Silver halide photographic material and method for forming image

The present invention provides a silver halide photographic material and an image forming method for obtaining a monochrome image using a dye image even if it is treated with a color developer free of benzyl alcohol; a photographic property of the monochrome image is less deteriorated by a toxic gas such as formaldehyde and an increase in sensitization and fog with time is improved. A silver halide photographic material comprising a support, at least one silver halide emulsion layer on the support and at least one non-photosensitive hydrophilic colloidal layer, in which a silver halide grain of the silver halide emulsion layer includes not less than 95% mol of silver halide and in which the silver halide emulsion layer includes a yellow coupler, a magenta coupler, a cyan coupler and a specific formalin scavenger and the silver halide emulsion layer and/or the non-photosensitive hydrophilic colloidal layer include a specific s-triazine type compound and a method for forming an image by developing the silver halide photographic material with a color developer substantially free of benzyl alcohol.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a silver halide photographic material and 
a method for forming an image by developing the material, and particularly 
relates to a monochrome photographic material involving the use of dye 
images which can be processed with a color developer substantially free 
from benzyl alcohol, has a photographic property that is less deteriorated 
by a toxic gas such as formaldehyde, has an improved sensitization and fog 
with time, and relates to a method for forming an image. 
2. Description of the Related Art 
Monochrome images are developed from conventional silver images using a 
monochrome developing agent such as hydroquinone. There is a few 
laboratories and photo studios where such development can be conducted. 
Color paper is generally developed with a color developer substantially 
free of benzyl alcohol. A treating machine suitable for the color 
development is widely used in the laboratories and photo studios. It is 
desirable that a material for forming the monochrome images is applied to 
the color development. 
It is known that a photographic system of forming the monochrome images 
utilizing a combination of cyan, magenta and yellow dyes (see, for 
example, WO 93/12465 corresponding to U.S. Pat. No. 5,362,616 and JP-A No. 
6-505580). In the system, dyes are formed from a mixture of cyan, magenta 
and yellow couplers during the development. When reacting with an oxidized 
color developing agent, the couplers produce a neutral (black-and-white) 
image. 
Recently, furniture and building materials reformed by formaldehyde, 
adhesives utilized formaldehyde as a curing agent, formaldehyde resin 
manufactured products, leather tanned by formaldehyde, clothing used 
formaldehyde as a bactericide and a bleaching agent are widely used. There 
are many chances that the photographic materials are contacted with a 
formaldehyde gas. 
The present inventors discovered that a magenta coupler is affected by the 
formaldehyde gas even in a photographic system where a combination of a 
cyan dye, a magenta dye and a yellow dye is used to form a monochrome 
image. For example, if the above-described photographic materials are 
stored in a cassette made of a formalin resin, photographic properties are 
degraded by the formalin. 
The present inventors discovered that a formalin scavenger is used to 
improve the degradation. However, the present inventors also found that 
the formalin scavenger sensitizes a portion of the photographic materials 
contacted with air, for example, an outermost surface or a side rim of a 
roll-shaped photographic material. Such phenomenon destroys an image 
balance upon exposure and development of the photographic material and is 
therefore not preferable. 
An object of the present invention is to provide a silver halide 
photographic material for obtaining a monochrome image with a dye image 
where a magenta coupler is less affected by the formaldehyde gas. 
Another object of the present invention is to provide a silver halide 
photographic material preventing sensitizing of a portion contacted with 
air for a while and decreasing fog. 
Still another object of the present invention is to provide a method for 
forming a monochrome image with a dye image by developing it with a color 
developer substantially free of benzyl alcohol. 
DISCLOSURE OF THE INVENTION 
To be solved the problems, the present invention provides a silver halide 
photographic material, comprising a support and at least one silver halide 
emulsion layer and at least one non-photosensitive hydrophilic colloidal 
layer, both provided on the support, silver halide grains of the silver 
halide emulsion layer including not less than 95% mol of silver chloride, 
the silver halide emulsion layer including a yellow coupler, a magenta 
coupler, a cyan coupler and at least one of the following compounds 
represented by the formula (I) or (II): 
##STR1## 
wherein R.sub.1 represents a hydrogen atom, an alkyl group having 1 to 4 
carbon atoms or an acyl group and Z.sub.1 represents an ethylenic chain or 
a trimethine chain, 
##STR2## 
wherein R.sub.2 to R.sub.6 represent a hydrogen atom, an alkyl group having 
1 to 4 carbon atoms, an aryl group or an aralkyl group, 
at least one of the silver halide emulsion layer and the non-photosensitive 
hydrophilic colloidal layer including at least one of the following 
compounds represented by the formula (III) or (IV): 
##STR3## 
wherein R.sub.7 represents a chlorine atom, a hydroxy group, an alkyl 
group, an alkoxy group, an alkylthio group, an --OM group, M being a 
monovalent metal atom, --NR.sub.9 R.sub.10 group or --NHCOR.sub.11 group, 
R.sub.9, R.sub.10 or R.sub.11 being a hydrogen atom, an alkyl group or an 
aryl group; R.sub.8 represents the same as R.sub.7 except the chlorine 
atom, 
##STR4## 
wherein R.sub.12 and R.sub.13 represent a chlorine atom, a hydroxy group, 
an alkyl group, an alkoxy group or an --OM group, M being a monovalent 
metal atom, Q.sub.1 and Q.sub.2 represent --O--, --S--or --NH--, and L 
represents an alkylene group or an arylene group, n.sub.1 and n.sub.2 
represent 0 or 1. The couplers are dye-forming couplers. 
Secondary, the present invention provides the material according to the 
above-mentioned silver halide photographic material, 
wherein the non-photosensitive hydrophilic colloidal layer includes at 
least one of the compounds represented by the formula (I) or (II). 
Thirdly, the present invention provides the material according to one of 
the above-mentioned silver halide photographic material, 
which comprises the support, the emulsion layer, provided on the support 
and the colloidal layer, provided on the emulsion layer. 
Fourthly, the present invention provides the material according to the 
firstly-mentioned silver halide photographic material, 
which comprises the support, the colloidal layer, provided on the support, 
and the emulsion layer, provided on the colloidal layer. 
Fifthly, the present invention provides a method for forming an image by 
comprising steps of exposing the material as defined in the firstly- or 
secondary- mentioned silver halide photosensitive material to 
image-carrying light and developing the material with a color developer 
substantially free of benzyl alcohol. 
Regarding a halogenated composition in the silver halide emulsion used in 
the present invention, it is preferred that silver halide grains comprise 
not less than 95 mol % of silver chloride and comprise silver 
chloride/bromide substantially free of silver iodide. 
An average grain size of the silver halide grains (an average diameter of 
sphere or sphere-like grains, or an average ridge length of cube grains 
based on a projected area) is not especially limited, but is preferably 
not more than 3 .mu.m. 
The grain size distribution may be narrow or wide. 
The silver halide grains may have a regular crystal form such as cube and 
octahedron, an anomalous crystal form such as sphere and tabular plate, a 
composite thereof or a mixture of grains having various crystal forms. 
An emulsion in which tabular silver halide grains having a diameter of five 
times or more larger than a thickness thereof occupy not less than 50% of 
the total projected area may be used. 
The grains may have a latent image mainly formed on surfaces thereof or 
inside the grains. 
The silver halide grains may have a laminated structure comprising 
different halogenated compositions on the inside and the outside of the 
grains or may be bonded with other silver halide grains having different 
halogen compositions by an epitaxial bonding. 
In the silver halide grains of the silver halide emulsion according to the 
present invention, it is preferred that a localized layer containing 30 to 
60 mol % of silver bromide is epitaxially grown locally on the surfaces, 
especially corners of the halogenated grains. The localized layer is 
preferably composed of 0.5 to 5% of silver based on the total weight of 
the silver constituting the silver halide grains. A method for producing 
the epitaxial silver halide grains is described in EP-A No. 273,430. 
The silver halide emulsion employed in the present invention can be 
prepared by using a method described in P. Glafkides, Chimie et Physique 
Photographique (Paul Montel, 1967), G. F. Duffin, Photographic Emulsion 
Chemistry (The Focal Press, 1966), V. L. Zelikman et al, Making and 
Coating Photographic Emulsion (The Focal Press, 1964) or the like. In 
other words, any of an acid process, a neutral process, an ammonia process 
and the like can be used. As a method of reacting a soluble silver salt 
with a soluble halogen salt, any conventional mixing method may be used, 
such as the normal order of introducing the silver salt into the halogen 
salt, a reversed order thereto, a simultaneous mixing and a combination 
thereof. 
As one of the simultaneous mixing, a method for keeping constantly pAg in 
the solution of the silver halide and a so-called control double jet 
method can be used. According to the method, a silver halide emulsion 
having a regular crystal form and an approximately uniform grain size can 
be obtained. 
Two or more of silver halide emulsions separately formed may be mixed for 
use. 
During a formation or a physical ripening of the silver halide grains, a 
cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt 
or a complex salt thereof, a rhodium salt or a complex salt thereof, an 
iron salt or a complex salt may coexist. 
The silver halide emulsion may be chemically sensitized in a conventional 
way. For example, a sulfur sensitizing method utilizing an active gelatin 
and a compound containing a reactive sulfur with silver, such as a 
thiosulphate, thio-ureas, a mercapto compound and rhodanine compounds, a 
reducing sensitizing method utilizing a reducing substance such as a 
stannous salt, amines, a hydrazine derivative, a formamidine sulfinic acid 
and a silane compound, or a noble metal-sensitizing method utilizing a 
noble metal compound such as a complex salt of a metal such as gold, 
platinum, iridium and palladium may be used alone or in combination. 
The compound represented by the formula (I) or (II) will be described 
below. 
##STR5## 
wherein R.sub.1 represents a hydrogen atom, an alkyl group having 1 to 4 of 
carbon atoms (i.e., a methyl group, an ethyl group, a propyl group, an 
ethoxymethyl group) or an acyl group (i.e., an acetyl group, a benzyl 
group), and Z.sub.1 represents an ethylenic chain or a trimethine chain. 
##STR6## 
wherein R.sub.2 to R.sub.6 represent a hydrogen atom, an alkyl group having 
1 to 4 of carbon atoms (i.e., a methyl group, an ethyl group, a propyl 
group) or an aryl group (i.e., a phenyl group), and aralkyl group (i.e., a 
benzyl group). 
Examples of the compound represented by the formula (I) or (II) is as 
follows: 
##STR7## 
The above-described compounds are commercially available and can also be 
synthesized by a method described in U.S. Pat. Nos. 3,187,004 and 
3,242,044. 
One or more of the compounds represented by the formula (I) or (II) are 
contained in a silver halide emulsion layer containing a yellow coupler, a 
magenta coupler and a cyan coupler, or both of the silver halide emulsion 
layer and a non-photosensitive hydrophilic colloidal layer. Examples of 
the non-photosensitive hydrophilic colloidal layer of the present 
invention includes a protective layer, an intermediate layer, a 
ultraviolet ray absorbing layer, a yellow filter layer, an antihalation 
layer, an antistatic layer or the like. A preferred layer of the 
non-photosensitive hydrophilic colloidal layer containing the compound 
represented by the formula (I) or (II) is a layer which is nearest to 
outside air in the photosensitive material, i.e., the protective layer. 
In order to add and introduce the compound represented by the formula (I) 
or (II) of the present invention to these layers, the compound may be 
dissolved in a suitable solvent such as water and methanol to add to a 
coating solution for forming a layer at any stage, generally at the same 
time when other additives are added or desirably directly before coating. 
An additive amount of the compound to the silver halide emulsion layer is 
in the range of 0.1 g to 1.0 g per 1 m.sup.2, 0.1 g to 1.0 g in the 
non-photosensitive hydrophilic colloidal layer, 0.1 g to 2.0 g in the 
whole photographic material to provide a preferred effect. 
The compound represented by the formula (III) or (IV) will be described. 
##STR8## 
wherein R.sub.7 represents a chlorine atom, a hydroxyl group, an alkyl 
group (i.e., a methyl group, an ethyl group, a butyl group), an alkoxy 
group (i.e., a methoxy group, an ethoxy group, a butoxy group), an 
alkylthio group, an --OM group (in which M is a monovalent metal atom, 
i.e., a sodium atom, a potassium atom), --NR.sub.9 R.sub.10 group or 
--NHCOR.sub.11 group (in which Rg, R.sub.10 or R.sub.11 represents a 
hydrogen atom, an alkyl group or an aryl group); R.sub.8 represents the 
same as R.sub.7 except the chlorine atom. 
The compound represented by the formula (III) is described in U.S. Pat. No. 
3,645,743, JP-B No. 47-6151, No. 47-33380 and No. 51-9607. 
##STR9## 
wherein R.sub.12 and R.sub.13 represent a chlorine atom, a hydroxyl group, 
an alkyl group (i.e., a methyl group, an ethyl group, a butyl group), an 
alkoxy group (i.e., a methoxy group, an ethoxy group, a buthoxy group) or 
an --OM group (in which M is a monovalent metal atom, i.e., a sodium atom, 
a potassium atom), Q.sub.1 and Q.sub.2 represent --O--, --S--or --NH--, 
and L represents an alkylene group (i.e., a methylene group, an ethylene 
group, a propylene group) or an arylene group (i.e., o-, m- or p-phenylene 
group). n.sub.1 and n.sub.2 represent 0 or 1. 
The compound represented by the formula (IV) is described in JP-B No. 
58-33542 and JP-A No. 57-40244. 
The compound represented by the formula (III) and (IV) of the present 
invention is dissolved in water or alcohol (i.e., methyl alcohol, ethyl 
alcohol) to add in an amount of 1 to 100 mg, preferably 5 to 50 mg per 1 g 
of gelatin. A method for adding may be a batch mode or an in-line mode, 
preferably the in-line mode of adding directly before coating. 
Examples of the compound represented by the formula (III) or (IV) are as 
follows: 
##STR10## 
The silver halide emulsion of the present invention is preferably spectral 
sensitized with at least one sensitizing dye represented by the formula 
(V), at least one sensitizing dye represented by the formula (VI) and at 
least one sensitizing dye represented by the formula (VII) or (VIII). 
##STR11## 
In the formula (V), wherein R.sub.21 and R.sub.22 represent an alkyl group 
having 1 to 6 of carbon atoms (i.e., a methyl group, an ethyl group, an 
n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, 
an n-hexyl group, an isohexyl group), a substituted alkyl group having 1 
to 4 of carbon atoms [for example, a hydroxyl alkyl group (i.e., a 
2-hydroxyl ethyl group, a 3-hydroxy propyl group, a 2-hydroxy propyl 
group), a sulfo alkyl group (i.e., a 2-sulfo ethyl group, a 3- sulfo 
propyl group, a 3-sulfo butyl group, a 4-sulfo butyl group), a carboxyl 
alkyl group (i.e., a 2-carboxyl ethyl group, a 3-carboxy propyl group, a 
3-carboxy butyl group, a 4-carboxy butyl group)], an aralkyl group (i.e., 
a benzyl group, a 2-phenylethyl group). Preferably either one of R.sub.21 
and R.sub.22 represent the substituted alkyl group. Z.sub.2 and Z.sub.3 
represent non-metal atoms that are required to form a benzene nucleus or a 
naphthalene nucleus which may have a substituted group (i.e., a halogen 
atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an 
alkoxy carbonyl group, a trifluoromethyl group, an alkyl sulfonyl group, 
an alkyl sulfamoyl group, an acyl amino group, an alkyl carbamoyl group, 
an acetoxy group). X.sub.1 represents an anionic group generally employed 
(i.e., a chloride ion, a bromide ion, an iodide ion, a perchlorate acid 
ion, a p-toluene sulfonate ion, an ethylsufate acid ion). P.sub.1 
represents 1 or 2, with a proviso that when P.sub.1 is 1, an 
intermolecular salt is formed. 
In the formula (VI), wherein R.sub.23 and R.sub.24 represent an alkyl group 
having 1 to 6 of carbon atoms that may have a sulfo group as a substituted 
group (i.e., a methyl group, an ethyl group, a n-propyl group, an 
isopropyl group, a n-butyl group, an isobutyl group, a n-hexyl group, a 
2-sulfoethyl group, a 3-sulfo propyl group, a 3-sulfobutyl group), A.sub.1 
represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms 
(i.e., a methyl group, an ethyl group, a n-propyl group, an isopropyl 
group) and an aryl group (i.e., a phenyl group), Y.sub.1 and Y.sub.2 
represent a sulfur atom, an oxygen atom, a selenium atom, and N--R.sub.25, 
and R.sub.25 represents an alkyl group having 1 to 3 carbon atoms (i.e., a 
methyl group, an ethyl group, an n-propyl group, an isopropyl group). 
Z.sub.4 and Z.sub.5 represent non-metal atoms that are required to form a 
benzene nucleus or a naphthalene nucleus which may have a substituted 
group (i.e., a halogen atom, an alkyl group, an alkoxy group, an aryl 
group, a carbonyl group, an alkoxy carbonyl group, a cyano group). X.sub.2 
represents an anionic group (i.e., a chlorine ion, a bromine ion, an 
iodine ion, a perchlorate ion, a p-toluene sulfonate ion, an ethylsufate 
acid ion). P.sub.2 represents 1 or 2, with a proviso that when P.sub.2 is 
1, an intermolecular salt is formed. 
In the formula (VII) or (VIII), wherein R.sub.26, R.sub.27, R.sub.28 and 
R.sub.29 represent an alkyl group having 1 to 6 of carbon atoms (i.e., a 
methyl group, an ethyl group, a n-propyl group, an isopropyl group, a 
n-butyl group, an isobutyl group, an n-hexyl group, an isohexyl group), a 
substituted alkyl group having 1 to 4 of carbon atoms [for example, a 
hydroxyl alkyl group (i.e., a 2-hydroxyl ethyl group, a 3-hydroxy propyl 
group, a 2-hydroxy propyl group), a sulfo alkyl group (i.e., a 2-sulfo 
ethyl group, a 3- sulfo propyl group, a 3-sulfo butyl group, a 4-sulfo 
butyl group), a carboxyl alkyl group (i.e., a 2-carboxyl ethyl group, a 
3-carboxy propyl group, a 3-carboxy butyl group, a 4-carboxy butyl 
group)], an aralkyl group (i.e., a benzyl group, a 2-phenylethyl group). 
Preferably, either one of R.sub.26 and R.sub.27 is the substituted alkyl 
group. Also, preferably either one of R.sub.28 and R.sub.29 is the 
substituted alkyl group. A.sub.2 represents a hydrogen atom, an alkyl 
group having 1 to 3 carbon atoms (i.e., a methyl group, an ethyl group, an 
n-propyl group, an isopropyl group) and an aryl group (i.e., a phenyl 
group). Z.sub.6, Z.sub.7, Z.sub.8 and Z.sub.9 represent non-metal atoms 
that are required to form a benzene nucleus or a naphthalene nucleus which 
may have a substituted group (i.e., a halogen atom, an alkyl group, an 
alkoxy group, an aryl group, a cyano group, an alkoxy carbonyl group, a 
trifluoromethyl group, an alkyl sulfonyl group, an alkyl sulfamoyl group, 
an acyl amino group, an alkyl carbamoyl group, an acetoxy group). Z.sub.10 
represents non-metal atoms that are required to form a six member ring 
nucleus which may have a substituted group (i.e., an alkyl group). X.sub.3 
and X.sub.4 represent an anionic group generally employed (i.e., a 
chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a p-toluene 
sulfonate ion, an ethylsufate acid ion). P.sub.3 and q represent 1 or 2, 
with a proviso that when P.sub.3 and q are 1, an intermolecular salt is 
formed. 
Examples of these sensitizing dyes are described in JP-A 10-20432 
(corresponding to U.S. Pat. No. 5,728,511). 
These sensitizing dyes have a concentration of 10.sup.-6 to 10.sup.-3 mol 
per 1 mol of the silver halide in the silver halide emulsion. Upon adding 
such sensitizing dyes to the silver halide emulsion, the sensitizing dyes 
may be directly dispersed into the silver halide emulsion, or may be 
dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, 
acetone, N,N-dimethyl formamide, ethyl acetate, a mixture thereof, or 
these solvent containing a surfactant to add to the silver halide 
emulsion. 
These sensitizing dyes can be added to the silver halide emulsion upon the 
formation or after the physical ripening of the silver halide grains. 
Preferably, the silver halide emulsion is added after the physical 
ripening, before a chemical ripening, during the chemical ripening, or 
after the chemical ripening. These sensitizing dyes may be used singly or 
in combination. The combination of the sensitizing dyes is often used 
especially for a purpose of supersensitization. 
The emulsion may contain, in addition to the above sensitizing dyes, a dye 
which does not exhibit any spectral sensitization effect in itself or a 
substance which scarcely absorbs visible light but exhibits a 
supersensitization effect. For example, the dye and the substance include 
an aminostyryl compound substituted by a heterocyclic ring containing 
nitrogen (i.e., a compound described in U.S. Pat. Nos. 2,933,390 and 
3,635,721), an aromatic organic acid formaldehyde condensate (i.e., a 
compound described in U.S. Pat. No. 3,743,510), a cadmium salt, an 
azaindene compound or the like. 
An example of the yellow coupler employed in the present invention includes 
an oil protect acylacetamide type coupler. Specific examples are described 
in U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506. Preferably, the two 
equivalent yellow coupler may be used for the present invention. For 
example, an oxygen atom eliminated yellow coupler is described in U.S. 
Pat. Nos. 3,408,194, 3,447,928, 3,933,501 and 4,401,752 and a nitrogen 
atom eliminated yellow coupler described in JP-B No. 58-10739, U.S. Pat. 
Nos. 4,022,620 and 4,326,024, Research Disclosure No. 18,053 (April, 
1987), GB patent No. 1,425,020, DE-A No. 2,219,917, No. 2,261,361, No. 
2,329,587 and No. 2,433,812. An .alpha.-pivaloyl acetanilide coupler has 
fastness of formed dyes and an .alpha.-benzoyl acetanilide coupler has an 
excellent coupling property. 
Examples of the magenta coupler used for the present invention includes an 
oil protect indazolone or cyano acetyl type, preferably a pyrazoloazole 
type coupler such as 5-pyrazolone type and pyrazotoriazole type. The 
5-pyrazolone type coupler is preferably substituted a third position with 
an aryl amino group or an acyl amino group in view of hue of the formed 
dyes and the rate of coupling. Such couplers are described in U.S. Pat. 
Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 
3,936,015. The use of a two equivalent 5-pyrazolone type coupler is 
especially preferred. An example of an elimination group includes a 
nitrogen atom eliminated group described in U.S. Pat. No. 4,30,619, and an 
arylthio group described in U.S. Pat. No. 4,351,897. A 5-pyrazolone type 
coupler having a ballast group described in EP Patent No. 73,636 has high 
coupling reactivity and thus is preferable. Examples of the pyrazoloazole 
type coupler includes pyrazolo [1,5-b][1,2,4] triazoles described in EP 
Patent No. 119,860, pyrazolo benzimidazoles described in U.S. Pat. No. 
3,369,897, pyrazolo tetrazoles described in Research Disclosure No. 24,220 
(June, 1984) and pyrazolo pyrazoles described in Research Disclosure No. 
24,230 (June, 1984). Imidazopyrazoles and pyrazolo [1,5-b] [1,2,4] 
triazoles described in JP-B No. 59-162548 have a small intensity of the 
secondary absorption in yellow and preferably have a high fastness to 
light. 
Examples of the cyan coupler used for the present invention includes an oil 
protect naphthole type or phenol type coupler, a naphthole type coupler 
disclosed in U.S. Pat. No. 2,474,293, preferably an oxygen atom eliminated 
highly active two equivalent naphthole type coupler disclosed in U.S. Pat. 
Nos. 4,052,212, 4,143,396, 4,228,233 and 4,296,200. An example of the 
phenol type coupler includes a coupler described in U.S. Pat. Nos. 
2,369,929, 2,423,730, 2,772,162, 2,801,171 and 2,895,826. The cyan coupler 
which is fast to temperature and moisture is preferred. Such coupler may 
include, for example, a phenol type cyan coupler described in U.S. Pat. 
No. 3,772,022, 2,5-diacylamino substituted phenol type coupler described 
in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396 and 4,327,137 and JP-A 
No. 59-166956, and a phenol type coupler having a phenyl ureide group at a 
second position and an acylamino group at a fifth position described in 
U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767. 
A preferred specific example of the coupler used for the present invention 
includes the coupler described in WO 93/12465. 
The coupler used for the present invention can be introduced into the 
silver halide emulsion by various dispersion methods. For example, a solid 
dispersion method, an alkali dispersion method, preferably a latex 
dispersion method, more preferably an oil-in-water dispersion method are 
cited. In the oil-in-water dispersion method, the coupler is dissolved in 
an organic solvent having a high boiling point of 175.degree. C. or more 
or in an auxiliary solvent having a low boiling point, or in a mixture 
thereof and is then finely dispersed in aqueous medium such as water or a 
gelatin solution in the presence of a surfactant. An example of the 
organic solvent having the high boiling point is described in U.S. Pat. 
No. 2,322,027. The dispersion may accompany a phase inversion, and the 
auxiliary solvent can be removed or reduced by distillation, a noodle 
wash, or ultrafiltration as required, and can be used for coating. 
In the silver halide photographic material of the present invention, a mol 
ratio of the yellow coupler (Y), the magenta coupler (M) and the cyan 
coupler (C) is Y:M C=2.0 to 4.0:1:2.0 to 4.5. 
Examples of the organic solvent having a high boiling point include 
phthalate ester (i.e., dibutyl phthalate, dicyclohexyl phthalate, 
di-2-ethyl hexyl phthalate, didodecyl phthalate), ester of a phosphoric 
acid or a phosphonic acid (i.e., triphenyl phosphate, tricresyl phosphate, 
2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl 
phosphate, trididecyl phosphate, tributoxyethyl phosphate, trichloropropyl 
phosphate, di-2-ethylhexylphenyl phosphate), benzoic ester (i.e., 
2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyloxyl-p-hydroxy benzoate), 
an amide (i.e., diethyldodecane amide, N-tetradecyl pyrrolidone), alcohol 
or phenol (i.e., isostearyl alcohol, 2,4-di-t-amyl phenol), aliphatic 
calboxylate ester (i.e., dioctyl azelate, glycerol tributylate, isostearyl 
lactate, trioctyl citrate), an aniline derivative (i.e., 
N,N-dibutyl-2-butoxy-5-t-octyl aniline), a hydrocarbon (paraffin, dodecyl 
benzene, diisopropyl naphthalene). 
The auxiliary solvent has a boiling point of about 30.degree. C. to about 
60.degree. C. Such auxiliary solvent may include, for example, ethyl 
acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, 
cyclohexanone, 2-ethoxy ethyl acetate, dimethyl formamide and the like. 
Steps and effects of the latex dispersion method and examples of latex for 
impregnation are described in U.S. Pat. No. 4,199,363, DE-A No. 2,541,274 
and No. 2,541,230. 
As a binder or a protective colloid used for the emulsion layer of the 
photographic material and the non-photosensitive hydrophilic colloidal 
layer of the present invention, gelatin is mainly used. Alternatively, a 
gelatin derivative, protein such as albumin and casein, a cellulose 
derivative such as ethyl cellulose and carboxy methyl cellulose, a sugar 
derivative such as a starch derivative, a hydrophilic homopolymer or 
copolymer such as polyvinyl alcohol, a polyacrylate, a polyacryl amide, 
and a polymethacrylate can be used. 
Various compounds can be added to the photographic material emulsion layer 
and the non-photosensitive hydrophilic colloidal layer of the present 
invention in order to avoid fog during process steps, storage or 
development, or to stabilize photograph performance. Examples of such 
compounds include conventionally well-known compounds as an anti-fogging 
agent or a stabilizer such as azoles, i.e., nitroindazoles, 
nitrobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, 
mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles 
(especially, 1-phenyl-5-mercaptotetrazoles); mercaptotriazines; 
thioketones; azaindenes, i.e., triazaindens, tetraazaindenes (especially, 
4-hydroxy-1,3,3a,7-tetraazaindenes); pentaazaindens; a benzenethiosulfonic 
acid; a benzenesulfinic acid; a benzene sulfonic acid amide. Especially 
preferred is benzotriazoles and nitroindazoles. These compounds may be 
included in a treating solution used for development. 
The photographic material emulsion layer and the non-photosensitive 
hydrophilic colloidal layer of the present invention can include a 
hydroquinone derivative, an amino phenol derivative, a gallic acid 
derivative, an ascorbic acid derivative and the like as the anti-fogging 
agent. 
The photographic material emulsion layer and the non-photosensitive 
hydrophilic colloidal layer of the present invention can include an 
inorganic or organic hardening agent. Such hardening agent may include, 
for example, a chromium salt (i.e., chromium alum), an N-methylol 
compound, a dioxane derivative, an active vinyl compound (i.e., 
1,2,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanole), 
mucohalogen acids (i.e., a mucochloric acid, a mucophenoxychloric acid). 
These hardening agents can be used singly or in combination. 
The photographic material emulsion layer and the non-photosensitive 
hydrophilic colloidal layer of the present invention can include a 
surfactant as a coating auxiliary, an antistatic agent, a sliding 
improving agent, an emulsifier, a dispersant, an adhesion inhibitor and a 
photographic property (i.e., development promotion, contrasty, 
sensitizing) improving agent. Examples of the surfactant include a 
nonionic surfactant such as saponin, an alkylene oxide derivative (i.e., 
polyethylene glycol, polyethylene glycol alkylethers), a glycidol 
derivative (i.e., alkenyl succinate polyglyceride, alkylphenol 
polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of 
sugar; an anionic surfactant having an acidic group, i.e., a carboxylic 
group, a sulfo group, a sulfuric ester group, a phosphoric ester group 
such as an alkyl carboxyate, alkyl sulfuric esters, alkyl phosphoric 
esters; an amphoteric surfactant such as amino acids, aminoalkyl sulfonic 
acids, a aminoalkyl sulfuric acid or phosphoric esters; a cationic surf 
actant such as aliphatic or aromatic quaternary ammonium salts, or 
heterocyclic quaternary ammonium salts. 
The photographic material emulsion layer and the non-photosensitive 
hydrophilic colloidal layer of the present invention can include a soluble 
or refractory synthetic polymer dispersion to improve dimensional 
stability. For example, a polymer having a monomer component of alkyl 
(meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, 
vinylester, glycidiyl (meth) acrylate, acrylonitrile, styrene singly or in 
combination, or a combination of an acrylic acid, a methacrylic acid, an 
.alpha., .beta.-unsaturated dicarboxylic acid, a styrene sulfonic acid 
with them. 
Examples of the non-photosensitive hydrophilic colloidal layer of the 
present invention include a protective layer, an intermediate layer, a 
ultraviolet ray absorbing layer, a yellow filter layer, an antihalation 
layer, an antistatic layer or the like. The protective layer can include a 
mat agent to inhibit adhesion and improve a surface condition. Examples of 
the mat agent include particulates such as a polymethylmetacrylate 
homopolymer, a copolymer of methylmethacrylate and a methacryl acid, 
starch, silica, magnesium oxide described in U.S. Pat. Nos. 2,701,245, 
2,992,101, 4,142,894 and 4,396,706. A silicone compound described in U.S. 
Pat. Nos. 3,489,576 and 4,047,958, a colloidal silica described in JP-B 
No. 56-23139 and other paraffin wax, higher fatty acid ester and the like 
can be added to the protective layer. 
The photographic material of the present invention may include a 
ultraviolet absorbing agent in the non-photosensitive hydrophilic 
colloidal layer. For example, benzotriazoles substituted with an aryl 
group described in U.S. Pat. Nos. 3,533,794 and 4,236,013, JP-B No. 
51-6540, and EP Patent No. 57, 160; butadienes described in U.S. Pat. No. 
4,195,999; cinnamic acid esters described in U.S. Pat. Nos. 3,705,805 and 
3,707,375; benzophenones described in U.S. Pat. No. 3,215,230 and GB 
Patent No. 1,321,355; and a polymer having a ultraviolet absorbing group 
described in U.S. Pat. Nos. 3,761,272 and 4,431,726. A ultraviolet 
absorbing fluorescent whitening agent described in U.S. Pat. Nos. 
3,499,762 and 3,700,455 may be used. 
The photographic material of the present invention may include an aqueous 
dye as a filter dye in the non-photosensitive hydrophilic colloidal layer 
to prevent irradiation and to attain other various purposes. Examples of 
the dye include an oxonol dye, a hemioxonol dye, a styryl dye, a 
merocyanine dye, a cyanine dye and an azo dye. Specifically, the oxonol 
dye, the hemioxonol dye and the merocyanine dye are useful. 
According to the photographic material of the present invention, a 
discoloring inhibitor can be used in the emulsion layer and the 
non-photosensitive hydrophilic colloidal layer. One or more kinds of the 
discoloring inhibitor may be used. Examples of the discoloring inhibitor 
include phenols or a phenyl ethers described in JP-A No. 59-125732, a 
metal complex described in JP-A No. 60-97353, a hindered amine or a 
hindered phenol compound described in JP-A No. 62-115157, and a metal 
complex described in JP-A No. 61-140941. 
The photographic material emulsion layer and the non-photosensitive 
hydrophilic colloidal layer of the present invention can include polyols 
such as trimethylolpropane, pentanediol, butanediol, ethyleneglycol, 
glycerin as a plasticizer. In addition, a fluorescent whitening agent, a 
development accelerators, a pH regulator, a thickener, an antistatic agent 
or the like can be added to the emulsion layer and the hydrophilic 
colloidal layer. 
As a support used for the photosensitive material of the present invention, 
a film composed of a synthetic polymer such as cellulose triacetate, 
cellulose diacetate, nitrocellulose, polystylene, polyethylene 
terephthalate, polycarbonate; baryta paper; .alpha.-olefinic polymer 
(i.e., polyethylene, polypropylene) coated or laminated paper; synthetic 
paper and the like can be used. The support may be colored with a dye or a 
pigment. When these supports are used for a reflecting material, a white 
pigment is preferably added to the support or a laminated layer thereof. 
Examples of the white pigment include titanium dioxide, barium sulfate, 
zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica 
white, alumina white and titanium phosphate. Specifically, titanium 
dioxide, barium sulfate and zinc oxide are useful. 
A surface of the support is generally under-coated in order to enhance the 
adhesion of the photographic emulsion. Before or after the under-coating, 
the surface of the support may be treated with a corona discharge or a 
ultraviolet ray radiation. When the support is used for the reflecting 
material, a hydrophilic colloidal layer containing a white pigment at high 
density is formed between the support and the emulsion layer, thereby 
improving whiteness and sharpness of the photographic image. 
When a synthetic resin film kneaded with a white pigment is used for the 
photographic material of the present invention, an photographic image can 
be obtained with an improvement in smoothness, luster and sharpness as 
well as an excellent fineness, a good delineation of shadow and a good 
image in the dark. As the synthetic resin film, polyethylene terephthalate 
and cellulose acetate are especially useful. As the white pigment, barium 
sulfate and titanium oxide are especially useful. 
The silver halide photographic material of the present invention forms a 
monochrome image by exposing an monochrome negative firm or a color 
negative film. 
A color developer used for the present invention is preferably an alkali 
solution mainly containing an aromatic primary amine developing agent. 
Examples of the developing agent include 4-amino-N,N-diethyl aniline, 
3-methyl-4-amino-N,N-diethyl aniline, 
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-metanesulfonamidoethylaniline, 
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline. 
The color developer may include a pH buffer such as carbonate, borate and 
phosphate and an anti-fogging agent such as bromide, iodide and an organic 
anti-fogging agent. Further, the solution may include, if necessary, a 
water softener, a sulphite of an alkali metal, an accelerator such as 
diethylene glycol, polyethylene glycol, a quaternary ammonium salt and 
amines, a competing coupler, a fogging agent such as sodium boron hydride, 
an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a 
tackifier, a polycarboxylic acid type chelating agent described in U.S. 
Pat. No. 4,082,723 and an antioxidant described in DE-A No. 2,622,950. 
"The developer is substantially free of benzyl alcohol" means that 5 ml/l 
or less of benzyl alcohol exists, if contained, in the developer. More 
preferably, the developer contains no benzyl alcohol. 
The silver halide photographic material of the present invention is 
generally bleached after a color development. Bleaching may be conducted 
concurrently with/or separately from fixing. As the bleaching agent, for 
example, a polyvalent metal compound such as iron (III), cobalt (III), 
chromium (VI) and copper (II); peracids; quinones; a nitroso compound or 
the like is used. For example, ferricyanide; dichromate; an organic acid 
salt of iron (III) or cobalt (III), i.e., aminopolycarbonic acids such as 
ethylenediamine tetraacetate, a nitrilotriacetic acid, 
1,3-diamino-2-propanol tetraacetate; a complex salt of an organic acid 
such as a citric acid, a tartaric acid and a malic acid; persulfate; 
manganate; nitrosophenol or the like can be used. Among them, sodium 
ethylenediamine tetraacetate (III) and ammonium ethylenediamine 
tetraacetate (III) are especially useful. The ethylenediamine tetraacetate 
(III) complex salt is useful both for an independent bleach solution and a 
monobath bleach fixer. After the color development or the bleach-fix, 
water washing may be conducted. The color development can be at any 
temperature ranging from 18.degree. C. to 55.degree. C. The color 
development is conducted preferably 30.degree. C. or more, more preferably 
35.degree. C. or more. Developing time is within about one minute and 30 
seconds to about 20 seconds, and shorter time is preferred. In case of 
continuous development, the solution is preferably replenished, preferably 
in an amount of 30 to 200 ml, more preferably 50 ml to 150 ml per square 
meter of a treated area. The bleach-fix can be conducted at any 
temperature ranging from 18.degree. C. to 50.degree. C., preferably 
30.degree. C. or more. If the temperature is 35.degree. C. or more, a 
treating time can be within 1 minute and an amount of the liquid 
replenished can be reduced. The water wash after the color development and 
the bleach-fix is generally within 1 minute and can be within 1 minute 
using a stabilizing bath. 
Formed dyes are not only deteriorated by light, heat or moisture, but also 
discolored by mould during a storage. The cyan dye is especially 
deteriorated by the mould, therefore a fungicide is preferably used. A 
specific example of the fungicide includes 2-thiazolylbenzimidazoles 
described in JP-A No. 57-157244. The fungicide may be included in the 
silver halide photosensitive material or may be added externally during 
the developing step. Coexisting with the processed photosensitive 
material, the fungicide can be added at any step.

EXAMPLES 
The present invention will be described based on the following examples. 
Example 1 
An silver chloride/bromide emulsion (a monodisperse cube, having an average 
grain size of 0.5.mu.m, containing 0.9 mol % of silver bromide; 
1.times.10.sup.-5 mol of a potassium hexachloroiridium (IV) acid per 1 mol 
of silver is contained over a surface of grains) was prepared and sodium 
thiosulfate was added thereto to conduct optimal chemical sensitizing. To 
the emulsion, 1.times.10.sup.-4 mol of a sensitizing dye A, 
1.3.times.10.sup.-4 mol of a sensitizing dye B and 4.times.10.sup.-5 mol 
of a sensitizing dye C per 1 mol of silver were added. After leaving 20 
minutes, 50 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per 1 mol of 
silver halide was added thereto as a stabilizer. 
##STR12## 
A coupler dispersion was prepared as follows: 
After a coupler was dissolved in dibutylphthalate and ethyl acetate, the 
coupler was added to a gelatin solution in the presence of a surfactant 
and was microdispersed using a ultrasonic wave homogenizer. 
The silver halide emulsion and the coupler dispersion were mixed and three 
layers having the following constructions were simultaneously coated on 
polyethylene coated paper. 
______________________________________ 
Top protective layer 
Gelatin 1.0 g/m.sup.2 
Cited compounds shown in Table 1 
Ultraviolet ray absorbing layer 
Ultraviolet ray absorbent A 
0.15 g/m.sup.2 
Ultraviolet ray absorbent B 
0.20 g/m.sup.2 
High boiling solvent 0.2 g/m.sup.2 
Gelatin 0.6 g/m.sup.2 
Silver halide emulsion layer 
Silver halide emulsion 
silver 0.7 
g/m.sup.2 
Coupler (C-1) 0.37 g/m.sup.2 
Coupler (M-1) 0.17 g/m.sup.2 
Coupler (Y-1) 0.68 g/m.sup.2 
High boiling solvent 1 g/m.sup.2 
Gelatin 1.5 g/m.sup.2 
Irradiation protect dye A 
0.03 g/m.sup.2 
Irradiation protect dye B 
0.03 g/m.sup.2 
Cited compounds shown in Table 1 
Support Polyethylene coated paper 
______________________________________ 
The couplers and the other additives used are as follows: 
##STR13## 
TABLE 1 
______________________________________ 
cited compounds in 
cited compounds in 
the protective layer 
the emulsion layer 
sample No. (mg/m.sup.2) (mg/m.sup.2) 
______________________________________ 
1 (Comparative) 
comparative none 
compound B (20) 
2 (Comparative) 
comparative comparative 
compound A (300) 
compound A (300) 
comparative 
compound B (20) 
3 (Comparative) 
I-1 (300) none 
comparative 
compound B (20) 
4 (Comparative) 
I-1 (600) none 
comparative 
compound B (20) 
5 (Comparative) 
comparative I-1 (300) 
compound B (20) 
6 (Comparative) 
comparative I-1 (600) 
compound B (20) 
7 (Comparative) 
I-1 (300) I-1 (300) 
comparative 
compound B (20) 
8 (Comparative) 
I-1 (600) I-1 (600) 
comparative 
compound B (20) 
9 (Comparative) 
comparative comparative 
compound B (20) 
compound B (30) 
10 (Comparative) 
III-1 (20) III-1 (30) 
11 (Comparative) 
comparative I-1 (300) 
compound B (20) 
comparative 
compound B (20) 
12 (Invention) 
III-1 (20) I-1 (300) 
III-1 (30) 
13 (Invention) 
III-1 (20) I-1 (600) 
III-1 (30) 
14 (Comparative) 
I-1 (300) I-1 (300) 
comparative comparative 
compound B (20) 
compound B (20) 
15 (Invention) 
I-1 (300) I-1 (300) 
III-1 (20) III-1 (30) 
______________________________________ 
Samples 1 to 15 were prepared and treated as follows: 
Treatment 1 
A liquid containing 300 ml of 35% glycerin solution was placed on a bottom 
of each sample. Each sample was kept for 3 days at 30.degree. C. in a 
closed vessel filled with air which was equilibrium with the liquid. 
Treatment 2 
A liquid containing 6 ml of 40% formaldehyde per 300 ml of 35% glycerin 
solution was placed on a bottom of each sample. Each sample was kept for 3 
days at 30.degree. C. in a closed vessel fulfilled with air which was 
equilibrium with the liquid. 
Treatment 3 
Each sample was kept for 72 hours at 25.degree. C., RH 60%. 
Treatment 4 
Each sample was kept for 72 hours at 60.degree. C., RH 60%. 
Each sample treated with the four types of treatments described above was 
exposed through an optical wedge using sensitometry actinometer 
(light-source color, temperature of 3200K), was color developed, was 
bleach fixed, was water washed and was then dried. 
______________________________________ 
Treatment step 
Treating temperature 
Treating time 
______________________________________ 
Color development 
35.degree. C. 45 sec 
Bleach-fix 35.degree. C. 45 sec 
Water wash 35.degree. C. 90 sec 
______________________________________ 
Color developer 
______________________________________ 
4-amino-3-methyl-N-ethyl-N-(.beta.- 
6.1 g 
methylsulfoneamidoethyl)aniline sesquisulfate monohydrate 
Triethanol amine 8.2 g 
Nitrilotriacetic acid 1.5 g 
1-hydroxyethylidene-1,1'-diphosphon acid (60% solution) 
1.6 g 
Potassium hydroxide 4.2 g 
Chinopal SFP 0.8 g 
Potassium carbonate 0.9 g 
N,N-dietylhydroxylamine 4.0 g 
______________________________________ 
To the above solution, water was added to be 1 1 and a 10% sulfuric acid or 
a 20% potassium hydroxide solution was then added to adjust to pH 10.10. 
The Chinopal SFP is a fluorescent whitening agent available from 
Chiba-Geigy Actiene Gesellshaft Co., Ltd. 
______________________________________ 
Bleach-fix 
______________________________________ 
Iron sodium ethylenediaminetetraacetate monohydrate 
48.0 g 
Disodium ethylenediaminetetraacetate dihydrate 
24.0 g 
Ammonium thiosulphate (70% solution) 
148 ml 
Sodium hydrogen sulfite (anhydrous) 
15.0 g 
______________________________________ 
To the above solution, water was added to be 1 1 and a 25% aqueous ammonia 
or a 90% acetic acid was added to adjust to pH 6.10. 
______________________________________ 
Washing solution 
______________________________________ 
Methanol 4.0 ml 
p-hydroxybenzoic acid-n-butylester 
0.01 g 
Thiabendazole 0.10 g 
Ethyleneglycol 6.0 ml 
______________________________________ 
To the above solution, water was added to be 1 1. The pH was 7.45. 
Maximum densities of yellow, magenta and cyan in each sample treated by 
Treatment 1 and 2 were measured using a Macbeth RD 918 densitometer and a 
color tone of each sample was examined. Results are shown in Tables 2 and 
3. Black densities in each sample treated by Treatment 3 and 4 were 
measured using the Macbeth RD 918 densitometer. A numerical value that an 
inverse number of light exposure to obtain a density of fog +0.6 was 
multiplied by one hundred was determined. The value of sample 1 treated by 
Treatment 3 was to be 100. Results are shown in Tables 4 and 5. 
TABLE 2 
__________________________________________________________________________ 
(Treatment 1) 
density of 
density of 
density of 
color tone on 
color tone on 
sample No. 
yellow 
magenta 
cyan whole surface 
rims 
__________________________________________________________________________ 
1 (Comparative) 
2.51 2.62 2.56 black black 
2 (Comparative) 
2.53 2.64 2.54 black black 
3 (Comparative) 
2.48 2.61 2.50 black black 
4 (Comparative) 
2.53 2.61 2.55 black black 
5 (Comparative) 
2.49 2.58 2.51 black black 
6 (Comparative) 
2.53 2.65 2.57 black black 
7 (Comparative) 
2.50 2.60 2.54 black black 
8 (Comparative) 
2.45 2.55 2.53 black black 
9 (Comparative) 
2.50 2.57 2.54 black black 
10 (Comparative) 
2.49 2.53 2.50 black black 
11 (Comparative) 
2.51 2.56 2.54 black black 
12 (Invention) 
2.48 2.51 2.50 black black 
13 (Invention) 
2.49 2.53 2.49 black black 
14 (Comparative) 
2.52 2.57 2.54 black black 
15 (Invention) 
2.50 2.55 2.52 black black 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
(Treatment 2) 
density of 
density of 
density of 
color tone on 
color tone on 
sample No. 
yellow 
magenta 
cyan whole surface 
rims 
__________________________________________________________________________ 
16 (Comparative) 
2.45 1.37 2.40 green green 
2 (Comparative) 
2.47 1.65 2.41 green green 
3 (Comparative) 
2.46 2.58 2.47 black green 
4 (Comparative) 
2.50 2.59 2.53 black green 
5 (Comparative) 
2.48 2.55 2.49 black black 
6 (Comparative) 
2.51 2.63 2.55 black black 
7 (Comparative) 
2.50 2.58 2.53 black black 
8 (Comparative) 
2.45 2.55 2.53 black black 
9 (Comparative) 
2.44 1.70 2.51 green green 
10 (Comparative) 
2.43 1.75 2.48 green green 
11 (Comparative) 
2.53 2.58 2.55 black black 
12 (Invention) 
2.51 2.53 2.51 black black 
13 (Invention) 
2.48 2.51 2.50 black black 
14 (Comparative) 
2.53 2.59 2.57 black black 
15 (Invention) 
2.51 2.58 2.54 black black 
__________________________________________________________________________ 
TABLE 4 
______________________________________ 
(Treatment 3) 
sample No. sensitivity 
fog 
______________________________________ 
1 (Comparative) 100 0.08 
2 (Comparative) 100 0.08 
3 (Comparative) 101 0.08 
4 (Comparative) 100 0.08 
5 (Comparative) 101 0.08 
6 (Comparative) 99 0.08 
7 (Comparative) 100 0.08 
8 (Comparative) 99 0.08 
9 (Comparative) 98 0.08 
10 (Comparative) 99 0.07 
11 (Comparative) 98 0.08 
12 (Invention) 100 0.07 
13 (Invention) 99 0.07 
14 (Comparative) 98 0.08 
15 (Invention) 99 0.07 
______________________________________ 
TABLE 5 
______________________________________ 
(Treatment 4) 
sample No. sensitivity 
fog 
______________________________________ 
1 (Comparative) 123 0.13 
2 (Comparative) 124 0.12 
3 (Comparative) 165 0.11 
4 (Comparative) 170 0.13 
5 (Comparative) 158 0.12 
6 (Comparative) 175 0.11 
7 (Comparative) 168 0.13 
8 (Comparative) 155 0.12 
9 (Comparative) 135 0.11 
10 (Comparative) 97 0.08 
11 (Comparative) 145 0.12 
12 (Invention) 101 0.08 
13 (Invention) 103 0.08 
14 (Comparative) 157 0.13 
15 (Invention) 102 0.08 
______________________________________ 
As apparent from Tables 2 to 5, when the samples 1 and 10 that contain no 
compound represented by the formula (I) of the present invention, the 
sample 2 containing a comparative compound A and the sample 9 containing a 
comparative compound B were treated by Treatment 2, they had a 
significantly decreased magenta density and had green color tones on whole 
surfaces and rims. When the samples 3 and 4 containing the compound 
represented by the formula (I) of the present invention only in the 
protective layers were treated by Treatment 2, they had black color tones 
on whole surfaces but had green color tones on rims. When the samples 5, 
6, 11, 12 and 13 that contain the compound represented by the formula (I) 
of the present invention in the emulsion layers and the samples 7, 8, 14 
and 15 that contain the same in both the emulsion layers and the 
protective layers were treated by Treatment 2, they had black color tones 
on both whole surfaces and rims with no change. When the samples 1 to 9, 
11 and 14 that contain no compound represented by the formula (III) of the 
present invention were treated by Treatment 3 and 4, they had a great 
sensitivity change; especially by Treatment 4, they had an increased fog. 
When the samples 12, 13 and 15 that contain the compound represented by 
the formula (I) of the present invention in the emulsion layers or both 
the emulsion layers and the protective layers and also contain the 
compound represented by the formula (III) of the present invention were 
treated by Treatment 1 and 2, they had no change in color tones and were 
black on whole surfaces and rims. When they were treated by Treatment 3 
and 4, they had a less sensitivity change and, by Treatment 4, had a less 
increased fog. 
Example 2 
Samples 16 to 25 were prepared as Example 1 except that the couplers of the 
sample 1 in Example 1 were replaced with the following C-2 (an additive 
amount is 0.33 g/m.sup.2), M-2 (an additive amount is 0.15 g/m.sup.2) and 
Y-2 (an additive amount is 0.55 g/m.sup.2) and the cited compounds of the 
sample 1 were replaced with the compounds shown in Table 6. 
##STR14## 
TABLE 6 
______________________________________ 
cited compounds 
cited compounds in 
in the protective 
the emulsion layer 
sample No. layer (mg/m.sup.2) 
layer (mg/m.sup.2) 
______________________________________ 
16 (Comparative) 
comparative none 
compound B(20) 
17 (Comparative) 
II-1 (500) none 
comparative 
compound B (20) 
18 (Comparative) 
comparative II-1 (500) 
compound B (20) 
19 (Comparative) 
II-1 (500) II-1 (500) 
comparative comparative 
compound B (20) 
compound B (30) 
20 (Comparative) 
comparative comparative 
compound B (20) 
compound B (30) 
21 (Comparative) 
IV-1 (20) IV-1 (30) 
22 (Comparative) 
comparative II-1 (500) 
compound B (20) 
comparative 
compound B (20) 
23 (Invention) 
IV-1 (20) II-1 (500) 
IV-1 (30) 
24 (Comparative) 
II-1 (500) comparative 
comparative compound B (30) 
compound B (20) 
25 (Invention) 
II-1 (500) II-1 (500) 
IV-1 (20) IV-1 (30) 
______________________________________ 
As in Example 1, the samples 16 to 25 were treated by Treatment 1 and 2 and 
were exposed and developed. Maximum densities of yellow, magenta and cyan 
in each sample obtained were measured using the Macbeth RD 918 
densitometer and a color tone of each sample was examined. Results are 
shown in Tables 7 and 8. 
TABLE 7 
__________________________________________________________________________ 
(Treatment 1) 
density of 
density of 
density of 
color tone on 
color tone on 
sample No. 
yellow 
magenta 
cyan whole surface 
rims 
__________________________________________________________________________ 
16 (Comparative) 
2.51 2.62 2.56 black black 
17 (Comparative) 
2.55 2.61 2.58 black black 
18 (Comparative) 
2.54 2.60 2.57 black black 
19 (Comparative) 
2.52 2.58 2.55 black black 
20 (Comparative) 
2.50 2.59 2.53 black black 
21 (Comparative) 
2.51 2.60 2.55 black black 
22 (Comparative) 
2.53 2.59 2.57 black black 
23 (Invention) 
2.52 2.57 2.55 black black 
24 (Comparative) 
2.53 2.61 2.54 black black 
25 (Invention) 
2.50 2.60 2.58 black black 
__________________________________________________________________________ 
TABLE 8 
__________________________________________________________________________ 
(Treatment 2) 
density of 
density of 
density of 
color tone on 
color tone on 
sample No. 
yellow 
magenta 
cyan whole surface 
rims 
__________________________________________________________________________ 
16 (Comparative) 
2.45 1.37 2.40 green green 
17 (Comparative) 
2.53 2.57 2.54 black green 
18 (Comparative) 
2.52 2.58 2.54 black black 
19 (Comparative) 
2.51 2.59 2.53 black black 
20 (Comparative) 
2.49 1.53 2.51 green green 
21 (Comparative) 
2.49 1.63 2.53 green green 
22 (Comparative) 
2.51 2.57 2.56 black black 
23 (Invention) 
2.51 2.55 2.52 black black 
24 (Comparative) 
2.50 2.59 2.53 black green 
25 (Invention) 
2.49 2.59 2.55 black black 
__________________________________________________________________________ 
The samples 16 to 25 were treated by Treatment 3 and 4 as in Example 1. The 
samples were exposed and developed as in Example 1. A black density in 
each sample treated was measured using the Macbeth RD 918 densitometer. A 
numerical value that an inverse number of light exposure to obtain a 
density of fog +0.6 was multiplied by one hundred was determined. The 
value of sample 16 treated by Treatment 3 was to be 100, which is a 
relative sensitivity of each sample. Results are shown in Tables 9 and 10. 
TABLE 9 
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(Treatment 3) 
sample No. sensitivity 
fog 
______________________________________ 
16 (Comparative) 100 0.08 
17 (Comparative) 101 0.08 
18 (Comparative) 102 0.08 
19 (Comparative) 102 0.08 
20 (Comparative) 99 0.08 
21 (Comparative) 99 0.08 
22 (Comparative) 100 0.08 
23 (Invention) 99 0.07 
24 (Comparative) 101 0.08 
25 (Invention) 100 0.07 
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TABLE 10 
______________________________________ 
(Treatment 4) 
sample No. sensitivity 
fog 
______________________________________ 
16 (Comparative) 128 0.13 
17 (Comparative) 153 0.12 
18 (Comparative) 165 0.12 
19 (Comparative) 178 0.12 
20 (Comparative) 135 0.12 
21 (Comparative) 105 0.08 
22 (Comparative) 161 0.12 
23 (Invention) 101 0.08 
24 (Comparative) 157 0.13 
25 (Invention) 102 0.08 
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As apparent from Tables 7 to 10, when the samples 16 and 21 that contain no 
compound represented by the formula (II) of the present invention and the 
sample 20 containing the comparative compound B were treated by Treatment 
2, they had a significantly decreased magenta density and had green color 
tones on whole surfaces and rims. Regarding the samples 17 and 24 
containing the compound represented by the formula (II) of the present 
invention only in the protective layers, they had black color tones on 
whole surfaces but had green color tones on rims. When the samples 18, 22 
and 23 that contain the compound represented by the formula (II) of the 
present invention in the emulsion layers and the samples 19 and 25 that 
contain the same in both the emulsion layers and the protective layers 
were treated by Treatment 2, they had black color tones on both whole 
surfaces and rims with no change. When the samples 17, 18, 19, 22 and 24 
that contain the compound represented by the formula (II) of the present 
invention and contain no compound represented by the formula (IV) of the 
present invention were treated by Treatment 3 and 4, they had a great 
sensitivity change and an increased fogging. When the samples 23 and 25 
that contain the compound represented by the formula (II) of the present 
invention in the emulsion layers or both the emulsion layers and the 
protective layers and also contain the compound represented by the formula 
(IV) of the present invention were treated by Treatment 1 and 2, they had 
less change in color tones and were black on whole surfaces and rims. When 
they were treated by Treatment 3 and 4, they had a less sensitivity change 
and had a less increased fogging. 
According to the present invention, even if the silver halide photographic 
material is treated with a color developer substantially free of benzyl 
alcohol, a monochrome image using a dye image can be obtained. The 
monochrome image has a photographic property that is less deteriorated by 
a toxic gas such as formaldehyde, has a less change in sensitivity when 
stored under a high temperature condition and has a less increase in fog.