.02 
-0.01 
-0.02 
-0.02 
4 
2-I-26 
108 0.19 .+-.0.00 
.+-.0.00 
.+-.0.00 
-0.02 
.+-.0.00 
.+-.0.00 
4 
Invention 
216 0.13 .+-.0.00 
+0.01 
+0.01 
.+-.0.00 
-0.02 
-0.02 
4 
2-C-1 91 0.50 +0.02 -0.01 
-0.01 
+0.01 
-0.01 
-0.01 
2 
Comparison 
182 0.35 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
3 
2-C-2 65 0.40 +0.03 +0.01 
-0.02 
.+-.0.00 
-0.02 
-0.02 
1 
Comparison 
129 0.31 +0.08 +0.04 
-0.04 
-0.03 
-0.04 
-0.04 
2 
2-C-3 144 1.8 +0.0 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
1 
Comparison 
288 1.0 +0.03 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
2 
Blank -- 3.4 -- -- -- -- -- -- 1 
Comparison 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
TABLE 2-2 
__________________________________________________________________________ 
(results in Developer (2-2)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Difference 
Material 
Material 
Material 
Material 
Compound 
(mg/l) 
Out (ppm) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
2-I-1 73 0.18 .+-.0.00 
.+-.0.00 
.+-.0.00 
+0.01 
-0.01 
.+-.0.00 
4 
Invention 
145 0.12 .+-.0.00 
+0.02 
+0.02 
+0.02 
-0.02 
.+-.0.01 
5 
2-I-2 87 0.17 +0.01 .+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.10 
.+-.0.00 
4 
Invention 
173 0.11 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
2-I-3 133 0.16 .+-.0.00 
.+-.0.00 
+0.01 
-0.01 
.+-.0.00 
.+-.0.00 
5 
Invention 
265 0.12 +0.01 +0.02 
+0.02 
-0.02 
+0.01 
+0.02 
5 
2-I-10 
64 0.18 +0.01 .+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
4 
Invention 
128 0.12 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
2-I-24 
88 0.17 .+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
-0.01 
4 
Invention 
177 0.12 +0.01 +0.01 
+0.01 
-0.02 
-0.02 
-0.02 
5 
2-I-25 
102 0.17 .+-.0.00 
.+-.0.00 
+0.01 
-0.01 
.+-.0.00 
.+-.0.00 
4 
Invention 
203 0.10 +0.01 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
4 
2-I-26 
108 0.16 .+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
.+-.0.00 
4 
Invention 
216 0.11 .+-.0.00 
+0.01 
+0.01 
+0.01 
-0.02 
-0.02 
4 
2-C-1 0.45 +0.02 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
3 
Comparison 0.35 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
2-C-2 65 0.50 +0.03 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
2 
Comparison 
129 0.40 +0.06 +0.02 
+0.02 
+0.02 
+0.02 
+0.02 
3 
2-C-3 144 1.7 +0.03 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
2 
Comparison 
288 1.0 +0.08 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
3 
Blank -- 2.8 +0.01 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
1 
Comparison 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
Comparative Compounds 2-C-1, 2-C-2 and 2-C-3 in Tables 2-1 and 2-2 had the 
following structural formulae: Comparative Compound 2-C-1: 
Compound described in JP-A-4-362942 
##STR33## 
Comparative Compound 2-C-2: 
Compound described in JP-A-5-303179, JP-A-5-61159 and JP-A-6-324435 
##STR34## 
Comparative Compound 2-C-3: 
Compound described in JP-A-56-24347 
##STR35## 
Example 3 
Developer (3-1) and (3-2) were prepared in the same manner as Developer 
(2-1) and (2-2), respectively, except for using the compounds shown in 
Table 3-1 and 3-2 instead of the compounds shown in Table 2-1 and 2-2, 
respectively. 
Example 3-1 
After dipping 16 sheets of contact film RU-100 (3.6 cm.times.12 cm) 
produced by Fuji Photo Film Co., Ltd. in 250 ml of a developer at 
38.degree. C. for 20 seconds while stirring by nitrogen bubbling, the 
silver concentration in the developer was measured. 
The results in Developer (3-1) are shown in Table 3-1 and the results in 
Developer (3-2) are shown in Table 3-2. The compounds of the present 
invention exhibited excellent capability to inhibit dissolving out of 
silver. 
Example 3-2 
In an automatic developing machine FG-460A (manufactured by Fuji Photo Film 
Co., Ltd.) filled with a developer and a fixing solution, Photosensitive 
Materials (1-1) to (1-4), output photosensitive material LS-5500 produced 
by the same company, dupe paper photosensitive material DU-150WP each was 
subjected to sensitometry. Developer (3-1) was used in combination with 
Fixing Solution (2-1) and Developer (3-2) was used in combination with 
Fixing Solution (2-2). The exposure and processing conditions were the 
same as in Example 1-2. 
In Tables 3-1 and 3-2, difference of the minimum density (Dmin) from blank 
and difference of sensitivity at a density of 3.0 (S3.0) from blank are 
shown. The smaller the difference, the smaller the influence on 
photographic properties and the more preferred. It is seen that the 
compounds of the present invention little affect the photographic 
properties. In particular, even when the addition amount is large, 
excellent result is obtained that the Dmin of dupe photosensitive material 
is not affected. The tolerance in practice is 0.03 or less for Dmin 
difference and within .+-.0.02 for S3.0 difference. 
Example 3-3 
After unexposed contact film RU-100 produced by the same company was 
processed at a rate of 100 m.sup.2 per day for 5 days in Example 3-2, 
unexposed contact paper photosensitive material KU-150WP (10.times.12 
inches) produced by the same company was processed and stains were 
observed. Developer (3-1) was replenished in an amount of 320 ml/m.sup.2, 
Developer (3-2) was replenished in an amount of 160 ml/m.sup.2 and the 
fixing solutions each was replenished in an amount of 260 ml/m.sup.2. The 
results obtained are shown in Tables 3-1 and 3-2. Samples on the level of 
4 or higher have no problem in practice. 
By using the compounds of the present invention, an excellent effect in 
preventing silver stains can be achieved without affecting the 
photographic properties at all. 
TABLE 3-1 
__________________________________________________________________________ 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Reduction 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Inhibition 
Difference 
Material 
Material 
Material 
Material 
Compound 
(mmol/l) 
Out (ppm) 
(days) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
(results in Developer (3-1)) 
3-I-1 0.5 0.15 10 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.1 15 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
5 
3-I-2 0.5 0.12 12 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.09 18 +0.01 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
5 
3-I-3 0.5 0.13 10 .+-.0 .+-.0 
+0.01 
-0.01 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.1 14 +0.01 +0.02 
+0.02 
-0.02 
+0.01 
+0.01 
5 
3-I-5 0.5 0.2 16 .+-.0 .+-.0 
.+-.0 
+0.01 
-0.01 
.+-.0 
4 
Invention 
1.0 0.15 19 .+-.0.01 
+0.02 
+0.02 
+0.02 
-0.02 
+0.01 
5 
3-II-4 
0.5 0.18 16 +0.01 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.12 19 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
3-II-8 
0.5 0.17 12 .+-.0 .+-.0 
+0.01 
-0.01 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.1 18 +0.01 +0.02 
+0.02 
-0.02 
+0.01 
+0.02 
5 
3-II-2 
0.5 0.2 15 +0.01 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.15 17 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
3-II-23 
0.5 0.2 16 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
-0.01 
4 
Invention 
1.0 0.16 19 +0.01 +0.01 
+0.01 
-0.02 
-0.02 
-0.02 
5 
3-II-28 
0.5 0.14 18 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 &gt;20 .+-.0 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
5 
3-II-31 
0.5 0.1 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.04 &gt;20 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
5 
3-II-32 
0.5 0.12 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.06 &gt;20 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
5 
(results in Developer (1-1)) 
3-II-35 
0.5 0.15 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.08 &gt;20 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
5 
3-I-9 0.5 0.13 17 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 &gt;20 .+-.0 +0.01 
.+-.0 
-0.01 
+0.01 
.+-.0 
5 
3-C-1 0.5 0.5 3 +0.02 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
2 
Comparison 
1.0 0.35 7 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
3 
3-C-2 0.5 0.45 4 +0.03 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
3 
Comparison 
1.0 0.32 8 +0.06 +0.02 
+0.02 
+0.02 
+0.02 
+0.02 
3 
3-C-3 0.5 1.8 &lt;1 +0.01 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
1 
Comparison 
1.0 1.0 1 +0.03 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
2 
Blank -- 3.4 just after 
-- -- -- -- -- -- 
Comparison addtion 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
TABLE 3-2 
__________________________________________________________________________ 
(results in Developer (3-2)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Silver 
Reduction 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
Dissolved 
Inhibition 
Difference 
Material 
Material 
Material 
Material 
Compound 
(mmol/l) 
Out (ppm) 
(days) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Stain 
__________________________________________________________________________ 
3-I-1 0.5 0.12 10 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.08 15 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
+0.01 
5 
3-I-2 0.5 0.1 12 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 18 +0.01 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
5 
3-I-3 0.5 0.11 10 .+-.0 .+-.0 
+0.01 
-0.01 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 14 +0.01 +0.02 
+0.02 
-0.02 
+0.01 
+0.02 
5 
3-I-5 0.5 0.18 16 .+-.0 .+-.0 
.+-.0 
+0.01 
-0.01 
.+-.0 
4 
Invention 
1.0 0.12 19 +0.01 +0.02 
+0.02 
+0.02 
-0.02 
+0.01 
5 
3-II-4 
0.5 0.17 16 +0.01 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.11 19 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
3-II-8 
0.5 0.16 12 .+-.0 .+-.0 
.times.0.01 
-0.01 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.12 18 +0.01 +0.02 
+0.02 
-0.02 
-0.01 
+0.02 
5 
3-II-2 
0.5 0.18 15 +0.01 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
4 
Invention 
1.0 0.12 17 +0.02 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
3-II-23 
0.5 0.17 16 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
-0.01 
4 
Invention 
1.0 0.12 19 +0.01 +0.01 
+0.01 
-0.02 
-0.02 
-0.02 
5 
3-II-28 
0.5 0.13 18 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 &gt;20 .+-.0 +0.01 
.+-.0 
.times.0.01 
+0.01 
.+-.0 
5 
3-II-31 
0.5 0.09 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.04 &gt;20 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
+0.01 
5 
3-II-32 
0.5 0.11 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.06 &gt;20 .+-.0 +0.01 
.+-.0 
+0.01 
+0.01 
.+-.0 
5 
3-II-35 
0.5 0.15 &gt;20 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.07 &gt;20 .+-.0 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
5 
3-I-9 0.5 0.13 17 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
5 
Invention 
1.0 0.06 &gt;20 +0.01 +0.01 
+0.01 
+0.01 
+0.01 
+0.01 
5 
3-C-1 0.5 0.45 3 +0.02 -0.01 
-0.01 
-0.01 
-0.01 
-0.01 
3 
Comparison 
1.0 0.3 7 +0.09 -0.02 
-0.02 
-0.02 
-0.02 
-0.02 
3 
3-C-2 0.5 0.4 4 .+-.0 .+-.0 
.+-.0 
.+-.0 
.+-.0 
.+-.0 
2 
Comparison 
1.0 0.3 8 .+-.0 +0.01 
+0.01 
+0.01 
-0.02 
-0.02 
3 
3-C-3 0.5 1.2 &lt;1 +0.01 -0.02 
-0.02 
-0.02 
-0.03 
-0.02 
2 
Comparison 
1.0 0.9 1 +0.03 -0.06 
-0.06 
-0.05 
-0.06 
-0.04 
2 
Blank -- 2.8 just after 
-- -- -- -- -- -- 1 
Comparison addtion 
__________________________________________________________________________ 
Level of stain: 
5: completely no stain 
4: solution was turbid but not bad effect in practice 
3: silver sludge was deposited on the tank bottom, paper bore thin stains 
2: edge of paper was stained 
1: stains were attached throughout the paper surface 
Comparative Compounds 3-C-1, 3-C-2 and 3-C-3 in Tables 3-1 and 3-2 had the 
following structural formulae: 
Comparative Compound 3-C-1: 
Compound described in JP-A-4-362942 
##STR36## 
Comparative Compound 3-C-2: 
Compound described in JP-B-46-11630 and JP-A-49-11333 
##STR37## 
Comparative Compound 3-C-3: 
Compound described in JP-A-56-24347, etc. 
##STR38## 
Example 4 
Developer (4-1) had the following composition per 1 l of the use solution. 
______________________________________ 
Potassium hydroxide 105.0 g 
Diethylenetriaminepentaacetic acid 
6.0 g 
Potassium carbonate 120.0 g 
Sodium metabisulfite 120.0 g 
Potassium bromide 9.0 g 
Hydroquinone 75.0 g 
5-Methylbenzotriazole 0.25 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3- 
1.35 g 
pyrazolidone 
Compound represented by formula (4) 
shown in Table 4-1 
Sodium erythorbate 9.0 g 
Diethylene glycol 60.0 g 
pH 10.7 
______________________________________ 
Upon use, 1 part of the above-described concentrated solution was diluted 
with 2 parts of water. The pH of the diluted solution was 10.5. 
______________________________________ 
Developer (4-2) had the following composition. 
______________________________________ 
Sodium hydroxide (beads, 99.5%) 
11.5 g 
Potassium sulfite (raw powder) 
63.0 g 
Sodium sulfite (raw powder) 
46.0 g 
Potassium carbonate 
62.0 g 
Hydroquinone (briquette) 
40.0 g 
______________________________________ 
The following components were collectively briquetted. 
______________________________________ 
Diethylenetriaminepentaacetic acid 
2.0 g 
5-Methylbenzotriazole 0.35 g 
4-Hydroxymethyl-4-methyl-1-phenyl-3- 
1.5 g 
pyrazolidone 
Compound represented by formula (4) 
shown in Table 4-1 
Sodium 3-(5-mercaptotetrazol-1-yl) 
0.1 g 
benzenesulfonate 
Sodium erythorbate 6.0 g 
Potassium bromide 6.6 g 
Dissolved in water to make 1l 
pH 10.65 
______________________________________ 
With respect to the shape of raw materials, the raw powder was a general 
industrial product used as it was and the beads of alkali metal salt were 
a commercially available product. 
The raw materials in the shape of a briquette each was compressed under 
pressure using a briquetting machine to have a plate form, and the 
briquette was crushed on use. With respect to the components in a small 
amount, respective components were blended and then briquetted. 
The thus-obtained processing agents (10 l portion) were each packed into a 
high density polyethylene-made container capable of folding and the 
takeout port was sealed with aluminum seal. On dissolving and replenishing 
the processing agent, a dissolving/replenishing apparatus having an 
automatic unsealing mechanism was used. 
Fixing solution (4-1) had the following formulation per 1 l of the use 
solution. 
______________________________________ 
Ammonium thiosulfate 360 g 
Disodium ethylenediaminetetraacetate 
0.09 g 
dihydrate 
Sodium thiosulfate pentahydrate 
33.0 g 
Sodium metasulfite 57.0 g 
Sodium hydroxide 37.2 g 
Acetic acid (100%) 90.0 g 
Tartaric acid 8.7 g 
Sodium gluconate 5.1 g 
Aluminum sulfate 25.2 g 
pH 4.85 
______________________________________ 
Upon use, 1 part of the above-described concentrated solution was diluted 
with 2 parts of water. The pH of the diluted solution was 4.8. 
Fixing agent (4-2) had the following composition. 
______________________________________ 
Agent A: (solid) 
Ammonium thiosulfate (compact) 
125.0 g 
Sodium thiosulfate anhydride (raw powder) 
19.0 g 
Sodium metabisulfite (raw powder) 
18.0 g 
Sodium acetate anhydride (raw powder) 
42.0 g 
Agent B: (liquid) 
Disodium ethylenediaminetetraacetate 
0.03 g 
dihydrate 
Citric anhydride 3.7 g 
Sodium gluconate 1.7 g 
Aluminum sulfate 8.4 g 
Sulfuric acid 2.1 g 
Dissolved in water to make 50 ml. 
Agent A and Agent B were dissolved in water to make 1l. 
pH 4.8 
______________________________________ 
Ammonium thiosulfate (compact) used was obtained by compressing flakes 
prepared by a spray drying method under pressure in a roller compactor 
into undefined form chips having a size of approximately from 4 to 6 mm 
and blending with sodium thiosulfate anhydride. Other raw powders used 
were a general industrial product. 
Agent A and Agent B each in a 10 l portion were separately packed in a high 
density polyethylene-made container capable of folding. The takeout port 
of Agent A was sealed with an aluminum seal and the port of Agent B 
container was sealed with a screw cap. On dissolving and replenishing the 
processing agent, a dissolving/replenishing apparatus having an automatic 
unsealing mechanism was used. 
Example 4-1 
In an automatic developing machine FG-680AG (manufactured by Fuji Photo 
Film Co., Ltd.) filled with a developer and a fixing solution, 
Photosensitive Materials (1-1) to (1-4), output photosensitive material 
LS-5500 produced by the same company, dupe paper photosensitive material 
DU-150WP which is imagewise exposed at a blackened ratio of 30% each was 
subjected to sensitometry after a 10-day processing of the photosensitive 
materials at a rate of 100 m.sup.2 per day. Photosensitive Materials 
(1-1), (1-2) and (1-4) were processed at a development temperature of 
35.degree. C. and a fixing temperature of 34.degree. C. for a development 
time of 30 seconds. The other photosensitive material was processed at a 
development temperature of 38.degree. C. and a fixing temperature of 
37.degree. C. for a development time of 20 seconds. The replenishment 
amount of the developers are shown in Tables 4-1 and 4-2. The fixing 
solutions each was replenished in an amount of 160 ml/m.sup.2. The 
exposure conditions for each photosensitive material were the same as in 
Example 1-2. 
In Table 4-1, difference of the minimum density (Dmin) from blank and 
difference of sensitivity at a density of 1.5 (S.sub.1.5) from blank are 
shown. The tolerance in practice is 0.03 or less for Dmin difference and 
within .+-.0.03 for S.sub.1.5 difference. 
TABLE 4-1 
__________________________________________________________________________ 
(results in Developer (4-1)) 
S3.0 Difference 
Amount of Photo- 
Photo- 
Photo- 
Photo- 
Addition 
Developer 
Dmin sensitive 
sensitive 
sensitive 
sensitive 
Amount 
replenished 
Difference 
Material 
Material 
Material 
Material 
Compound 
(mmol/l) 
(ml/m.sup.2) 
DU-150WP 
1-1 1-2 1-3 1-4 LS-5500 
Remark 
__________________________________________________________________________ 
4-I-1 1.0 160 0.01 0.02 0.01 0.01 0 -0.01 
Invention 
4-I-3 0.08 160 0 0 0.01 0.01 0.01 0.01 Invention 
4-I-4 1.0 160 0 0.01 0 0.01 -0.02 
-0.02 
Invention 
4-I-5 1.0 160 0 0.01 0 0.01 0.01 0.01 Invention 
4-I-6 1.0 160 0 0.01 0 0.01 -0.01 
0.01 Invention 
4-I-8 1.0 160 0.2 -0.02 
0.01 -0.01 
0.01 0 Invention 
4-I-16 
1.0 160 0.01 0.01 0.01 -0.01 
0.01 -0.01 
Invention 
4-I-33 
1.0 160 0.02 -0.02 
0.01 -0.01 
0.01 0.01 Invention 
4-I-3 0.008 
160 0 -0.01 
-0.01 
-0.02 
0 0.02 Comparison 
4-C-1 1.0 160 0.08 -0.04 
-0.06 
-0.04 
-0.05 
-0.04 
Comparison 
4-C-2 1.0 160 0.04 -0.03 
-0.03 
-0.02 
0.03 -0.03 
Comparison 
__________________________________________________________________________ 
Comparative Compounds 4-C-1 and 4-C-2 in Table 4-1 had the following 
structural formulae: 
Comparative Compound 4-C-1: 
##STR39## 
Comparative Compound 4-C-2: 
##STR40## 
Example 4-2 
After processing unexposed Photosensitive Material (3) was processed at a 
rate of 100 m.sup.2 per day for 10 days under the same conditions as in 
Example 4-1, generation of sludge in the development tank was visually 
observed. Then, unexposed contact paper photosensitive material KU-150WP 
(10.times.12 inches) produced by Fuji Photo Film Co., Ltd. was processed 
and stains were evaluated. The results obtained are shown in Table 4-2. 
Samples on the level of 4 or higher have no problem in practice. 
TABLE 4-2 
______________________________________ 
Amount of Reduc- 
Addition Developer tion In- 
Com- Amount Replenished 
Silver 
Silver 
hibition 
pound (mmol/l) (ml/m.sup.2) 
sludge 
Stain 
(days) 
Remark 
______________________________________ 
4-I-1 1.0 160 4 4 19 Invention 
4-I-3 0.08 160 4 4 20 Invention 
4-I-4 1.0 160 4 4.5 &gt;20 Invention 
4-I-5 1.0 160 5 5 &gt;20 Invention 
4-I-6 1.0 160 5 5 20 Invention 
4-I-8 1.0 160 4.5 4 &gt;20 Invention 
4-I-16 
1.0 160 4.5 4.5 &gt;20 Invention 
4-I-33 
1.0 160 4 4 18 Invention 
4-I-3 0.008 160 3.5 3 10 Compari- 
son 
4-C-1 1.0 160 2.5 2.5 3 Compari- 
son 
4-C-2 1.0 160 2.5 2 2 Compari- 
son 
Blank -- 160 1 1 &lt;1 Compari- 
son 
Blank -- 390 2 2 &lt;1 Compari 
son 
______________________________________ 
Silver sludge 
5: no stain in the bottom of the tank and the rack 
4: rack discolored slightly 
3: rack discolored 
2: precipitate was formed at the bottom of the tank and rack discolored 
1: great amount of precipitate was formed at the bottom of the tank, 
solution became turbid and rack also discolored 
Level of stain: 
5: completely no stain 
4: slightly stained but not bad effect in practice 
3: edge of paper was stained 
2: paper was stained entirely 
1: stains were attached throughout the paper surface and processed film 
Reduction Inhibition: Days required for silver ion concentration to be 
reduced to 20 ppm or lower 
Example 4-4 
The same experiments as in Examples 4-1 and 4-2 were carried out using a 
solid developer (Developer 4-2) and a solid fixing agent (Fixing Agent 
(4-2). As a result, the same results as in Examples 4-1 and 4-2 were 
obtained. 
Example 4-5 
The same processings as in Examples 4-1 and 4-2 were carried out except for 
replacing the automatic developing machine with an automatic developing 
machine FG-680AS produced by Fuji Photo Film Co., Ltd. and changing the 
developing time to 11 seconds. As a result, the same results as in 
Examples 4-1 and 4-2 were obtained. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.