Silver halide color photographic light-sensitive material and image-forming method

There is disclosed a silver halide color photographic light-sensitive material having at least one photographic constitutional layer coated on a support, wherein at least one of the photographic constitutional layers contains at least one reducing agent for color formation represented by formula (I), at least one coupler for forming a diffusive dye, and at least one mordant. The material is capable of reducing the amount of developer and to be replenished or discharged after processing, and of reducing the occurrence of stain after development during storage of the material. There is also disclosed an image-forming method using the material. ##STR1## wherein C.alpha. represents a carbon atom; Z represents a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonyl group; and Q represents a group of atoms to form, together with C.alpha., an unsaturated ring.

FIELD OF THE INVENTION 
The present invention relates to an image-forming technique for use in 
color photography. In particular, the present invention relates to a 
silver halide color photographic light-sensitive material that is 
excellent from the standpoint of environmental protection and safety; that 
is excellent in convenient and rapid processability; that shows good 
color-forming property and hue; and that has reduced stains occurring 
after treatment; and further the present invention relates to a method of 
forming a color image. 
BACKGROUND OF THE INVENTION 
Generally, when a color photographic light-sensitive material is exposed to 
light image-wise and then color-developed, the oxidized p-phenylenediamine 
derivative reacts with couplers to form an image. In this system, color 
reproduction by the subtractive color technique is used, and, to reproduce 
blue, green, and red colors, dye images are formed that are yellow, 
magenta, and cyan in color, respectively complementary to blue, green, and 
red. 
Color development is achieved by immersing a light-exposed color 
photographic light-sensitive material in an aqueous alkali solution having 
a p-phenylenediamine derivative dissolved therein (a color developer). 
However, there is a problem that the p-phenylenediamine derivative in an 
aqueous alkali solution is unstable and is apt to deteriorate over time, 
and in order to retain stable development performance, the color developer 
must be replenished frequently. Further, the disposal of used color 
developers containing a p-phenylenediamine derivative is burdensome, and 
together with the above frequent replenishment, the treatment of used 
color developers discharged in large quantities gives rise to a serious 
problem. Thus, there is a strong demand for the attainment of low 
replenishment and reduced discharge of color developers. 
One effective measure proposed for attaining low replenishment and reduced 
discharge of color developers is a method wherein an aromatic primary 
amine developing agent or its precursor is built in a hydrophilic colloid 
layer of a light-sensitive material, and examples of the aromatic primary 
amine developing agents or their precursors that can be built in include 
compounds described, for example, in U.S. Pat. Nos. 2,507,114, 3,764,328, 
and 4,060,418, and JP-A ("JP-A" means unexamined published Japanese patent 
application) Nos. 6235/1981 and 192031/1983. However, since these aromatic 
primary amine developing agents and their precursors are unstable, there 
is the defect that, when the unprocessed light-sensitive material is 
stored for a long period of time or is color-developed, stain occurs. 
Another effective measure proposed is a method wherein a 
sulfonylhydrazine-type compound, as described, for example, in European 
Patent Nos. 0545491A1 and 565165A1, is built in a hydrophilic colloid 
layer of a light-sensitive material. However, the sulfonylhydrazine-type 
compounds listed therein still cannot attain satisfactory color density 
when chromogenically developed, and there is the problem that, when the 
sulfonylhydrazine-type compound is used with a two-equivalent coupler, the 
color formation is little. In comparison with four-equivalent couplers, 
two-equivalent couplers have such merits that stain originating in the 
couplers can be reduced, the activity of the couplers is easily adjusted, 
and coupling split-off groups in couplers can be allowed to have various 
functions. It is desired to develop a technique that can utilize these 
merits. 
On the other hand, a dye obtained from a hydrazine compound, such as a 
carbamoyl hydrazine compound, and a dye-forming coupler is a 
dissociating-type dye that dissociates to form color. Therefore, color 
images cannot be obtained unless the dye is dissociated by immersion into 
an alkali solution after a color development treatment. However, under 
such a condition that the dye is dissociated, a remaining hydrazine 
compound itself is dissociated, and this dissociated compound tends to 
react with the coupler, to bring about the problem of causing considerable 
stain during long-time storage after the treatment. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a light-sensitive material 
capable of reducing the amount of replenishing and discharging of a 
developer and capable of reducing stain of the light-sensitive material 
during storage after color development treatment. 
Another object of the present invention is to provide an image-forming 
method that is capable of conveniently and rapidly treating a silver 
halide color photographic light-sensitive material. 
Other and further objects, features, and advantages of the invention will 
appear more apparent from the following description. 
DETAILED DESCRIPTION OF THE INVENTION 
It has been found that the foregoing objects of the present invention can 
be attained by the following means. 
(1) A silver halide color photographic light-sensitive material having at 
least one photographic constitutional layer coated on a support, wherein 
at least one of the photographic constitutional layers contains at least 
one reducing agent for color formation, represented by the following 
formula (I), at least one coupler for forming a diffusive dye, and at 
least one mordant: 
##STR2## 
wherein C.alpha. represents a carbon atom; Z represents a carbamoyl group, 
an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; and Q 
represents a group of atoms to form, together with the C.alpha., an 
unsaturated ring. 
(2) The silver halide color photographic light-sensitive material as stated 
in (1) above, wherein Z in formula (I) is a carbamoyl group having at 
least one hydrogen atom on a nitrogen atom. 
(3) The silver halide color photographic light-sensitive material as stated 
in (2) above, wherein the unsaturated ring formed with the C.alpha. and Q 
in formula (I) is a heterocyclic ring. 
(4) The silver halide color photographic light-sensitive material as stated 
in (2) above, wherein the unsaturated ring formed with the C.alpha. and Q 
in formula (I) is a benzene ring having at least one substituent, and 
wherein the sum of .sigma. values for the Hammett's substituent constant 
of the substituents (.sigma.p value is used for the substituents on the 
carbon atom in 1,2 or 1,4 relation with the C.alpha. (C.alpha. is at 
1-position), while .sigma.m value is used for the substituents on the 
carbon atom in 1,3 relation with the C.alpha.) is 0.8 or more. 
(5) An image-forming method, wherein the silver halide color photographic 
light-sensitive material stated in (1) above is subjected to development 
with an alkali solution after exposure to light image-wise. 
(6) The image-forming method as stated in (5) above, wherein Z in formula 
(I) is a carbamoyl group having one or more hydrogen atoms on a nitrogen 
atom. 
(7) The image-forming method as stated in (6) above, wherein the 
unsaturated ring formed with the C.alpha. and Q in formula (I) is a 
heterocyclic ring. 
(8) The image-forming method as stated in (6) above, wherein the 
unsaturated ring formed with the C.alpha. and Q in formula (I) is a 
benzene ring having one or more substituents, and wherein the sum of 
.sigma. value for the Hammett's substituent constant of the substituents 
(.sigma.p value is used for the substituents on the carbon atom in 1,2 or 
1,4 relation with the C.alpha., while cm value is used for the 
substituents on the carbon atom in 1,3 relation with the C.alpha.) is 0.8 
or more. 
The alkali solution referred to in (5) above is a developer (a developing 
solution) containing substantially no color-developing agent. This is 
different from that for alkali treatment after bleach-fixing and water 
washing (rinsing) used in examples to be described later. Since a dye 
formed from a conventional coupler does not dissociate under a neutral (or 
acidic) condition, and does not develop a color as a dye having a desired 
hue, the alkali treatment after the water washing to be described later is 
applied, in order to dissociate the dye and change it into the dye having 
the desired hue. 
In the system of using a conventional coupler, a dye with a desired hue is 
not formed unless an alkali treatment is applied after water washing 
(rinsing). Moreover, there is also an additional problem of causing 
fogging in color formation (Dmin) with lapse of time under wet heat. On 
the contrary, in the system of the present invention, a dye with a desired 
hue can be formed without the alkali treatment. Moreover, since the alkali 
treatment is not applied, it is free from the problem of fogging in color 
formation with lapse of time under wet heat. 
A dye obtained from a reducing agent for color formation and a coupler for 
forming a dye according to the present invention dissociates, to develop a 
color. A feature of the present invention resides in dissociating only the 
dye formed but not dissociating a remaining reducing agent for color 
formation, in order to prevent stains. 
PREFERRED EMBODIMENTS OF THE INVENTION 
The present invention is to be explained by way of practical embodiments in 
more detail. 
Description is to be made specifically to a reducing agent for color 
formation used in the present invention. 
The reducing agent for color formation represented by formula (I) used in 
the present invention is a compound capable of being oxidized, in an 
alkali solution, with a light-exposed silver halide, or a compound capable 
of being oxidized with an oxidized auxiliary developing agent by redox 
reaction, and each of the resulting oxidized products further forms a dye 
by reaction with a coupler for forming a dye. 
The compound represented by formula (I) used in the present invention will 
be explained more in detail. 
In formula (I), Z represents a carbamoyl group, an acyl group, an 
alkoxycarbonyl group, or an aryloxycarbonyl group. Preferred among them is 
a carbamoyl group, and a carbamoyl group having one or two hydrogen atoms 
on a nitrogen atom is particularly preferred. 
The carbamoyl group preferably has from 1 to 50 carbon atoms, and more 
preferably 1 to 40. Specific examples include a carbamoyl group, a 
methylcarbamoyl group, an ethylcarbamoyl group, an n-propylcarbamoyl 
group, a sec-butylcarbamoyl group, an n-octylcarbamoyl group, a 
cyclohexylcarbamoyl group, a tert-butylcarbamoyl group, a dodecylcarbamoyl 
group, a 3-dodecyloxypropylcarbamoyl group, an octadecylcarbamoyl group, a 
3-(2,4-tert-pentylphenoxy)-propylcarbamoyl group, a 2-hexyldecylcarbamoyl 
group, a phenylcarbamoyl group, a 4-dodecyloxyphenylcarbamoyl group, a 
2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group, a naphthylcarbamoyl 
group, a 3-pyridylcarbamoyl group, a 
3,5-bis-octyloxycarbonylphenylcarbamoyl group, a 
3,5-bis-tetradecyloxyphenylcarbamoyl group, a benzyloxycarbamoyl group, 
and a 2,5-dioxo-1-pyrrolidinylcarbamoyl group. 
The acyl group preferably has from 1 to 50 carbon atoms, and more 
preferably from 1 to 40. Specific examples include a formyl group, an 
acetyl group, a 2-methylpropanoyl group, a cyclohexylcarbonyl group, an 
n-octanoyl group, a 2-hexyldecanoyl group, a dodecanoyl group, a 
chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 
4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 
3-(N-hydroxy-N-methylaminocarbonyl)propanoyl group. 
The alkoxycarbonyl group and the aryloxycarbonyl group, respectively, 
preferably have from 2 to 50 carbon atoms, and more preferably from 2 to 
40. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl 
group, an isobutyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 
dodecyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl 
group, a 4-octyloxyphenoxycarbonyl group, a 2-hydroxymethylphenoxycarbonyl 
group, and a 4-dodecyloxyphenoxycarbonyl group. 
Q represents a group of atoms that form an unsaturated ring together with 
the C.alpha., in which the unsaturated ring formed is preferably a 3- to 
8-membered ring, and more preferably a 5- to 6-membered ring. Examples of 
this unsaturated ring include aromatic rings (e.g. a benzen ring) and 
heterocyclic rings, and the preferable number of members in the ring is as 
described above. Preferred examples of them are a benzene ring, a pyridine 
ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 
1,2,4-triazine ring, a 1,3,5-triazine ring, a pyrrole ring, an imidazole 
ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a 
tetrazole ring, a 1,3,4-thiadiazole ring, a 1,2,4-thiadiazole ring, a 
1,2,5-thiadiazole, a 1,3,4-oxadiazole ring, a 1,2,4-oxadiazole ring, a 
1,2,5-oxadiazole ring, a thiazole ring, an oxazole ring, an isothiazole 
ring, an isooxazole ring, and a thiophene ring, and a condensed ring 
formed from the above-mentioned rings condensed with each other is also 
preferably used. 
Further, the above-mentioned ring may have a substituent. Examples of the 
substituent include a straight-chain or branched, chain or cyclic alkali 
group having 1 to 50 carbon atoms (e.g. trifluoromethyl, methyl, ethyl, 
propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, 
cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl and dodecyl); a 
straight-chain or branched, chain or cyclic alkenyl group having 2 to 50 
carbon atoms (e.g. vinyl, 1-methylvinyl, and cyclohexene-1-yl), an alkynyl 
group having 2 to 50 total carbon atoms (e.g. ethynyl and 1-propynyl), an 
aryl group having 6 to 50 carbon atoms (e.g. phenyl, naphthyl, and 
anthryl), an acyloxy group having 1 to 50 carbon atoms (e.g. acetoxy, 
tetradecanoyloxy, and benzoyloxy), a carbamoyloxy group having 1 to 50 
carbon atoms (e.g. N,N-dimethylcarbamoyloxy), a carbonamide group having 1 
to 50 carbon atoms (e.g. formamide, N-methylacetoamide, acetoamide, 
N-methylformamide, and benzamide), a sulfoneamide group having 1 to 50 
carbon atoms (e.g. methanesulfoneamide, dodecanesulfoneamide, 
benzenesulfoneamide, and p-toluene-sulfoneamide), a carbamoyl group having 
1 to 50 carbon atoms (e.g. N-methylcarbamoyl, N,N-diethylcarbamoyl, and 
N-mesylcarbamoyl), a sulfamoyl group having 0 to 50 carbon atoms (e.g. 
N-butylsulfamoyl, N,N-diethylsulfamoyl, 
N-methyl-N-(4-methoxyphenyl)sulfamoyl), an alkoxy group having 1 to 50 
carbon atoms (e.g. methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, 
dodecyloxy, and 2-(2,4-di-t-pentylphenoxy)ethoxy), an aryloxy group having 
6 to 50 carbon atoms (e.g. phenoxy, 4-methoxyphenoxy, and naphthoxy), an 
aryloxycarbonyl group having 7 to 50 carbon atoms (e.g. phenoxycarbonyl 
and naphthoxycarbonyl), an alkoxycarbonyl group having 2 to 50 carbon 
atoms (e.g. methoxycarbonyl and t-butoxycarbonyl), an N-acylsulfamoyl 
group having 1 to 50 carbon atoms (e.g. N-tetradecanoylsulfamoyl and 
N-benzoylsulfamoyl), an alkylsulfonyl group having 1 to 50 carbon atoms 
(e.g. methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl and 
2-hexyldecylsulfonyl), an arylsulfonyl group having 6 to 50 carbon atoms 
(e.g. benzenesulfonyl, p-toluenesulfonyl, and 
4-phenylsulfonylphenylsulfonyl), an alkoxycarbonylamino group having 2 to 
50 carbon atoms (e.g. ethoxycarbonylamino), an aryloxycarbonylamino group 
having 7 to 50 carbon atoms (e.g. phenoxycarbonylamino and 
naphthoxycarbonylamino), an amino group having 0 to 50 carbon atoms (e.g. 
amino, methylamino, diethylamino, diisopropylamino, anylino, and 
morpholino), a cyano group, a nitro group, a carboxyl group, a hydroxy 
group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 
50 carbon atoms (e.g. methanesulfinyl and octanesulfinyl), an arylsulfinyl 
group having 6 to 50 carbon atoms (e.g. benzenesulfinyl, 
4-chlorophenylsulfinyl, and p-toluenesulfinyl), an alkylthio group having 
1 to 50 carbon atoms (e.g. methylthio, octylthio, and cyclohexylthio), an 
arylthio group having 6 to 50 carbon atoms (e.g. phenylthio and 
naphthylthio), an ureido group having 1 to 50 carbon atoms (e.g. 
3-methylureido, 3,3-dimethylureido, and 1,3-diphenylureido), a 
heterocyclic group having 2 to 50 carbon atoms (a 3- to 12-membered 
monocyclic or condensed ring containing, for example, at least one 
nitrogen, oxygen, or sulfur as hetero atoms, e.g. 2-furyl, 2-pyranyl, 
2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 
2-benzimidazolyl, 2-benzothiazolyl and 2-benzooxazolyl), an acyl group 
having 1 to 50 carbon atoms (e.g. acetyl, benzoyl and trifluoroacetyl), a 
sulfamoylamino group having 0 to 50 carbon atoms (e.g. 
N-butylsulfamoylamino and N-phenylsulfamoylamino), a silyl group having 3 
to 50 carbon atoms (e.g. trimethylsilyl, dimethyl-t-butylsilyl and 
triphenylsilyl) and a halogen atom (e.g. fluorine atom, chlorine atom, and 
bromine atom). The substituent described above may have a substituent, and 
those substituents mentioned above can be mentioned as examples for such a 
substituent. 
The number of carbon atoms of the substituent is preferably 50 or below, 
and more preferably 42 or below. Further, the total carbon atoms of the 
unsaturated ring formed with Q and the C.alpha. and the substituents 
thereon is preferably 30 or below, more preferably 24 or below, and most 
preferably 18 or below. 
When the ring formed with Q and the C.alpha. consists only of carbon atoms, 
on which the substituents are present (e.g. a benzene ring, a naphthalene 
ring, and an anthrathene ring), the sum of the .sigma. values of the 
Hammett's substituent constant (.sigma.p value is used when the 
substituent is at 1,2, 1,4, . . . relation with the C.alpha. and .sigma.m 
value is used when the substituent is at 1,3, 1,5, . . . relation with the 
C.alpha.) for all substituents is 0.8 or more, more preferably 1.2 or 
more, and most preferably 1.5 or more. There is no particular restriction 
on the upper limit, but it is preferably 3.8 or below, in view of easy 
availability of the compound. 
Herein, Hammett substituent constants .sigma.p and .sigma.m are described 
in detail in such books as "Hammett no Hosoku/Kozo to Hannousei," written 
by Naoki Inamoto (Maruzen); "Shin-jikken Kagaku-koza 14/Yukikagoubutsu no 
Gosei to Hanno V," page 2605 (edited by Nihonkagakukai, Maruzen); "Riron 
Yukikagaku Kaisetsu," written by Tadao Nakaya, page 217 (Tokyo 
Kagakudojin); and "Chemical Review" (Vol. 91), pages 165 to 195 (1991). 
Now, specific examples of the reducing agent for color formation 
represented by formula (I) used in the present invention are described 
below, but the scope of the present invention is not limited to them. 
##STR3## 
The reducing agent for color formation for use in the present invention is 
used together with a compound that can form a dye by oxidation coupling 
reaction (a coupler). The coupler can be a coupler not substituted or 
substituted, at a coupling position with the oxidized product of the 
developing agent (i.e. a four-equivalent coupler, a two-equivalent 
coupler), but in the present invention, a two-equivalent coupler 
(substituted at its coupling position) is preferred. Specific examples of 
the coupler are described in detail, for example, in "Theory of the 
Photographic Process" (4th Ed., Edited by T. H. James, Macmillan, 1977), 
pp. 291 to 334 and pp. 354 to 361, and in JP-A Nos. 12353/1983, 
149046/1983, 149047/1983, 11114/1984, 124399/1984, 174835/1984, 
231539/1984, 231540/1984, 2951/1985, 14242/1985, 23474/1985, and 
66249/1985. 
As the coupler for use in the present invention, any coupler can be used, 
provided that a diffusive dye formed by coupling with an oxidized product 
of a reducing agent for color formation for use in the present invention 
reaches a mordant. Preferably the diffusive dye formed has one or more 
dissociation groups with a pKa of 12 or below, more preferably one or more 
dissociation groups with a pKa of 8 or below, and particularly preferably 
one or more dissociation group with a pKa of 6 or below. Further, from the 
viewpoint of providing diffusibility, the molecular weight of the 
diffusive dye formed is preferably 200 or more but 2000 or below. Further, 
the ratio of the molecular weight of dye formed to the number of 
dissociation groups with pKa of 12 or below is preferably 100 or more but 
2000 or below, and more preferably 100 or more but 1000 or below. The 
value measured by using a solvent at dimethylformamide:water=1:1, is used 
for the value of pKa. 
As the solubility of the diffusive dye formed by the coupling of the 
coupler for use in the present invention and the oxidized product of the 
reducing agent for color formation for use in the present invention, the 
diffusive dye is dissolved in an alkali solution of pH 11 at 25.degree. C. 
in an amount of preferably 1.times.10.sup.-6 mol/l or more, more 
preferably 1.times.10.sup.-5 mol/l or more, and particularly preferably 
1.times.10.sup.-4 mol/l or more. Further, the diffusion constant of the 
diffusive dye formed by the coupling between the coupler for use in the 
present invention and the oxidized product of the reducing agent for color 
formation for use in the present invention, when the diffusive dye is 
dissolved at a concentration of 10.sup.-4 mol/l in an alkali solution at 
pH 11 at 25.degree. C., is preferably 1.times.10.sup.-8 m.sup.2 /s.sup.-1 
or more, more preferably 1.times.10.sup.-7 m.sup.2 /s.sup.-1 or more, and 
particularly preferably 1.times.10.sup.-6 m.sup.2 /s.sup.-1 or more. 
Examples of the coupler used preferably in the present invention are 
described below. 
The coupler used preferably in the present invention can include compounds 
of the structure described by one of the following formulae (1) to (12). 
They are compounds generally referred to collectively as active 
methylenes, pyrazolones, pyrazoloazoles, phenols, naphthols, and 
pyrrolotriazoles, respectively, which are compounds known in the relevant 
field of the art. 
##STR4## 
Formulae (1) to (4) represent couplers that are called active 
methylene-series couplers, and, in the formulae, R.sup.14 represents an 
acyl group, a cyano group, a nitro group, an aryl group, a heterocyclic 
residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl 
group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl 
group, optionally substituted. 
In formulae (1) to (3), R.sup.15 represents an optionally substituted alkyl 
group, aryl group, or heterocyclic residue. In formula (4), R.sup.16 
represents an optionally substituted aryl group or heterocyclic residue. 
Examples of the substituent that may be possessed by R.sup.14, R.sup.15, 
and R.sup.16 include those mentioned for the substituent on the ring 
formed with Q and the C.alpha.. 
In formulae (1) to (4), Y is a hydrogen atom or a group that provides the 
coupler a resistance to diffusion and that is capable of coupling 
split-off by coupling reaction with the oxidized product of the reducing 
agent for color formation. Examples of Y are a hydrogen atom, a 
heterocyclic group (a saturated or unsaturated 5-membered to 7-membered 
monocyclic or condensed ring having as a hetero atom at least one nitrogen 
atom, oxygen atom, sulfur atom, or the like, e.g. succinimido, 
maleinimido, phthalimido, diglycolimido, pyrrole, pyrazole, imidazole, 
1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, 
benzotriazole, imidazolin-2,4-dione, oxazolidin-2,4-dione, 
thiazolidin-2,4-dione, imidazolidin-2-one, oxazolin-2-one, 
thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, 
benzthiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, 
indolin-2,3-dione, 2,6-dioxypurine, parabic acid, 
1,2,4-triazolidin-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 
6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolodine, and 
2-imino-1,3,4-thiazolidin-4-one), a halogen atom (e.g. a chlorine atom and 
a bromine atom), an aryloxy group (e.g. phenoxy and 1-naphthoxy), a 
heterocyclic oxy group (e.g. pyridyloxy and pyrazolyoxy), an acyloxy group 
(e.g. acetoxy and benzoyloxy), an alkoxy group (e.g. methoxy and 
dodecyloxy), a carbamoyloxy group (e.g. N,N-diethylcarbamoyloxy and 
morpholinocarbonyloxy), an aryloxycarbonyloxy group (e.g. 
phenylcarbonyloxy), an alkoxycarbonyloxy group (e.g. methoxycarbonyloxy 
and ethoxycarbonyloxy), an arylthio group (e.g. phenylthio and 
naphthylthio), a heterocyclic thio group (e.g. tetrazolylthio, 
1,3,4-thiadiazolylthio, 1,3,4-oxadiazolylthio, and benzimidazolylthio), an 
alkylthio group (e.g. methylthio, octylthio, and hexadecylthio), an 
alkylsulfonyloxy group (e.g. methanesulfonyloxy), an arylsulfonyloxy group 
(e.g. benzenesulfonyloxy and toluenesulfonyloxy), a carbonamido group 
(e.g. acetamido and trifluoroacetamido), a sulfonamido group (e.g. 
methanesulfonamido and benzenesulfonamido), an alkylsulfonyl group (e.g. 
methanesulfonyl), an arylsulfonyl group (e.g. benzenesulfonyl), an 
alkylsulfinyl group (e.g. methanesulfinyl), an arylsulfinyl group (e.g. 
benzenesulfinyl), an arylazo group (e.g. phenylazo and naphthylazo), and a 
carbamoylamino group (e.g. N-methylcarbamoylamino). 
Y may be substituted, and examples of the substituent that may be possessed 
by Y include those mentioned for the substituent on the ring formed by Q 
and the C.alpha.. Total number of carbon atoms included in Y are 
preferably 6 or more but 50 or below, more preferably 8 or more but 40 or 
below, and most preferably 10 or more but 30 or below. 
Preferably Y represents an aryloxy group, a heterocyclic oxy group, an 
acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or 
a carbamoyloxy group. 
In formulae (1) to (4), R.sup.14 and R.sup.15, and R.sup.14 and R.sup.16, 
may bond together to form a ring. 
Formula (5) represents a coupler that is called a 5-pyrazolone-series 
coupler, and in the formula, R.sup.17 represents an alkyl group, an aryl 
group, an acyl group, or a carbamoyl group. R.sup.18 represents a phenyl 
group or a phenyl group that is substituted by one or more halogen atoms, 
alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or 
acylamino groups. 
Preferable 5-pyrazolone couplers represented by formula (5) are those 
wherein R.sup.17 represents an aryl group or an acyl group, and R.sup.18 
represents a phenyl group that is substituted by one or more halogen 
atoms. 
With respect to these preferable groups, more particularly, R.sup.17 is an 
aryl group, such as a phenyl group, a 2-chlorophenyl group, a 
2-methoxyphenyl group, a 2-chloro-5-tetradecaneamidophenyl group, a 
2-chloro-5-(3-octadecenyl-1-succinimido)phenyl group, a 
2-chloro-5-octadecylsulfonamidophenyl group, and a 
2-chloro-5-2-(4-hydroxy-3-t-butylphenoxy)tetradecaneamido!phenyl group; 
or R.sub.17 is an acyl group, such as an acetyl group, a 
2-(2,4-di-t-pentylphenoxy)butanoyl group, a benzoyl group, and a 
3-(2,4-di-t-amylphenoxyacetamido)benzoyl group, any of which may have a 
substituent, such as a halogen atom or an organic substituent that is 
bonded through a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur 
atom. Y has the same meaning as defined above. 
Preferably R.sup.18 represents a substituted phenyl group, such as a 
2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group, and a 
2-chlorophenyl group. 
Formula (6) represents a coupler that is called a pyrazoloazole-series 
coupler, and, in the formula, R.sup.19 represents a hydrogen atom or a 
substituent. Q.sup.3 represents a group of nonmetal atoms required to form 
a 5-membered azole ring containing 2 to 4 nitrogen atoms, which azole ring 
may have a substituent (including a condensed ring). 
Preferable pyrazoloazole couplers represented by formula (6), in view of 
spectral absorption characteristics of the color-formed dyes, are 
imidazo1,2-b!pyrazoles described in U.S. Pat. No. 4,500,630, 
pyrazolo1,5-b!-1,2,4-triazoles described in U.S. Pat. No. 4,500,654, and 
pyrazolo5,1-c!-1,2,4-triazoles described in U.S. Pat. No. 3,725,067. 
Details of substituents of the azole rings represented by the substituents 
R.sup.19 and Q.sup.3 are described, for example, in U.S. Pat. No. 
4,540,654, the second column, line 41, to the eighth column, line 27. 
Preferable pyrazoloazole-series couplers are pyrazoloazole couplers having 
a branched alkyl group directly bonded to the 2-, 3-, or 6-position of the 
pyrazolotriazole group, as described in JP-A No. 65245/1986; pyrazoloazole 
couplers containing a sulfonamido group in the molecule, as described in 
JP-A No. 65245/1986; pyrazoloazole couplers having an 
alkoxyphenylsulfonamido ballasting group, as described in JP-A No. 
147254/1986; pyrazolotriazole couplers having an alkoxy group or an 
aryloxy group at the 6-position, as described in JP-A No. 209457/1987 or 
307453/1988; and pyrazolotriazole couplers having a carbonamido group in 
the molecule, as described in Japanese Patent Application No. 22279/1989. 
Y has the same meaning as defined above. 
Formulae (7) and (8) are respectively called phenol-series couplers and 
naphthol-series couplers, and in the formulae R.sup.20 represents a 
hydrogen atom or a group selected from the group consisting of 
--CONR.sup.22 R.sup.23, --SO.sub.2 NR.sup.22 R.sup.23, --NHCOR.sup.22, 
--NHCONR.sup.22 R.sup.23, and --NHSO.sub.2 NR.sup.22 R.sup.23. R.sup.22 
and R.sup.23 each represent a hydrogen atom or a substituent. In formulae 
(7) and (8), R.sup.21 represents a substituent, 1 is an integer selected 
from 0 to 2, and m is an integer selected from 0 to 4. When 1 and m are 2 
or more, R.sup.21 's may be different. The substituents of R.sup.21 to 
R.sup.23 include those mentioned for substituent of the unsaturated ring 
formed by Q and the C.alpha.. Y has the same meaning as defined above. 
Preferable examples of the phenol-series couplers represented by formula 
(7) include 2-acylamino-5-alkylphenol couplers described, for example, in 
U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826, and 3,772,002; 
2,5-diacylaminophenol couplers described, for example, in U.S. Pat. Nos. 
2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West Germany 
Patent Publication No. 3,329,729, and JP-A No. 166956/1984; and 
2-phenylureido-5-acylaminophenol couplers described, for example, in U.S. 
Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427,767. Y has the same 
meaning as defined above. 
Preferable examples of the naphthol-series couplers represented by formula 
(8) include 2-carbamoyl-1-naphthol couplers described, for example, in 
U.S. Pat. Nos. 2,474,293, 4,052,212, 4,146,396, 4,282,233, and 4,296,200; 
and 2-carbamoyl-5-amido-1-naphthol couplers described, for example, in 
U.S. Pat. No. 4,690,889. Y has the same meaning as defined above. 
Formulas (9) to (12) are couplers called pyrrolotriazoles, and R.sup.32, 
R.sup.33, and R.sup.34 each represent a hydrogen atom or a substituent. Y 
has the same meaning as defined above. Examples of the substituent of 
R.sup.32, R.sup.33, and R.sup.34 include those mentioned as examples for 
substituent being capable of substituting on the ring formed by Q and the 
C.alpha. in formula (I). Preferable examples of the pyrrolotriazole-series 
couplers represented by formulae (9) to (12) include those wherein at 
least one of R.sup.32 and R.sup.33 is an electron-attracting group, which 
specific couplers are described in European Patent Nos. 488,248A1, 
491,197A1, and 545,300. Y has the same meaning as defined above. 
Further, a fused-ring phenol, an imidazole, a pyrrole, a 3-hydroxypyridine, 
an active methylene, an active methine, a 5,5-ring-fused heterocyclic, and 
a 5,6-ring-fused heterocyclic coupler, can be used. 
As the fused-ring phenol-series couplers, those described, for example, in 
U.S. Pat. Nos. 4,327,173, 4,564,586, and 4,904,575, can be used. 
As the imidazole-series couplers, those described, for example, in U.S. 
Pat. Nos. 4,818,672 and 5,051,347, can be used. 
As the 3-hydroxypyridine-series couplers, those described, for example, in 
JP-A No. 315736/1989, can be used. 
As the active methylene-series and active methine-series couplers, those 
described, for example, in U.S. Pat. Nos. 5,104,783 and 5,162,196, can be 
used. 
As the 5,5-ring-fused heterocyclic couplers, for example, pyrrolopyrazole 
couplers described in U.S. Pat. No. 5,164,289, and pyrroloimidazole 
couplers described in JP-A No. 174429/1992, can be used. 
As the 5,6-ring-fused heterocyclic couplers, for example, 
pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, 
pyrrolotriazine couplers described in JP-A No. 204730/1992, and couplers 
described in European Patent No. 556,700, can be used. 
In the present invention, in addition to the above couplers, use can be 
made of couplers described, for example, in West Germany Patent Nos. 
3,819,051A and 3,823,049, U.S. Pat. Nos. 4,840,883, 5,024,930, 5,051,347, 
and 4,481,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 
374,781A2, 379,110A2, and 386,930A1, and JP-A Nos. 141055/1988, 
32260/1989, 32261/1989, 297547/1990, 44340/1990, 110555/1990, 7938/1991, 
160440/1991, 172839/1991, 172447/1992, 179949/1992, 182645/1992, 
184437/1992, 188138/1992, 188139/1992, 194847/1992, 204532/1992, 
204731/1992, and 204732/1992. 
In the coupler used in the present invention, the total number of carbon 
atoms in the portion except for Y, from the viewpoint that a released dye 
tends to be diffusive, is preferably 3 or more but 30 or below, more 
preferably 3 or more but 24 or below, and most preferably 3 or more but 18 
or below. 
Specific examples of the couplers that can be used in the present invention 
are shown below, but, of course, the present invention is not limited to 
them: 
##STR5## 
The reducing agent for color formation according to the present invention 
is preferably used in an amount of 0.01 mmol/m.sup.2 to 10 mmol/m.sup.2 in 
one color-forming layer, in order to obtain satisfactory color density. 
More preferably the amount to be used is 0.05 mmol/m.sup.2 to 5 
mmol/m.sup.2, and particularly preferably 0.1 mmol/m.sup.2 to 1 
mmol/m.sup.2. 
A preferable amount of the coupler to be used in the color-forming layer in 
which the reducing agent for color formation according to the present 
invention is used, is 0.05 to 20 times, more preferably 0.1 to 10 times, 
and particularly preferably 0.2 to 5 times, the amount of the reducing 
agent for color formation in terms of mol. 
Now the mordant for use in the present invention will be described. The 
mordant for use in the present invention may be used in any layer in a 
light-sensitive material, and it is preferably used in a layer that does 
not contain the reducing agent for color formation for use in the present 
invention, since the stability of the reducing agent for color formation 
is deteriorated if the mordant is added to a layer containing the reducing 
agent for color formation. Further, a dye formed from the reducing agent 
for color formation and the coupler diffuses in the gelation membrane 
swollen during treatment, and is dyed with the mordant. Therefore, the 
shorter a diffusing distance is, the more preferable it is, in order to 
obtain a good sharpness. Accordingly, the mordant is preferably added to a 
layer adjacent to the layer containing the reducing agent for color 
formation. Further, since the dye formed from the reducing agent for color 
formation for use in the present invention and the coupler for use in the 
present invention, is a water-soluble dye, it may dissolved out into a 
treating solution. Accordingly, to prevent this, preferably the layer to 
which the mordant is added is situated on the same side of the support but 
opposite to the layer containing the reducing agent for color formation 
(on the same side of a support, a mordant-containing layer is situated 
more remote from the support than a layer containing the reducing agent 
for color formation). In a case wherein a barrier layer, as described in 
JP-A No. 168335/1995, is provided to the opposite side of the support 
relative to the layer to which the mordant is added (on the same side of a 
support, the barrier layer is situated more remote from the support than 
the mordant-containing layer), also preferably the layer to which the 
mordant is added is situated nearer to the support relative to the layer 
containing the reducing agent for color formation. 
Further, the mordant for use in the present invention may be added to 
multiple layers, and, particularly when multiple layers contain the 
reducing agent for color formation, it is also preferred to add the 
mordant to each of adjacent layers. 
The mordant that can be used in the present invention, can be selected 
optionally from mordants that are usually used in the photographic 
light-sensitive material and that can fix the diffusive dye. Among them, a 
polymer mordant is particularly preferred. Examples of the polymer mordant 
include a polymer having a tertialy amino group, a polymer having a 
nitrogen-containing heterocyclic portion, and a polymer having a 
quarternary cationic group thereof. 
Preferred examples of homopolymers or copolymers containing vinyl monomer 
units having the tertiary amino group include the following. Numerical 
values for the monomer units represent mol % (the same meaning is also 
applied to hereinafter). 
##STR6## 
Examples of homopolymers or copolymers containing vinyl monomer units 
having a tertiary imidazole group include the following, also including 
mordants as described, for example, in U.S. Pat. Nos. 4,282,305, 
4,115,124, and 3,148,061, and JP-A Nos. 118834/1985, 122941/1985, 
244043/1987, and 244036/1987. 
##STR7## 
Preferred examples of homopolymers or copolymers containing vinyl monomer 
units having a quarternary imidazolium salt include the following, also 
including mordants as described, for example, in British Patent Nos. 
2,056,101, 2,093,041, and 1,594,961, U.S. Pat. Nos. 4,124,386, 4,115,124, 
and 4,450,224, and JP-A No. 28325/1973. 
##STR8## 
In addition to the above, preferred examples of homopolymers and copolymers 
containing vinyl monomer units having a quarternary ammonium salt include 
the following, also including mordants as described, for example, in U.S. 
Pat. Nos. 3,709,690, 3,898,088, and 3,958,995, and JP-A Nos. 57836/1985, 
60643/1985, 122940/1985, 122942/1985, and 235134/1985. 
##STR9## 
In addition, there can be mentioned vinyl pyridine polymers and vinyl 
pyridinium cation polymers as disclosed, for example, in the 
specifications of U.S. Pat. Nos. 2,548,564, 2,484,430, 3,148,161, and 
3,756,814; polymer mordants capable of crosslinking with gelatin or the 
like, as disclosed, for example, in the specifications of U.S. Pat. Nos. 
3,625,694, 3,859,096, and 4,128,538, and British Patent No. 1,277,453; 
aqueous sol-type mordants as disclosed in U.S. Pat. Nos. 3,958,995, 
2,721,852, and 2,798,063, and JP-A Nos. 115228/1979, 145529/1979, and 
26027/1979; water-insoluble mordants as disclosed in the specification of 
U.S. Pat. No. 3,898,088; reactive mordants capable of forming covalent 
bonds with a dye, as disclosed in the specification of U.S. Pat. No. 
4,168,976 (JP-A No. 137333/1979); and, further, those mordants as 
disclosed in the specifications of U.S. Pat. Nos. 3,709,690, 3,788,855, 
3,642,482, 3,488,706, 3,557,066, and 3,271,147, and JP-A Nos. 71332/1975, 
30328/1978, 155528/1977, 125/1978, and 1024/1978. 
In addition, there can also be mentioned mordants as described in the 
specifications of U.S. Pat. Nos. 2,675,316 and 2,882,156. 
The molecular weight of the polymer mordants for use in the present 
invention is appropriately 1,000 or more but 1,000,000 or below, and 
particularly preferably 10,000 or more but 200,000 or below. 
The polymer mordant described above can be used usually as an admixture 
with a hydrophilic colloid. As the hydrophilic colloid, gelatin and/or 
highly hygroscopic synthetic polymer can be used, with gelatin being most 
typical. The mixing ratio between the polymer mordant and the hydrophilic 
colloid and the coating amount of the polymer mordant can be determined 
with ease by those skilled in the art, in accordance with the amount of 
dye to be mordanted, the kind and the composition of the polymer mordant, 
and the process used for forming an image. The mordant/hydrophilic colloid 
ratio is generally 20/80 or more but 80/20 or below (weight ratio), and 
the coating amount of the mordant is appropriately 0.2 g/m.sup.2 or more 
but 15 g/m.sup.2 or below, and more preferably it is used in an amount 0.5 
g/m.sup.2 or more but 8 g/m.sup.2 or below. 
If the reducing agent for color formation for use in the present invention 
is dispersed in an oleophilic high boiling organic solvent, the redox 
reaction with the silver halide cannot be conducted directly. Accordingly, 
for forming a color image from the image-wise-exposed silver halide, it is 
necessary to use a compound having a function of cross oxidation between 
the silver halide and the reducing agent for color formation (hereinafter 
referred to as an auxiliary developing agent). Such a compound may be 
added to a treating solution, as described later, but preferably the 
compound is not contained in the treating solution, in view of safety and 
the handleability of the treating solution, and accordingly it is 
preferable to incorporate the compound in the light-sensitive material. 
An auxiliary developing agent and a precursor thereof used in the 
light-sensitive material of the present invention are explained below. 
The auxiliary developing agent used in the present invention is a compound 
that can develop silver halide particles exposed to light, and the 
oxidized product of the compound can oxidize a reducing agent for color 
formation (hereinafter referred to as cross oxidation). 
As the auxiliary developing agent for use in the present invention, 
pyrazolidones, dihydroxybenzenes, reductones, or aminophenols can be used 
preferably, with pyrazolidones being used particularly preferably. 
Preferably that the diffusibility in a hydrophilic colloidal layer is low, 
and, for example, the solubility to water (25.degree. C.) is preferably 
0.1% or below, more preferably 0.05% or below, and particularly preferably 
0.01% or below. 
The precursor of the auxiliary developing agent used in the present 
invention is a compound that is present stably in the light-sensitive 
material, but it rapidly releases the auxiliary developing agent after it 
has been treated by a treating solution. Also in a case of using the 
compound, preferably the diffusibility in the hydrophilic colloidal layer 
is low. For example, the solubility to water (25.degree. C.) is preferably 
0.1% or below, more preferably 0.05% or below, and particularly preferably 
0.01% or below. There is no particular restriction on the solubility of 
the auxiliary developing agent released from the precursor, but preferably 
the solubility of the auxiliary developing agent itself is low. 
The precursor for the auxiliary developing agent for use in the present 
invention is preferably represented by formula (A), and the auxiliary 
developing agent is preferably represented by formula (B-1) or (B-2). 
##STR10## 
Formula (A) 
EQU A--(L)n-PUG 
A represents a blocking group whose bond to (L)n-PUG will be split off at 
the time of development processing, L represents a linking group that 
splits from the bonding between L and PUG, after splitting of the bond 
between L and A in the formula (A); n represents an integer of 0 to 3, and 
PUG represents an auxiliary developing agent. 
Groups represented in formula (A) will now be described. 
As the blocking group represented by A, the following already known groups 
can be used: blocking groups described, for example, in JP-B ("JP-B means 
examined Japanese patent publication) No. 9968/1973, JP-A Nos. 8828/1977 
and 82834/1982, U.S. Pat. No. 3,311,476, and JP-B No. 44805/1972 (U.S. 
Pat. No. 3,615,617), such as an acyl group and a sulfonyl group; blocking 
groups that use the reverse Michael reaction, as described, for example, 
in JP-B Nos. 17369/1980 (U.S. Pat. No. 3,888,677), 9696/1980 (U.S. Pat. 
No. 3,791,830), and 34927/1980 (U.S. Pat. No. 4,009,029), and JP-A Nos. 
77842/1981 (U.S. Pat. No. 4,307,175), 105640/1984, 105641/1984, and 
105642/1984; blocking groups that use the formation of quinone methide or 
a compound similar to quinone methide, by intramolecular electron 
transfer, as described, for example, in JP-B No. 39727/1979, U.S. Pat. 
Nos. 3,674,478, 3,932,480, and 3,993,661, and JP-A Nos. 135944/1982, 
135,945/1982 (U.S. Pat. No. 4,420,554), 136640/1982, 196239/1986, 
196240/1986 (U.S. Pat. No. 4,702,999), 185743/1986, 124941/1986 (U.S. Pat. 
No. 4,639,408), and 280140/1990; blocking groups that use intramolecular 
nucleophilic replacement reaction, as described, for example, in U.S. Pat. 
Nos. 4,358,525 and 4,330,617, and JP-A Nos. 53330/1980 (U.S. Pat. No. 
4,310,612), 121328/1984, 218439/1984, and 318555/1988 (European 
Publication Patent No. 0295729); blocking groups that use ring cleavage of 
a 5-membered ring or 6-membered ring, as described, for example, in JP-A 
Nos. 76541/1982 (U.S. Pat. No. 4,335,200), 135949/1982 (U.S. Pat. No. 
4,350,752), 179842/1982, 137945/1984, 140445/1984, 219741/1984, 
202459/1984, 41034/1985 (U.S. Pat. No. 4,618,563), 59945/1987 (U.S. Pat. 
No. 4,888,268), 65039/1987 (U.S. Pat. No. 4,772,537), 80647/1987, 
236047/1991, and 238445/1991; blocking groups that use the addition 
reaction of a nucleophilic reagent to a conjugated unsaturated bond, as 
described, for example, in JP-A Nos. 201057/1984 (U.S. Pat. No. 
4,518,685), 95346/1986 (U.S. Pat. No. 4,690,885), 95347/1986 (U.S. Pat. 
No. 4,892,811), 7035/1989, 42650/1989 (U.S. Pat. No. 5,066,573), 
245255/1989, 207249/1990, 235055/1990 (U.S. Pat. No. 5,118,596), and 
186344/1992; blocking groups that use the .beta.-elimination reaction, as 
described, for example, in JP-A Nos. 93442/1984, 32839/1986, and 
163051/1987, and JP-B No. 37299/1993; blocking groups that use the 
nucleophilic replacement reaction of diarylmethanes, as described in JP-A 
No. 188540/1986; blocking groups that uses the Lossen rearrangement 
reaction, as described in JP-A No 187850/1987; blocking groups that use 
the reaction between the N-acylated product of thiazolidin-2-thion and 
amines, as described in JP-A Nos. 80646/1987, 144163/1987, and 
147457/1987; and blocking groups that have two nucleophilic groups to 
react with two nucleophilic agents, as described in JP-A Nos. 296240/1990 
(U.S. Pat. No. 5,019,492), 177243/1992, 177244/1992, 177245/1992, 
177246/1992, 177247/1992, 177248/1992, 177249/1992, 179948/1992, 
184337/1992, and 184338/1992, International Publication Patent No. 
92/21064, JP-A No. 330438/1992, International Publication Patent No. 
93/03419, and JP-A No. 45816/1993, as well as JP-A Nos. 236047/1991 and 
238445/1991. 
The group represented by L in the compound represented by formula (A) may 
be any linking group that can be split off from the group represented by 
A, at the time of development processing, and that then can split 
(L).sub.n-1 -PUG. Examples are groups that use the split of a hemi-acetal 
ring, as described in U.S. Pat. Nos. 4,146,396, 4,652,516, and 4,698,297; 
timing groups that bring about an intramolecular nucleophilic substitution 
reaction, as described in U.S. Pat. Nos. 4,248,962, 4,847,185, or 
4,857,440; timing groups that use an electron transfer reaction to bring 
about a cleavage reaction, as described in U.S. Pat. No. 4,409,323 or 
4,421,845; groups that use the hydrolysis reaction of an iminoketal to 
bring about a cleavage reaction, as described in U.S. Pat. No. 4,546,073; 
groups that use the hydrolysis reaction of an ester to bring about a 
cleavage reaction, as described in West German Publication Patent No. 
2,626,317; or groups that use a reaction with sulfite ions to bring about 
a cleavage reaction, as described in European Patent No. 0572084. 
PUG in formula (A) will now be described. 
In the present invention, preferably the auxiliary developing agent is a 
compound capable of releasing electrons according to the Kendall-Pelz 
rule, which compound is represented preferably by formula (B-1) or (B-2), 
more preferably by formula (B-1). 
In formulae (B-1) and (B-2), R.sup.51 to R.sup.54 each represent a hydrogen 
atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, 
or a heterocyclic group. 
R.sup.55 to R.sup.59 each represent a hydrogen atom, a halogen atom, a 
cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl 
group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an 
aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy 
group, an amino group, an anilino group, a heterocyclicamino group, an 
alkylthio group, an arylthio group, a heterocyclicthio group, a silyl 
group, a hydroxyl group, a nitro group, an alkoxycarbonyloxy group, a 
cycloalkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a 
carbamoyloxy group, a sulfamoyloxy group, an alkanesulfonyloxy group, an 
arenesulfonyloxy group, an acyl group, an alkoxycarbonyl group, a 
cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, 
a carbonamido group, a ureido group, an imido group, an 
alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido 
group, a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl 
group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, 
a sulfo group, a phosphinoyl group, or a phosphinoylamino group. 
q is an integer of 0 to 5, and when q is 2 or more, R.sup.55 's may be 
different. R.sup.60 represents an alkyl group or an aryl group. 
When the auxiliary developing agent represented by formula (B-1) or (B-2) 
corresponds to PUG of formula (A), the bonding position is at the oxygen 
atom or nitrogen atom of the auxiliary developing agent. 
Compounds represented by formula (A), (B-1) or (B-2) are shown specifically 
below, but the auxiliary developing agent or its precursor used in the 
present invention is not limited to these specific examples. 
##STR11## 
The above compound may be added to any of the light-sensitive layer, an 
intermediate layer, an undercoat layer, and a protective layer of a 
light-sensitive material, and preferably it is added to and used in a 
non-light-sensitive layer when an auxiliary developing agent is contained 
in the light-sensitive material. 
The methods of incorporating the compound into the light-sensitive material 
include, for example, a method of dissolving the compound in a 
water-miscible organic solvent, such as methanol, and directly adding this 
to a coating solution; a method of forming a solution or a colloidal 
dispersion of the compound, with a surface-active agent also included, and 
adding the same to a coating solution; a method of dissolving the compound 
into a solvent or oil substantially immiscible with water, and then 
dispersing the solution into water or a hydrophilic colloid, and then 
adding the same to a coating solution; or a method of adding the compound, 
in a state of a dispersion of fine solid particles, to a coating solution. 
The known methods described above may be applied singly or in combination. 
The addition amount of the compound to the light sensitive material is 
generally 1 mol % to 200 mol %, preferably 5 mol % to 100 mol %, and more 
preferably 10 mol % to 50 mol %, based on the reducing agent for color 
formation. 
The color light-sensitive material of the present invention basically 
comprises photographic constitutional layers including at least one 
hydrophilic colloidal layer coated on a support, and the light-sensitive 
silver halide, the dye-forming coupler (the coupler for forming a dye), 
the reducing agent for color formation, the mordant, and the like are 
contained in one or more photographic constituent layers. 
The dye-forming coupler and the reducing agent for color formation used in 
the present invention are added to an identical layer, in the most typical 
embodiment, but they can be added divisionally into separate layers, as 
long as they can react with each other. These ingredients are preferably 
added to a silver halide emulsion layer or a layer adjacent therewith in 
the light-sensitive material, and particularly preferably they are added 
together to an identical silver halide emulsion layer. In this embodiment, 
both of the compounds are preferably co-emulsified in a high boiling 
organic solvent. 
Examples of the high boiling organic solvent that can be used in the 
present invention are described, for example, in U.S. Pat. No. 2,322,027. 
High boiling organic solvents having a boiling point at a normal pressure 
of 160.degree. C. or higher, particularly 175.degree. C. or higher, are 
preferred, and examples of them include, for example, phthalic acid esters 
e.g. dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl 
phthalate, decyl phthalate, bis(2,4-di-tert-aminophenyl) phthalate, 
bis(2,4-di-tert-amyl-phenyl) isophthalate, and bis(1,1-diethylpropyl) 
phthalate!; phosphoric acid aryl esters (e.g. triphenyl phosphate and 
tricresyl phosphate); benzoic acid esters (e.g. 2-ethylhexyl benzoate, 
dodecyl benzoate, and 2-ethylhexyl-p-hydroxybenzoate); sulfonamides (e.g. 
N-butylbenzenesulfonamide); alcohols or phenols (e.g. isostearyl alcohol 
and 2,4-di-tert-amylphenol); aliphatic carboxylic acid ester (e.g. 
bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributylate, 
isostearyl lactate, and trioctyl citrate); hydrocarbons (e.g. paraffin, 
dodecylbenzene, and diisopropylnaphthalene); and chlorinated paraffins. 
Further, as an auxiliary solvent, organic solvents having a boiling point 
of 30.degree. C. or higher, preferably 50.degree. C. or higher, and lower 
than about 160.degree. C., can be used, and typical examples thereof 
include, for example, ethyl acetate, butyl acetate, ethyl propyonate, 
methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and 
dimethylformamide. The usage amount of the high boiling organic solvent 
that can be used in the present invention can be changed depending on the 
purpose, with no particular restriction. The solvent is preferably used in 
an amount in the range of 0.01 to 20, more preferably 0.01 to 10, and 
further preferably 0.02 to 5, by weight ratio to the reducing agent for 
color formation to be used. 
The preferable means of placing the reducing agent for color formation and 
the dye-forming coupler to be used in the present invention contained in 
any one of photographic constitutional layers, is that these compounds are 
dissolved in the high-boiling-point organic solvent (if necessary, used in 
combination with the above auxiliary solvent); the solution is finely 
emulsified and dispersed in a hydrophilic colloid; and the resulting 
emulsified dispersion (in admixture with a silver halide emulsion as a 
preferred embodiment) is coated on a support. 
To emulsify and disperse the compounds to be used in the present invention, 
a known polymer dispersion method may be used. Namely, specific examples 
of the steps and the effects of the latex dispersion method, which is a 
polymer dispersion method, and specific examples of latexes for 
impregnation, are described, for example, in U.S. Pat. No. 4,199,363, West 
German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-B No. 
41091/1978, and European Patent Laid-Open Publication No. 029104; and the 
dispersion method using a polymer that is insoluble in water but soluble 
in an organic solvent, is described in PCT International Laid-Open 
Publication No. WO 88/00723. The latter dispersion method is preferably. 
The average particle size of the lipophilic fine particles containing the 
reducing agent for color formation according to the present invention is 
not particularly limited, and the average particle size is preferably 0.05 
to 0.3 .mu.m, and more preferably 0.05 to 0.2 .mu.m, in view of the 
color-forming property. 
Making the average particle size of the lipophilic fine particles small is 
generally attained, for example, by selecting an appropriate type of 
surface-active agent; by increasing the amount of a surface-active agent 
to be used; by increasing the viscosity of the hydrophilic colloid 
solution; by lowering the viscosity of the lipophilic organic layer by, 
for example, the combined use of a low-boiling-point organic solvent; by 
increasing the shearing force, for example, by intensifying the rotation 
of the stirring blades of an emulsifying apparatus; by prolonging the 
emulsifying period. 
The particle size of lipophilic fine particles can be measured, for 
example, by such an apparatus as a Nanosizer (trade name; manufactured by 
British Coulter Co.). 
As the support to be used in the present invention, any support can be used 
if it is a transmissible support or a reflective support on which a 
photographic emulsion layer can be coated, such as glass, paper, and 
plastic film. 
As the plastic film to be used in the present invention, for example, 
polyester films made, for example, of polyethylene terephthalates, 
polyethylene naphthalates, cellulose triacetate, or cellulose nitrate; 
polyamide films, polycarbonate films, and polystyrene films can be used. 
"The reflective support" that can be used in the present invention refers 
to a support that increases the reflecting properties to make bright the 
dye image formed in the silver halide emulsion layer, and such a 
reflective support includes a support coated with a hydrophilic resin 
containing a light-reflecting substance, such as titanium oxide, zinc 
oxide, calcium carbonate, and calcium sulfate, dispersed therein, or a 
support made of a hydrophilic resin itself containing a dispersed 
light-reflecting substance. Examples are a polyethylene-coated paper, a 
polyester-coated paper, a polypropylene-series synthetic paper, a support 
having a reflective layer or using a reflecting substance, such as a glass 
sheet; a polyester film made, for example, of a polyethylene 
terephthalate, cellulose triacetate, or cellulose nitrate; a polyamide 
film, a polycarbonate film, a polystyrene film, and a vinyl chloride 
resin. As the polyester-coated paper, particularly a polyester-coated 
paper whose major component is a polyethylene terephthalate, as described 
in European Patent EP 0,507,489, is preferably used. 
The reflective support to be used in the present invention is preferably a 
paper support, both surfaces of which are coated with a water-resistant 
resin layer, and at least one of the water-resistant resin layers contains 
fine particles of a white pigment. Preferably the particles of a white 
pigment are contained in a density of 12% by weight or more, and more 
preferably 14% by weight or more. Preferably the light-reflecting white 
pigment is kneaded well in the presence of a surface-active agent, and the 
surface of the pigment particles is preferably treated with a dihydric to 
tetrehydric alcohol. 
In the present invention, a support having the second kind diffuse 
reflective surface can also be used, preferably. "the second kind diffuse 
reflectivity" means diffuse reflectivity obtained by making a specular 
surface uneven, to form finely divided specular surfaces facing different 
directions, which finely divided surfaces, specular surfaces, are 
dispersed in their directions. The unevenness of the second kind diffuse 
reflective surface has a three-dimensional average coarseness of generally 
0.1 to 2 .mu.m, and preferably 0.1 to 1.2 .mu.m, for the center surface. 
Details about such a support are described in JP-A No. 239244/1990. 
In order to obtain colors ranging widely on the chromaticity diagram by 
using three primary colors: yellow, magenta, and cyan, use is made of a 
combination of at least three silver halide emulsion layers photosensitive 
to respectively different spectral regions. For examples, a combination of 
three layers of a blue-sensitive layer, a green-sensitive layer, and a 
red-sensitive layer, and a combination of a green-sensitive layer, a 
red-sensitive layer, and an infrared-sensitive layer, and the like can be 
coated on the above support. The photosensitive layers can be arranged in 
various orders known generally for color light-sensitive materials. 
Further, each of these light-sensitive layers can be divided into two or 
more layers if necessary. 
In the light-sensitive material, photographic constitutional layers 
comprising the above photosensitive layers and various auxiliary layers, 
such as a protective layer, an underlayer, an intermediate layer, an 
antihalation layer, and a backing layer, can be provided. Further, in 
order to improve the color separation, various filter dyes can be added to 
the photographic constitutional layer. 
The silver halide grains used in the present invention are made of silver 
bromide, silver chloride, silver iodide, silver chlorobromide, silver 
chloroiodide, silver iodobromide, or silver chloroiodobromide. Other 
silver salts, such as silver rhodanate, silver sulfide, silver selenide, 
silver carbonate, silver phosphate, or a silver salt of an organic acid, 
may be contained in the form of independent grains or as part of silver 
halide grains. If it is desired to make the development/desilvering 
(bleaching, fixing, and bleach-fix) step rapid, silver chlorobromide 
grains or silver chloride grains having a high silver chloride content 
(preferably 95 mol % or more) are desirable. Further, if the development 
is to be restrained moderately, it is preferable to contain silver iodide. 
The preferable silver iodide content varies depending on the intended 
light-sensitive material. For example, in the case of X-ray photographic 
materials, the preferable silver iodide content is in the range of 0.1 to 
15 mol %, and in the case of graphic art and micro photographic materials, 
the preferable silver iodide content is in the range of 0.1 to 5 mol %. In 
the case of photographic materials represented by color negatives, 
preferably silver halide contains 1 to 30 mol %, more preferably 5 to 20 
mol %, and particularly preferably 8 to 15 mol %, of silver iodide. It is 
preferable to incorporate silver chloride in silver iodobromide grains, 
because the lattice strain can be made less intense. For a reflect-type 
light-sensitive material that is necessary to be rapidly processed, the 
silver iodide content is preferably 0, or 1 mol % or below. 
In the silver halide grains used in the present invention, in accordance 
with the purpose, any of regular crystals having no twin plane, and those 
described in "Shashin Kogyo no Kiso, Ginen Shashin-hen", edited by Nihon 
Shashin-gakkai (Corona Co.), page 163, such as single twins having one 
twin plane, parallel multiple twins having two or more parallel twin 
planes, and nonparallel multiple twins having two or more nonparallel twin 
planes, can be chosen and used. An example in which grains different in 
shape are mixed is disclosed in U.S. Pat. No. 4,865,964, and if necessary 
this method can be chosen. In the case of regular crystals, cubes having 
(100) planes, octahedrons having (111) planes, and dodecahedral grains 
having (110) planes, as disclosed in JP-B No. 42737/1980 and JP-A No. 
222842/1985, can be used. Further, (h11) plane grains represented by 
(211), (hh1) plane grains represented by (331), (hk0) plane grains 
represented by (210) planes, and (hk1) plane grains represented by (321) 
planes, as reported in "Journal of Imaging Science", Vol. 30, page 247 
(1986), can be chosen and used in accordance with the purpose, although 
the preparation is required to be adjusted. Grains having two or more 
planes in one grain, such as tetradecahedral grains having (100) and (111) 
planes in one grain, grains having (100) and (110) planes in one grain, or 
grains having (111) and (110) planes in one grain, can be chosen and used 
in accordance with the purpose. 
The value obtained by dividing the diameter of the projected area, which is 
assumed to be a circle, by the thickness of the grain, is called an aspect 
ratio, which defines the shape of tabular grains. Tabular grains having an 
aspect ratio of 1 or more can be used in the present invention. Tabular 
grains can be prepared by methods described, for example, by Cleav in 
"Photography Theory and Practice" (1930), page 131; by Gutof in 
"Photographic Science and Engineering", Vol. 14, pages 248 to 257 (1970); 
and in U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and 
British Patent No. 2,112,157. When tabular grains are used, such merits 
are obtained that the covering power is increased and the color 
sensitization efficiency due to a sensitizing dye is increased, as 
described in detail in the above-mentioned U.S. Pat. No. 4,434,226. The 
average aspect ratio of 80% or more of all the projected areas of grains 
is desirably 1 or more but less than 100, more preferably 2 or more but 
less than 20, and particularly preferably 3 or more but less than 10. As 
the shape of tabular grains, a triangle, a hexagon, a circle, and the like 
can be chosen. A regular hexagonal shape having six approximately equal 
sides, described in U.S. Pat. No. 4,798,354, is a preferable mode. 
In many cases, the grain size of tabular grains is expressed by the 
diameter of the projected area assumed to be a circle, and grains having 
an average diameter of 0.6 microns or below, as described in U.S. Pat. No. 
4,748,106, are preferable, because the quality of the image is made high. 
An emulsion having a narrow grain size distribution, as described in U.S. 
Pat. No. 4,775,617, is also preferable. It is preferable to restrict the 
shape of tabular grains so that the thickness of the grains may be 0.5 
microns or below, and more preferably 0.3 microns or below, because the 
sharpness is increased. Further, an emulsion in which the grains are 
highly uniform in thickness, with the deviation coefficient of grain 
thickness being 30% or below, is also preferable. Grains in which the 
thickness of the grains and the plane distance between twin planes are 
defined, as described in JP-A No. 163451/1988, are also preferable. 
In the case of tabular grains, the dislocation lines can be observed by a 
transmission electron microscope. In accordance with the purpose, it is 
preferable to choose grains having no dislocation lines, grains having 
several dislocation lines, or grains having many dislocation lines. 
Dislocation introduced straight in a specific direction in the crystal 
orientation of grains, or curved dislocation, can be chosen, and it is 
possible to choose from, for example, dislocation introduced throughout 
grains, dislocation introduced in a particular part of grains, and 
dislocation introduced limitedly, for example, to the fringes of grains. 
In addition to the case of introduction of dislocation lines into tabular 
grains, also preferable is the case of introduction of dislocation lines 
into regular crystalline grains or irregular grains, represented by potato 
grains. In this case, a preferable mode is that introduction is limited to 
a particular part of grains, such as vertexes and edges. 
The silver halide emulsion used in the present invention may be subjected 
to a treatment for making grains round, as disclosed, for example, in 
European Patent Nos. 96,727B1 and 64,412B1, or it may be improved in the 
surface, as disclosed in West Germany Patent No. 2,306,447C2 and JP-A No. 
221320/1985. 
Generally, the grain surface has a flat structure, but it is also 
preferable in some cases to make the grain surface uneven intentionally. 
Examples are a technique in which part of crystals, for example, vertexes 
and the centers of planes, are formed with holes, as described in JP-A 
Nos. 106532/1983 and 221320/1985, and ruffled grains, as described in U.S. 
Pat. No. 4,643,966. 
The grain size of the emulsion used in the present invention is evaluated, 
for example, by the diameter of the projected area equivalent to a circle 
using an electron microscope; by the diameter of the grain volume 
equivalent to a sphere, calculated from the projected area and the grain 
thickness; or by the diameter of a volume equivalent to a sphere, using 
the Coulter Counter method. A selection can be made from ultrafine grains 
having a sphere-equivalent diameter of 0.05 microns or below, and coarse 
grains having a sphere-equivalent diameter of 10 microns or more. 
Preferably grains of 0.1 microns or more but 3 microns or less are used as 
photosensitive silver halide grains. 
As the emulsion used in the present invention, an emulsion having a wide 
grain size distribution, that is, a so-called polydisperse emulsion, or an 
emulsion having a narrow grain size distribution, that is, a so-called 
monodisperse emulsion, can be chosen and used in accordance with the 
purpose. As the scale for representing the size distribution, the 
deviation coefficient of the diameter of the projected area of the grain 
equivalent to a circle, or the deviation coefficient of the 
sphere-equivalent diameters of the volume, can be used. If a monodisperse 
emulsion is used, it is good to use an emulsion having such a size 
distribution that the deviation coefficient is 25% or below, more 
preferably 20% or below, and further more preferably 15% or below. 
Further, in order to allow the light-sensitive material to satisfy the 
intended gradation, in an emulsion layer having substantially the same 
color sensitivity, two or more monodisperse silver halide emulsions 
different in grain size are mixed and applied to the same layer or are 
applied as overlaid layers. Further, two or more polydisperse silver 
halide emulsions can be used as a mixture; or they can be used to form 
overlaid layers; or a combination of a monodisperse emulsion and a 
polydisperse emulsion can be used as a mixture; or the combination can be 
used to form overlaid layers. 
The photographic emulsion used in the present invention can be prepared by 
a method described, for example, by P. Glafkides in "Chemie et Phisique 
Photographique," Paul Montel, 1967; by G. F. Duffin in "Photographic 
Emulsion Chemistry," Focal Press, 1966; or by V. L. Zelikman et al. in 
"Making and Coating Photographic Emulsion," Focal Press, 1964. That is, 
any of the acid process, the neutral process, the ammonia process, and the 
like can be used; and to react a soluble silver salt with a soluble 
halogen salt, any of the single-jet method, the double-jet method, a 
combination thereof, and the like can be used. A method wherein grains are 
formed in the presence of excess silver ions (the so-called reverse 
precipitation process) can also be used. As one type of the double-jet 
method, a method wherein pAg in the liquid phase, in which a silver halide 
will be formed, is kept constant, that is, the so-called controlled 
double-jet method, can also be used. According to this method, a silver 
halide emulsion wherein the crystals are regular in shape and whose grain 
size is approximately uniform, can be obtained. 
When the emulsion according to the present invention is prepared, in 
accordance with the purpose, it is preferable to allow a salt of a metal 
ion to be present, for example, at the time when grains are formed, in the 
step of desalting, at the time when the chemical sensitization is carried 
out, or before the application. When the grains are doped, the addition is 
preferably carried out at the time when the grains are formed; or after 
the formation of the grains, but before the completion of the chemical 
sensitization, when the surface of the grains is modified or when the salt 
of a metal ion is used as a chemical sensitizer. As to the doping of 
grains, selection can be made from a case in which the whole grains are 
doped, one in which only the core parts of the grains are doped, one in 
which only the shell parts of the grains are doped, one in which only the 
epitaxial parts of the grains are doped, and one in which only the 
substrate grains are doped. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, 
Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, 
Tl, In, Sn, Pb, and Bi can be used. These metals can be added if they are 
in the form of a salt that is soluble at the time when grains are formed, 
such as an ammonium salt, an acetate, a nitrate, a sulfate, a phosphate, a 
hydroxide, a six-coordinate complex, and a four-coordinate complex. 
Examples include CdBr.sub.2, CdCl.sub.2, Cd(NO.sub.3).sub.2, 
Pd(NO.sub.3).sub.2, Pb(CH.sub.3 COO).sub.2, K.sub.3 Fe(CN).sub.6 !, 
(NH.sub.4).sub.4 Fe(CN).sub.6 !, K.sub.3 IrCl.sub.6, (NH.sub.4).sub.3 
RhCl.sub.6, and K.sub.4 Ru(CN).sub.6. As a ligand of the coordination 
compound, one can be selected from a halogen, H.sub.2 O, a cyano group, a 
cyanate group, a thiocyanate group, a nitrosyl group, a thionitrosyl 
group, an oxo group, and a carbonyl group. With respect to these metal 
compounds, only one can be used, but two or more can also be used in 
combination. 
In some cases, a method wherein a chalcogen compound is added during the 
preparation of the emulsion, as described in U.S. Pat. No. 3,772,031, is 
also useful. In addition to S, Se, and Te, a cyanate, a thiocyanate, a 
selenocyanate, a carbonate, a phosphate, or an acetate may be present. 
The silver halide grains according to the present invention can be 
subjected to at least one of sulfur sensitization, selenium sensitization, 
tellurium sensitization (these three are called chalcogen sensitization, 
collectively), noble metal sensitization, and reduction sensitization, in 
any step of the production for the silver halide emulsion. A combination 
of two or more sensitizations is preferable. Various types of emulsions 
can be produced, depending on the steps in which the chemical 
sensitization is carried out. There are a type wherein chemical 
sensitizing nuclei are embedded in grains, a type wherein chemical 
sensitizing nuclei are embedded at parts near the surface of grains, and a 
type wherein chemical sensitizing nuclei are formed on the surface. In the 
emulsion according to the present invention, the location at which 
chemical sensitizing nuclei are situated can be selected in accordance 
with the purpose, and generally preferably at least one type of chemical 
sensitizing nucleus is formed near the surface. 
Chemical sensitizations that can be carried out preferably in the present 
invention are chalcogen sensitization and noble metal sensitization, which 
may be used singly or in combination; and the chemical sensitization can 
be carried out by using active gelatin, as described by T. H. James in 
"The Theory of the Photographic Process," 4th edition, Macmillan, 1997, 
pages 67 to 76, or by using sulfur, selenium, tellurium, gold, platinum, 
palladium, or iridium, or a combination of these sensitizing agents, at a 
pAg of 5 to 10, a pH of 5 to 8, and a temperature of 30.degree. to 
80.degree. C., as described in Research Disclosure, Item 12008 (April 
1974); Research Disclosure, Item 13452 (June 1975); Research Disclosure, 
Item 307105 (November 1989); U.S. Pat. Nos. 2,642,361, 3,297,446, 
3,772,031, 3,857,711, 3,901,714, 4,266,018, and 3,904,415, and British 
Patent No. 1,315,755. 
In the photographic emulsion used in the present invention, various 
compounds can be incorporated for the purpose of preventing fogging during 
the process of the production of the light-sensitive material, during the 
storage of the light-sensitive material, or during the photographic 
processing, or for the purpose of stabilizing the photographic 
performance. That is, compounds known as antifoggants or stabilizers can 
be added, such as thiazoles including benzothiazolium salts, 
nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, 
bromobenzimidazoles, mercaptothiazoles, 
mercaptobenzothiazoles,amircaptobenzimidazoles, mercaptothiadiazoles, 
aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles 
(particularly 1-phenyl-5-mercaptotetrazole, 
1-(5-methylureidophenyl)-5-mercaptotetrazole, 
1-(5-acetylaminophenyl)-5-mercaptotetrazole and the like); 
mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as 
oxazolinthione; and azaindenes, such as triazaindenes; tetraazaindenes 
(particularly 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindenes), and 
pentaazaindenes. For examples, those described in U.S. Pat. Nos. 3,954,474 
and 3,982,947, and JP-B No. 28660/1987, can be used. A preferable compound 
is a compound described in JP-A No. 212932/1988. In accordance with the 
purpose, the antifoggant and the stabilizer can be added at various times, 
for example, before the formation of the grains, during the formation of 
the grains, after the formation of the grains, in the step of washing with 
water, at the time of dispersion after the washing with water, before the 
chemical sensitization, during the chemical sensitization, after the 
chemical sensitization, and before the application. In addition to the 
case wherein the antifoggant and the stabilizer are added during the 
preparation of the emulsion, so that the antifogging effect and the 
stabilizing effect, which are their essential effects, may be achieved, 
they can be used for various other purposes, for example, for controlling 
the habit of the crystals, for making the grain size small, for reducing 
the solubility of the grains, for controlling the chemical sensitization, 
and for controlling the arrangement of the dyes. 
In order to exhibit the effect of the present invention, the photographic 
emulsion used in the present invention is preferably spectrally-sensitized 
by methin dyes or other dyes. Dyes that can be used include a cyanine dye, 
a merocyanine dye, a composite cyanin dye, a composite merocyanine dye, a 
halopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol 
dye. Particularly useful dyes are those belonging to a cyanine dye, a 
merocyanine dye, and a composite merocyanine dye. In these dyes, any of 
nuclei generally used in cyanine dyes as a basic heterocyclic nuclei can 
be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a 
thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole 
nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, 
and a pyridine nucleus; and a nucleus formed by fusing an cycloaliphatic 
hydrocarbon ring or an aromatic hydrocarbon ring to these nuclei, such as 
an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a 
benzoxazole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, a 
naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole 
nucleus, and a quinoline nucleus, can be applied. These nuclei may be 
substituted on the carbon atom. 
In the merocyanine dye or the composite merocyanine dye, as a nucleus 
having a ketomethylene structure, a 5- to 6-membered heterocyclic nucleus, 
such as a pyrazolin-5-one nucleus, a thiohydantoine nucleus, a 
2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a 
rhodanine nucleus, and a thiobarbituric acid nucleus, can be applied. 
Further, as the red-sensitive spectrally sensitizing dye of silver halide 
emulsion grains high in silver chloride content, red-sensitive spectrally 
sensitizing dyes described in JP-A No. 123340/1991 are quite preferable, 
in view of the stability, the powerfulness of the absorption, the 
dependency of exposure on temperature, etc. 
In the light-sensitive material of the present invention, if the infrared 
region is to be spectrally sensitized efficiently, sensitizing dyes 
described in JP-A No. 15049/1991 (the left upper column, page 12, to the 
left lower column, page 21), JP-A No. 20730/1991 (the left lower column, 
page 4, to the left lower column, page 15), EP-0,420,011 (page 4, line 21, 
to page 6, line 54), EP-0,420,012 (page 4, line 12, to page 10, line 33), 
EP-0,443,466, and U.S. Pat. No. 4,975,362 are preferably used. 
The time at which the sensitizing dye is added to the emulsion may be at 
any stage for preparing the emulsion that is known to be useful. Most 
generally, although the addition of the sensitizing dye is carried out at 
a time after the completion of chemical sensitization and before the 
coating, the sensitizing dye may be added together with a chemical 
sensitizer simultaneously, to carry out the spectral sensitization and the 
chemical sensitization at the same time, as described in U.S. Pat. Nos. 
3,628,969 and 4,225,666; or the sensitizing dye may be added before the 
chemical sensitization, as described in JP-A No. 113,928/1983; or the 
sensitizing dye may be added before the completion of the formation of the 
silver halide grain precipitation, to start the spectral sensitization. 
Further, as taught in U.S. Pat. No. 4,225,666, the above compounds may be 
added in portions; that is, it is possible that part of these compounds is 
added before the chemical sensitization, with the remaining part added 
after the chemical sensitization; thus they may be added at any time 
during the formation of silver halide grains, for example, as shown in a 
method disclosed in U.S. Pat. No. 4,183,756. 
In the present invention, in combination with the water-soluble dye, a 
colored layer that can be decolored by processing can be used. The colored 
layer to be used that can be decolored by processing may be directly 
adjacent to the emulsion layer, or it may be arranged to be adjacent to 
the emulsion layer through an intermediate layer containing a processing 
color-mixing inhibitor, such as gelatin and hydroquinone. Preferably the 
colored layer is arranged below (on the side of the support) an emulsion 
layer that will form the same primary color as the color of the colored 
layer. All or some of colored layers corresponding to respective primary 
colors may be arranged. Also, colored layer corresponding to primary color 
regions may be arranged. The optical reflection density of the colored 
layer is preferably such that the optical density value at the wavelength 
having the highest optical density in the wavelength region used for 
exposure (the visible light region of from 400 nm to 700 nm, in the case 
of usual printer exposure, and the wavelength of the scanning exposure 
light source to be used, in the case of scanning exposure) is 0.2 or more, 
but 3.0 or less, more preferably 0.5 or more, but 2.5 or less, and 
particularly preferably 0.8 or more, but 2.0 or less. 
To form the colored layer, conventionally known methods can be applied in 
combination. For example, use can be made of a method wherein dyes 
described in JP-A No. 282244/1990 (page 3, the right upper column, to page 
8), or dyes described in JP-A No. 7931/1991 (page 3, the right upper 
column, to page 11, the left lower column), are made into a solid fine 
particle dispersion state and are contained in a hydrophilic colloid 
layer; a method wherein a cationic polymer is mordanted with an anionic 
dye; a method wherein a dye is adsorbed to fine particles, for example, of 
a silver halide, and is fixed in a layer; and a method, as described in 
JP-A No. 239544/1989, wherein colloidal silver is used. One method wherein 
a fine powder of a dye is dispersed in the solid state is described in 
JP-A No. 308244/1990 (pages 4 to 13); in the method, for example, a fine 
powder dye, which is substantially insoluble in water, at least at a pH of 
6 or below, but which is substantially soluble in water, at least at a pH 
of 8 or over, is contained. Further, a method wherein a cation polymer is 
mordanted with an anionic dye is described in JP-A No. 84637/1990 (pages 
18 to 26). Methods of the preparation of colloidal silver as a light 
absorber are described in U.S. Pat. Nos. 2,688,601 and 3,459,563. Among 
these methods, one in which a fine powder dye is contained, and one in 
which colloidal silver is used, are preferable. 
As a binder or a protective colloid that can be used in the light-sensitive 
material according to the present invention, a gelatin is advantageously 
used, and other hydrophilic colloids can be used alone or in combination 
with a gelatin. As the gelatin, a low-calcium gelatin having a calcium 
content of 800 ppm or less, and more preferably 200 ppm or less, is 
preferably used. Further, in order to prevent the proliferation of various 
molds and fungi that will proliferate in a hydrophilic colloid layer, to 
deteriorate an image, preferably mildew-proofing agents, as described in 
JP-A No. 271247/1988, are added. 
When the light-sensitive material of the present invention is subjected to 
printer exposure, it is preferable to use a band stop filter described in 
U.S. Pat. No. 4,880,726, by which light color-mixing is removed, to 
noticeably improve color reproduction. 
Although the above various additives are used in the light-sensitive 
material in the art, other various additives can also be used, depending 
on the purpose. 
These additives are described in more detail in Research Disclosure Item 
17643 (December 1978), Research Disclosure Item 18716 (November 1979), and 
Research Disclosure Item 307105 (November 1989); and the particular 
sections are summarized in the Table given below. 
__________________________________________________________________________ 
Additive RD 17643 
RD 18716 RD 307105 
__________________________________________________________________________ 
1 Chemical sensitizers 
p. 23 p. 648 
(right column) 
p. 996 
2 Sensitivity-enhancing agents 
-- p. 648 
(right column) 
-- 
3 Spectral sensitizers 
pp. 23-24 
pp. 648- 
(right column) 
pp. 996- 
(right column) 
and Supersensitizers 
649 (right column) 
998 (right column) 
4 Brightening agents 
p. 24 -- p. 998 
(right column) 
5 Antifogging agents 
pp. 24-25 
p. 649 
(right column) 
pp. 998- 
(right column) 
and Stabilizers 1000 (right column) 
6 Light absorbers, Filter 
pp. 25-26 
pp. 649- 
(right column) 
p. 1003 
(left to 
dyes, and UV Absorbers 
650 (left column) 
right column) 
7 Stain-preventing agents 
p. 25 (right 
p. 650 
(left to right 
-- 
column) 
column) 
8 Image dye stabilizers 
p. 25 -- -- 
9 Hardeners p. 26 p. 651 
(left column) 
pp. 1004- 
(right column) 
1005 (left column) 
10 
Binders p. 26 p. 651 
(left column) 
pp. 1003- 
(right column) 
1004 (right column) 
11 
Plasticizers and Lubricants 
p. 27 p. 650 
(right column) 
p. 1006 
(left to 
right column) 
12 
Coating aids and 
pp. 26-27 
p. 650 
(right column) 
pp. 1005- 
(left column) 
Surface-active agents 1006 (left column) 
13 
Antistatic agents 
p. 27 p. 650 
(right column) 
pp. 1006- 
(right column) 
1007 (left column) 
__________________________________________________________________________ 
The light-sensitive material of the present invention is used in a print 
system using usual negative printers, and also it is preferably used for 
digital scanning exposure that uses monochromatic high-density light, such 
as a second harmonic generating light source (SHG) that comprises a 
combination of a nonlinear optical crystal with a semiconductor laser or a 
solid state laser using a semiconductor laser as an excitation light 
source, a gas laser, a light-emitting diode, or a semiconductor laser. To 
make the system compact and inexpensive, it is preferable to use a 
semiconductor laser or a second harmonic generating light source (SHG) 
that comprises a combination of a nonlinear optical crystal with a 
semiconductor laser or a solid state laser. Particularly, to design an 
apparatus that is compact, inexpensive, long in life, and high in 
stability, the use of a semiconductor laser is preferable, and it is 
desired to use a semiconductor laser for at least one of the exposure 
light sources. 
If such a scanning exposure light source is used, the spectral sensitivity 
maximum of the light-sensitive material of the present invention can 
arbitrarily be set by the wavelength of the light source for the scanning 
exposure to be used. In an SHG light source obtained by combining a 
nonlinear optical crystal with a semiconductor laser or a solid state 
laser that uses a semiconductor laser as an excitation light source, since 
the emitting wavelength of the laser can be halved, blue light and green 
light can be obtained. Therefore, the spectral sensitivity maximum of the 
light-sensitive material can be present in each of the usual three 
regions, the blue region, the green region and the red region. In order to 
use a semiconductor laser as a light source to make the apparatus 
inexpensive, high in stability, and compact, preferably each of at least 
two layers has a spectral sensitivity maximum at 670 nm or over. This is 
because the emitting wavelength range of the available, inexpensive, and 
stable III-V group semiconductor laser is present now only in from the red 
region to the infrared region. However, on the laboratory level, the 
oscillation of a II-VI group semiconductor laser in the green or blue 
region is confirmed and it is highly expected that these semiconductor 
lasers can be used inexpensively and stably if production technique for 
the semiconductor lasers be developed. In that event, the necessity that 
each of at least two layers has a spectral sensitivity maximum at 670 nm 
or over becomes lower. 
In such scanning exposure, the time for which the silver halide in the 
light-sensitive material is exposed is the time for which a certain very 
small area is required to be exposed. As the very small area, the minimum 
unit that controls the quantity of light from each digital data is 
generally used and is called a picture element. Therefore, the exposure 
time per picture element is changed depending on the size of the picture 
element. The size of the picture element is dependent on the density of 
the picture element, and the actual range is from 50 to 2,000 dpi. If the 
exposure time is defined as the time for which a picture size is exposed 
with the density of the picture element being 400 dpi, preferably the 
exposure time is 10.sup.-4 sec or less, more preferably 10.sup.-6 sec or 
less. 
Processing materials and processing methods used in the present invention 
will now be described in detail. In the present invention, the 
light-sensitive material is developed (silver development/cross oxidation 
of the built-in reducing agent), desilvered, washed with water, and 
stabilized. In some cases, after the washing with water or the stabilizing 
processing, a treatment of alkalinization for color formation 
intensification is carried out. 
In the present invention, when the auxiliary developing agent is not 
contained in the light-sensitive material, the auxiliary developing agent 
is preferably contained in a developing solution, for the reasons 
described previously. As the auxiliary developing agent added to the 
developing solution, pyrazolidones, dihydroxybenzenes, reductones, and 
aminophenols can be used preferably, with pyrazolidones being used 
particularly preferably. 
Among pyrazolidones, 1-phenyl-3-pyrazolidones are preferable, and they 
include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 
1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone, 
1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 
1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 
1-p-chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 
1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 
1-phenyl-2-acetyl-3-pyrazolidone, and 
1-phenyl-2-hydroxymethyl-5-phenyl-3-pyrazolidone. 
Dihydroxybenzenes include hydroquinone, chlorohydroquinone, 
bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 
2,5-dimethylhydroquinone, and potassium hydroquinonemonosulfonate. 
Among reductones, ascorbic acid and derivatives thereof are preferable, and 
preferably compounds described in JP-A No. 148822/1994 on pages 3 to 10, 
can be used. Particularly, sodium L-ascorbate and sodium erysorbate are 
preferable. 
P-aminophenols include N-methyl-p-aminophenol, 
N-(.beta.-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl) glycine, 
2-methyl-p-aminophenol. 
These compounds are generally used alone, but use of two or more of them in 
combination is also preferable, to enhance the development and cross 
oxidation activity. 
The amount of these compounds to be used in the developing solution is 
generally 2.5.times.10.sup.-4 to 0.2 mol/liter, preferably 0.0025 to 0.1 
mol/liter, and more preferably 0.001 to 0.05 mol/liter. 
The present invention, when the auxiliary developing agent, for example 
pyrazolidones, is built in the light-sensitive material as described 
previously, preferably the auxiliary developing agent is not contained in 
the developing solution. That is, it is preferable to apply a treatment 
using an alkali solution that does not contain any auxiliary developing 
agent. 
The developing solution used in the present invention preferably has a pH 
of 8 to 13, and more preferably 9 to 12. 
To retain the above pH, it is preferable to use various buffers. In the 
developing solution, an organic preservative, a development accelerator, 
an antisettling agent, a fluorescent whitening agent, and the like which 
have been known hitherto, can be added. 
The processing temperature of the developing solution to be applied to the 
present invention is generally 20.degree. to 50.degree. C., and preferably 
30.degree. to 45.degree. C. The processing time is generally 5 sec to 2 
min, and preferably 10 sec to 1 min. With respect to the replenishing 
rate, a small amount is preferable, and the replenishing rate is generally 
15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 100 ml, 
per m.sup.2 of the light-sensitive material. 
After the development, a desilvering process is generally carried out. The 
desilvering process comprises a fixing process, or both bleaching process 
and a fixing process. When both bleaching and fixing are carried out, the 
bleaching process and the fixing process may be carried out separately or 
simultaneously (bleach-fixing process). Also, according to the purpose, 
the processing may be carried out in a bleach-fixing bath having two 
successive tanks; or the fixing process may be carried out before the 
bleach-fixing process; or the bleaching process may be carried out after 
the bleach-fixing process. As these bleaching bath and fixing bath, those 
known hitherto can be used. 
It is preferable to carry out the stabilizing process, to stabilize silver 
salts and dye images, without carrying out the desilvering process after 
the development. 
After the development, a process for intensifying image (intensification) 
that uses peroxides, halorous acids, iodoso compounds, and cobalt(III) 
complex compounds, described, for example, in West German Patent (OLS) 
Nos. 1,813,920, 2,044,993, and 2,735,262, and JP-A Nos. 9728/1973, 
84240/1974, 102314/1974, 53826/1976, 13336/1977, and 73731/1977, can be 
carried out. In order to intensify an image further, the above oxidizing 
agent for the intensification of an image can be added to the above 
developing solution, so that the development and the image-intensifying 
can be conducted in one bath simultaneously. Particularly, hydrogen 
peroxide is preferable, because the amplification rate is high. These 
image-intensifying methods are a processing method that is preferable in 
view of environmental conservation, because the amount of silver in the 
light-sensitive material can be reduced drastically, for example, to make 
a bleaching process unnecessary and to allow silver (and silver salts) not 
to be discharged in a stabilizing process or the like. 
The processing temperature of the desilvering step is generally 20.degree. 
to 50.degree. C., and preferably 30.degree. to 45.degree. C. The 
processing time is generally 5 sec to 2 min, and preferably 10 sec to 1 
min. A small replenishing rate is preferable, and the replenishing rate is 
generally 15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 
100 ml, per m.sup.2 of the light-sensitive material. The processing is 
also preferably carried out without replenishment in such a way that the 
evaporated amount is supplemented with water. 
The light-sensitive material of the present invention is generally passed 
through a washing (rinsing) step after the desilvering process. If a 
stabilizing process is carried out, the washing step can be omitted. The 
pH of the washing water and the stabilizing solution is generally 4 to 9, 
and preferably 5 to 8. The processing temperature is generally 15.degree. 
to 45.degree. C., and preferably 25.degree. to 40.degree. C. The 
processing time is generally 5 sec to 2 min, and preferably 10 sec to 40 
sec. 
The overflow solution associated with the replenishment of the above 
washing water and/or the stabilizing solution, can be reused in other 
processes, such as the desilvering process. 
The amount of the washing water and/or the stabilizing solution can be set 
in a wide range depending on various conditions, and the replenishing rate 
is preferably 15 to 360 ml, and more preferably 25 to 120 ml, per m.sup.2 
of the light-sensitive material. 
The processing time in each process according to the present invention 
means the time required from the start of the processing of the 
light-sensitive material at any process, to the start of the processing in 
the next process. The actual processing time in an automatic developing 
machine is determined generally by the linear speed and the volume of the 
processing bath, and in the present invention, as the linear speed, 500 to 
4,000 mm/min can be mentioned as a guide. Particularly in the case of a 
small-sized developing machine, 500 to 2,500 mm/min is preferable. 
The processing time in the whole processing steps, that is, the processing 
time from the developing process to the drying process, is preferably 360 
sec or below, more preferably 120 sec or below, and particularly 
preferably 90 to 30 sec. Herein the processing time means the time from 
the dipping of the light-sensitive material into the developing solution, 
till the emergence from the drying part of the processor. 
The silver halide color photographic light-sensitive material of the 
present invention provides excellent effects capable of reducing the 
amount of processing solutions to be replenished and discharged, and 
capable of reducing stains after processing caused by long time 
preservation. Further, according to the image-forming method of the 
present invention, convenient and rapid processing can be attained while 
reducing the replenishment and discharging amount of the processing 
solution.

EXAMPLES 
The present invention will now be described specifically with reference to 
the Examples, but of course the present invention is not limited to them. 
Example 1 
A paper base, both surfaces of which had been laminated with a 
polyethylene, was subjected to surface corona discharge treatment; then it 
was provided with a gelatin undercoat layer containing sodium 
dodecylbenzensulfonate, and it was coated with three photographic 
constitutional layers, to produce a photographic printing paper, Sample 
(100), having the three-layer constitution shown below. The coating 
solutions were prepared as follows. 
First-Layer Coating Solution 
17 g of a coupler (ExY), 20 g of a reducing agent for color formation (36), 
and 80 g of a solvent (Solv-1) were dissolved in ethyl acetate, and the 
resulting solution was emulsified and dispersed into 16% gelatin aqueous 
solution containing 10% sodium dodecylbenzensulfonate and citric acid, to 
prepare an emulsified dispersion A. On the other hand, a silver 
chlorobromide emulsion A (cubes, a mixture of a large-size emulsion A 
having an average grain size of 0.88 .mu.m, and a small-size emulsion A 
having an average grain size of 0.70 .mu.m (3:7 in terms of mol of 
silver), the deviation coefficients of the grain size distributions being 
0.08 and 0.10, respectively, and each emulsion having 0.3 mol % of silver 
bromide locally contained in part of the grain surface whose substrate was 
made up of silver chloride) was prepared. To the large-size emulsion A of 
this emulsion, had been added 1.4.times.10.sup.-4 mol, per mol of silver, 
of each of blue-sensitive sensitizing dyes A, B, and C shown below, and to 
the small-size emulsion A of this emulsion, had been added 
1.7.times.10.sup.-4 mol, per mol of silver, of each of blue-sensitive 
sensitizing dyes A, B, and C shown below. The chemical ripening of this 
emulsion was carried out optimally with a sulfur sensitizer and a gold 
sensitizer being added. The above emulsified dispersion A and this silver 
chlorobromide emulsion A were mixed and dissolved, and a first-layer 
coating solution was prepared so that it would have the composition shown 
below. The coating amount of the emulsion is in terms of silver. 
In the similar way as the method of preparing the first-layer coating 
solution, coating solutions for the second layer and the third layer were 
prepared. 
As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine 
sodium salt was used. 
Further, to each layer, were added Cpd-2, Cpd-3, Cpd-4, and Cpd-5, so that 
the total amounts would be 15.0 mg/m.sup.2, 60.0 mg/m.sup.2, 50.0 
mg/m.sup.2, and 10.0 mg/m.sup.2, respectively. 
For the silver chlorobromide emulsion of the first layer, the following 
spectral sensitizing dye was used. 
##STR12## 
Further, 1-(5-methylureidophenyl)-5-mercaptotetrazol was added to the 
first-layer in amount of 3.0.times.10.sup.-3 mol per mol of the silver 
halide. 
Layer Constitution 
The composition of each layer is shown below. The numbers show coating 
amounts (g/m.sup.2). In the case of the silver halide emulsion, the 
coating amount is in terms of silver. 
______________________________________ 
Base 
Polyethylene-Laminated Paper 
The polyethylene on the first layer side contained a 
white pigment (TiO.sub.2 14% by weight) and a blue dye 
(ultramarine)! 
First Layer 
The above silver chlorobromide emulsion A 
0.20 
Gelatin 1.50 
Yellow coupler (ExY) 0.17 
Reducing agent for color formation (36) 
0.20 
Solvent (Solv-1) 0.80 
Second Layer 
Gelatin 3.17 
Third Layer (protective layer) 
Gelatin 1.01 
Acryl-modified copolymer of polyvinyl alcohol 
0.04 
(modification degree: 17%) 
Liquid paraffin 0.02 
Surface-active agent (Cpd-1) 
0.01 
______________________________________ 
Samples (101) to (105) were prepared using the same procedures used for the 
preparation of Sample (100), except for replacing each of the yellow 
coupler and the reducing agent for color formation in the coating solution 
of the first layer, respectively, with an equimolar amount of each of the 
yellow coupler and the reducing agent for color formation shown in Table 
1, and except for adding the mordant, shown in Table 1, in the coating 
solution of the second layer, such that the mordant would be coated by 
3.21 g per m.sup.2. 
Further, Samples (200) to (205) were prepared using the same procedures 
used for the preparation of Sample (100), except for replacing a silver 
chlorobromide emulsion A in the coating solution of the first layer with a 
silver chlorobromide emulsion B, shown below, in the same amount of 
silver, and except for replacing each of the coupler and the reducing 
agent for color formation, respectively, with an equimolar amount of each 
of the magenta couplers and the reducing agent for color formation shown 
in Table 2, and except for adding a mordant, shown in Table 2, in the 
coating solution of the second layer, such that the mordant would be 
coated by 3.21 g per m.sup.2. 
A silver chlorobromide emulsion B: cubes, a mixture of a large-size 
emulsion B having an average grain size of 0.55 .mu.m, and a small-size 
emulsion B having an average grain size of 0.39 .mu.m (1:3 in terms of mol 
of silver). The deviation coefficients of the grain size distributions 
were 0.10 and 0.08, respectively, and each emulsion had 0.8 mol % of AgBr 
locally contained in part of the grain surface whose substrate was made up 
of silver chloride. 
For the silver chlorobromide emulsion B, the following spectrally 
sensitizing dyes were used: 
##STR13## 
(The sensitizing dye D was added to the large-size emulsion in an amount of 
3.0.times.10.sup.-4 mol per mol of the silver halide, and to the 
small-size emulsion in an amount of 3.6.times.10.sup.-4 mol per mol of the 
silver halide; the sensitizing dye E was added to the large-size emulsion 
in an amount of 4.0.times.10.sup.-5 mol per mol of the silver halide, and 
to the small-size emulsion in an amount of 7.0.times.10.sup.-5 mol per mol 
of the silver halide; and the sensitizing dye F was added to the 
large-size emulsion in an amount of 2.0.times.10.sup.-4 mol per mol of the 
silver halide, and to the small-size emulsion in an amount of 
2.8.times.10.sup.-4 mol per mol of the silver halide.) 
Further, Samples (300) to (305) were prepared in the same manner as Sample 
(100), except that, in the coating solution of the first layer, the silver 
chlorobromide emulsion A was changed to the following silver chlorobromide 
emulsion C, in the same amount of silver, and that the coupler and the 
reducing agent for color formation were changed to the cyan couplers and 
the reducing agents for color formation, shown in Table 3, in the same 
molar amounts, respectively, and that the mordant shown in Table 3 was 
added into the coating solution of the second layer, such that the mordant 
would be coated by 3.21 g per m.sup.2. 
A silver chlorobromide emulsion C: cubes, a mixture of a large-size 
emulsion C having an average grain size of 0.5 .mu.m, and a small-size 
emulsion having an average grain size of 0.41 .mu.m (1:4 in terms of mol 
of silver). The deviation coefficients of the grain size distributions 
were 0.09 and 0.11, respectively, and each emulsion had 0.8 mol % of AgBr 
locally contained in part of the grain surface whose substrate was made up 
of silver chloride. 
For the silver chlorobromide C, the following spectrally sensitizing dyes 
were used: 
##STR14## 
(Each was added to the large-size emulsion in an amount of 
5.0.times.10.sup.-5 mol per mol of the silver halide, and to the 
small-size emulsion in an amount of 8.0.times.10.sup.-5 mol per mol of the 
silver halide.) 
The used compounds are shown below. 
##STR15## 
Using an FWH-type sensitometer (color temperature of the light source: 
3,200.degree. K), manufactured by Fuji Photo Film Co., Ltd., gradation 
exposure was given to the thus prepared Samples (100) to (105) through a 
blue filter for sensitometry, to the thus prepared Samples (200) to (205) 
through a green filter for sensitometry, and to the thus prepared Samples 
(300) to (305) through a red filter for sensitometry. 
The thus light-exposed Samples were processed with the following processing 
solutions in the following processing steps 1 or 2. 
______________________________________ 
Processing step 1 
Processing step 
Temperature Time 
______________________________________ 
Development 40.degree. C. 15 sec 
Bleach-fix 40.degree. C. 45 sec 
Rinse room temperature 
45 sec 
Alkali treatment 
room temperature 
30 sec 
______________________________________ 
Processing step 2 
Processing step 
Temperature Time 
______________________________________ 
Development 40.degree. C. 15 sec 
Bleach-fix 40.degree. C. 45 sec 
Rinse room temperature 
45 sec 
______________________________________ 
Developing Solution 
Water 600 ml 
Potassium phosphate 40 g 
Disodium N,N-bis(sulfonatoethyl)hydroxylamine 
10 g 
KCl 5 g 
Hydroxylethylidene-1,1-diphosphonic acid (30%) 
4 ml 
1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 
2 g 
Water to make 1,000 ml 
pH (at 25.degree. C. by using potassium hydroxide) 
12 
Bleach-fix Solution 
Water 600 ml 
Ammonium thiosulfate (700 g/liter) 
93 ml 
Ammonium sulfite 40 ml 
Ethylenediaminetetraacetic acid iron(III) ammonium salt 
55 g 
Ethylenediaminetetraacetic acid 
2 g 
Nitric acid (67%) 30 g 
Water to make 1,000 ml 
pH (at 25.degree. C. by using acetic acid and ammonia water) 
5.8 
Rinsing Solution 
Sodium chlorinated isocyanurate 
0.02 g 
Deionized water (conductivity: 5 .mu.S/cm or below) 
1,000 ml 
pH 6.5 
Alkali Treatment Solution 
Water 800 ml 
Potassium carbonate 30 g 
Water to make 1,000 ml 
pH 10 
______________________________________ 
Both for the samples processed in the processing step 1 and the samples 
processed in the processing step 2, a maximum color density part was 
measured by blue light for the Samples (100) to (105), by green light for 
the Samples (200) to (205), and by red light for the Samples (300) to 
(305). The maximum color density of the sample processed in the processing 
step 1 is defined as Da(max), and the maximum color density of the sample 
processed in the processing step 2 is defined as Dn(max). The results are 
shown in Tables 1, 2, and 3, respectively. 
Further, respective two sheets of the samples that had not been exposed to 
light or processed, were prepared, and they were subjected to desilvering 
in the above bleach-fixing step. In this process, the alkali treatment was 
applied to one sheet of a sample, while no alkali treatment was applied to 
the other sheet of the sample, and both two sheets of each sample were 
subjected to a compulsory thermo-test at a temperature of 50.degree. C. 
and humidity of 70% for one week, respectively. After the thermo-test, the 
density was measured, both for the samples with alkali treatment and 
samples without alkali treatment, by blue light for the Samples (100) to 
(105), by green light for the Samples (200) to (205), and by red light for 
the Samples (300) to (305). The density of the sample with alkali 
treatment is defined as Da(min), and the density of the sample without 
alkali treatment is defined as Dn(min). The results are shown in Tables 1, 
2, and 3, respectively. 
TABLE 1 
__________________________________________________________________________ 
Reducing 
agent for With alkali 
Without alkali 
Sample 
color 
Yellow treatment 
treatment 
No. formation 
coupler 
Mordant 
Da(max) 
Da(min) 
Dn(max) 
Dn(min) 
Remarks 
__________________________________________________________________________ 
100 (36) Ex Y 
-- 1.88 1.80 
0.48 0.12 Comparative 
Example 
101 (36) C-2 P-27 1.92 1.90 
1.82 0.11 This 
Invention 
102 (1) Ex Y 
-- 1.72 1.68 
0.52 0.12 Comparative 
Example 
103 (1) C-2 P-27 1.76 1.72 
1.70 0.11 This 
Invention 
104 (42) C-2 " 1.70 1.68 
1.65 0.11 This 
Invention 
105 (52) C-2 " 1.65 1.63 
1.63 0.11 This 
Invention 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
Reducing 
agent for With alkali 
Without alkali 
Sample 
color 
Magenta treatment 
treatment 
No. formation 
coupler 
Mordant 
Da(max) 
Da(min) 
Dn(max) 
Dn(min) 
Remarks 
__________________________________________________________________________ 
200 (36) Ex M.sub.1 
-- 1.72 1.69 
0.32 0.12 Comparative 
Example 
201 (36) C-38 P-27 1.82 1.76 
1.72 0.11 This 
Invention 
202 (1) Ex M.sub.2 
-- 2.34 2.29 
0.38 0.12 Comparative 
Example 
203 (1) C-21 P-27 2.35 2.28 
2.27 0.11 This 
Invention 
204 (42) C-38 " 1.68 1.82 
1.60 0.11 This 
Invention 
205 (41) C-38 " 1.55 1.50 
1.50 0.11 This 
Invention 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
Reducing 
agent for With alkali 
Without alkali 
Sample 
color 
Cyan treatment 
treatment 
No. formation 
coupler 
Mordant 
Da(max) 
Da(min) 
Dn(max) 
Dn(min) 
Remarks 
__________________________________________________________________________ 
300 (36) Ex C.sub.1 
-- 1.46 1.40 
0.13 0.08 Comparative 
Example 
301 (36) C-30 
P-27 1.58 1.52 
1.54 0.08 This 
Invention 
302 (1) Ex C.sub.2 
-- 1.49 1.43 
0.16 0.08 Comparative 
Example 
303 (1) C-29 
P-27 1.62 1.56 
1.58 0.08 This 
Invention 
304 (42) C-30 
" 1.54 1.41 
1.50 0.08 This 
Invention 
305 (50) C-30 
" 1.44 1.38 
1.37 0.08 This 
Invention 
__________________________________________________________________________ 
As is apparent from the results in Tables 1, 2, and 3, samples for which 
only the reducing agent for color formation and the comparative coupler 
were used, did not form color unless the alkali treatment was applied. 
However, when the alkali treatment was applied, the density in the 
not-exposed part was increased to near the maximum color density, during 
storage under a wet heat condition. On the contrary, the samples using the 
reducing agent for color formation, the coupler, and the mordant, 
according to the present invention, could provide a sufficient color 
density even without applying an alkali treatment, and the density for the 
not-exposed part was scarcely increased under the condition of not 
applying the alkali treatment, showing that satisfactory storability could 
be obtained. 
Example 2 
A paper base, both surfaces of which had been laminated with a 
polyethylene, was subjected to surface corona discharge treatment; then it 
was provided with a gelatin undercoat layer containing sodium 
dodecylbenzensulfonate, and it was coated with four photographic 
constitutional layers, to produce a photographic printing paper, referred 
to as sample (400), having the four-layer constitution shown below. In the 
same way as the preparation of the first-layer coating solution of Example 
1, a coating solution for the second-layer was prepared. 
In the similar way as the method of preparing the second-layer coating 
solution, coating solutions for the first, third and fourth layer were 
prepared. As the gelatin hardeners for each layers, 
1-oxy-3,5-dichloro-s-triazine sodium salt was used. 
Further, to each layer, were added, Cpd-2, Cpd-3, Cpd-4, and Cpd-5 in the 
same way as Example 1, so that the total amounts would be 15.0 mg/m.sup.2, 
60.0 mg/m.sup.2, 50.0 mg/m.sup.2, and 10.0 mg/m.sup.2, respectively. 
To the second-layer was added 1-(5-methylureidophenyl)-5-mercaptotetrazole 
in amounts of 3.0.times.10.sup.-3 mol, per mol of the silver halide. 
Layer Constitution 
The composition of each layer is shown below. The numbers show coating 
amounts (g/m.sup.2). In the case of the silver halide emulsion, the 
coating amount is in terms of silver. 
______________________________________ 
Base 
Polyethylene-Laminated Paper 
The polyethylene on the first layer side contained a 
white pigment (TiO.sub.2 14% by weight) and a blue dye 
(ultramarine)! 
First Layer 
Gelatin 1.12 
1,5-diphenyl-3-pyrazolidone 
0.02 
Second Layer 
The silver chlorobromide emulsion A 
0.20 
described in the Example 1 
Gelatin 1.50 
Yellow coupler (ExY) 0.17 
Reducing agent for color formation (36) 
0.20 
Solvent (Solv-1) 0.80 
Third Layer 
Gelatin 3.17 
Fourth Layer (Protective Layer) 
Gelatin 1.01 
Acryl-modified copolymer of polyvinyl alcohol 
0.04 
(modification degree: 17%) 
Liquid paraffin 0.02 
Surface-active agent (Cpd-1) 
0.01 
______________________________________ 
Samples (401) to (408) were prepared using the same procedures used for the 
preparation of the Sample (400), except for replacing each of the yellow 
coupler and the reducing agent for color formation in the coating solution 
of the second layer with an equimolar amount of each of the yellow coupler 
and the reducing agent for color formation shown in Table 4, respectively, 
and except for adding the mordant, shown in Table 4, in the coating 
solution of the second layer, such that it would be coated by 3.21 g per 
m.sup.2. 
In the sample using P-9, as a hardening agent, 
1,2-bis(vinylsulfonylacetoamide)ethane was used instead of sodium 
1-oxy-3,5-dichloro-s-triazine. 
The thus prepared Samples (400) to (408) were given gradation exposure 
using a blue filter for sensitometry, using an FWH-type sensitometer 
(color temperature of the light source: 3200.degree. K), manufactured by 
Fuji Film Co., Ltd. 
The samples after the exposure to light were processed by the following 
processing step 1 or 2 using the developing solution described below, and 
using the bleach-fixing solution, rinsing solution, and the alkali 
treatment solution of Example 1. 
______________________________________ 
Processing step 1 
Processing step 
Temperature Time 
______________________________________ 
Development 40.degree. C. 15 sec 
Bleach-fix 40.degree. C. 45 sec 
Rinse room temperature 
45 sec 
Alkali treatment 
room temperature 
30 sec 
______________________________________ 
Processing step 2 
Processinp step 
Temperature Time 
______________________________________ 
Development 40.degree. C. 15 sec 
Bleach-fix 40.degree. C. 45 sec 
Rinse room temperature 
45 sec 
______________________________________ 
Developing Solution 
Water 600 ml 
Potassium phosphate 40 g 
KCl 5 g 
Hydroxylethylidene-1,1-diphosphonic acid (30%) 
4 ml 
Water to make 1,000 ml 
pH (at 25.degree. C. by using potassium hydroxide) 
12 
______________________________________ 
For the Samples (400) to (408), Da(max), Dn(max), Da(min), and Dn(min) were 
measured by blue light in the same method as in Example 1. The obtained 
results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Reducing 
agent for With alkali 
Without alkali 
Sample 
color 
Yellow treatment 
treatment 
No. formation 
coupler 
Mordant 
Da(max) 
Da(min) 
Dn(max) 
Dn(min) 
Remarks 
__________________________________________________________________________ 
400 (36) Ex Y 
-- 2.13 2.10 
0.48 0.12 Comparative 
Example 
401 (36) C-2 P-27 2.20 2.16 
2.10 0.11 This 
Invention 
402 (1) Ex Y 
-- 1.95 1.92 
0.62 0.12 Comparative 
Example 
403 (1) C-2 P-27 2.08 2.02 
2.03 0.11 This 
Invention 
404 (42) C-2 " 2.00 1.98 
1.94 0.11 This 
Invention 
405 (52) C-2 " 1.93 1.90 
1.90 0.11 This 
Invention 
406 (36) C-2 P-9 2.18 2.15 
2.12 0.11 This 
Invention 
407 (36) C-2 P-26 2.16 2.14 
2.13 0.11 This 
Invention 
408 (36) C-2 P-22 2.13 2.10 
2.09 0.11 This 
Invention 
__________________________________________________________________________ 
As can be seen from the results in Table 4, the color density was increased 
when 1,5-diphenyl-3-pyrazolidone was built in a photographic printing 
paper. In addition, similar results as those in Example 1 could be 
obtained besides those described above. 
Having described our invention as related to the present embodiments, it is 
our intention that the invention not be limited by any of the details of 
the description, unless otherwise specified, but rather be construed 
broadly within its spirit and scope as set out in the accompanying claims.