Dye image forming method

A method of forming a dye image suitable for a rapid process is disclosed. The method comprises the steps of, PA1 (i) imagewise exposing a light-sensitive silver halide photographic material comprising a support and provided thereon a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein said green-sensitive silver halide emulsion layer contains silver halide grains of which silver chloride content is not less than 90 mol %, and a magenta dye-forming coupler having a pKa value of not more than 8.80; and wherein the total amount of silver halide contained in said blue-sensitive, green-sensitive and red-sensitive layers being not more than 7.8 mg/dm.sup.2 in terms of silver; PA1 (ii) color developing said photographic material; and immediately after the color development, PA1 (iii) processing said photographic material with a solution having a bleaching capability and having a pH value of from 4.5 to 6.5

FIELD OF THE INVENTION 
The invention relates to a dye image forming method, in particular, to a 
dye image forming method suitable for rapid processing and capable of 
providing an image with considerably low minimum density. 
BACKGROUND OF THE INVENTION 
Recently, in the photographic art, light-sensitive silver halide 
photographic materials which are adaptable to rapid processing, which are 
capable of providing a high quality image and superior processing 
stability, and which can be manufactured at a lower cost have been in 
need. The particular need is for the material capable of ultra-rapid 
processing. 
Usually, a light-sensitive silver halide photographic material is subjected 
to continuous treatment with an automatic developing machine installed in 
a development laboratory. To improve user-oriented service, same-day 
processing is required; the light-sensitive material is developed and 
returned to a user within the same day the material had been submitted to 
the laboratory. More recently, an even shorter processing service is 
required; the light-sensitive material is returned to a user within a few 
hours from the reception of the material. Thus, there are increasing needs 
for more rapid processing. At the same time, decreasing the processing 
time means improved processing productivity, and, possibly, lower costs. 
Therefore, rapid processing is an inevitable necessity. 
Studies for achieving rapid processing have been centered on two aspects; 
the light-sensitive material and the processing solutions. In color 
developing, studies for achieving rapid processing have been based on 
higher temperature, higher pH level, higher concentration of color 
developing agents, and, further, additional additives such as development 
accelerators. Examples of such a development accelerator include 
1-phenyl-3-pyrazolidones described in British Patent No. 811,185, 
N-methyl-p-aminophenols described in British Patent No. 2,417,514, and 
N,N,N',N'-tetramethyl-p-phenylenediamines described in Japanese Patent 
Publication Open to Public Inspection (hereinafter referred to as Japanese 
Patent O.P.I. Publication) No. 15554/1975. However, these methods often 
fail to achieve sufficiently rapid processing and even incur deterioration 
such as increased fog. 
Meanwhile, it is known that the configuration, size, and composition of 
silver halide grains in a silver halide emulsion greatly affect the 
developing speed and the like. It is also known that the halogen 
composition particularly affects the developing speed, and that an 
emulsion with high silver chloride content provides a remarkably high 
developing speed. 
However, maintaining the rapid developability of a high chloride silver 
halide emulsion usually incurs increased fog. 
Especially in the color developing system, because colored dye is formed, 
the fog density is more conspicuous than in that of a black and white 
developing system; this poses a serious problem in positively ensuring the 
rapid processability of high chloride silver halide emulsions. 
Generally, antifogging agents are used to decrease the fog density. One of 
the most commonly known antifogging agents is potassium bromide which has 
been used in various developers. However, when a sample having high 
chloride silver halide emulsion is processed in a color developer system 
containing potassium bromide, its rapid processability is remarkably 
jeopardized. This means that potassium bromide acts as an extremely strong 
developing inhibitor o the high chloride silver halide emulsion rather 
than acting as an antifogging agent. Therefore, it is essential for rapid 
processing that potassium bromide is not virtually contained in the color 
developer system in which the high chloride silver halide emulsion is 
processed. Further, the fogging problem remains more difficult to solve. 
Meanwhile, various other organic inhibitors are known as antifogging 
agents. For example, such agents are described in "Stabilization of 
Photographic Silver Halide Emulsions" by E.J. Birr, Focal Press (1974). 
Among these antifogging agents, many heterocyclic mercapto compounds have 
a strong antifogging effect and have been commonly used. 
In general, light-sensitive silver halide photographic materials are 
uninterruptedly treated in various processing laboratories, with 
replenishers being continuously fed. It is impossible, in such an 
operation, to keep the compositions of processing solutions constant from 
the beginning through to the end of the running treatment. The resultant 
composition change of the processing solution causes a fluctuation in 
photographic properties. This problem is becoming more serious owing to 
the recent trend toward lower replenishing rates for processing solutions. 
In regard to the composition change above, it is virtually impossible to 
completely avoid the developer becoming contaminated with the 
bleach-fixer, even by taking measures such as strictly predetermined 
replenishing rates for replenishers, evaporation prevention, and 
elimination of substances possibly eluted from the light-sensitive 
material. Therefore, especially in the case of a roller-conveyance type 
automatic developing machine, the degree to which the developer becomes 
contaminated with the bleach-fixer tends to fluctuate greatly depending on 
the amount of material being treated, and the squeezing manner. A lower 
replenishing rate of the processing solution causes greater contamination 
because the recycling rate of the processing solution decreases. 
Furthermore, since the pH of the color developer is maintained at a high 
level, pH fluctuation of the color developer is unavoidable owing to the 
accumulated amount of the replenisher or air oxidation during the running 
treatment. 
Such fluctuation in the color developer tends to induce fogging. Said 
antifogging agents can inhibit fogging to some extent if the agents are 
properly used. 
However, an increase in minimum density (in magenta dye image, in 
particular) is induced during transition from the color developing process 
to the bleaching process in an automatic developing machine. Although this 
phenomenon can be prevented by using a considerable amount of said agents, 
a new problem occurs: developability and desilvering properties of the 
light-sensitive material deteriorate. 
SUMMARY OF THE INVENTION 
The invention has been intended to solve the above-mentioned disadvantages 
of the prior art, and, therefore, the object of the invention is to 
provide a dye image forming method that, without deteriorating 
developability and desilvering properties of the sensitive material, 
prevents magenta stain by means of rapid processing. 
The above-mentioned object of the invention is achieved by a method of 
forming a dye image comprising the steps of, (i) imagewise exposing a 
light-sensitive silver halide photographic material comprising a support 
and provided thereon a blue-sensitive silver halide emulsion layer, a 
green-sensitive silver halide emulsion layer and a red-sensitive silver 
halide emulsion layer, wherein said green-sensitive silver halide emulsion 
layer contains silver halide grains of which silver chloride content is 
not less than 90 mol%, and a magenta dye-forming coupler of which pKa 
value is not more than 8.80; and wherein the total amount of silver halide 
contained in said blue-sensitive, green-sensitive and red-sensitive layers 
being not more than 7.8 mg/dm.sup.2 in terms of silver; (ii) color 
developing said photographic material, and immediately after the color 
development, (iii) processing said photographic material with a solution 
having a bleaching capability and pH value of from 4.5 to 6.5. 
DETAILED DESCRIPTION OF THE INVENTION 
Preferred silver halide grains used in the invention have not less than 90 
mol% of silver chloride, not less than 10 mol% of silver bromide. More 
specifically, the silver halide grains are silver chlorobromide having 0.1 
to 2 mol% of silver bromide. 
The silver halide grains of the invention may be used singly, or used after 
being mixed with other silver halide grains having a different 
composition, or used after being mixed with silver halide grains having 
not more than 10 mol% of silver chloride. 
In the silver halide emulsion layer containing the silver halide grains 
having not less than 90 mol% silver chloride content of the invention, the 
proportion of silver halide grains having not less than 90 mol% of silver 
chloride content to the total silver halide grains is not less than 60 
wt%, or, preferably, not less than 80 wt%. 
The composition of silver halide grains of the invention may be homogeneous 
from the interior to the surface of the grains, or may be different 
between the interior and the surface. In the case of different composition 
between the interior and the surface, the composition may change 
continuously or discontinuously. 
There is no specific limitation on the grain size of silver halide grains 
of the invention. However, in view of rapid-processability, sensitivity, 
and other photographic performance criteria, the preferred grain size is 
0.2 to 1.6 .mu.m, in particular, 0.25 to 1.2 .mu.m. The grain size can be 
achieved by various methods known in the photographic art. Typical methods 
are described in "Analysis Method of Grain Size" (by Labrand), A.S.T.M. 
Symposium on Light Microscopy (1955), pp. 94-122; "The Theory of the 
Photographic Process:" by Mees and James, 3rd edition, Chapter 2, 
Published from Macmillan Company (1966). 
The grain sizes can be measured based on projected areas or approximate 
diameter values of grains. When silver halide grains have virtually 
identical configurations, the grain size distribution can be expressed 
with considerable precision by diameter or projected area. 
The grain size distribution of the silver halide grains used in the present 
invention may be either a multi-dispersed or monodispersed type. However, 
the monodispersed silver halide grains preferably have the variation 
coefficient of not more than 0.22, or, more preferably, not more than 
0.15, in terms of the size distribution of the silver halide grains 
contained in an emulsion. The variation coefficient is a coefficient 
indicating the range of the grain size distribution and is defined by the 
following expressions. 
##EQU1## 
In the above expressions, ri represents sizes of independent grains; ni, a 
number of independent grains counted. The term "grain size" here means a 
diameter of an independent spherical silver halide grain; a diameter, when 
the grain is cubic or has any shape other than a spherical shape, of a 
projected image converted into a circular image. 
The silver halide grains used in the emulsion of the invention are prepared 
by any of the acid process, neutral process, and ammonium process. The 
grains may be grown at once, or may be grown after forming seed grains. A 
method for forming seed grains may be identical with or different from a 
method for growing the grains. 
As a method for reacting soluble silver salt with soluble halide salt, the 
normal precipitation method, reverse precipitation method or double-jet 
precipitation method, or a combination of these methods is arbitrarily 
used. Among these methods, the double-jet precipitation method is 
advantageous. Furthermore, a pAg-controlled double-jet method disclosed in 
Japanese Patent O.P.I. Publication No. 48521/1979, a modification of the 
double-jet precipitation method, may also be used. 
If necessary, a solvent for silver halide such as thioether may be used. A 
mercapto-group containing compound, nitrogen containing heterocyclic 
compound, or sensitizing dye or the like may be also added during the 
formation of silver halide grains or after the formation of the grains. 
The configurations of silver halide grains according to the invention are 
arbitrarily selected. The preferred example is a cubic grain having {100} 
face as a crystal face. Additionally, octahedral, tetradecahedral or 
dodecahedral grains may be prepared using the methods described in U.S. 
Pat. Nos. 4,183,756, and 4,225,666, Japanese Patent O.P.I. Publication No. 
26589/1980, Japanese Patent Examined Publication No. 42737/1980, and in 
the Journal of Photographic Science 21, 39 (1973), and the like, thereby 
the resultant silver halide grains may be used in embodying the invention. 
Also, grains having twin planes may be used. The silver halide grains may 
comprise grains of a common configuration, or may be a mixture of various 
configurations. 
In silver halide grains used in the emulsion of the invention, during the 
grain forming process and/or grain growing process, any metal ion selected 
from cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or 
complex salt thereof, rhodium slat or complex salt thereof, iron salt or 
complex salt thereof can be added and contained in the interior and/or the 
surface of the grains, and, under a suitable reducing atmosphere, the 
sensitizing cores can be endowed in the interior and/or the surface of the 
grains. 
Excess soluble salts in the emulsion containing silver halide grains of the 
invention (hereinafter referred to as the emulsion of the invention) may 
be either removed or left unremoved after the termination of silver halide 
grain-growing. Such salt can be removed in compliance with the methods 
described in Research Disclosure No. 17643. 
The silver halide grains of the invention may be those where latent images 
are primarily formed either on the surface thereof or in the interior 
thereof. The preferred grains are those where latent images re primarily 
formed on the surface thereof. 
The emulsion of the invention is chemically sensitized using the 
conventional methods such as sulfur sensitizing methods using compounds 
containing sulfur reactive with silver ion, or containing activated 
gelatin; selenium sensitizing methods using selenium compounds; reducing 
sensitizing methods using reducing substances; noble metal sensitizing 
methods using gold or other noble metal compounds, wherein these methods 
can be used singly or in combination. 
According to the invention, chemical sensitizers such as a chalcogen 
sensitizer can be used. The chalcogen sensitizer is a general term 
covering sulfur sensitizer, selenium sensitizer, and tellurium sensitizer. 
Sulfur or selenium sensitizer is advantageous for photographic 
application. The useful sulfur sensitizers include thiosulfate, 
allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluene 
thiosulfonate, and rhodanine. Other useful sulfur sensitizers are 
described, for example, in U.S. Pat. Nos. 1,574,994, 2,410,689, 2,278,947, 
2,728,668, 3,501,313, 3,656,955, West Germany OLS 1,422,869, and Japanese 
Patent O.P.I. Publication Nos. 24937/1971 and 45016/1980. The amount of 
sulfur sensitizer being added is 10.sup.-7 to 10.sup.-1 mol per mol silver 
halide, although the amount greatly varies depending on various conditions 
such as pH, temperature and silver halide grain size. 
Selenium sensitizers may be used instead of sulfur sensitizers. The 
examples of useful selenium sensitizers include aliphatic 
isoselenocyanates such as allylisocyanate; selenoureas; selenoketones; 
selenoamides; selenocarboxylic salts and esters; selenophosphates; and 
selenides such as diethyl selenide and diethyl diselenide. The typical 
examples of these selenium sensitizers are described in U.S. Pat. Nos. 
1,574,944, 1,602,592, and 1,623,499. 
Further, reduction sensitizers can be used in conjunction with the above 
chalcogen sensitizers. The useful reducing agents, although not 
specifically limited, include stannous chloride, thiourea dioxide, 
hydrazine, and polyamine. 
Noble metal compounds other than gold compounds, such as palladium 
compounds are also used in conjunction. 
The silver halide grains of the invention preferably contain a gold 
compound. The oxidation number of the gold of such gold compounds can be 
either +1 or +3. The useful gold compounds include chloroaurate, potassium 
chloroaurate, auric trichloride, potassium auric thiocyanate, potassium 
iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl 
trichloro gold, gold sulfide, and gold selenide. These gold compounds can 
be used either to sensitize or virtually not to sensitize the silver 
halide grains. 
The amount of gold sensitizer added varies depending on various conditions. 
As a guideline, the amount is 10.sup.-8 to 10.sup.-1 mol, or preferably, 
10.sup.-7 to 10.sup.-2 mol per mol silver halide. The timing of adding 
these compounds can be arbitrarily selected from during the formation of 
silver halide grains, during physical ripening, during chemical ripening, 
and after the termination of chemical ripening. 
The photographic emulsion according to the invention is spectrally 
sensitized to have sensitivity to an intended spectral range, by using a 
dye known in the photographic art as a sensitizing dye. The sensitizing 
dyes may be used either singly or in a combination of more than two types. 
In conjunction with a sensitizing dye, a supersensitizer, that is, a 
compound capable of enhancing the sensitizing action of a sensitizing dye, 
though it does not provide spectral sensitization action nor absorb 
visible light, may be incorporated into a photographic emulsion. 
According to the invention, a compound represented by the following Formula 
[S] is preferably incorporated into the green-sensitive emulsion layer 
containing not only silver halide grains having not less than 90 mol% of 
silver chloride content but also a magenta coupler having pKa value not 
more than 8.80. 
##STR1## 
In this formula, Q represents a five- or six-membered heterocyclic ring or 
an atomic group necessary for completing a five- or six-membered 
heterocyclic ring condensed with a benzene ring; M represents a hydrogen 
atom, alkali metal atom, or ammonium. 
The examples of the five-membered heterocyclic ring represented by Q in 
Formula [S] include an imidazole ring, tetrazole ring, thiazole ring, 
oxazole ring, selenazole ring, benzimidazole ring, naphthoimidazole ring, 
benzothiazole ring, naphthothiazole ring, benzoselenazole ring, 
naphthoselenazole ring and benzoxazole ring. The examples of the 
six-membered heterocyclic ring represented by Q include a pyridine ring, 
pyrimidine ring, and quinoline ring. Also included are the similar five- 
and six-membered heterocyclic ring having a substituent. 
The examples of alkali metal represented by M include sodium, and potassium 
atoms. 
The particularly preferable compounds, among the compounds represented by 
Formula [S], are represented by the following Formulas [SA] and [SB]. 
##STR2## 
In this formula, R.sub.A represents a hydrogen atom, an alkyl group, alkoxy 
group, aryl group, halogen atom; carboxyl group or salt thereof; sulfo 
group or salt thereof; or amino group. Z represents --NH--, --O--, or 
--S--. M is synonymous with M in Formula [S]. 
##STR3## 
In this formula, Ar represents 
##STR4## 
R.sub.B represents an alkyl group, alkoxy group; carboxyl group or salt 
thereof; sulfo group or salt thereof; hydroxyl group, amino group, 
acylamino group, carbamoyl group or sulfonamide group. n represents an 
integer from 0 to 2. M is synonymous with M in Formula [S]. 
The examples of the alkyl group represented either by R.sub.A or R.sub.B in 
Formula [SA] or [SB] include a methyl group, ethyl group, and butyl group; 
the examples of the alkoxy group include a methoxy group and ethoxy group; 
the examples of the salt of carboxyl or sulfo group include sodium salt 
and ammonium salt. 
The examples of an aryl group represented by R.sub.A in Formula [SA] 
include a phenyl group and naphthyl group; the examples of the halogen 
atom include a chloride atom and bromine atom. 
The examples of an acrylamino group represented by R.sub.B in Formula [SB] 
include a methylcarbonylamino group and benxoylamino group; the examples 
of the carbamoyl group include an ethylcarbamoyl group, and 
phenylcarbamoyl group; the examples of the sulfonamide group include a 
methylsulfonamide group, and phenylsulfonamide group. 
These alkyl group, alkoxy group, aryl group, amino group, acylamino group, 
carbamoyl group, and sulfonamide group may have a substituent. 
The typical examples of the compounds represented by Formula [S] are as 
follows. 
##STR5## 
In order to incorporate the compound represented by Formula [S] 
(hereinafter referred to as compound [S]) of the invention into the silver 
halide emulsion layer of the invention, the compound [S] is dissolved in 
water or any organic solvent, such as methanol or ethanol compatible with 
water, and the solution is incorporated into the layer. The compound [S] 
can be used singly or in conjunction with any other compound represented 
by Formula [S], with stabilizers other than the compound [S], or with 
antifogging agents. 
Timing of adding the compound [S] can be arbitrarily selected among the 
following periods: before or during the formation of silver halide grains; 
a period between the termination of silver halide grain formation and 
before the initiation of chemical ripening during chemical ripening; at 
the termination of chemical ripening; or a period after the termination of 
chemical ripening and before coating operation. Preferable timing of the 
addition is during chemical ripening, at the termination of chemical 
ripening, or a period after the termination of chemical ripening and 
before coating operation. Prescribed amount of the compound [S] can be 
added all at once or in steps. 
The compound [S] can be directly added to silver halide emulsion or the 
coating solution of the silver halide emulsion. Optionally, the compound 
[S] may be added to the coating solution for a non-light-sensitive 
hydrophilic colloid layer adjacent to the silver halide emulsion layer, 
thereby the compound [S] is incorporated into the silver halide emulsion 
layer of the invention by diffusion from the colloid layer during the 
multilayer coating operation. 
The amount of the compound [S] added to the silver halide emulsion layer is 
not specifically limited. However, usually, the amount is 
1.times.10.sup.-6 to 1.times.10.sup.-1 mol, or, preferably, 
1.times.10.sup.-5 to 1.times.10.sup.-2 mol per mol silver halide. 
Magenta couplers used in the invention have the pKa value of not more than 
8.80. 
The pKa value according to the invention means a value determined by 
measuring the pH of a solution at 25.degree. C. using a titration method, 
wherein the coupler anions (coupler ions whose proton in the active site 
is released) and the coupler have reached the equibration (both are 
present in equivalent mol) in the ethanol-water (4:1) mixture solvent. 
Detailed pKa value measuring methods are described in the Journal of 
Photographic Science (aforementioned), 13, 248 (1965), and elsewhere. 
Any type of couplers can be used if their pKa value is not more than 8.80. 
However, the preferable couplers are magenta couplers of 5-pyrazolone 
type. 
The typical examples of the magenta couplers of the invention are as 
follows, although usable couplers are not limited to them. 
##STR6## 
Usually, the magenta coupler of the invention is used in an amount of 
1.times.10.sup.-3 mol to 1 mol, or, preferably, 1.times.10.sup.-2 to 
8.times.10.sup.-1 mol per mol silver halide. 
Every dye forming coupler used in the light-sensitive silver halide 
photographic material of the invention is desired to have within its 
molecular structure a group called the ballasts group that comprises not 
less than 8 carbon atoms and renders the coupler non-diffusible. 
As a yellow dye forming coupler, acylacetanilide couplers are 
advantageously used, and of which benzoylacetanilide and 
pyvaloylacetanilide compounds are particularly advantageous. Preferable 
compounds are represented by the following Formula [Y]. 
##STR7## 
In this formula, R.sub.1 represents a halogen atom, or alkoxy group; 
R.sub.2, a hydrogen atom, halogen atom, or alkoxy group; R.sub.3, an 
acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl 
group, arylsulfonamide group, alkylureide group, arylureide group, 
succinimide group, alkoxy group, or aryloxy group; Z.sub.1, a group 
capable of being split off upon a coupling reaction with the oxidation 
product of a color developing agent. 
The typical examples of the useful yellow coupler are those described in 
British Patent No. 1,077,874, Japanese Patent Examined Publication No. 
40757/1970; Japanese Patent O.P.I. Publication Nos. 1031/1972, 26133/1972, 
94432/1973, 87650/1975, 3631/1976, 115219/1977, 99433/1976, 133329/1979, 
and 30127/1981, U.S. Pat. Nos. 2,875,057, 3,253,924, 3,265,506, 3,408,194, 
3,551,155, 3,551,156, 3,664,841, 3,725,072, 3,730,722, 3,891,445, 
3,900,483, 3,929,484, 3,933,500, 3,973,968, 3,990,896, 4,012,259, 4 
022,620, 4,029,508, 4,057,432, 4,106,942, 4,133,958, 4,269,936, 4,286,053, 
4,304,845, 4,314,023, 4,336,327, 4,356,258, 4,386,155, 4,401,752, and the 
like. 
Phenol-type and naphthol-type cyan couplers are used as a cyan dye image 
forming coupler. The preferable couplers ar represented by the following 
Formulas [C-I] and [C-II]. 
##STR8## 
In this formula, R.sub.4 represents an aryl group, cycloalkyl group, or 
heterocyclic group; R.sub.5, an alkyl group, or phenyl group, R.sub.6, a 
hydrogen atom, halogen atom, alkyl group, or alkoxy group; Z.sub.2, a 
hydrogen atom, or a group capable of being split off upon a reaction with 
the oxidation product of an aromatic primary amine color developing agent. 
##STR9## 
In this formula, R.sub.7 represents an alkyl group (such as methyl group, 
ethyl group, propyl group, butyl group, nonyl group); R.sub.8, an alkyl 
group (such as methyl group, ethyl group); R.sub.9, a hydrogen atom, 
halogen atom (such as fluorine, chlorine, and bromine), or alkyl group 
(such as methyl group, ethyl group); Z.sub.3, a hydrogen atom, or a group 
capable of being split off upon a reaction with the oxidation product of 
an aromatic primary amine color developing agent. 
These cyan dye image forming couplers are described in U.S. Pat. Nos. 
2,306,410, 2,356,475, 2,362,598, 2,367,531, 2,369,929, 2,423,730, 
2,474,293, 2,476,008, 2,498,466, 2,545,687, 2,728,660, 2,772,162, 
2,895,826, 2,976,146, 3,002,836, 3,419,390, 3,446,622, 3,476,563, 
3,737,316, 3,758,308, 3,839,044, British Patent Nos. 478,991, 945,542, 
1,084,480, 1,377,233, 1,388,024, 1,543,040, Japanese Patent O.P.I. 
Publication Nos. 37425/1972, 10135/1975, 25228/1975, 112038/1975, 
117422/1975, 130441/1975, 6551/1976, 37647/1976, 52828,1976, 108841/1976, 
109630/1978, 48237/1979, 66129/1979, 131931/1979, 32071/1980, 146050/1984, 
31953/1984, 117249/1985. 
The quantity of the dye image forming coupler used in the invention is 
usually in a range of 1.times.10.sup.-3 to 1 mol, or, preferably, 
1.times.10.sup.-2 to 8.times.10.sup.-1 mol per mol silver halide in each 
silver halide emulsion layer. 
The above dye image forming couplers are usually dissolved in a high 
boiling organic solvent having a boiling point of not less than 
150.degree. C., and, if necessary, in conjunction with other low boiling 
and/or water soluble organic solvents, and then, the solution is 
emulsified and dispersed in a hydrophilic binder such as an aqueous 
gelatin solution by using surface-active agents. Then, the resultant 
emulsion is added to the intended hydrophilic colloidal layer. A process 
for removing the low boiling organic solvent after or during dispersion 
may be incorporated. 
Preferable high boiling organic solvents used in the invention are 
compounds having a dielectric constant not more than 6.0. The examples are 
esters such as phthalic acid esters and phosphoric acid esters; organic 
acid amides; ketones; and hydrocarbons; each having a dielectric constant 
not more than 6.0. Particularly preferable high boiling organic solvents 
are those that have a dielectric constant of a range not more than 6.0 and 
not less than 1.9, and that have a vapor pressure not more than 0.5 mmHg 
at 100.degree. C. Those particularly advantageous are phthalic acid esters 
and phosphoric acid esters. These solvents may be used as a mixture of two 
or more than two types. 
The dielectric constant according to the invention is a value measured at 
30.degree. C. 
The phthalic acid esters useful in embodying the invention are represented 
by the following Formula (A). 
##STR10## 
In this formula, R.sub.10 and R.sub.11 independently represent an alkyl 
group, alkenyl group, or aryl group, provided that the total number of 
carbon atoms of the groups represented by R.sub.10 and R.sub.11 is 8 to 
32, preferably, 16 to 24. 
The alkyl groups represented by R.sub.10 and R.sub.11 of the above Formula 
[A] can be either straight-chained or branched groups, and the examples of 
which include a butyl group, pentyl, hexyl, 2-ethylhexyl, 
3,5,5-trimethylhexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and 
octadecyl; the aryl groups represented by R.sub.10 and R.sub.11 include a 
phenyl group, and naphthyl group; the alkenyl groups represented by 
R.sub.10 and R.sub.11 include a hexenyl, heptenyl, and octadecenyl. These 
alkyl groups, alkenyl groups, and aryl groups include those having a 
single or plural substituents. The substituents of the alkyl groups and 
the alkenyl groups include a halogen atom, alkoxy group, aryl group, 
aryloxy group, alkenyl group, and alkoxycarbonyl group; the substituents 
of the aryl groups include a halogen atom, alkyl group, alkoxy group, aryl 
group, aryloxy group, alkenyl group, and alkoxycarbonyl group. 
The preferable group of the above R.sub.10 and R.sub.11 is alkyl group, 
such as 2-ethylhexyl group, 3,5,5-trimethylhexyl, octyl, and nonyl. 
The phosphoric acid esters preferable in the invention include those 
represented by the following Formula (B). 
##STR11## 
In this formula, R.sub.12, R.sub.13, and R.sub.14 independently represent 
an alkyl group, alkenyl group, or aryl group, provided that the total 
number of the carbon atoms of the groups represented by R.sub.12, 
R.sub.13, and R.sub.14 is 24 to 54. 
The alkyl groups represented by R.sub.12, R.sub.13, and R.sub.14 of Formula 
[B], include a butyl group, pentyl, hexyl, 2-ethylhexyl, heptyl, nonyl, 
decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and nonadecyl; the aryl 
groups similarly represented include a phenyl group, and naphthyl group; 
the alkenyl groups similarly represented include a hexenyl group, 
heptenyl, and octadecenyl. 
These alkyl groups, alkenyl groups, and aryl groups include those having a 
single or plural substituents. The preferable R.sub.12, R.sub.13, and 
R.sub.14 are alkyl groups such as a 2-ethylhexyl group, octyl, 
3,5,5-trimethylhexyl, nonyl, decyl, sec-decyl, sec-dodecyl, and t-octyl. 
The typical examples of high boiling organic solvents used in the invention 
are as follows. However, the scope of useful solvents is not limited only 
to these examples. 
Example High Boiling Organic Solvents 
##STR12## 
The amount of these high boiling organic solvents added is usually 0 to 400 
wt. %, preferably, 10 to 100 wt. % per amount coupler. 
The light-sensitive silver halide photographic material of the invention 
can be a color negative or positive film of the color negative-positive 
system, or color photographic paper, and the effect of the method 
according to the invention is positively achieved with a color 
photographic paper that is visually appreciated. 
The light-sensitive silver halide photographic materials of the invention 
including the color photographic paper can be monochromatic or multicolor 
materials. For multi-color reproduction by the subtractive color process, 
the light-sensitive silver halide photographic material usually comprises 
each silver halide emulsion layers having magenta, yellow, or cyan 
couplers and non-light-sensitive layers on a support in a laminated 
structure. The structure has an appropriate number and sequence of the 
above layers. However, the number and the sequence can be changed 
according to the main performance being achieved or the purpose being 
used. 
In the case of a multicolor photographic light-sensitive material among the 
light-sensitive silver halide photographic materials used in the 
invention, an especially preferable layer constitution formed on a support 
is in the order of a yellow dye image forming layer, an intermediate 
layer, a magenta dye image forming layer, an intermediate layer, a cyan 
dye image forming layer, an intermediate layer, and a protective layer. 
The advantageous binder (or a protective colloid) used in the 
light-sensitive silver halide photographic materials of the invention is 
gelatin. However, other protective colloids, such as gelatin derivatives, 
graft polymers of gelatin with other polymer or polymers, proteins, sugar 
derivatives, cellulose derivatives, synthetic hydrophilic macromolecule 
materials being monopolymers or copolymers are useful. 
The photographic emulsion layers, and the other hydrophilic colloid layers, 
of the light-sensitive silver halide photographic materials of the 
invention can be hardened by using one or two or more types of hardeners 
that cross-link the binder (or the protective colloid) molecules to 
enhance layer strength. Hardeners are added to the layers to a degree that 
is sufficient to harden the layers and eliminate the hardeners added to 
the processing solution. However, the hardeners may be added to the 
processing solution. 
The preferable hardeners for hardening the silver halide emulsion layer of 
the invention are those of chlorotriazine series represented by the 
following Formula [HDA] or [HDB]. 
##STR13## 
In the formula, R.sup.1 represents a chlorine atom, hydroxy group, alkyl 
group, alkoxy group, alkylthio group, --OM group (M represents a univalent 
metal atom.), --NR.sup.3 R.sup.4 group (R.sup.3 and R.sup.4 independently 
represent a hydrogen atom, alkyl group, and aryl group), or an 
--NHCOR.sup.5 group (in which R.sup.5 is a hydrogen atom, analkyl group or 
an aryl group). R.sup.2 is synonymous with the above R.sup.1, except in 
that a chlorine atom is precluded. 
##STR14## 
In this formula, R.sup.6 and R.sup.7 independently represent a chlorine 
atom, hydroxyl group, alkyl group, alkoxy group, or --OM group (M 
represents a univalent metal atom). Q and Q' independently represent 
--O--, --S--, or --NH--, as a bonding group; L, alkylene group, or arylene 
group; and p and q, independently, 0 or 1. 
The typical examples of the preferable hardeners represented by the above 
Formulas, [HDA] and [HDB], are as follows. 
__________________________________________________________________________ 
Formula [HDA] 
##STR15## 
Compound No. R.sup.1 R.sup.2 
__________________________________________________________________________ 
HD-1 OH ONa 
HD-2 Cl ONa 
HD-3 OCH.sub.3 ONa 
HD-4 Cl OC.sub.2 H.sub.5 
HD-5 Cl OK 
HD-6 OH OK 
HD-7 Cl NH.sub.2 
HD-8 Cl NHCOCH.sub.3 
HD-9 OH NHC.sub.2 H.sub.5 
__________________________________________________________________________ 
Formula [HDB] 
##STR16## 
Compound 
No. R.sup.6 
R.sup.7 
Q p Q' q L 
__________________________________________________________________________ 
HD-10 Cl Cl O 1 O 1 
##STR17## 
HD-11 ONa ONa O 1 O 1 CH.sub.2 CH.sub.2 
HD-12 ONa ONa -- 0 -- 0 CH.sub.2 CH.sub.2 
HD-13 OCH.sub.3 
OCH.sub.3 
S 1 S 1 CH.sub.2 CH.sub.2 
HD-14 ONa ONa NH 1 NH 1 CH.sub.2 CH.sub.2 
HD-15 ONa ONa NH 1 O 1 CH.sub.2 CH.sub.2 
__________________________________________________________________________ 
The hardeners represented by Formula [HDA] or [HDB] are first dissolved in 
water or water miscible solvents (such as methanol or ethanol). Then the 
resultant solution is added to coating solutions which make the silver 
halide emulsion layers or other structural layers. The addition method can 
be either by the batch or in-line system. The timing of the addition is 
not particularly limited; but, preferably, just before coating. 
The amount of these hardeners added is 0.5 to 100 mg, preferably, 2.0 to 50 
mg per gram gelatin. 
To increase the flexibility of the silver halide emulsion layers and/or 
other hydrophilic colloid layers, plasticizers can be added to the 
light-sensitive silver halide photographic materials used in the invention 
(hereinafter referred to as the light-sensitive silver halide photographic 
materials of the invention). 
To improve the dimension stability and the like of the photographic 
emulsion layers and other hydrophilic colloid layers, a dispersion (latex) 
of water insoluble or slightly soluble synthetic polymers can be added to 
the layers in the light-sensitive silver halide photographic materials of 
the invention. 
To prevent deteriorated dye images, the light-sensitive silver halide 
photographic materials of the invention can incorporate image stabilizers. 
Ultraviolet absorbents can be added to the hydrophilic colloid layers, such 
as a protective layer, and an intermediate layer, of the light-sensitive 
silver halide photographic materials of the invention in order to prevent 
fogging caused by discharging of triboelectricity or the like, and prevent 
image deterioration caused by ultraviolet ray. 
Auxiliary layers, such as a filter layer, an antihalation layer, and/or an 
anti-irradiation layer, can be incorporated into the light-sensitive 
silver halide photographic materials of the invention. These layers and/or 
the emulsion layers may contain a dye that is capable of being eluted from 
the color light-sensitive materials during the developing process, or that 
is capable of being bleached during the bleaching process. 
Matting agents can be incorporated into the silver halide emulsion layers, 
and/or other hydrophilic colloid layers of the light-sensitive silver 
halide photographic materials of the invention in order to decrease gloss, 
increase retouchability, and prevent mutual adhesion of the 
light-sensitive materials. 
To decrease sliding friction, lubricants can be added to the 
light-sensitive silver halide photographic materials of the invention. 
To prevent electrification, anti-static agents can be added to the 
light-sensitive silver halide photographic materials of the invention. 
These anti-static agents can be added to an anti-static layer formed on a 
side of the support opposite to the emulsion laminated side, or to the 
emulsion layers and/or protective layers other than the emulsion layers. 
Various surface active agents can be used in the photographic emulsion 
layers and/or other hydrophilic colloid layers of the light-sensitive 
silver halide photographic materials of the invention in order to meet 
photographic requirements such as improved coating property, prevention of 
electrification, improved sliding property, emulsification and dispersion, 
prevention of adhesion, improved photographic properties (such as 
developing acceleration, high gradation, and higher sensitivity). 
The photographic emulsion layers and the other layers of the 
light-sensitive silver halide photographic materials of the invention can 
be formed, by coating, on baryta paper, papers laminated with 
.alpha.-olefin polymers and the like; flexible, reflective supports such 
as synthetic papers; films made of semisynthetic or synthetic polymers 
such as cellulose acetate, cellulose nitrate, polystyrene, 
polyvinylchloride, polyethylene terephthalate, polycarbonate, polyamide; 
or solid materials such as glass, metal, ceramics. 
If necessary, corona discharge, ultraviolet irradiation, flame treatment, 
and the like can be conducted on the surface of the support used as a 
constituent of the light-sensitive material of the invention. After such 
treatment, the layers of the light-sensitive material of the invention can 
be formed directly on the surface of the support, or indirectly on one or 
two subbing layers that are intended for improving properties such as 
adhesion-readiness, electrification prevention, dimension stability, 
wear-resistance, hardness, halation prevention, and improved friction 
resistance of the support. 
In the coating operation of the silver halide emulsion of the photographic 
light-sensitive materials of the invention, thickeners may be used to 
improve coating property. Particularly advantageous coating methods are 
extrusion coating and curtain coating each of which can form plural 
coating layers at one process. 
Color developing agents used in the color developers of the invention 
include conventionally known agents used over a wide range of various 
color photographic processes. These developing agents include aminophenol 
derivatives and p-phenylenediamine derivatives. These compounds are 
generally used in their salt forms, such as hydrochlorides or sulfates, 
which are stabler than in their free states. The amount of these compounds 
used is about 0.1 g to 30 g, preferably, about 1 g to 15 g, per liter 
color developer solution. 
The examples of aminophenol series developers include o-aminophenol, 
p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, and 
2-hydroxy-3-amino-1,4-dimethylbenzene. 
The particularly useful aromatic primary amine color developing agents are 
N,N-dialkyl-p-phenylenediamine compounds whose alkyl and phenyl groups may 
independently have an arbitrary substituent group. The examples of 
particularly useful typical compounds are N,N-diethyl-p-phenylenediamine 
hydrochloride, N-methyl-p-phenylenediamine hydrochloride, 
N,N-dimethyl-p-phenylenediamine hydrochloride, 
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 
N-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4-aminoaniline 
hydrochloride, N-ethyl-N-.beta.-hydroxylethylaminoaniline, 
4-amino-3-methyl-N,N-diethylaniline, 
4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-tolunesulfonate. 
In addition to the above aromatic primary amine color developing agents, an 
arbitrary conventionally known developer constituent compounds can be 
added to the color developing solution used for processing the silver 
halide photographic light-sensitive materials of the invention, and the 
examples of which include alkali agents, such as sodium hydroxide, sodium 
carbonate, potassium carbonate; alkali metal thiocyanate, benzyl alcohol, 
water softeners, and thickeners. 
The pH value of the color developer is usually not less than 7, preferably, 
about 10 to 13. 
The temperature for performing the color developing is usually not lower 
than 15.degree. C., preferably, in a range of 20.degree. to 50.degree. C. 
The recommendable temperature for rapid developing is not lower than 
30.degree. C. Color developing time is usually in a range of 20 to 60 
sec., preferably, 30 to 50 sec. 
The light-sensitive silver halide photographic materials of the invention 
contain the above color developing agents as their complete form or as 
their precursor form in the hydrophilic colloid layers, and can be 
processed in an activating bath. A color developing agent precursor is a 
compound being capable of forming a complete color developing agent under 
an alkaline condition, and the examples of which include Schiff base type 
precursors of aromatic aldehyde derivatives; multivalent metal ion complex 
precursors; imide phthalate derivative precursors; amide phosphate amide 
derivative precursors; sugar amine reactant precursors; and urethane type 
precursors. Examples of these aromatic primary amine color developing 
agent precursors are described in U.S. Pat. Nos. 3,342,599, 2,507,114, 
2,695,234, 3,179,492, British Patent No. 803,786, Japanese Patent O.P.I. 
Publication Nos. 185628/1978, 79035/1979, Research Disclosure Nos. 15159, 
12146, and 13924. 
These aromatic primary amine color developing agents or their precursor is 
required to be added in an amount sufficient for ensuring positive 
coloration when subjected to an activating process. The amount, depending 
on the type of the light-sensitive material, is in a range of 0.1 to 5 
mol, preferably, 0.5 to 3 mol per mol silver halide. These color 
developing agents or their precursors can be used singly or in 
combination. These developing agents or precursors are incorporated into 
the light-sensitive materials by one of the following three methods: 
addition by dissolving them in appropriate solvents such as water, 
methanol, ethanol, and acetone; addition by emulsifying/dispersing them in 
high boiling organic solvents such as dibutyl phthalate, dioctyl 
phthalate, tricresyl phthalate; addition by having them being impregnated 
in latex polymers as described in Research Disclosure No. 14850. 
According to the invention, after color developing, the light-sensitive 
materials are immediately processed with a processing solution having 
bleaching power. This solution may also have fixing power (called a 
bleach-fixer). 
In the bleaching process, organic acid metal complexes are used as a 
bleaching agent. The metal complexes oxidize the metal silver produced by 
the developing process, restore it to the former silver halide, and, at 
the same time, allow the non-colored portions of the dye to exhibit 
coloration. The metal complex is a compound in which an organic acid such 
as aminopolycarboxylic acid, oxalic acid, or citric acid is attached to a 
metal ion such as iron, cobalt, or copper iron by means of a coordinate 
covalent bond. The preferable organic acids for forming their metal 
complexes are polycarboxylic acids or aminopolycarboxylic acids. The 
polycarboxylic acids or aminopolycarboxylic acids may be used in the form 
of their alkali metal salt, ammonium salt or water soluble amine salt. 
The typical examples are as follows: 
[1] ethylenediaminetetraacetic acid 
[2] nitrilotriacetic acid 
[3] iminodiacetic acid 
[4] disodium ethylenediaminetetraacetate 
[5] tetra(trimethylammonium) ethylenediaminetetraacetate 
[6] tetrasodium ethylenediaminetetraacetate 
[7] sodium nitrilotriacetate 
The bleaching solution can contain various additives in addition to the 
above bleaching agents, organic acid metal complexes. The desirable 
additives are alkali halides or ammonium halides, as a re-halogenizing 
agent, such as potassium bromide, sodium bromide, sodium chloride, and 
ammonium bromide; metal salts, or chelating agents. 
Further, conventionally known additives which are used in the bleaching 
solution can be optionally added, and the examples of which include pH 
buffer agents, such as borate, oxalates, acetates, carbonates, and 
phosphates; alkylamines, and polyethylene oxides. 
In addition, the bleacher and the bleach-fixer may contain one or more pH 
buffer agents consisting of salts such as sulfites, for example, ammonium 
sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, 
sodium sulfite, ammonium metabisulfite, potassium disulfite, and sodium 
metabisulfite; boric acid, borax, sodium hydroxide, potassium hydroxide, 
sodium carbonate, potassium carbonate, sodium bisulfite, sodium 
hydrogencarbonate, potassium hydrogencarbonate, acetic acid, sodium 
acetate, ammonium hydroxide. 
When performing the processing of the invention while adding the 
bleach-fixer replenisher to the bleach-fixer solution (bath), the 
bleach-fixer solution (bath) may contain thiosulfate, thiocyanate, or 
sulfite; otherwise, the bleach-fixer replenisher may contain these salts 
in order to add them to the processing bath. 
According to the invention, to enhance the activity of the bleach-fixer, 
air or oxygen gas may be bubbled into the bleach-fixer bath and the 
reservoir tank of the bleach-fixer replenisher according to a requirement; 
or an appropriate oxidizing agent such as hydrogen peroxide, bromate salt, 
and persulfate salt.