Light-sensitive silver halide photographic material

There is disclosed a light-sensitive silver halide photographic material having at least one light-sensitive layer constituted of a plural number of silver halide emulsions provided on a support, and a non-light-sensitive intermediate layer containing a diffusion resistant coupler capable of forming a migratable color forming dye or a compound capable of forming a flow-out type coupling product provided at least adjacent to the silver halide emulsion layer with the highest light sensitivity among the plural number of silver halide emulsion layers on its support side. The light-sensitive material according to this invention exhibits excellent photographic characteristics such as sensitivity, graininess, sharpness, storability and gradation.

BACKGROUND OF THE INVENTION 
This invention relates to a light-sensitive silver halide photographic 
material, more particularly to a light-sensitive silver halide 
photographic material improved in photographic characteristics such as 
sensitivity, graininess, sharpness, storability and gradation. 
Heretofore, as the light-sensitive silver halide photographic material 
(hereinafter abbreviated as light-sensitive material), development of a 
light-sensitive material having high sensitivity and finely 
micropulverized grains has been desired, and a number of improved 
light-sensitive materials, particularly color light-sensitive materials, 
have been proposed. 
As one of the light-sensitive materials suited for the above object, for 
example, U.K. Pat. No. 923,045 states that sensitivity can be enhanced 
without deterioration by applying the same color sensitive silver halide 
emulsion in separated layers in a high sensitivity silver halide emulsion 
layer (hereinafter called as high sensitivity emulsion layer) and a low 
sensitivity silver halide emulsion layer (hereinafter called as low 
sensitivity emulsion layer) and further by controlling the maximum color 
forming density at a low level. 
In recent years, however, particularly the color light-sensitive material 
for photography is required progressively to be higher in sensitivity, 
whereby it is obliged to use coarse silver halide inferior in graininess 
and/or a coupler with greater coupling speed in the silver halide emulsion 
layer. For this reason, in the method described in the above U.K. Pat. No. 
923,045, the degree of improvement became insufficient, and further 
elaborations have been done for improvement of graininess. 
For example, in Japanese Patent Publication No. 15495/1974, the graininess 
is stated to be improved by provision of a gelatin layer between the high 
sensitivity emulsion layer and the low sensitivity emulsion layer. In this 
method, while graininess at lower density regions can be improved, bad 
influences on gradation are markedly observed. On the other hand, for 
restoration of gradation, if sensitivity of the low sensitivity emulsion 
layer enhanced according to the prior art, for example, by increasing the 
grain size of silver halide, the graininess in the medium density region 
which is important particularly in practical technique will unfavorably be 
deteriorated. Further, in the multi-layer color light-sensitive material 
having the above constitution, there is also involved the drawback that 
the color formed image density will be deteriorated in its stability 
depending on the changes in the developing processing conditions such as 
pH value, temperature and time. 
As another example, Japanese Provisional Patent Publication No. 155536/1982 
states that both graininess and gradation can be improved by providing a 
non-light-sensitive hydrophilic colloid layer between the high sensitivity 
emulsion layer and the low sensitivity emulsion layer, containing a 
diffusion resistant coupler for photography which is color formed to 
substantially the same hue as the diffusion resistant coupler for 
photography contained in the high sensitivity and low sensitivity emulsion 
layers, and has a coupling speed not greater than that of the diffusion 
resistant coupler for photography contained in the high sensitivity 
emulsion layer. This method involves no failure in gradation and is 
improved in graininess, but it is not yet satisfactory in improvement in 
graininess at the regions from low density to medium density. For example, 
in the above Japanese Patent Publication No. 15495/1974 and Japanese 
Provisional Patent Publication No. 7230/1978, there is described a method 
in which a medium sensitivity emulsion layer is provided between the high 
sensitivity emulsion layer and the low sensitivity emulsion layer and a 
compound capable of releasing a diffusive developing inhibiting compound 
(hereinafter called as DIR compound) through the reaction with the 
oxidized product of a color developing agent is incorporated in said 
layer. However, these methods have the drawbacks of increased fog 
accompanying the increased amount of silver halide as well as increase in 
amounts of valuable silver resources. 
Also, in a light-sensitive material having two or more layers of silver 
halide emulsion layers sensitive to the same color, it is a general 
practice to improve graininess by making the silver halide emulsion layer 
having higher sensitivity lower in coupler density (in this case, it 
appears that the oxidized product of a developing agent formed in the 
developing reaction will be diffused in a wide scope searching for 
partners for coupling reaction, thereby forming an unfocused dye cloud 
with low density without worsening graininess). However, the oxidized 
product of the developing agent formed by development of the silver halide 
in said silver halide emulsion layer having higher light sensitivity does 
not exist only within the layer formed, but will be diffused even to the 
siler halide emulsion layer having lower light sensitivity to form a dye 
cloud with conspicuous graininess therein. As the result, when viewing the 
light-sensitive material, the influence of the developed silver grains in 
the silver halide emulsion having higher sensitivity will reach even the 
density (or light-sensitive) region under question, thus ensuing the 
problem of deterioation of graininess. 
Accordingly, an object of this invention is to provide a light-sensitive 
material having high sensitivity as well as good gradation, further 
improved in sharpness, image storability and graininess, requiring only a 
small amount of silver to be employed. 
SUMMARY OF THE INVENTION 
As the result of various studies made by the present inventors, it has been 
found that the above object can be accomplished by a light-sensitive 
silver halide photographic material having at least one light-sensitive 
layer constituted of a plural number of silver halide emulsions which are 
substantially the same in color sensitiveness but different in light 
sensitivity and containing a diffusion resistant coupler for photography 
capable of forming a diffusion resistant color forming dye through the 
reaction with the oxidized product of a color developing agent provided on 
a support, which comprises a non-light-sensitive intermediate layer 
provided at least adjacent to the silver halide emulsion layer with the 
highest light sensitivity among said plural number of silver halide 
emulsion layers on its support side, said non-light-sensitive intermediate 
layer containing a diffusion resistant coupler capable of forming a mobile 
color forming dye which can be color formed to substantially the same hue 
as the said diffusion resistant color forming dye through the coupling 
reaction with the oxidized product of a color developing agent or a 
compound capable of forming a flow-out type coupling product through the 
coupling reaction with the oxidized product of a color developing agent. 
In short, this invention proposes a novel improved light-sensitive material 
as a trial for overcoming the above-mentioned task. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
This invention is to be described in detail below by referring primarily to 
one embodiment of this invention. For example, in this invention, the 
light-sensitive material comprises light-sensitive layers different in 
light sensitivity, namely a high sensitivity emulsion layer and a low 
sensitivity emulsion layer with an intermediate layer according to this 
invention therebetween. 
In this case, each of the high sensitivity emulsion layer and the low 
sensitivity emulsion may be constituted of one layer, or preferably two or 
more layers, since the effect of the method described in U.K. Pat. No. 
923,045 as cited above can additively be added further to the effect of 
this invention. Also, in this invention it is preferable to provide the 
high sensitivity layer region apart farther from the support than the low 
sensitivity emulsion layer, and when each of the high sensitivity emulsion 
layer and the low sensitivity emulsion layer is constituted of two or more 
layers, it is preferable to provide a layer with lower sensitivity nearer 
to the support. 
The sensitivity difference between the high sensitivity emulsion layer and 
the low sensitivity emulsion layer may be determined optimally according 
to the known method with considerations about gradation and graininess, 
but may preferably be approximately 0.1 to 1.0 log E (E: dosage of 
exposure). 
Further, the high sensitivity emulsion layer and the low sensitivity 
emulsion layer have substantially the same color sensitiveness, and after 
the color developing processing, both of the emulsion layers should 
preferably contain diffusion resistant couplers for photography capable of 
forming color forming dyes having substantially the same hue. In this 
case, it is preferred that the contents of the diffusion resistant 
couplers for photography contained in the respective high sensitivity and 
low sensitivity emulsion layers should be such that the color forming 
density of the color forming dye formed as the result of the coupling 
reaction with the oxidized product of a color developing agent is higher 
in the low sensitivity emulsion layer than in the high sensitivity 
emulsion layer. 
It is also possible to incorporate in the intermediate layer according to 
this invention the diffusion resistant coupler for photography to be 
contained in both of the emulsion layers. 
The intermediate layer according to this invention should be provided by 
coating at a dry film thickness, ranging preferably from 0.2.mu. to 
2.0.mu.. 
And, the intermediate layer according to this invention contains a 
diffusion resistant coupler capable of forming a mobile color forming dye 
which can be color formed to substantially the same hue as the said 
diffusion resistant color forming dye through the coupling reaction with 
the oxidized product of a color developing agent or a compound capable of 
forming a flow-out type coupling product through the coupling reaction 
with the oxidized product of a color developing agent. 
Now, the diffusion resistant coupler according to this invention will be 
explained in the following: 
The term "diffusion resistant" herein used has a meaning ordinarily applied 
in light-sensitive materials, and for all practical purposes, it means the 
property such that the coupler will not be moved or drifted through an 
organic colloid layer such as gelatin layer, when the light-sensitive 
layer of this invention is treated in an alkali atmosphere, preferably in 
a medium of pH 10 or higher. 
The coupler of this invention has a ballast group at the coupling position 
which immobilizes the coupler to make it diffusion resistant, and also a 
control group at the non-coupling position for controlling the mobility of 
the color forming dye formed by the coupling reaction with the oxidized 
product of a color developing agent. When the coupler couples with the 
oxidized product of a color developing agent, the ballast group will be 
eliminated, whereby the color forming dye formed becomes mobile. 
The "mobility" of "the diffusion resistant coupler capable of forming a 
mobile color forming dye" according to this invention means a mobility to 
the extent that the color forming dye formed by the coupling reaction with 
the oxidized product of a color developing agent can be moved within the 
layer containing the diffusion resistant coupler. Such a mobility can be 
controlled by the above-mentioned control group of the coupler. The 
control group depends on the coupler mother nucleus to which this groups 
is bonded, other substituents introduced into the coupler and the color 
developing agent employed. 
The light-sensitive material of this invention, as described above, has at 
least one light-sensitive layer constituted of a plural number of silver 
halide emulsions which are substantially the same in color sensitiveness 
but different in light sensitivity and containing a diffusion resistant 
coupler for photography capable of forming a diffusion resistant color 
forming dye through the reaction with the oxidized product of a color 
developing agent provided on a support, and further a non-light-sensitive 
intermediate layer is provided at least adjacent to the silver halide 
emulsion layer with the highest light sensitivity among said plural number 
of silver halide emulsion layers on its support side, and further said 
non-light-sensitive intermediate layer contains a diffusion resistant 
coupler capable of forming a migratable color forming dye which can be 
color formed to substantially the same hue as the said diffusion resistant 
color forming dye through the coupling reaction with the oxidized product 
of a color developing agent. 
The effect of this invention can be exhibited by such a light-sensitive 
material, and this effect, although not clearly understood, may be 
considered to be due to the fact that deterioration of sharpness and 
graininess in the adjacent silver halide emulsion layer with lower 
sensitivity caused by the oxidized product of a color developing agent 
formed excessively in the silver halide emulsion having the highest 
sensitivity during color development of the light-sensitive material after 
exposure can be prevented and also gradation can be controlled, and 
further at the same time due to marked improvement of graininess at leg 
portion by formation of a mobile color forming dye within the intermediate 
layer according to this invention through the coupling reaction of the 
"diffusion resistant coupler capable of forming a mobile color forming 
dye" according to this invention with the oxidized product of a color 
developing agent. 
The diffusion resistant coupler capable of forming a mobile color forming 
dye according to this invention as mentioned above may be represented by 
the following formula [I]: 
##STR1## 
wherein Coup is a coupler mother nucleus capable of forming a color 
forming dye through the coupling reaction with the oxidized product of a 
color developing agent; Ballast group is a group which is bonded to the 
coupling position of said coupler and can be eliminated from Coup during 
the coupling reaction between said coupler and the oxidized product of a 
color developing agent, said Ballast group having a size and a shape of 
molecule enough to make the coupler non-diffusive; and Control group is a 
group bonded to Coup at the non-coupling position for controlling the 
color forming dye formed through the coupling reaction between the coupler 
and the oxidized product of a color developing agent so that it may be 
mobile. 
The above Coup, which represents a coupler mother nucleus, may be any of 
the coupler mother nuclei which is known or used in this field of the art 
for forming a color forming dye by the coupling reaction with the oxidized 
product of a color developing agent. 
For example, as the yellow couplers, there may be employed 
benzoylacetanilide type yellow couplers or pivaloylacetanilide type yellow 
couplers as disclosed in U.S. Pat. Nos. 2,298,448, 2,407,210, 2,875,057, 
3,408,194, 3,265,506 and 3,447,928; and 
"Farb-Kuppler-eine-Literaturubersicht" Agfa Mitteilung, Vol. 2, pp. 
112-126, 1961. As for magenta couplers, it is possible to use various 
kinds of magenta couplers such as pyrazolone type magenta couplers, 
indazolone type magenta couplers, pyrazolotriazole type magenta couplers 
and pyrazolobenzimidazole type magenta couplers as disclosed in U.S. Pat. 
Nos. 2,369,489, 2,343,703, 2,311,082, 2,600,788, 2,908,573, 3,152,896 and 
3,519,429 and the report of Agfa AG. as cited above, pp. 126-156. Further, 
in the case of cyan couplers, naphthol type or phenol type couplers, as 
disclosed in U.S. Pat. Nos. 2,367,531, 2,433,730, 2,474,293, 2,772,162, 
2,895,826, 3,002,836, 3,034,892 and 3,041,236; and the report of Agfa AG. 
as cited above, pp. 156-175, may be used. 
Next, the ballast group indicated in the formula [I] has a size and a shape 
of molecule enough to make the coupler non diffusive. Useful ballast 
groups of this kind are groups having an alkyl moiety or an aryl moiety 
with 8 or more carbon atoms, preferably 8 to 32 carbon atoms, said alkyl 
moiety and aryl moiety being bonded at the coupling position to the 
coupler mother nucleus directly or through a connecting group [e.g. --O--, 
--S--, --N.dbd.N--, 
##STR2## 
(wherein Z is a group of atoms necessary for forming a 5- to 7-membered 
heterocyclic ring)]. Preferably, the ballast group may be one bonded 
through a connecting group, such as alkoxy, aryloxy, alkylthio, arylthio 
and nitrogen-containing heterocyclic ring. 
The control group in this invention is a group having a size and a shape of 
molecule suitable for imparting mobility to the color forming dye formed 
as described above. 
As the group suitable for imparting mobility to the color forming dye as 
described above, it is preferred to use an alkyl group having 1 to 20 
carbon atoms and an aryl group having 6 to 20 atoms. These groups may also 
be substituted with a group for changing the spectral characteristics or 
mobility of the color forming dye. These control groups may also have 
connecting groups for bonding said control group to the coupler mother 
nucleus. Such connecting groups may include, for example, --O--, --S--, 
--CO--, --COO--, --NR--, --CONR--, --NRCO--, --SO.sub.2 NR--, --NRSO.sub.2 
--, --NRCONR-- (wherein R is a hydrogen atom, an alkyl group or an aryl 
group) and the like. 
Of the diffusion resistant couplers for forming mobile color forming dyes 
in this invention, the couplers preferable as the yellow coupler may be 
represented by the following formula [II]: 
##STR3## 
wherein R.sup.1 is an aryl group (e.g. a phenyl group) or an alkyl group 
(e.g. a tertiary alkyl group such as t-butyl); R.sup.2 is the ballast 
group as defined above; R.sup.3 is the control group as defined above; and 
R.sup.4 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy 
group or the control group as defined above. 
Next, preferable cyan couplers may be represented by the following formulae 
[III] and [IV]: 
##STR4## 
In the formulae [III] and [IV], R.sup.2 has the same meaning as defined in 
the formula [II]; at least one of R.sup.5 is the control group as defined 
above, and the remainder representing either identical or different 
hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylamino 
groups or acylamide groups; l is an integer of 1 to 3, preferably 3; and 
R.sup.6 represents the control group as defined above. 
Further, preferably magenta couplers can be represented by the following 
formulae [V] and [VI]: 
##STR5## 
In the formulae [V] and [VI], R.sup.2 is the same as defined defined above; 
R.sup.7 is the control group as defined above; Ar is a phenyl group which 
may have at least one of a substituent selected from the group of a 
halogen atom, an alkyl group, an alkoxy group and an amino group, and said 
phenyl group may have the control group; one of R.sup.8 and R.sup.9 
represents the control group and the other represents a hydrogen atom, 
halogen atom, alkyl group, alkoxy group, aryl group, amino group or 
acylamide group. 
In the above couplers, unless otherwise specifically noted, the alkyl 
group, the alkoxy group and the alkylamide group each contains 1 to 8 
carbon atoms, the aryl group contains 6 to 10 carbon atoms, and the amino 
group is inclusive of primary, secondary and tertiary amino groups. These 
substituents and ballast groups also include those substitued with the 
groups such as halogen atom, hydroxy, carboxy, amino, amide, carbamoyl, 
sulfamoyl, sulfonamide, alkyl, alkoxy and aryl. 
In the following, typical specific examples of the diffusion resistant 
couplers capable of forming mobile color forming dyes in this invention 
are enumerated, but this invention is not lilmited thereto. 
##STR6## 
Having thus enumerated specific examples of the couplers of this invention, 
the couplers, including both of those as enumerated above and other 
couplers of this invention, may be used either singly or as a combination 
of two or more kinds. 
In the following, representative synthesis examples about these couplers 
according to this invention are described, but other couplers can also 
easily be synthesized according to the procedures similar to these 
synthetic methods. 
SYNTHESIS EXAMPLE 1 
(Synthesis of example compound [I-1]) 
##STR7## 
To a solution of 8.2 g of 
.alpha.-pivaloyl-.alpha.-bromo-2-chloro-5-(2-methoxycarbonyl)ethoxycarbony 
l-acetanilide and 8.7 g of 3-phenyl-4-(4-dodecylbenzyl)urazole dissolved in 
100 ml of ethyl acetate, 1.4 g of anhydrous potassium carbonate was added 
and the mixture was refluxed for 5 hours. The reaction mixture was washed 
with addition of 200 ml of water, then dried over magnesium sulfate, 
followed by evaporation of ethyl acetate under reduced pressure. The oily 
product obtained was dissolved by heating in 10 ml of n-hexane, and left 
to stand, whereby white powdery crystals were precipitated. Yield: 10.7 g. 
SYNTHESIS EXAMPLE 2 
(Synthesis of example compound [I-6]) 
##STR8## 
To 50 ml of chloroform was added 6.5 g of 3-octadecylcarbamoylthiophenol, 
and under room temperature chlorine gas was passed through the mixture for 
30 minutes to obtain a yellow solution. The chloroform was evaporated 
under reduced pressure to give sulphenyl chloride as an yellow oily 
product. The sulphenyl chloride was dissolved without purification in 100 
ml of chloroform, and 7.4 g of 
1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-butanesulfonamido)aniline-5-pyrazo 
lone, followed by refluxing for 2 hours. Then, chloroform was evaporated 
under reduced pressure, and the residue obtained was chromatographed on a 
silica gel column with a solvent mixture of n-hexane and ethyl acetate 
(mixing ratio 2:1) as the eluant, to obtain the title compound. 
This was recrystallized from acetonitrile to give pale yellow crystals. 
Yield: 5.2 g. 
The title compound obtained according to the above synthetic method was 
confirmed to be identical with the example compound by NMR and Mass 
spectrum. 
The coupler of this invention is to be incorporated in the intermediate 
layer according to this invention which is provided more adjacent to the 
support side than the silver halide emulsion layer having the highest 
light sensitivity among the plural number of silver halide emulsion layers 
with different light sensitivities, as described above. In this case, the 
amount of the coupler of this invention may generally range from 
1.times.10.sup.-7 to 8.times.10.sup.-4 mole/m.sup.2, preferably from 
4.times.10.sup.-7 to 3.times.10.sup.-4 mole/m.sup.2. However, the color 
formed density in the non-sensitive intermediate layer by the amount of 
the coupler added as specified above should be 0.02 to 0.7, preferably 
0.05 to 0.6, particularly 0.05 to 0.2. Here, color fomation of the coupler 
in the non-sensitive intermediate layer may be considered to be due to the 
reaction with the oxidized product of a developing agent formed during 
development of the high sensitivity emulsion layer and the low sensitivity 
emulsion layer. 
Also, in the above-mentioned embodiment, it is also possible to use in 
combination with the coupler of this invention, a diffusion resistant 
coupler capable of forming a diffusion resistant color forming dye after 
the coupling reaction with the oxidized product of a color developing 
agent in the above intermediate layer. In this case, at least one of said 
diffusion resistant couplers should preferably have a coupling speed which 
is equal to or greater than the greatest coupling speed among the 
diffusion resistant couplers contained in the high sensitivity emulsion 
layer. 
Next, the compound according to this invention will be explained in the 
following: 
The compound according to this invention is capable of forming a flow-out 
type coupling product through the coupling reaction with the oxidized 
product of a color developing agent. The "flow-out type" herein mentioned 
means that the coupling product formed by the coupling reaction of the 
compound according to this invention with the oxidized product of a color 
developing agent has mobility within the light-sensitive material during 
developing processing, namely at the time of color developing processing 
or thereafter, and is flown out of the system of said light-sensitive 
material substantially without remaining within said light-sensitive 
material. 
The compound according to this invention, which forms a flow-out type 
coupling product through the reaction with the oxidized product of a color 
developing agent as described above, may preferably a compound capable of 
providing the coupling product which is a color forming dye or colorless. 
The compound according to this invention has a ballast group at the 
coupling site for immobilizing the compound according to this invention 
and a solubilizing group at the non-coupling site for imparting mobility 
of the coupling product after the coupling reaction with the oxidized 
product of a color developing agent. When the coupling occurs with the 
oxidized product of a color developing agent, the stabilizing group will 
be eliminated. As the result, the coupling product has mobility. 
The compound according to this invention forms a coupling product having 
mobility through the reaction with the oxidized product of a color 
developing agent. The mobility in this case may be imparted to the extent 
as mentioned above such that it may be flown out of the system of the 
light-sensitive material. 
The compound according to this invention can be represented by the 
following formula [VII]: 
##STR9## 
wherein COUP is a coupler mother nucleus having a coupling site (asterisk 
*); BALL is a group which is bonded to the coupling site of COUP and can 
be eliminated from COUP during the reaction between said COUP and the 
oxidized product of a color developing agent, said BALL being a Ballast 
group having a size and a shape enough to make the compound of the formula 
[VII] diffusion resistant; and SOL is a solubilizing group, which is 
bonded to COUP at the non-coupling position and imparts mobility to the 
coupling product formed by coupling between COUP and the oxidized product 
of a color developing agent so as to be flown out of the system from 
within the light-sensitive material during or after color developing 
processing. 
As the coupler mother nucleus represented by COUP, there may be included 
any of coupler mother nuclei, which are known or used in this field for 
forming a reaction product, having a hue or no color, through the coupling 
reaction with the oxidized product of a color developing agent. For 
example, the coupler mother nucleus for forming yellow dye may be 
acylacetanilide such as acetoacetanilides and benzoylacetanilides; the 
coupler mother nucleus for forming magenta coupler may be pyrazolones, 
pyrazolotriazoles, pyrazolobenzimidazoles and indazolones; and the coupler 
mother nucleus for forming cyan dye may be phenols and naphthols. 
BALL is a ballast group having a size and a shape of molecule which will 
make the compound of the formula [VII] diffusion resistant and it is not 
particularly limited, so long as it can impart diffusion resistance to the 
compound of the formula [VII]. Useful groups represented by BALL may 
include alkyl groups, aryl groups and heterocyclic groups having 8 to 32 
carbon atoms. These groups may be either unsubstituted or subsituted. As 
substituents, there may be included those which will icrease diffusion 
resistance of the compound of the formula [VII], change the reactivity of 
the compound of the formula [VII] or undergo coupling reaction to increase 
diffusibility of BALL after elimination. Further, BALL may preferably be 
bonded at the coupling site of COUP through a connecting group. Typical 
connecting groups are oxy (--O--) and thio (--S--). 
The solubilizing group represented by SOL is a group for imparting mobility 
to the coupling product formed by the coupling reaction to the extent such 
that it can be flown out of the system of the light-sensitive material, as 
exemplified by ionizable hydroxyl group, carboxyl group, sulfo group and 
aminosulfonyl group and ionizable salts thereof. One or two or more groups 
of these groups may be preferably bonded to COUP at the non-coupling 
sites. Alternatively, there may also advantageously be employed compounds 
in which solubilizing groups of an appropriate size, such as alkyl groups 
having 1 to 10 carbon atoms or aryl groups having 6 to 12 groups, which 
has one or two or more inoizable groups as defined above, are bonded to 
COUP at the non-coupling sites. 
Compounds, in which SOL is bonded to COUP at the non-coupling site through 
a connecting group, are also preferred. Typical connecting groups may 
include oxy (--O--), thio (--S--), carbonyl group, carboxyl group, 
oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, 
ureido group, sulfamoyl group and aminosulfonyl group. 
Among the useful solubilizing groups as set forth above, particularly 
preferable solubilizing groups may include carboxyl group, sulfo group or 
ionizable salts thereof bonded directly to COUP at the non-coupling site, 
or alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 12 
carbon atoms containing one or two or more carboxyl group, sulfo group or 
ionizable salts thereof bonded directly or through amino group or carbonyl 
group to COUP at the non-coupling site. 
Further, the compound according to this invention capable of forming 
yellow, magenta and cyan dyes preferably used in this invention can be 
represented by the formulae [VIII]-[XII] as shown below. 
Of the compounds capable of forming a flow-out type coupling product in 
this invention, the compounds preferable as the yellow dye forming 
compound may be represented by the following formula [VIII]: 
##STR10## 
wherein R.sup.10 is an aryl group (e.g. a phenyl group) or an alkyl group 
(e.g. a tertiary alkyl group such as t-butyl); R.sup.11 is the ballast 
group as defined above (BALL); R.sup.12 is the control group or the 
solubilizing group (SOL) as defined above; R.sup.13 is a hydrogen atom, a 
halogen atom, an alkyl group or an alkoxy group; and n and m are integers 
satisfing the relation of n+m=5 (provided that each n and m are not zero, 
and when n and m are 2 or more, the plural groups may be either indentical 
or different). 
Next, preferable cyan dye forming compounds may be represented by the 
following formulae [IX] and [X]: 
##STR11## 
In the formulae [IX] and [X], R.sup.11 has the same meaning as defined in 
the formula [VIII]; at least one of R.sup.14 and R.sup.15 is the 
solubilizing group (SOL) as defined above, the remainder representing 
either identical or different hydrogen atoms, halogen atoms, alkyl groups, 
alkoxy groups or alkylamide groups; p is an integer of 1 to 3; and 
R.sup.16 represents the solubilizing group (SOL) as defined above. 
Further, preferable magneta dye forming compounds can be represented by the 
following formulae [XI] and [XII]: 
##STR12## 
In the formulae [XI] and [XII], R.sup.11 is the same as defined in the 
formula [VIII]; R.sup.17 represents the solubilizing group (SOL) as 
defined above; R.sup.18 represents a hydrogen atom, a halogen atom, an 
alkyl group, an alkoxy group or an amino group; q is an integer of 1 to 5 
(provided that when q is 2 or more, the plural groups may be either 
idential or different); and one of R.sup.19 and R.sup.20 represents the 
solubilizing group (SOL) as defined above and the other represents a 
hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an amino 
group. 
In the above compounds, unless otherwise specifically noted, the alkyl 
group, the alkoxy group and the alkylamide group each contains 1 to 8 
carbon atoms, the aryl group contains 6 to 10 carbon atoms, and the amino 
group is inclusive of primary, secondary and tertiary amino groups. These 
substituents and ballast groups (BALL) also include those substitued with 
the groups such as halogen atom, hydroxy, carboxy, amino, amide, 
carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl. 
In the following, typical specific examples of the compounds according to 
this invention are enumerated, but these are not limitative of this 
invention. 
##STR13## 
Having thus enumerated specific examples of the compounds of this 
invention, the compounds, including both of those as enumerated above and 
other compounds of this invention, may be used either singly or as a 
combination of two or more kinds. 
In the following, representative synthesis examples about these compounds 
according to this invention are described, but other compounds can also 
easily be synthisized according to the procedures similar to these 
synthetic methods. 
SYNTHESIS EXAMPLE 3 
(Synthesis of example compound [VII - 2]) 
##STR14## 
(a) Synthesis of the above [1] 
To a solution of 7.4 g (0.018 mol) of 
.alpha.-pivalyl-.alpha.-bromo-2-chloro-5-ethoxycarbonylacetanilide and 8.0 
g (0.018 mol) of 3-phenyl-4-(4-dodecylbenzyl)urazole in 100 ml of of ethyl 
acetate, 1.3 g (0.009 mol) of anhydrous potassium carbonate was added, and 
the mixture was refluxed for 3 hours. The reaction product was mixed with 
200 ml of water for extraction of the ethyl acetate layer, followed by 
concentration, to give the above [1] as a yellow viscous material. 
(b) Synthesis of example compound [VII - 2] 
The compound [1] obtained in (a) was dissolved in 50 ml of ethyl alcohol, a 
solution of 5.0 g of potassium hydroxide dissolved in 10 ml of water was 
added thereto and the reaction was carried out for 2 hours. When the 
reaction product was added into ice-water containing 10 ml of conc. 
hydrochloric acid under stirring, white solid was precipitated. This was 
filtered, washed with water and dried, followed by recrystallization from 
ethyl acetate-n-hexane, to give 10.3 g of the example compound [VII - 2]. 
Mass spectrum: m/e=731 (M.sup.+ +1) 
SYNTHESIS EXAMPLE 4 
(Synthesis of example compound [VII - 9]) 
To a solution of 10.6 g (0.024 mol) of 
1-(3-carboxyphenyl)-3-methylpyrazolone and 9.1 g (0.012 mol) of 
4-octadecyloxy benzaldehyde dissolved in 200 ml of ethyl alcohol, 3 drops 
of triethylamine were added and the reaction was carried out for 5 hours. 
The solid obtained after concentration was washed with ethyl acetate to 
give 14.6 g of the example compound [VII - 9]. 
Mass spectrum: m/e=792 (M.sup.+). 
SYNTHESIS EXAMPLE 5 
(Synthesis of example compound [VII - 18]) 
##STR15## 
(a) Synthesis of the above [2] 
While nitrogen gas was bubbled into a solution of 20.4 g (0.1 mol) of 
1,4-dihydroxy-2-naphthoic acid and 14.1 g (0.1 mol) of 
p-nitrofluorobenzene dissolved in 300 ml of dimethylformamide, a solution 
of 8.5 g of sodium hydroxide in 20 ml of water was added thereto, and the 
reaction was carried out for one hour. When the reaction product was added 
into ice-water containing 20 ml of hydrochloric acid, it was formed into a 
viscous mass. When this mass was stirred by heating on a water bath, it 
was then solidified. The crystals obtained were filtered, washed with 
water, washed with acetonitrile and dried to obtain 23.2 g of [2] as pale 
yellow solid. 
(b) Synthesis of the above [3] 
To a solution of 21.8 g (0.067 mol) of [2] obtained in (a) and 11.1 g 
(0.067 mol) of ethyl p-aminobenzoate dissolved in 200 ml of dioxane, 13.8 
g (0.067 mol) of N,N'-dicyclohexylcarbodiimide was added and the reaction 
was carried out. The precipitated urea was separated by filtration, and 
the urea was further washed three times with 20 ml of hot dioxane. The 
filtrate was concentrated, and the resultant solid was washed with hot 
ethyl acetate to give 21 g of [3] as a yellowish green solid. 
(c) Synthesis of the above [4] 
The compound [3] obtained in (b) (21 g) was dissolved in 450 ml of 
tetrahydrofuran and catalytic hydrogenation was conducted for 10 hours 
with the use of 4 g of a 5% palladium/carbon catalyst. After removal of 
the catalyst, the solid obtained after concentration was washed with ethyl 
alcohol to obtain 9.2 g of [4] as a white solid. 
(d) Synthesis of the above [5] 
To a solution of 9.2 g (0.021 mol) of [4] obtained in (c) and 7.1 g (0.021 
mol) of .alpha.-(2,4-di-t-pentylphenoxy)butyroyl chloride dissolved in 100 
ml of tetrahydrofuran, 1.7 g (0.021 mol) of pyridine was dissolved and the 
reaction was carried out for 2 hours. The pyridinium hydrochloride was 
filtered and concentrated to obtain a reddish brown viscous material. 
Silica gel column treatment with a solvent mixture of chloroform-n-hexane 
1:1 gave 10 g of [5] as a pale yellow viscous material. 
(e) Synthesis of example compound [VII - 18] 
The compound [5] (7 g) obtained in (d) was dissolved in 50 ml of ethyl 
alcohol and a solution of 6.0 g of potassium hydroxide dissolved in 10 ml 
of water was added to the resultant solution, followed by the reaction for 
3 hours. When the reaction product was added into ice-water containing 10 
ml of conc. hydrochloric acid under stirring, white crystals were formed. 
The crystals were filtered, washed with water and then with acetonitrile. 
Recrystallization from acetonitrile-ethyl acetate gave 4.7 g of the 
example compound [VII - 18]. 
EQU Mass spectrum: m/e=717 (M.sup.+ +1) 
The compound according to this invention contained in the intermediate 
layer may be added in an amount, which is not particularly limited, but 
preferably up to 8.times.10.sup.-2 mole/m.sup.2, more preferably up to 
3.times.10.sup.-2 mole/m.sup.2, the lower limit being approximately 
1.times.10.sup.-7 mole/m.sup.2. 
The intermediate layer according to this invention can also incorporate, in 
addition to the compound according to this invention, other kinds of 
diffusion resistant couplers for photography, hydroquinone derivatives for 
controlling progress of development, couplers exhibiting no color, fine 
grains of silver halide and others. Said intermediate layer may also be 
constituted of two or more layers. 
In general, light-sensitive materials containing couplers are constituted 
of a red-sensitive silver halide emulsion layer containing a diffusion 
resistant coupler for photography for cyan color formation, a 
green-sensitive emulsion layer containing a coupler for magenta color 
formation and a blue-sensitive emulsion layer containing a coupler for 
yellow color formation. The wording "substantially the same in color 
sensitiveness" as used in this specification means having the sensitive 
region in substantially the same spectral region, indicating broadly 
demarcation between the three color regions of red, green and blue, and 
the sensitive regions with slight changes in spectrum are to be regarded 
as substantially the same. Also, when the light-sensitive material is 
applied for each layer of red-sensitive, green-sensitive and 
blue-sensitive layers, marked effects can be recognized, respectively. 
But, such a constitution is not imperative and a preferable result can be 
obtained when at least the green-sensitive layer takes the embodiment of 
the present invention. Thus, application of the present invention for all 
of the color-sensitive layers should be appreciated as an embodiment for 
creating further excellent image quality of the final color image. 
In the intermediate layer according to this invention, two or more kinds of 
the compounds according to this invention may be employed in combination. 
When two or more kinds of compounds are employed, at least one of the 
compounds according to this invention to be contained in the intermediate 
layer according to this invention should preferably have a coupling speed 
which is equal to or greater than the greatest coupling speed among the 
diffusion resistant couplers for photography contained in the high 
sensitivity emulsion layer. The compound according to this invention, 
having a coupling speed which is equal to or greater than the greatest 
coupling speed among the diffusion resistant couplers for photography 
contained in the high sensitivity emulsion layer, should preferably be 
contained at a proportion of 30% or more, particularly preferably 70% or 
more, of the above compounds according to this invention and/or various 
compounds as mentioned above. 
Comparison of the coupling speed of the aforesaid couplers or compounds 
contained in the high sensitivity emulsion and the intermediate layer 
according to this invention is conducted by adding 0.02 mole of each 
coupler or 0.05 mole of each compound per mole of silver halide into a 
silver halide emulsion prepared according to the method well known in the 
art, performing sensitometry generally known in the art and comaring the 
sensitivities at the fog density of +0.1. During this operation, 
comparison is made with the amount of silver developed between the 
respective samples under the same exposure conditions after being 
subjected to the treatment process of the fixing step et seq without 
carrying out bleaching step after color developing. As for the coupling 
speed, the coupler or the compound according to this invention used in the 
sample in which the amount of silver develop is greater formed is defined 
as being more rapid in coupling speed. Couplers or compounds of the 
present invention are added according to the method, in which 0.02 mole of 
a coupler is dissolved by heating in a mixed solvent of 0.04 mole of 
tricresyl phosphate and 0.5 mole of ethyl acetate, thereafter mixing the 
resultant solution with an aqueous gelatin solution containing sodium 
dodecylbenzene sulfonate and then emulsifying the mixture by means of a 
high speed rotary mixer, followed by addition into the silver halide 
emulsion. The coupler insoluble in the above mixed solvent is dissolved 
together with a high boiling solvent at equal moles in a solvent capable 
of dissolving the coupler, emulsified and added. 
As preferable ones among the compounds according to this invention, there 
may significantly be used those which can give greater amounts of the 
developed silver in the above comparison method for coupling speed. 
According to this invention, the light-sensitive material of this invention 
can contain, in the light-sensitive layer comprising a plural number of 
silver halide emulsion layers having substantially the same color 
sensitiveness and different sensitivities, diffusion resistant couplers 
for photography capable of forming diffusion resistant color forming dyes 
to give color tones corresponding to said sensitiveness. For example, the 
diffusion resistant cyan couplers for photography as mentioned above may 
preferably be phenol type compounds or naphthol type compounds, which may 
be selected from those disclosed in, for example, U.S. Pat. Nos. 
2,369,929; 2,434,272; 2,474,293; 2,895,826; 3,253,924; 3,034,892; 
3,311,476; 3,386,301; 3,419,390; 3,458,315; 3,476,563 and 3,591,383, and 
the methods for synthesis thereof are also disclosed in these 
specifications. 
The diffusion resistant magenta couplers for photography to be used in the 
present invention may include compounds of the pyrazolone type, the 
pyrazolotriazole type, pyrazolinobenzimidazole type and the indazolone 
type. As the pyrazolone type magenta couplers, there may be included the 
compounds disclosed in U.S. Pat. Nos. 2,600,788; 3,062,653; 3,127,269; 
3,311,476; 3,419,391; 3,519,429; 3,558,318; 3,684,514 and 3,888,680; and 
Japanese Provisional Patent Publications Nos. 29639/1974, 11163/1974, 
29538/1974 and 13041/1975. As the pyrazolotriazole type magenta couplers, 
there are the compounds as disclosed in U.S. Pat. No. 1,247,493 and 
Belgian Patent No. 792,525. The pyrazolinobenzimidazole type magenta 
couplers may be, for instance, those disclosed in U.S. Pat. No. 3,061,432; 
West German Pat. No. 2,156,111; and Japanese Patent Publication No. 
60479/1971. Further, the indazolone type magenta couplers may include the 
compounds disclosed in Belgian Pat. No. 769,116. All of these compounds 
can be advantageously used in the present invention. 
As the diffusion resistant yellow couplers for photography to be used in 
this invention, open-chain keto-methylene compounds have been used, and 
there may be included the benzoylacetanilide type yellow couplers and the 
pivaloylacetanilide type yellow couplers, which have generally widely been 
used. Further, the divalent type yellow couplers, in which the carbon atom 
at the coupling position is substituted with a substituent which can be 
eliminated during coupling reaction, may also advantageously be used. 
Examples of these compounds are disclosed, together with their synthetic 
methods, in U.S. Pat. Nos. 2,875,057; 3,265,506; 3,664,841; 3,408,194; 
3,447,928; 3,277,155 and 3,415,652; Japanese Patent Publication No. 
13576/1974; and Japanese Provisional Patent Publications Nos. 29432/1973, 
66834/1973, 10726/1974, 122335/1974, 28834/1975 and 132926/1975. 
In this invention, it is also possible to employ a colored coupler in 
combination with the diffusion resistant coupler for photogaphy as 
described above, if desired. For example, as the diffusion resistant 
colored cyan coupler for photography to be used, there may generally be 
used phenol or naphthol derivatives, as exemplified by those disclosed, 
together with their synthetic methods, in U.S. Pat. Nos. 2,521,908 and 
3,034,892; U.K. Pat. No. 1,255,111; Japanese Provisional Patent 
Publications Nos. 22028/1973, 123341/1975 and No. 10135/1975; and U.S. 
Pat. No. 3,476,563. As the diffusion resistant colored magenta coupler for 
photography to be used in the present invention, there may generally be 
used compounds arylazo-substituted at the coupling position of colorless 
magenta couplers, such as those disclosed in U.S. Pat. Nos. 2,801,171; 
2,983,608; 3,005,712 and 3,684,514; U.K. Pat. No. 937,621; and Japanese 
Provisional Patent Publications Nos. 123625/1974 and 31448/1974. Further, 
it is also possible to use a colored magenta coupler of the type in which 
the dye is flown out into the treating solution through reaction with the 
oxidized product of a developing agent, as disclosed in U.S. Pat. No. 
3,419,391. 
The amount of the above diffusion resistant coupler for photography in this 
invention may generally range from 2.times.10.sup.-3 mole to 
5.times.10.sup.31 1 mole per mole of silver in the light-sensitive silver 
halide emulsion layer, preferably from 5.times.10.sup.-3 mole to 
5.times.10.sup.-2 mole in the high sensitivity emulsion layer, and from 
2.times.10.sup.-2 mole to 3.times.10.sup.-1 mole in the low sensitivity 
emulsion layer. In the intermediate layer according to this invention, it 
may be added in an amount which does not impair the effect of the compound 
of this invention, namely from 1.times.10.sup.-7 mole/dm.sup.2 to 
8.times.10.sup.-3 mole/dm.sup.2, preferably from 4.times.10.sup.-6 
mole/dm.sup.2 to 3.times.10.sup.-3 mole/dm.sup.2. 
The compound according to this invention and other kinds of diffusion 
resistant couplers for photography to be used in this invention may be 
dispersed according to various methods such as the so-called alkaline 
aqueous dispersing method, the solid dispersing method and the oil 
droplet-in-water type dispersing method, which may suitably be selected 
depending on the chemical structure or others of the diffusion resistant 
coupler employed. 
In this invention, the latex dispersing method or the oil droplet-in-water 
type emulsion dispersing method is particularly effective. These 
dispersing methods are well known in the art, and the latex dispersing 
method and its effect are described in Japanese Provisional Patent 
Publications Nos. 74538/1974, 59943/1976 and 32552/1979; and Research 
Disclosure No. 14850, pp. 77-79, August 1976. 
Suitable latices may include homopolymers, copolymers and terpolymers of 
monomers such as styrene, ethyl acrylate, n-butyl acrlate, n-butyl 
methacrylate, 2-acetoacetoxyethyl methacrylate, 
2-(methacryloyloxy)ethyltrimethylammonium methosulfate, sodium 
3-(methacryloyloxy)propane-1-sulfonate, N-isopropylacrylamide, 
N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylpropane 
sulfonic acid, etc. In the oil droplet-in-water type emulsion dispersing 
method, there may be employed a method known in the art for dispersing a 
hydrophobic additive such as couplers. For example, after dissolving in a 
single kind or a solvent mixture selected from high boiling point organic 
solvents having boiling points of 175.degree. C. or higher such as 
tricresyl phosphate, dibutyl phthalate and/or low boiling point organic 
solvents such as ethyl acetate, butyl propionate, etc., the resultant 
mixture is dissolved in an aqueous solution containing a surfactant, 
followed by emulsification by means of a high speed rotatary mixer or a 
colloid mill, and the resultant emulsion is added directly into a silver 
halide emulsion layer or an intermediate layer, or alternatively said 
emulsion after stripping the low boiling solvent therefrom according to a 
known method may be added into the silver halide emulsion or the 
intermediate layer according to this invention. 
Further, the colorless couplers to be used in combination with this 
invention may be selected from those disclosed in U.K. Pat. Nos. 861,138, 
914,145 and 1,109,963; Japanese Patent Publication No. 14033/1970; U.S. 
Pat. No. 3,580,722; and Mitteilungen aus den Forschunings Laboratorien der 
Agfa Leberkusen Vol. 4, pp. 352-367, 1964. 
Also, for enhancing the effect of this invention, it is preferred to 
incorporate a compound capable of releasing a development inhibitor 
through the reaction with the oxidized product of a developing agent 
(hereinafter called as DIR compound) in the high sensitivity emulsion 
layer, the low sensitivity emulsion layer and/or the intermediate layer 
therebetween according to the embodiments as described above. DIR 
compounds are described in detail in, for example, U.S. Pat. No. 3,227,554 
or Japanese Provisional Patent Publication No. 45315/1979. A DIR compound 
may be used in the above-mentioned constituent layers in an amount up to 2 
mg/dm.sup.2, particularly preferably from 0.1 up to 0.9 mg/dm.sup.2. 
Further, other than the embodiments as described above, this invention can 
be preferably be applied for a light-sensitive material having at least 
one light-sensitive layer, which has 3 or more silver halide emulsion 
layers with different sensitivities. For example, preferable effect of 
this invention can be also exhibited by an embodiment in which the 
above-mentioned light-sensitive layer has a constitution comprising a 
silver halide emulsion layer with the highest sensitivity on the side 
farthest from the support side, an intermediate layer according to this 
invention and two or more silver halide emulsion layers with sequentially 
lowered sensitivities provided successively on the support. 
As the silver halide to be used in the silver halide emulsion, there may be 
included any one conventionally used in silver halide photographic 
emulsions such as silver chloride, silver bromide, silver iodide, silver 
chlorobromide, silver iodobromide, silver chloroiodobromide and mixtures 
thereof. 
The silver halide grains may be either coarse or fine, and the distribution 
of the grain sizes may be either narrow or broad. The crystals of these 
silver halide grains may be either normal or twin crystals, and the 
crystals with any desired ratio of [100] plane to [111] plane may be 
available. These silver halide grains may have a crystalline structure 
which is uniform from the inner portion to the outer portion, or a layered 
structure with different inner and outer layers. Further, these silver 
halides may be either of the type forming latent images on its surface or 
of the type forming latent images internally of the grains. These silver 
halide grains can be prepared according to any of the methods known in the 
art. 
The silver halide emulsion to be used in this invention may preferably be 
one from which soluble salts have been removed, but it is also possible to 
use one without removal of such salts. Also, two or more kinds of silver 
halide emulsions prepared separately can be used as a mixture. 
As the binder for the silver halide emulsion layer in the light-sensitive 
material of this invention, there may be used those known in the art, for 
example, most preferably gelatin or otherwise gelatin derivatives such as 
phenylcarbamylated gelatin, acylated gelatin phthalated gelatin, etc., 
which may be also be added as a compatible mixture, if desired. 
The silver halide emulsion having the above-described silver halide grains 
in a binder solution can be sensitized with a chemical sensitizer. 
Chemical sensitizers to be used advantageously in this invention may be 
classified broadly into the four kinds of noble metal sensitizers, sulfur 
sensitizers, selenium sensitizers and reducing sensitizers, and these may 
also be used in combination. 
Noble metal sensitizers may include gold compounds and compounds of 
ruthenium, rhodium, palladium, iridium and platinum. 
When a gold compound is used, ammonium thiocyanate or sodium thiocyanate 
may be used in combination. 
Sulfur sensitizers may include, in addition to active gelatin, sulfur 
compounds. 
Selenium sensitizers may include active and inactive selenium compounds. 
As the reducing sensitizers, there are monovalent tin salts, polyamine, 
bisalkylaminosulfide, silane compounds, iminoaminomethanesulfinic acid, 
hydrazinium salts, hydrazine derivatives, etc. 
In the light-sensitive material of this invention, in addition to the 
additives as described above, it is also possible to use various additives 
useful for light-sensitive material such as stabilizers, development 
accelerators, film hardeners, surfactants, contamination preventives, 
lubricants, UV-ray absorbers, etc. 
The light-sensitive material of this invention can also conveniently have 
any auxiliary layer, e.g. protective layer, other intermediate layers, 
filter layer, halation preventive layer, back layer, etc. in addition to 
the silver halide emulsion layer and the intermediate layer according to 
this invention. 
The support to be used in the light-sensitive material of this invention 
may be suitably selected from those known in the art depending on the 
purpose of use of the light-sensitive material, such as plastic films, 
plastic laminated papers, baryta papers, synthetic papers, etc. These 
supports are generally applied with subbing treatment for reinforcement of 
adhesion to the photographic emulsion layer. 
Now, preferable embodiments of the primary constituting layers in the color 
light-sensitive material according to this invention are set forth below. 
The layers are arranged in the order from the surface layer side toward 
the support side. 
EXAMPLE CONSTITUTION 1 
1. Blue-sensitive silver halide emulsion layer containing one layer or two 
or more layers of diffusion resistant yellow couplers for photography; 
2. Yellow filter layer which can absorb blue light; 
3. High sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography; 
4. Intermediate layer containing a diffusion resistant coupler or a 
compound according to this invention; 
5. Low sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography; 
6. Red-sensitive silver halide emulsion layer containing one layer or two 
or more layers of diffusion resistant cyan couplers for photography; 
7. Support. 
EXAMPLE CONSTITUTION 2 
1. Blue-sensitive silver halide emulsion layer containing one layer or two 
or more layers of diffusion resistant yellow couplers for photography; 
2. Yellow filter layer which can absorb blue light; 
3. High sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography; 
4. Intermediate layer containing a diffusion resistant coupler or a 
compound according to this invention; 
5. Low sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography at a density lower relative to 
the layer 6 below; 
6. Low sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography at a density higher relative to 
the layer 5 above; 
7. Red-sensitive silver halide emulsion layer containing one layer or two 
or more layers of diffusion resistant cyan couplers for photography; 
8. Support. 
EXAMPLE CONSTITUTION 3 
1. Blue-sensitive silver halide emulsion layer containing one layer or two 
or more layers of diffusion resistant yellow couplers for photography; 
2. Yellow filter layer which can absorb blue light; 
3. High sensitivity green-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography; 
4. High sensitivity red-sensitive emulsion layer containing a diffusion 
resistant cyan coupler for photography; 
5. Intermediate layer containing a diffusion resistant coupler or a 
compound according to this invention; 
6. Low sensitivity red-sensitive emulsion layer containing a diffusion 
resistant magenta coupler for photography; 
7. Support. 
The color light-sensitive material of this invention as described above can 
be exposed to light and thereafter subjected to a color developing method 
conventionally employed to obtain images. The basic processing steps 
include color developing, bleaching and fixing steps. These respective 
basic processing steps may be sometimes performed independently, or 
alternatively in place of performing 2 or more processing steps, one 
processing may be performed with a processing liquor having those 
functions. For example, there may be employed one-bath color processing 
method wherein the bath contains a color developing agent, a ferric salt 
bleaching component and a thiosulfate fixing component or one-bath 
bleach-fixing method wherein the bath contains a bleaching component of 
ethylendiamine tetraacetic iron (III) complex salt and a thiosulfate 
fixing component. 
For the light-sensitive material, all of the treating methods may be 
applicable. Typical examples may include the method, in which after color 
developing, bleach-fixing processing is performed, followed further by 
washing with water, stabilizing processing, if desired; the method, in 
which pre-film-hardening, neutralization, color developing, stopping 
fixing, washing with water, bleaching, fixing, washing with water, 
post-film-hardening and washing with water are performed in the order 
mentioned; the method in which color developing, washing with water, 
supplementary color developing, stopping, bleaching, fixing, washing with 
water and stabilizing are performed in the order mentioned; the developing 
method in which the developed silver after halogenation bleach is 
subjected again to color developing to increase the amount of dye formed; 
the method for treating a low silver content light-sensitive material with 
the use of an amplifier agent such as a peroxide or a cobalt salt; and 
others. 
The color developing agent may be selected typically from those of the 
p-phenylenediamine type. 
The precursor for a color developing agent to be used in the present 
invention, which can be used by addition in the light-sensitive color 
photographic material may include Schiff base type for color developers as 
disclosed in U.S. Pat. Nos. 2,507,114; 2,695,234 and 3,342,599 or Research 
Disclosure Vol. 151, No. 15159, November 1979 and also those as disclosed 
in Research Disclosure Vol. 129, No. 12924, October 1976; ibid Vol. 121, 
No. 12146, June 1974; and ibid Vol. 139, No. 13924, November 1975. 
Various additives may also be added into the color developing liquor, if 
desired.

The present invention is further illustrated by referring to the following 
Examples, by which the present invention is not limited. 
EXAMPLE 1 
Each of Samples 1, 2, 3, 4, 5 and 6 was prepared by providing by way of 
coating the respective layers as shown below successively on a support of 
a cellulose triacetate film applied with subbing treatment. 
SAMPLE--1 
Layer 1: Low sensitivity green-sensitive silver halide emulsion layer 
A silver iodobromide containing 6 mole % of silver iodide (average grain 
size 0.5.mu., containing 0.25 mole of silver halide and 40 g of gelatin 
per 1 kg of emulsion) was prepared in a conventional manner and 1 kg of 
this emulsion was chemically sensitized with gold and sulfur sensitizers, 
and further mixed with, as green sensitive sensitizing dyes, 32.5 mg of 
anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine 
hydroxide; 55 mg of anhydrous 
5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; 
and 42.5 mg of anhydrous 
9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide, 
followed by addition of 0.25 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 20 mg of 
1-phenyl-5-mercaptotetrazole, 0.5 g of polyvinyl pyrrolidone and 500 ml of 
the dispersion (M-1) shown below to prepare a low sensitivity green 
sensitive silver halide emulsion, which was then applied to a dry film 
thickness of 3.0.mu. . 
Layer - 2. . .Intermediate layer 
An aqueous gelatin solution was applied to a dry film thickness of 1.0.mu.. 
Layer - 3. . .High sensitivity green-sensitive silver halide emulsion layer 
A silver iodobromide containing 7 mole % of silver iodide (average grain 
size 0.9 .mu., containing 0.25 mole of silver halide and 30 g of gelatin 
per 1 kg of emulsion) was prepared in a conventional manner and 1 kg of 
this emulsion was chemically sensitized with gold and sulfur sensitizers, 
and further mixed with, as green sensitive sensitizing dyes, anhydrous 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; 
anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine 
hydroxide; and anhydrous 
9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide, 
followed by addition of 0.25 g of 
4-hydroxy-6-methyl1,3,3a,7-tetrazaindene, 5 mg of 
1-phenyl-5-mercaptotetrazole, 0.2 g of polyvinyl pyrrolidone and 200 ml of 
the dispersion (M-2) shown below to prepare a high sensitivity green 
sensitive silver halide emulsion, which was then applied to a dry film 
thickness of 2.0.mu.. 
Layer - 4. . .Yellow filter layer 
An aqueous gelatin solution having yellow colloidal silver dispersed 
therein was applied to dry film thickness of 1.2.mu., with the gelatin 
being at a proportion of 0.9 g/m.sup.2 and a silver of 0.12 g/m.sup.2. 
Sample - 2 
Sample - 2 was prepared in the same manner as in preparation of Sample - 1, 
except that the intermediate layer of Layer - 2 in Sample - 1 was replaced 
with the intermediate layer which was prepared by adding the dispersion 
(AS) shown below in the aqueous gelatin solution employed for Layer - 2 in 
Sample - 1 and applying the mixture to a dry film thickness of 1.0 .mu., 
with 2,5-di-t-octyl- hydroquinone content of 0.07 g/m.sup.2. 
Sample - 3 
Sample - 3 was prepared similarly as Sample - 2 except for the dispersion 
(M - 3) shown below in place of the dispersion (AS) employed for the Layer 
- 2 in Sample 2. 
Sample - 4 
Sample - 4 was prepared similarly as Sample - 2 except for the dispersion 
(M - 4) shown below in place of the dispersion (AS) employed for the Layer 
- 2 in Sample 2. 
Sample - 5 
Sample - 5 was prepared similarly as Sample - 2 except for the dispersion 
(M - 5) shown below in place of the dispersion (AS) employed for the Layer 
- 2 in Sample 2. 
Sample - 6 
Layer - 1. . .Low sensitivity green-sensitive silver halide emulsion layer 
The same layer as Layer - 1 in Sample 1 
Layer - 2. . .Intermediate layer 
The same layer as Layer - 2 in Sample 1 except for the dry film thickness 
which is 0.5.mu. 
Layer - 3. . .Intermediate layer 
The same layer as Layer - 2 in Sample - 5 
Layer - 4. . .Intermediate layer 
The same layer as Layer - 2 in Sample - 6 
Layer - 5. . .High sensitivity green-sensitive silver halide emulsion layer 
The same layer as Layer - 3 in Sample 1 
Layer - 6. . .Yellow filter layer 
The same layer as Layer - 4 in Sample 1 
The dispersions employed in the above respective emulsion layers were 
prepared as follows: 
Dispersion (M - 1) 
A solution of 54 g of the magenta coupler (M - 1) shown below, 14 g of the 
colored magenta coupler (CM - 1), 0.5 g of the DIR compound (D - 3) and 
0.5 g of the DIR compound (D - 1) as shown below dissolved in a mixture of 
68 g of tricresyl phosphate (TCP) and 280 ml of ethyl alcohol (EA) was 
added to 500 ml of a 7.5% gelatin solution containing 8 g of sodium 
triiropropylnaphthalene sulfonate, followed by emulsification in a colloid 
mill, to be made up to 1,000 ml. 
Dispersion (M - 2) 
A solution of 30 g each of the magenta couplers (M - 1) and (M - 2) shown 
below, 12 g of the colored magenta coupler (CM - 1) and 0.3 g of the DIR 
compound (D - 2) shown below dissolved in a mixture of 70 g of TCP and 280 
ml of EA was added into 500 ml of a 7.5% gelatin solution containing 8 g 
of sodium triisopropylnaphthalene sulfonate, followed by emulsification in 
a colloid mill, to be made up to 1,000 ml. 
Dispersion (AS) 
A solution of 50 g of 2,5-di-tert-octylhydroquinone dissolved in a mixture 
of 50 g of TCP and 100 ml of EA was added into 500 ml of a 7.5% aqueous 
gelatin solution containing 6 g of sodium triisopropylnaphthalene 
sulfonate, followed by emulsification in a colloid mill, to be made up to 
800 ml. 
Dispersion (M - 3) 
A solution of 60 of the magenta coupler (M - 3) shown below dissolved in a 
mixture of 60 g of TCP and 180 ml of EA was added into 500 ml of a 7.5% 
gelatin solution containing 8 g of sodium triisopropylnaphthalene 
sulfonate, followed by emulsification in a colloid mill, to be made up to 
1,000 ml. 
Dispersion (M - 4) 
Prepared by dispersing in the same manner as in preparation of Dispersion 
(M - 3) except that the Example compound [I - 5]of this invention was 
employed as the magenta coupler in place of the magenta coupler (M - 3). 
Dispersion (M - 5) 
Prepared by dispersing in the same manner as in preparation of Dispersion 
(M - 3) except that the Example compound [I - 4]of this invention was 
employed as the magenta coupler in place of the magenta coupler (M - 3). 
Magenta coupler (M - 1): 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzamido]-5- 
pyrazolone 
Magenta coupler (M - 2): 
4,4'-methylenebis{1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyaceta 
mide)benzamido]-5-pyrazolone} 
Magenta coupler (M - 3): 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyhexylamide)benzamido]-5 
-pyrazolone 
Colored magenta coupler (CM - 1): 
1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccin 
imidoanilino)-5-pyrazolone 
DIR compound (D - 1): 
2-(1-phenyl-5-tetrazolythio)-4-octadecylsuccinimido-1-indanone 
DIR compound (D - 2): 
1-hydroxy-N-(2-n-tetradecyloxyphenyl)-4-[1-phenyl-3-methyl-4-(1-phenyl-5-te 
trazolylthio)methyl-5-pyrazolyl-oxy]-2-naphthoamide 
DIR compound (D - 3): 
2-(2-amino-1,3,4-thiadiazolyl-5-thio)-4-octadecylsuccinimido-1-indanone 
These samples were subjected to white light exposure through an optical 
wedge, followed by processing according to the following processing steps. 
______________________________________ 
Processing steps (38.degree. C.) 
Processing time 
______________________________________ 
Color development 2 minutes 10 seconds 
Bleaching 6 minutes 30 seconds 
Washing with water 3 minutes 15 seconds 
Fixing 6 minutes 30 seconds 
Washing with water 3 minutes 15 seconds 
Stabilization 1 minute 30 seconds 
______________________________________ 
The following processing solutions were used in the processing steps: 
______________________________________ 
[Composition of color developing solution] 
______________________________________ 
4-Amino-3-methyl-N--ethyl-N-- 
4.8 g 
(.beta.-hydroxyethyl)aniline sulfate 
Anhydrous sodium sulfite 0.14 g 
Hydroxylamine 1/2 sulfate 
1.98 g 
Sulfuric acid 0.74 g 
Anhydrous potassium carbonate 
28.85 g 
Anhydrous potassium hydrogen carbonate 
3.46 g 
Anhydrous potassium sulfite 
5.10 g 
Potassium bromide 1.16 g 
Sodium chloride 0.14 g 
Trisodium nitrilotriacetate 
1.20 g 
(monohydrate) 
Potassium hydroxide 1.48 g 
Made up to 1 liter with water. 
______________________________________ 
______________________________________ 
[Composition of bleaching solution] 
______________________________________ 
Ferric ammonium salt of ethylenediamine- 
100.0 g 
tetraacetic acid 
Diammonium salt of ethylenediamine- 
10.0 g 
tetraacetic acid 
Ammonium bromide 150.0 g 
Glacial acetic acid 10.0 ml 
Made up to 1 liter with water and adjusted to pH 6.0 with 
aqueous ammonia. 
______________________________________ 
______________________________________ 
[Composition of fixing solution] 
______________________________________ 
Ammonium thiosulfate 175.0 g 
Anhydrous sodium sulfite 
3.6 g 
Sodium metasulfite 2.3 g 
Made up to 1 liter with water and adjusted to pH 6.0 
with acetic acid. 
______________________________________ 
______________________________________ 
[Composition of stabilizing solution] 
______________________________________ 
Formalin (37% aqueous solution) 
1.5 ml 
Konidax (available from Konishiroku Photo 
7.5 ml 
Industry Co., Ltd.) 
Made up to 1 liter with water. 
______________________________________ 
For each of the color image formed on each of the above Samples, the 
results of fog sensitivity and gamma on the same day and after storage for 
3 days under the conditions of 55.degree. C., 10% relative humidity, 
graininess and sharpness were measured. The results are shown in Table 1. 
In the Tables, gamma and graininess are values measured when giving white 
light exposure and graininess (RMS) is shown in terms of 1000-fold values 
of the standard deviations of fluctuations in density values which occur 
during scanning by means of a microdensitometer with a circular scanning 
orifice diameter of 2.5.mu.. 
Detection of image sharpness was conducted by determining MTF (Modulation 
Transfer Function) and making comparison between the greatness of MTF 
values at space frequencies of 10 lines/mm and 30 lines/mm. 
TABLE 1 
__________________________________________________________________________ 
On the same day Storability 
Sample Sensi- Sensi- Graininess (RMS) 
Sharpness (MTF) 
No. Fog 
tivity 
Gamma 
Fog 
tivity 
Gamma 
Fog + 0.1 
Fog + 0.4 
10/mm 
30/mm 
__________________________________________________________________________ 
1 0.13 
100 0.57 0.13 
100 0.56 32 45 90 37 
(Compara- 
tive) 
2 0.13 
98 0.58 0.16 
85 0.65 29 40 95 45 
(Compara- 
tive) 
3 0.14 
100 0.59 0.14 
100 0.58 33 50 92 42 
(Compara- 
tive) 
4 0.13 
105 0.58 0.14 
100 0.58 25 35 93 41 
(This 
invention) 
5 0.12 
100 0.58 0.13 
100 0.59 23 30 93 40 
(This 
invention) 
6 0.13 
100 0.57 0.13 
100 0.58 21 29 93 40 
(This 
invention) 
__________________________________________________________________________ 
As apparently seen from the results in the above Table 1, excellent 
characteristics were exhibited in all of graininess, sharpness, 
storability and gradation in Samples 4 to 6 of this invention, as compared 
with Samples 1 to 3 for comparative purpose. In particular, in spite of 
addition of the mobile coupler of this invention in the intermediate 
layer, sharpness was not deteriorated but slightly improved. Such an 
effect is indeed surprising enough and cannot be expected within the scope 
of the prior art. 
EXAMPLE 2 
On a support of a cellulose triacetate layer applied with subbing 
treatment, the respective layers as shown below were provided by coating 
successively from the support side to prepare Samples 7, 8 and 9. 
Sample - 7 
Layer - 1. . .Low sensivity green-sensitive silver halide emulsion layer 
A silver iodobromide emulsion containing 6 mole % of silver iodide (average 
grain size 0.35 .mu., containing 0.25 mole of silver halide and 40 g of 
gelatin per kg of emulsion) was prepared in a conventional manner and 1 kg 
of this emulsion was chemically sensitized with gold and sulfur 
sensitizers, and further mixed with, as green sensitive sensitizing dyes, 
anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine 
hydroxide; anhydrous 
5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine hydroxide; 
and anhydrous 9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5', 
6'-dibenzoxacarbocyanine hydroxide, followed by addition of 0.25 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 20 mg of 
1-phenyl-5-mercaptotetrazole, and 0.2 g of polyvinyl pyrrolidone to 
prepare a sensitized emulsion A. Also, a silver iodobromide emulsion 
containing 6 mole % of silver iodide (average grain size 0.35.mu., 
containing 0.25 mole of silver halide and 40 g of gelatin per kg of 
emulsion) was prepared in a conventional manner and sensitized according 
to the same procedure as in preparation of the above sensitized emulsion A 
but separately with the use of half amounts of sensitizers and stabilizers 
to prepare a sensitized emulsion B. The emulsions A and B were mixed at a 
ratio of 1:1. Then, 500 ml of the dispersion (M - 1) was added to 1 kg of 
the mixed dispersion to prepare a low sensitivity green-sensitive silver 
halide emulsion, which was then applied to a dry film thickness of 
3.0.mu.. 
Layer - 2. . .Medium sensitivity silver halide emulsion 
To 1 kg of an emulsion prepared by mixing the emulsion A and the emulsion B 
as shown in Layer - 1 was added 200 ml of the dispersion (M - 3) to 
prepare a medium sensitivity silver halide emulsion, which was then coated 
to a dry film thickness of 1.5.mu.. 
Layer - 3. . .Intermediate layer 
An aqueous gelatin solution was applied to a dry film thickness of 1.0.mu.. 
Layer - 4. . .High sensitivity green-sensitive silver halide emulsion layer 
A silver iodobromide containing 7 mole % of silver iodide (average grain 
size 0.9.mu., containing 0.25 mole of silver halide and 30 g of gelatin 
per 1 kg of emulsion) was prepared in a conventional manner and 1 kg of 
this emulsion was chemically sensitized with gold and sulfur sensitizers, 
and further mixed with, as green sensitive sensitizing dyes, anhydrous 
5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; 
anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbo-cyanine 
hydroxide; and anhydrous 9-ethyl-3,3-di-(3-sulfopropyl)-5,6,5', 
6'-dibenzoxacarbocyanine hydroxide, followed by addition of 0.25 g of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 5 mg of 
1-phenyl-5-mercaptotetrazole, 0.2 g of polyvinyl pyrrolidone. Then, to the 
resultant mixture was added 200 ml of the above dispersion (M-2) to 
prepare a high sensitivity green-sensitive silver halide emulsion, which 
was then applied to a dry film thickness of 2.0.mu.. 
Layer - 5. . .Yellow filter layer (the same as Layer - 4 in Sample - 1 in 
Example 1) 
Sample - 8 
Layer - 1. . .Low sensitivity green-sensitive silver halide emulsion layer 
(the same as Layer -1 in Sample - 7 in Example 2) 
Layer - 2. . .Medium sensitivity green-sensitive silver halide emulsion 
layer (the same as Layer -2 in Sample - 7 in Example 2) 
Layer - 3. . .Intermediate layer (the same as Layer - 2 in Sample - 5 in 
Example 1) 
Layer - 4. . .High sensitivity green-sensitive silver halide emulsion layer 
(the same as Layer -4 in Sample - 7 in Example 2) 
Layer - 5. . .Yellow filter layer (the same as Layer - 4 in Sample - 7 in 
Example 1) 
Sample - 9 
Layer - 1. . .Low sensitivity green-sensitive silver halide emulsion layer 
(the same as Layer -1 in Sample - 7 in Example 2) 
Layer - 2. . .Intermediate layer (the same as Layer - 2 in Sample - 5 in 
Example 1) 
Layer - 3. . .Medium sensitivity green-sensitive silver halide emulsion 
layer (the same as Layer -2 in Sample - 7 in Example 2) 
Layer - 4. . .High sensitivity green-sensitive silver halide emulsion layer 
(the same as Layer -4 in Sample - 7 in Example 2) 
Layer - 5. . .Yellow filter layer (the same as layer - 4 in Sample - 1 in 
Example 1) 
The Samples thus prepared were processed similarly as in Example 1 and 
evaluated for graininess and sharpness of the green-sensitive layers. As 
the result, as compared with Samples 7 and 9 for comparative purpose, the 
Sample 8 of this invention was found to exhibit the effect of this 
invention similarly as in Example 1, particularly marked improvement at 
the leg portion graininess. 
EXAMPLE 3 
On a support of a cellulose triacetate layer applied with subbing 
treatment, the respective layers as shown below were provided by coating 
successively from the support side to prepare Samples 10 through 15. 
Sample - 10 
Same as Sample - 1 in Example 1 
Sample - 11 
Same as Sample - 2 in Example 1 
Sample - 12 
Except for adding the dispersion (X - 1) shown below in place of the 
dispersion (AS) used in Layer - 2 in the above Sample - 11, the procedure 
in preparation of Sample - 11 was followed to prepare Sample - 3. 
Sample - 13 
Except for adding the dispersion (C - 1) shown below in place of the 
dispersion (AS) used in Layer - 2 in the above Sample - 11, the procedure 
in preparation of Sample - 11 was followed to prepare Sample - 4. 
Sample - 14 
Except for adding the dispersion (Y - 1) shown below in place of the 
dispersion (AS) used in Layer - 2 in the above Sample - 11, the procedure 
in preparation of Sample - 11 was followed to prepare Sample - 5. 
Sample - 15 
Layer - 1. . .Low sensitivity green-sensitive emulsion layer 
Same as Layer - 1 in Sample - 1 in Example 1. 
Layer - 2. . .Intermediate layer 
Layer - 2 in Sample - 1 in Example - 1 was applied to a dry thickness of 
0.5.mu.. 
Layer - 3. . .Intermediate layer 
Same as Layer - 2 in Sample - 14. 
Layer - 4. . .Intermediate layer 
Same as Layer - 2 in Sample - 14. 
Layer - 5. . .High sensitivity green-sensitive emulsion layer 
Same as Layer - 3 in Sample - 1 in Example 1 
Layer - 6. . .Yellow filter layer 
Same as Layer - 4 in Sample - 1 in Example 1 
The dispersions employed in the respective emulsion layers and intermediate 
layers were prepared as follows. 
Dispersion (X - 1): 
A solution of 60 g of the Example compound [VII - 9] of this invention 
dissolved in a mixture of 60 g of TPC and 180 ml of EA was added into 500 
ml of 7.5 % gelatin solution containing 8 g of sodium 
triisopropylnaphthalene sulfonate and emulsified in a colloid mill, 
followed by make-up to 1,000 ml. 
Dispersion (C - 1): 
Except for using the Example compound [VII - 22] of this invention in place 
of the Example compound [VII - 9] of this invention, emulsification and 
make-up were conducted similarly as in preparation of the above Dispersion 
(X -1). 
Dispersion (Y - 1): 
Except for using the Example compound [VII - 2] of this invention in place 
of the Example compound [VII - 9] of this invention, emulsification and 
make-up were conducted similarly as in preparation of the above Dispersion 
(X -1). 
After having given white light exposure on these Samples through an optical 
wedge, processing was performed, following the same processing steps as in 
Example 1, except for changing the composition of fixing solution as 
follows. 
______________________________________ 
[Composition of fixing solution] 
______________________________________ 
Ammonium thiosulfate 175.0 g 
Anhydrous sodium sulfite 
8.6 g 
Sodium metasulfite 2.3 g 
Made up to one liter with addition of water and adjusted 
to pH 6.0 with acetic acid. 
______________________________________ 
Subsequently, for the color images formed on the above respective Samples, 
the results on the same day of fog, sensitivity and gamma, and the results 
thereof after storage for 3 days under the conditions of 55.degree. C., 
10% relative humidity were measured similarly as in Example 1. These 
results are given in Table 2. 
TABLE 2 
__________________________________________________________________________ 
On the same day Storability 
Sample Sensi- Sensi- Graininess (RMS) 
Sharpness (MTF) 
No. Fog 
tivity 
Gamma 
Fog 
tivity 
Gamma 
Fog + 0.1 
Fog + 0.4 
10/mm 
30/mm 
__________________________________________________________________________ 
10 0.13 
100 0.57 0.13 
100 0.56 32 45 90 37 
(Compara- 
tive) 
11 0.13 
98 0.58 0.16 
85 0.65 29 40 95 45 
(Compara- 
tive) 
12 0.12 
100 0.57 0.13 
100 0.57 22 29 95 48 
(This 
invention) 
13 0.13 
100 0.58 0.14 
100 0.58 18 25 97 50 
(This 
invention) 
14 0.12 
100 0.58 0.13 
100 0.59 19 26 97 50 
(This 
invention) 
15 0.12 
100 0.58 0.12 
100 0.57 18 26 95 44 
(This 
invention) 
__________________________________________________________________________ 
As apparently seen from the results in the above Table 2, Samples 12, 13, 
14 and 15 according to this invention, as compared with Samples 10 and 11 
outside the scope of the present invention, exhibited excellent 
characteristics in all of storability, graininess and sharpness. In 
particular, improvement in graininess is marked, which should be 
appreciated to be a surprising effect surpassing to a great extent the 
result expected from the system employing the dispersion (AS). 
EXAMPLE 4 
On a support of a cellulose triacetate layer applied with subbing 
treatment, the respective layers as shown below were provided by coating 
successively from the support side to prepare Samples 16, 17 and 18. 
Sample - 16 
Layer - 1. . .Low sensitivity green-sensitive emulsion layer 
Same as Layer - 1 in Sample - 7 in Example 2 
Layer - 2. . .Medium sensitivity emulsion layer 
To 1 Kg of a mixture of the emulsion A and the emulsion B at a ratio of 1:1 
as shown in Layer - 1 in Example 2 was added 200 ml of the above 
dispersion (X - 1) to prepare a medium sensitivity emulsion (2), which was 
applied to a dry film thickness of 1.5.mu.. 
Layer - 3. . .Intermediate layer 
Same as Layer - 3 in Sample - 7 in Example 2 
Layer - 4. . .High sensitivity green-sensitive emulsion layer 
Same as Layer - 4 in Sample - 7 in Example 2 
Layer - 5. . .Yellow filter layer 
Same as Layer - 4 in Sample - 10 in Example 3. 
Sample - 17 
Layer - 1. . .Low sensitivity green-sensitive emulsion layer 
Same as Layer - 1 in Sample - 16 
Layer - 2. . .Medium sensitivity green-sensitive emulsion layer 
Same as Layer - 2 in Sample - 16 
Layer - 3. . .Intermediate layer 
Same as Layer - 2 in Sample - 14 in Example 3 
Layer - 4. . .High sensitivity green-sensitive emulsion layer 
Same as Layer - 4 in Sample - 16 
Layer - 5. . .Yellow filter layer 
Same as Layer - 4 in Sample - 10 in Example 3 
Sample - 18 
Layer - 1. . .Low sensitivity green-sensitive emulsion layer 
Same as Layer - 1 in Sample - 16 
Layer - 2. . .Intermediate layer 
Same as Layer - 2 in Sample - 14 in Example 3 
Layer - 3. . .Medium sensitivity green-sensitive emulsion layer 
Same as Layer - 2 in Sample - 16 
Layer - 4. . .High sensitivity green-sensitive emulsion layer 
Same as Layer - 4 in Sample - 16 
Layer - 5. . .Yellow filter layer 
Same as Layer - 4 in Sample - 10 in Example 3 
The Samples thus prepared were processed similarly as in Example 3 and 
evaluated for graininess and sharpness of the green-sensitive layers. As 
the result, as compared with Samples - 16 and 18 for comparative purpose, 
the Sample - 17 of this invention was found to exhibit the effect of this 
invention similarly as in Example 3, particularly marked improvement at 
the leg portion graininess.