Silver halide color photographic material

A silver halide color photographic material having improved granularity and sharpness is disclosed which comprises at least one coupler represented by formula (Ia), (Ib), or (Ic). ##STR1## wherein A represents a coupler residue which can split away from the coupler by A--X bond cleavage upon reaction with an oxidation product of a developing agent; X represents an oxygen atom, or a sulfur atom; R.sub.1 and R.sub.2 each represents an aliphatic group, an aromatic group, or a heterocyclic group; Y represents a substituent group; and n represents 0, 1, or 2, and when n is 2, the two Y's represent the same or different substituent groups, or two of substituents R.sub.1, R.sub.2 and Y represent divalent groups that combine with each other to form a ring structure.

FIELD OF THE INVENTION 
The present invention relates to a silver halide color photographic 
material comprising a photographic coupler for improving sharpness and 
granularity. 
BACKGROUND OF THE INVENTION 
It is well known that when a silver halide color photographic material is 
subjected to color development, couplers present therein undergo reaction 
with oxidized aromatic primary amine type color developing agents to 
produce indophenol dyes, indoaniline dyes, indamine dyes, azomethine dyes, 
phenoxazine dyes, phenazine dyes, or analogues thereof, whereby color 
images are formed. In this method, the subtractive color process is 
generally employed for color reproduction, and silver halide emulsions 
sensitized selectively to blue light, green light, and red light, 
respectively, and yellow-, magenta-, and cyan-dye-forming agents which 
bear a complementary color relationship to their corresponding emulsions 
are used in combination. In order to form a yellow dye image, couplers of, 
e.g., the acylacetoanilide type or the dibenzoylmethane type are employed. 
In order to form a magenta dye image, couplers of the pyrazolone, 
pyrazolobenzimidazole, cyanoacetophenone or indozolone type are generally 
used. In order to form a cyan dye image, phenolic couplers, e.g., phenols 
and naphthols, are generally used. 
In recent years, it has acquired a greater importance than in the past to 
enhance image qualities of silver halide photographic materials, 
particularly those for taking color photographs, as disk cameras and 
110-size cameras have been popularized. Especially, improvements in 
sharpness and granularity are of importance. 
It is also well known that couplers can be employed not only for forming 
dye images, but also for the purpose of releasing photographically useful 
groups. On the other hand, various compounds capable of releasing 
photographically useful groups have been used for a wide variety of 
purposes, respectively, for instance, enhancement of color 
reproducibility, improvement in granularity, improvement in sharpness, 
increase in photographic speed, and so on. 
Moreover, certain couplers which can release, from their coupling sites, 
compounds capable of capturing oxidation products of color developing 
agents have been described, for example, in Japanese Patent Applications 
(OPI) Nos. 28318/77, 111537/82 and 138636/82, and so on. In detail, 
Japanese Patent Application (OPI) No. 28318/77 discloses a coupler capable 
of releasing a so-called competing coupler residue upon reaction with an 
oxidation product of an aromatic primary amine developing agent. Japanese 
Patent Application (OPI) No. 111537/82 discloses a coupler illustrated by 
the following formula: 
##STR2## 
wherein Non-diffusible COUP (A) is a non-diffusible coupling component (A) 
bonding to the oxygen atom at the position at which a coupling reaction 
takes place with an oxidation product of a color developing agent to form 
a colored or colorless compound, and Diffusible COUP (B) is a diffusible 
coupling componet (B) bonding to Non-diffusible COUP (A) through the 
oxygen atom in such a manner that it is released upon the coupling 
reaction between Non-diffusible COUP (A) and the oxidation product and it 
also reacts with an oxidation product of the color developing agent as a 
4-equivalent coupler to form a dye. Japanese Patent Application (OPI) No. 
138636/82 discloses a coupler represented by COUP-ED, wherein COUP is a 
photographic coupler residue capable of forming a dye image by a reaction 
with an oxidation product of a color developing agent, and ED is a group 
bonding to the coupling site of COUP and being released from COUP to 
undergo an oxidation-reduction reaction with an oxidation product of a 
color developing agent. Such couplers, though employed with the intention 
of improving granularity or controlling the gradation, do not have much 
effect, so further improvement on such couplers has been desired. In 
addition, compounds released from these known couplers to capture 
oxidation products of developing agents have been found to have not only 
weak capturing power, but also little diffusibility. Accordingly, they 
cannot fully achieve the desired improvement in sharpness, and further, 
cannot produce the interimage effect due to diffusion into other layers. 
SUMMARY OF THE INVENTION 
Therefore, an object of the present invention is to provide a color 
photographic material which contains a novel coupler which releases 
compounds capable of capturing oxidation products of developing agents 
upon the reaction with the oxidation products of the developing agents, 
whereby improvements in granularity, sharpness, or color reproducibility 
through the interimage effect are satisfactorily achieved. 
The above-described object is attained with a silver halide color 
photographic material which contains at least one coupler represented by 
formula (Ia), (Ib), or (Ic): 
##STR3## 
wherein A represents a coupler residue which can split away from the 
coupler by A--X bond cleavage upon reaction with an oxidation product of a 
developing agent; X represents an oxygen atom or a sulfur atom; R.sub.1 
and R.sub.2 each represents an aliphatic group, an aromatic group, or a 
heterocyclic group; Y represents a substituent group; and n represents 0, 
1, or 2, and when n is 2, the two Y's represent the same or different 
substituent groups, or two of substituents R.sub.1, R.sub.2, and Y 
represent divalent groups that combine with each other to form a ring 
structure. 
DETAILED DESCRIPTION OF THE INVENTION 
The couplers represented by the foregoing formula (Ia) release aromatic 
alcohols or aromatic thiols, each of which is subsituted with two hydroxyl 
groups. These compounds when released have strong reducing power, whereby 
oxidation products of developing agents are reduced. In addition, two 
hydroxy substituents (or three hydroxy substituents when X represents an 
oxygen atom) enhance the solubility in water, so the diffusibility of the 
moiety released from the coupler in an emulsion is heightened. Further, if 
the group represented by Y is controlled so as to have a proper size, the 
diffusibility of the released moiety can be easily controlled. 
Couplers represented by the foregoing formula (Ib) release aromatic 
alcohols or aromatic thiols each of which is substituted with two or more 
sulfonamido groups by reaction with oxidation products of developing 
agents. It is necessary for one of these sulfonamido groups to be situated 
at the para-position to X. The bissulfonamidophenols or 
bissulfonamidothiophenols eliminated from A exhibit their strong reducing 
power, and reduce oxidation products of developing agents. In addition, 
two sulfonamido groups enhance moderately the solubility to water, and 
heighten the diffusibility also. Further, the diffusibility is also easily 
controlled by properly choosing the size of the substituent R.sub.1, 
R.sub.2, or Y. 
Although couplers having sulfoamido groups situated at the 2- and 
5-positions with respect to X are disclosed in the aforesaid Japanese 
Patent Application (OPI) No. 138636/82, compounds released from these 
couplers suffer from the fatal defect that they undergo the coupling 
reaction with oxidation products of developing agents at the para-position 
to their hydroxyl group. Accordingly, the compounds have weak reducing 
power and cause a problem in that dyes formed by the coupling reaction are 
responsible for color turbidity. On the other hand, these defects are not 
observed in the compounds released from the coupler (Ib) of the present 
invention. 
Examples of the coupler which can release a phenoxy group having a 
sulfonamido group at the o-position are disclosed in U.S. Pat. No. 
4,401,752. The couplers of this kind are used for the purpose of improving 
color density of the developed image, particularly reducing the amount of 
developed silver per amount of dye produced (equivalency). They show their 
capability to certain extents with respect to this purpose, and produce 
dyes using silver in an amount close to two equivalents required 
theoretically. However, the couplers (Ib) of the present invention which 
release a phenoxy group having sulfonamido groups at not only the 
o-position but also the p-position cannot function as two equivalent 
couplers. This is because compounds released from the couplers (Ib) have 
strong reducing power and thereby, oxidation products of developing agents 
are quickly reduced. That is, the couplers (Ib) of the present invention 
bring about increase in the equivalent number, and require a larger amount 
of silver in order to attain the same color density of the developed 
image. In other words, it is impossible to use the couplers (Ib) of the 
present invention as two equivalent couplers with the intention of 
heightening color density of the developed image. 
Couplers represented by the foregoing formula (Ic) release aromatic 
alcohols or aromatic thiols each of which is substituted with a 
sulfonamido group and a hydroxyl group. These compounds released have a 
strong reducing power, and reduce oxidation products of developing agents. 
In addition, both the hydroxyl substituent and the sulfonamido substituent 
enhance moderately the solubility to water, and heighten the diffusibility 
of the compounds released from the couplers in emulsions. Further, the 
diffusibility can also be easily controlled by properly choosing the sizes 
of the substituents R.sub.1 and Y. 
The couplers of the present invention can remove effectively through their 
reducing power an excess portion of oxidation products of developing 
agents which are produced at the time of development-processing. Thereby, 
the growth of individual dye clouds exceeding a certain limit is 
suppressed, to result in preventing mottle from generating, and 
consequently, providing an improvement in granularity. In addition, when 
reducing agents released from the couplers of the present invention have 
great diffusibility, the edge effect and the interimage effect are 
observed. In particular, these effects are observed significant in color 
reversal photosensitive materials. In order to achieve the edge effect and 
the interimage effect, it has been known to use, for instance, couplers 
capable of releasing development inhibitors (DIR couplers). In the case of 
color reversal photosensitive materials, however, conventional DIR 
couplers are unable to exhibit their development inhibiting effect in 
color reversal photosensitive materials, so they cannot be used for that 
purpose. This is because conventional DIR couplers utilize inhibitors of 
the type which are adsorbed by silver halide, and their development 
inhibiting function yield no results in the color reversal step having 
great developing activity. On the other hand, the couplers of the present 
invention produce excellent granularity and sharpness effects, even in 
color reversal photosensitive materials. More specifically, compounds 
released from the couplers of the present invention function to capture 
oxidation products of developing agent in the second developing step of 
the color reversal photographic processing, and consume the oxidation 
products of the developing agents. Thereby, developable silver is 
consumed, to result in inhibition of color development; that is, a 
development inhibiting effect is produced. 
Details of the couplers of the present invention are described below. 
Preferred examples of the substituent group represented by Y in formulae 
(Ia), (Ib) and (Ic) include an aliphatic group, an aromatic group, a 
heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an 
arylthio group, an alkoxycarbonyl group, a thioureido group, an acylamino 
group, a sulfonamido group, a cyano group, a nitro group, a carbamoyl 
group, a sulfamoyl group, an acyloxy group, an alkylthio group, an amino 
group, a sulfonyl group, a ureido group, an aryloxycarbonyl group, an 
alkoxycarbonylamino group, a sulfamoylamino group, and an acyl group. In 
addition, when n is 2, the substituent group represented by (Y).sub.n is 
preferably 
##STR4## 
(wherein Y' has the same meaning as Y described above or represents a 
hydrogen atom). When these substituent groups contain an aliphatic moiety, 
the aliphatic moiety contains from 1 to 32 carbon atoms, preferably from 1 
to 16 carbon atoms, and it may be a straight or branched chain, chain-form 
or cyclic, saturated or unsaturated, substituted or unsubstituted group. 
On the other hand, when Y contains an aryl moiety, the aryl moiety 
contains from 6 to 10 carbon atoms, and preferably is a substituted or 
unsubstituted phenyl group. Of these substituent groups, an aliphatic 
group, an aromatic group, an alkoxy group, an acylamino group and a 
sulfoamido group are more preferred for Y in formulae (Ia) and (Ic), and 
an aliphatic group, an aromatic group and an alkoxy group are more 
preferred for Y in formula (Ib). 
In formulae (Ib) and (Ic), each of aliphatic groups represented by R.sub.1 
and R.sub.2 contains from 1 to 32 carbon atoms, and preferably from 1 to 
16 carbon atoms (not including carbon atoms of substituents if any), and 
it may be a substituted or unsubstituted, straight or branched chain, 
chain-form or cyclic, saturated or unsaturated group. Suitable examples of 
a substituent with which the aliphatic group may be substituted include a 
halogen atom, an aryl group, an alkoxy group, an aryloxy group, an 
arylthio group, an alkoxycarbonyl group, a hydroxyl group, an acylamino 
group, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, 
a sulfonamido group, an acyloxy group, an alkylthio group, an amino group, 
a sulfonyl group, an acyl group, a ureido group, and an aryloxycarbonyl 
group. When these substituents contain an aliphatic moiety, the moiety 
contains from 1 to 16 carbon atoms, and it may be a straight or branched 
chain, chain-form or cyclic, saturated or unsaturated, substituted or 
unsubstituted group. On the other hand, when the substituents set forth 
above contain an aromatic group, the moiety contains from 6 to 10 carbon 
atoms, and it is preferably a substituted or unsubstituted phenyl group. 
In formulae (Ib) and (Ic), each of aromatic groups represented by R.sub.1 
and R.sub.2 contains from 6 to 10 carbon atoms (not including carbon atoms 
of substituents if any), and it is preferably a substituted or 
unsubstituted phenyl group. Suitable examples of substituents with which 
the aromatic group may be substituted include an aliphatic group, an 
aromatic group, a heterocyclic group, a halogen atom, an alkoxy group, an 
aryloxy group, an arylthio group, an alkoxycarbonyl group, a hydroxyl 
group, an acylamino group, a cyano group, a nitro group, a carbamoyl 
group, a sulfamoyl group, a sulfonamido group, an acyloxy group, an 
alkylthio group, an amino group, a sulfonyl group, a ureido group, an 
aryloxycarbonyl group, a carboxyl group, an acyl group, an 
alkoxycarbonylamino group, and sulfamoylamino group. When these 
substituents contain an aliphatic moiety, the moiety contains from 1 to 32 
carbonatoms, preferably from 1 to 16 carbon atoms, and it may be a 
straight or branched chain, chain-form or cyclic, saturated or 
unsaturated, substituted or unsubstituted group. In another case, where 
the substituents set forth above contain an aromatic moiety, the moiety 
contains from 6 to 10 carbon atoms, and it is preferably a substituted or 
unsubstituted phenyl group. In still another case where the substituents 
set forth above contain a heterocyclic ring structure, the ring structure 
may be that of imidazole, pyrrole, thiophene, tetrahydrofuran, 
benzimidazole, pyridine, triazole, pyrazole, imidazolidine-2,4-dione, or 
the like. 
In formulae (Ib) and (Ic), each of heterocyclic groups represented by 
R.sub.1 and R.sub.2 is preferably a 5- to 7-membered ring group containing 
one or more hereto atom selected from the group consisting of a nitrogen 
atom, a sulfur atom, an oxygen atom, and a selenium atom. Suitable 
examples of such rings include imidazole, pyrazole, 1,2,4-triazole, 
thiophene, furan, benzoimidazole, pyridine, teterahydrofuran and so on, 
each of which may have a certain substituent. Preferred examples of such 
substituents include an aliphatic group, an aromatic group, an acylamino 
group, a sulfonamido group, an alkoxy group, a halogen atom, an 
aryloxycarbonyl group, an alkoxycarbonyl group, an alkylthio group, a 
ureido group, a cyano group, an amino group, and an aryloxy groups. When 
these substituents contain an aliphatic moiety, the moiety contains from 1 
to 32 carbon atoms, preferably from 1 to 16 carbon atoms, and it may be a 
straight or branched chain, chain-form or cyclic, saturated or 
unsaturated, substituted or unsubstituted group. On the other hand, when 
the substituents set forth above contains an aromatic moiety, the moiety 
contains from 6 to 10 carbon atoms, and it is preferably a substituted or 
unsubstituted phenyl group. 
In formulae (Ia), (Ib) and (Ic), X is preferably an oxygen atom, and n is 
preferably 0, i.e., having no substituents represented by Y. 
The couplers represented by formula (Ia) or (Ic) preferably have the two OH 
groups, or the OH group and the NHSO.sub.2 R.sub.1 group, respectively, at 
the 2- and 4-positions with respect to X. 
In formulae (Ia), (Ib), and (Ic), respectively, A is a coupler residue 
represented by formula (II), (III), (IV), (V), (VI), (VII) or (VIII): 
##STR5## 
The free bond (indicated by *) derived from the coupling site in each of 
the foregoing formulae represents the bonding position of the coupling 
eliminable group (X in the formula (I)). When R.sub.3, R.sub.4, R.sub.5, 
R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, 
R.sub.13, R.sub.14, or R.sub.15 in the formulae illustrated above contains 
a non-diffusible group, the total number of carbon atoms contained in each 
of R.sub.3 to R.sub.15 may range from 8 to 32, and preferably from 10 to 
22. In other cases, the total number of carbon atoms contained in each 
group is preferably 15 or less. 
Detailed descriptions of R.sub.3 to R.sub.15 and l in formulae (II) to 
(VIII) are set forth below. 
In formula (II), R.sub.3 represents an aliphatic group, an aromatic group, 
an alkoxy group, or a heterocyclic group, and R.sub.4 represents an 
aromatic group or a heterocyclic group. 
The aliphatic group represented by R.sub.3 preferably contains from 1 to 22 
carbon atoms and it may be substituted or unsubstituted, chain-form or 
cyclic group. When the aliphatic group is an alkyl group, the alkyl group 
may have a substituent such as an alkoxy group, an aryloxy group, an amino 
group, an acylamino group, and a halogen atom. The substituent may be 
further substituted. Preferred examples of the aliphatic group for R.sub.3 
include an isopropyl group, an isobutyl group, a tert-butyl group, an 
isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl group, a 
1,1-dimethylhexyl group, a 1,1-diethylhexyl group, a dodecyl group, a 
hexadecyl group, an octadecyl group, a cyclohexyl group, a 
1-methoxyisopropyl group, a 1-phenoxyisopropyl group, a 
1-p-tert-butylphenoxyisopropyl group, an .alpha.-aminoisopropyl group, an 
.alpha.-(diethylamino)isopropyl group, an .alpha.-(succinimido)isopropyl 
group, an .alpha.-(phthalimido)isopropyl group, and an 
.alpha.-(benzenesulfonamido)isopropyl group. 
The aromatic group (particularly a phenyl group) represented by R.sub.3 or 
R.sub.4 may be substituted by an alkyl group, an alkenyl group, an alkoxy 
group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic 
amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an 
alkylureido group, an alkylsubstituted succinimido group, or so on, each 
of which contains not more than 26 carbon atoms. The above-described alkyl 
groups may include those containing an arylene group like a phenylene 
group in their chain structures. When the aromatic group is a phenyl 
group, the phenyl group may be substituted with, in addition to the groups 
set forth above, an aryloxy group, an aryloxycarbonyl group, an 
arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an 
arylsulfonamido group, an arylureido group, or so on. Each of aryl 
moieties contained in these substituent groups may further be substituted 
with one or more of an alkyl group containing from 1 to 22 carbon atoms. 
Moreover, a phenyl group represented by R.sub.3 or R.sub.4 may be 
substituted with an amino group including one substituted with a lower 
alkyl group containing from 1 to 6 carbon atoms, a hydroxyl group, a 
carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano 
group, or a halogen atom. 
Further, a phenyl group represented by R.sub.3 or R.sub.4 may be a group 
formed by fusing together the phenyl group and another ring, such as a 
naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, 
a coumaranyl group, a tetrahydronaphthyl group, or the like. These 
substituents may themselves be further substituted. 
When R.sub.3 represents an alkoxy group, its alkyl moiety includes a 
straight or branched chain alkyl or alkenyl group containing from 1 to 32 
carbon atoms, preferably from 1 to 22 carbon atoms, and a cycloalkyl or 
cycloalkenyl group, each of which may be substituted with a halogen atom, 
an aryl group, an alkoxy group or so on. 
A heterocyclic group represented by R.sub.3 pr R.sub.4 is attached to the 
carbon atom of the acyl carbonyl group or the nitrogen atom of the amido 
group, respectively, in the .alpha.-acetylacetoamido group, through one of 
carbon atoms which form its ring. Specific examples of such heterocyclic 
rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, 
pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, 
oxazole, triazine, thiadiazine, oxazine and like rings. These rings each 
may further have a substituent group on the ring. 
In formula (III), R.sub.5 represents a straight or branched chain alkyl 
group containing from 1 to 32 carbon atoms, preferably from 1 to 22 carbon 
atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), an 
alkenyl group (e.g., allyl, etc.), a cycloalkyl group (e.g., cyclopentyl, 
cyclohexyl, norbornyl, etc.), an aralkyl group (e.g., benzyl, 
.beta.-phenylethyl, etc.), or a cycloalkenyl group (e.g., cyclopentenyl, 
cyclohexenyl, etc.), each of which may be substituted with a halogen atom, 
a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy 
group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl 
group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a 
sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino 
group, a ureido group, a urethane group, a thiourethane group, a 
sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkyl 
sulfonyl group, an arylthio group, an alkylthio group, an alkylamino 
group, a dialkylamino group, an anilino group, an N-arylanilino group, an 
N-alkylanilino group, an N-acylanilino group, a hydroxyl group, and so on. 
Further, R.sub.5 may represent an aryl group (e.g., phenyl, 
.alpha.-naphthyl, .beta.-naphthyl, etc.). The aryl group may have one or 
more of a substituent. Specific examples of such a substituent include an 
alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a 
cycloalkenyl group, a halogen atom, a nitro group, a cyano group, an aryl 
group, an alkoxy group, an aryloxy group, a carboxy group, an 
alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl 
group, a carbamoyl group, an acylamino group, a diacylamino group, a 
ureido group, a urethane group, a sulfonamido group, a heterocyclic group, 
an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an 
alkylthio group, an alkylamino group, a dialkylamino group, an anilino 
group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino 
group, a hydroxyl group and so on. Of these aryl groups, a phenyl group 
which is substituted with an alkyl group, an alkoxy group, a halogen atom 
or the like at at least one of the o-positions is more preferred as 
R.sub.5. This is because when the resulting couplers remain in a 
photosensitive film, little coloration thereof is caused by light or heat. 
Thus, they are very useful. 
Furthermore, R.sub.5 may represent a heterocyclic group (e.g. a 5- or 
6-membered heterocyclic group containing nitrogen, oxyten or/and sulfur 
atoms, which may form a condensed ring by fusing together with another 
ring, with specific examples including a pyridyl group, a quinolyl group, 
a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl 
group, a naphthooxazolyl group, and the like), a substituted heterocyclic 
group whose substituents are included in those set forth with respect to 
the above-described aryl group for R.sub.5, an aliphatic or aromatic acyl 
group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl 
group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or an 
arylthiocarbamoyl group. 
In the foregoing formula (III), R.sub.6 represents a hydrogen atom, a 
straight or branched chain alkyl group containing from 1 to 32 carbon 
atoms, preferably from 1 to 22 carbon atoms, an alkenyl group, a 
cycloalkyl group, an aralkyl group, a cycloalkenyl group (which groups 
each may have one or more of the substituents set forth with respect to 
R.sub.5), an aryl or heterocyclic group (which may have one or more of the 
substituents set forth with respect to R.sub.5), an alkoxycarbonyl group 
(e.g., methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl, etc.), an 
aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthoxycarbonyl, etc.), an 
aralkyloxycarbonyl group (e.g., benzyloxycarbonyl, etc.), an alkoxy group 
(e.g., methoxy, ethoxy, heptadecyloxy, etc.), an aryloxy group (e.g., 
phenoxy, tolyoxy, etc.), an alkylthio group (e.g., ethylthio, dodecylthio, 
etc.), an arylthio group (e.g., phenylthio, .alpha.-naphthylthio, etc.), a 
carboxyl group, an acylamino group (e.g., acetylamino, 
3-[(2,4-di-tert-amylphenoxy)acetamido]benzamido, etc.), a diacylamino 
group, an N-alkylacylamino group (e.g., N-methylpropionamido, etc.), an 
N-arylacylamino group (e.g., N-phenylacetamido, etc.), a ureido group, 
(e.g., ureido, N-arylureido, N-alkylureido, etc.), a urethane group, a 
thiourethane group, an arylamino group (e.g., phenylamino, 
N-methylanilino, diphenylamino, N-acetylanilino, 
2-chloro-5-tetradecanamidoanilino, etc.), an alkylamino group (e.g., 
n-butylamino, methylamino, cyclohexylamino, etc.), a cycloamino group 
(e.g., piperidino, pyrrolidino, etc.), a heterocyclic amino group (e.g., 
4-pyridylamino, 2-benzoxazolylamino, etc.), an alkylcarbonyl group (e.g., 
methylcarbonyl, etc.), an arylcarbonyl group (e.g., phenylcarbonyl, etc.), 
a sulfonamido group (e.g., alkylsulfonamido, arylsulfonamido, etc.), a 
carbamoyl group (e.g., ethylcarbamoyl, dimethylcarbamoyl, 
N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), a sulfamoyl group 
(e.g., N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, 
N-alkyl-N-arylsulfamoyl, N,N-diarylsulfamoyl, etc.), a cyano group, or a 
hydroxyl group. 
In formula (IV), R.sub.7 represents an aliphatic group, or an aromatic 
group. Preferred aliphatic groups contain from 1 to 22 carbon atoms, and 
they may be substituted or unsubstituted chain-form or cyclic groups. 
Substituents suitable for these aliphatic groups include an alkoxy group, 
an alkylthio group, an aryloxy group, a carboxyl group, a halogen atom, an 
acylamino group and so on, which themselves may be further substituted. 
Specific examples of useful aliphatic groups as R.sub.7 include a dodecyl 
group, a hexadecyl group, a dodecyloxypropyl group, a cyclohexyl group, a 
tert-butyl group, a n-butyl group, a 3-(2,4-di-tert-amylphenoxy)propyl 
group, a 1-(2,4-di-tert-amylphenoxy)propyl group and so on. 
When R.sub.7 represents an aromatic group, it may have one or more of the 
substituents set forth in the above-described case where R.sub.3 is an 
aryl group. 
In formula (IV), R.sub.8 represents an aliphatic group (e.g., methyl, 
ethyl, etc.), a halogen atom (e.g. chlorine, fluorine, etc.), an alkoxy 
group (e.g., methoxy, ethoxy, etc.), or an aromatic group (e.g., phenyl). 
In the foregoing formula (V), R.sub.9 and R.sub.10 each represents a 
hydrogen atom, an aliphatic group, or an aromatic group. When R.sub.9 or 
R.sub.10 represents an aliphatic group, it contains from 1 to 32 carbon 
atoms, preferably from 1 to 18 carbon atoms, and may be a substituted or 
unsubstituted chain-form or cyclic group. Suitable examples of groups with 
which the aliphatic group may be substituted include an aryloxy groups, an 
alkoxy group, a halogen atom, an aryl group, a hydroxyl group, a carboxyl 
group, a cyano group, a nitro group, an alkoxycarbonyl group, an acylamino 
group, a sulfonamido group, an acyloxy group, each of which may be further 
substituted. Specific examples of aliphatic groups useful as R.sub.9 or 
R.sub.10 include a dodecyl group, a hexadecyl group, a dodecyloxypropyl 
group, a cyclohexyl group, a tert-butyl group, a 
3-(2,4-di-tert-amylphenoxy)propyl group, a 
1-(2,4-di-tert-amylphenoxy)propyl group, and so on. 
When R.sub.9 or R.sub.10 represents an aromatic group, the aromatic group 
contains from 6 to 10 carbon atoms, and preferably is a substituted or 
unsubstituted phenyl group. Suitable examples of groups with which the 
phenyl group may be substituted include an alkoxy group, an aliphatic 
group, an acylamino group, an alkoxycarbonyl group, a halogen atom, a 
sulfonamido group, a sulfamoyl group, a carbamoyl group, a carboxyl group, 
a hydroxyl group, a cyano group, a nitro group, and so on. Specific 
examples of aromatic groups useful as R.sub.9 or R.sub.10 include a 
2-tetradecyloxyphenyl group, a 4-tetradecyloxyphenyl group, a 
3-dodecyloxycarbonylphenyl group, a 2-chloro-5-dodecyloxycarbonylphenyl 
group, a phenyl group, a 4-carboxyphenyl group, and so on. 
In formula (V) and (VI), R.sub.11 represents a halogen atom, an acylamino 
group (e.g., acetamido, 2,4-di-tert-amylphenoxyacetamido, etc.), a 
sulfonamido group (e.g., methanesulfonamido, hexadecylsulfonamido, etc.), 
an alkoxy group (e.g., methoxy, dodecyloxy, etc.), or an aliphatic group 
(e.g., methyl, ethyl, etc.). 
In formula (VII), R.sub.12 represents an arylcarbonyl group, an alkanoyl 
group containing from 2 to 32 carbon atoms, preferably from 2 to 22 carbon 
atoms, an arylcarbamoyl, group, an alkanecarbamoyl group containing from 2 
to 32 carbon atoms, preferably from 2 to 22 carbon atoms, an 
alkoxycarbonyl group containing from 2 to 32 carbon atoms, preferably from 
2 to 22 carbon atoms, or an aryloxycarbonyl group. These groups each may 
have a substituent group. Suitable examples of substituents thereof 
include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an 
alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido 
group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, 
an alkyl group, an aryl group, and so on. 
R.sub.13 in formula (VII) represents an arylcarbonyl group, an alkanoyl 
group containing from 2 to 32 carbon atoms, preferably from 2 to 22 carbon 
atoms, an arylcarbamoyl group, an alkanecarbamoyl group containing from 2 
to 32 carbon atoms, preferably from 2 to 22 carbon atoms, an 
alkoxycarbonyl group containing from 2 to 32 carbon atoms, preferably from 
2 to 22 carbon atoms, an aryloxycarbonyl group, an alkanesulfonyl group 
containing from 1 to 32 carbon atoms, preferably from 1 to 22 carbon 
atoms, an arylsulfonyl group, an aryl group, or 5- or 6-membered 
heterocyclic group (which contains nitrogen, oxygen, or/and sulfur atoms 
as hetero atoms, with specific examples including a triazolyl group, an 
imidazolyl group, a phthalimido group, a succinimido group, a furyl group, 
a pyridyl group or a benzotriazolyl group). These groups each may have one 
or more of the substituents set forth with respect to the above-described 
R.sub.12. 
In formula (VIII), R.sub.14 represents an aliphatic group, an aromatic 
group, a heterocyclic group, or an anilino group. Suitable examples of 
such aliphatic, aromatic, and heterocyclic groups include those set forth 
with respect to R.sub.3. When R.sub.14 represents an anilino group, its 
phenyl moiety may have one or more of the substituents described above for 
the case where R.sub.5 represents a phenyl group. Examples of groups 
preferred as R.sub.14 include a pentafluoropropyl group, a 
1,1,2,2,3,3-hexafluoropropyl group, a p-cyanoanilino group, a 
3,4-dichloroanilino group, a p-propanesulfonylanilino group, a 
2-ethanesulfonamidophenyl group, and so on. 
In formula (VIII), R.sub.15 represents an aliphatic group or an aromatic 
group, exemplified by those set forth with respect to R.sub.5. Suitable 
examples of groups represented by R.sub.15 include a tert-butyl group, a 
1-(2,4-di-tert-amylphenoxy)propyl group, a 
1-(2,4-di-tert-amylphenoxy)pentyl group, an isoamyl group, a 
1-(2,4-di-tert-octylphenoxy)heptyl group, and so on. 
In formulae (IV), (V) and (VI), l is 0, 1 or 2, and when l is 2, the two 
R.sub.8 's or R.sub.11 's represent the same or different groups. 
The couplers represented by formula (Ia) produce more desirable effects 
when used in combination with other conventional couplers. They are 
generally used in an amount of from 0.001 to 0.8 mol, preferably from 0.1 
to 0.5 mol, per mol of conventional coupler in the material. 
Also, it is desired that the couplers represented by formula (Ib) or those 
represented by formula (Ic) are used in combination with other 
conventional couplers. They are generally used in an amount of from 
1.times.10.sup.-4 to 1 mol, preferably from 0.05 to 0.5 mol, per mol of 
conventional coupler in the material. 
Specific examples of the couplers of the present invention are illustrated 
below. However, the present invention should not be construed as being 
limited to these examples. 
##STR6## 
Methods for synthesizing the couplers of the present invention are 
illustrated in detail below.

SYNTHESIS EXAMPLE 1 
Synthesis of Compound (1) 
Compound (1) was synthesized taking the following route. 
##STR7## 
(1) Synthesis of Compound (iii) 
30 g of Compound (ii) and 12.1 g of potassium hydroxide were refluxed in 
toluene under heating and thereby, the solvent was distilled away to yield 
the potassium salt of Compound (ii). To this salt was added 200 ml of an 
N,N-dimethylformamide solution containing 45 g of Compound (i). The 
reaction was run at 90.degree. C. for 5 hours. After post-treatment of the 
reaction product, 52 g of Compound (iii) was obtained. 
(2) Synthesis of Compound (iv) 
52 g of Compound (iii) was added to 500 ml of 10% hydrous ethanol 
containing 40 g of potassium hydroxide to undergo the reaction at room 
temperature for 5 hours. The reaction product was post-treated in a 
conventional manner to yield 27 g of Compound (iv). 
(3) Synthesis of Compound (v) 
27 g of Compound (iv) was added to 500 ml of ethyl acetate and thereto, 36 
g of anhydrous heptafluorobutyric acid was added dropwise at room 
temperture. After one hour reaction, the product was post-treated in a 
conventional manner to yield 36 g of Compound (v). 
(4) Synthesis of Compound (vi) 
To a mixed solvent consisting of 400 ml of isopropanol, 40 ml of water and 
40 ml of acetic acid was added 40 g of iron powder. The resulting mixture 
was stirred at 80.degree. C. for 10 minutes. Thereto, 36 g of Compound (v) 
was added, and refluxed for 1 hour under heating. After carrying out a 
conventional post-treatment, 32 g of Compound (vi) was obtained. 
(5) Synthesis of Compound (vii) 
32 g of Compound (vi) was added to 300 ml of acetonitrile and refluxed 
under heating. Thereto, 25 g of 2-(2,4-di-tert-amylphenoxy)hexanoyl 
chloride was added dropwise. After reacting for one hour under reflux, 
conventional post-treatment was carried out to yield 38 g of Compound 
(vii). 
(6) Synthesis of Compound (1) 
To 300 ml of methylene chloride, 38 g of Compound (vii) was added, and 
cooled to 0.degree. C. Thereafter, 42 g of boron tribromide was added to 
the cooled solution. After the dropwise addition, these ingredients were 
allowed to react with each other at a temperature of 10.degree. C. or 
lower over a period of 3 hours. The reaction mixture was slowly added to 1 
liter of water saturated with sodium hydrogen carbonate for the purpose of 
neutralization. Then, the resulting mixture was separated into two phases 
using a separatory funnel. After washing with water, the oily phase was 
concentrated, and the residue was recrystallized from ethyl acetate and 
hexane. Thus, the desired Coupler (1) was obtained in a yield of 28 g. 
SYNTHESIS EXAMPLE 2 
Synthesis of Compound (2) 
Compound (2) was synthesized in the same manner as in Synthesis Example 1 
except that p-cyanophenylisocyanate was employed in place of anhydrous 
heptafluorobutyric acid in the step (3) of Synthesis Example 1. 
SYNTHESIS EXAMPLE 3 
Synthesis of Compound (3) 
Compound (3) was synthesized in the same manner as in Synthesis Example 1 
except that 2,3-dimethoxyphenol was employed in place of Compound (ii) in 
the step (1) of Synthesis Example 1. 
SYNTHESIS EXAMPLE 4 
Synthesis of Compound (27) 
Compound (27) was synthesized taking the following route. 
##STR8## 
(i) Synthesis of Compound (x) 
204 g of 1,4-dihydroxy-2-naphthoic acid was dissolved in 500 ml of dimethyl 
formamide and thereto, 386 g of a 28% methanol solution of sodium 
methoxide was added. After 10 minute stirring, 300 ml of a dimethyl 
formamide solution containing 186 g of 2,4-dinitrofluorobenzene was added 
dropwise to this reaction mixture at room temperature. The stirring was 
continued for 2 hours and then, 101.4 g of concentrated hydrochloric acid 
was gradually added to the resulting reaction mixture to precipitate 
crystals. The crystals were filtered off, washed with water, and dried. 
Thus, 274 g of Compound (x) was obtained. 
(2) Synthesis of Compound (xi) 
To a mixture of 274 g of Compound (x), 226 g of o-tetra-decyloxyaniline and 
2.5 liters of dimethyl formamide was added dropwise 400 ml of a chloroform 
solution containing 160.4 g of dicyclohexylcarbodiimide (DCC). After 4 
hour stirring, the reaction solution was filtered. To the filtrate, 200 ml 
of water was added dropwise at a low speed. Crystals precipitated was 
filtered off, and dried. Thus, 292 g of Compound (xi) was obtained. 
(3) Synthesis of Compound (27) 
A mixture containing 500 g of reduced iron, 30 g of ammonium chloride, 30 
ml of acetic acid, 350 ml of water and 2.5 liters of isopropyl alcohol was 
allowed to undergo reduction for 10 minutes. To this reaction mixture, 292 
g of Compound (xi) was added slowly under refluxing. After 30 minutes, the 
reaction solution was filtered, and the filtrate was concentrated. The 
concentrate was dissolved in 1 liter of tetrahydrofuran and thereto, 78.5 
g of benzenesulfonyl chloride was added dropwise at room temperature. 
Thereto, 35.1 g of pyridine was further added dropwise. Thereafter, the 
stirring was continued for 12 hours. The resulting solution was extracted 
with ethyl acetate, and the organic phase was washed with water. Further, 
the organic phase was dried over anhydrous sodium sulfate. Then, the 
solvent was distilled away, and the resulting concentrate was 
recrystallized from an acetonitrile-ethyl acetate mixture. Thus, 273.2 g 
of Compound (27) was obtained. (Melting Point 167.0.degree. C.) 
SYNTHESIS EXAMPLE 5 
Synthesis of Compound (28) 
Compound (28) was synthesized in the same manner as in Synthesis Example 4 
except that methanesulfonyl chloride was employed in place of 
benzenesulfonyl chloride in the step (3) of Synthesis Example 4. (Melting 
Point 146.0.degree. C.) 
SYNTHESIS EXAMPLE 6 
Synthesis of Compound (51) 
Compound (51) was synthesized taking the following route. 
##STR9## 
(1) Synthesis of Compound (xiv) 
30 g of Compound (xii), 10.4 g of Compound (xiii) and 6 g of triethylamine 
were added to 200 ml of acetonitrile, and refluxed for 5 hours under 
heating. After cooling to room temperature, 1 liter of ethyl acetate was 
added to the reaction mixture, and washed with water. The resulting 
solution was neutralized with dilute hydrochloric acid, and washed with 
water repeatedly. After the separation of the oily phase, it was 
concentrated, and the residue was recrystallized using a mixed solvent 
composed of ethyl acetate and hexane. Thus, 19.3 g of Compound (xiv) was 
obtained. 
(2) Synthesis of Compound (xv) 
19.3 g of Compound (xiv) was added to 200 ml of a 10% hydrous ethanol 
containing 8 g of potassium hydroxide, and stirred at room temperature for 
5 hours. Thereto, 1 liter of ethyl acetate was added, washed with water, 
and neutralized with acetic acid. Therefrom, the oily phase was separated 
after the washing with water, and concentrated. The residue was 
crystallized using a mixed solvent composed of ethyl acetate and hexane. 
Thus, 12.6 g of Compound (xv) was obtained. 
(3) Synthesis of Compound (51) 
12.6 g of Compound (xv), 6 g of pyridine and 3.5 g of benzenesulfonyl 
chloride were added to 100 ml of chloroform, and refluxed under heating. 
After 3-hour refluxing, the reaction mixture was cooled, and washed 
successively with dilute hydrochloric acid and water. After the separation 
of the oily phase, the solvent was distilled away, and the residue was 
crystallized using a mixed solvent composed of ethyl acetate and hexane. 
Thus, 10.3 g of the desired coupler was obtained. 
SYNTHESIS EXAMPLE 7 
Synthesis of Compound (52) 
Coupler (52) was synthesized in the same manner as in Synthesis Example 6 
except that 6-hydroxy-2-tert-butylbenzoxazole was employed in place of 
Compound (xiii) in the step (1) of Synthesis Example 6. 
SYNTHESIS EXAMPLE 8 
Synthesis of Compound (53) 
Compound (53) was synthesized taking the following route. 
##STR10## 
(1) Synthesis of Compound (xviii) 
41 g of Compound (xvi) and 22 g of sodium methoxide were added to 200 ml of 
N,N-dimethylformamide and thereto, 51.2 g of Compound (xvii) was further 
added to room temperature. The resulting mixture was heated up to 
50.degree. C., and the reaction was continued for 8 hours. Thereafter, the 
reaction product was post-treated in a conventional manner. Thus, 48 g of 
Compound (xviii) was obtained. 
(2) Synthesis of Compound (xix) 
The dehydrating condensation reaction was achieved using 48 g of Compound 
(xviii), 34.7 g of 2-tetradecyloxyaniline and 23.4 g of 
N,N'-dicyclohexylcarbodiimide to yield 50.2 l g of Compound (xix). 
(3) Synthesis of compound (xx) 
50.2 g of Compound (xix) was hydrolized in 400 ml of methanol using 20 g of 
potassium hydroxide to yield 42.3 g of Compound (xx). 
(4) Synthesis of Compound (53) 
42.3 g of Compound (xx), 12.8 g of benzenesulfonyl chloride and 11.5 g of 
pyridine were refluxed in chloroform under heating to yield 28.3 g of 
Compound (53). 
The couplers of the present invention and other couplers usable in 
combination therewith, which are described hereinafter, can be introduced 
into a photosensitive material using various kinds of known dispersion 
method. Typical examples of such methods include a solid dispersion 
method, an alkali dispersion method, a latex dispersion method, an 
oil-in-water dispersion method, and so on. Of these methods, a latex 
dispersion method is used to advantage, and an oil-in-water dispersion 
method is more advantageous. In an oil-in-water dispersion method, 
substances to be dispersed are firstly dissolved in a single solvent, 
i.e., either a high boiling point solvent having a boiling point of 
175.degree. C. or above or a so-called auxiliary solvent having a low 
boiling point, or in a mixture of both solvents, and then finely dispersed 
into water on an aqueous medium like an aqueous solution of gelatin in the 
presence of a surface active agent. Specific examples of high boiling 
point solvents are described in U.S. Pat. No. 2,322,027, and so on. The 
dispersion may be accompanied by phase inversion and the auxiliary solvent 
contained in the dispersion may optionally be removed or reduced by 
distillation, a noodle washing method, an ultrafiltration method, and so 
on before the coating step. 
Specific examples of high boiling point solvents which can be used include 
phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, 
di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric or 
phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 
2-etylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl 
phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl 
phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters 
(e.g., 2-ethylhexylbenzoate, dodecylbenzoate, 
2-ethylhexyl-p-hydroxybenzoate, etc.), amides (e.g., diethyldodecaneamide, 
N-tetradecylpyrrolidone, etc.), alcohols or phenols (e.g., isostearyl 
alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carbonic acid esters 
(e.g., dioctyl azalate, glycerol tributyrate, isostearyl lactate, 
trioctylcitrate, etc.), aniline derivatives (e.g., 
N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (e.g., 
paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and so on. 
Auxiliary solvents which can be used are those having a boiling point 
ranging from about 30.degree. C. to about 160.degree. C., and typical 
examples thereof include ethyl acetate, butyl acetate, ethyl propionate, 
methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethyl 
formamide, and so on. 
Steps and effects of a latex dispersion method, and specific examples of 
latexes usable as impregnant in the dispersion method are described in 
U.S. Pat. No. 4,199,365, German Patent Applications (OLS) Nos. 2,541,274 
and 2,541,230, and so on. 
Various kinds of color couplers, in addition to the couplers of the present 
invention, can be used in the practice of the present invention. The term 
color couplers used herein refers to the compounds capable of producing 
dyes by reacting with oxidation products of aromatic primary amine 
developing agents. Typical examples of useful color couplers include 
naphthol or phenol compounds, pyrazolone or pyrazoloazole compound, and 
open-chain or heterocyclic ketomethylene compounds. Specific examples of 
cyan, magenta and yellow couplers which can be used in the present 
invention are described in patent specifications cited in Research 
Disclosure (hereafter "RD"), RD No. 17643, VII-D (December, 1978), and RD 
No. 18717 (November, 1979). 
In using color couplers in a condition that they are incorporated in a 
photosensitive material, it is desired that they should be nondiffusible 
by containing a ballast group or having a polymeric structure. 
Two-equivalent couplers having an eliminable group at the coupling active 
site in place of a hydrogen atom are preferable to four-equivalent 
couplers having a hydrogen atom at the coupling active site. In addition, 
couplers of the kind which can produce dyes having moderate diffusibility 
through color development, colorless couplers, couplers capable of 
releasing a development inhibitor upon development (so-called DIR 
couplers), or couplers capable of releasing a development accelerator can 
be employed. 
Typical representative yellow couplers which can be used in the present 
invention are oil protected acylacetoamide couplers. Specific examples 
thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057 and 
3,265,506, and so on. In the present invention, it is preferable to use 
two-equivalent yellow couplers. Typical examples thereof include yellow 
couplers of oxygen atom splitting-off type described in U.S. Pat. Nos. 
3,408,194, 3,447,928, 3,933,501 and 4,022,620, and so on; and yellow 
couplers of nitrogen atom splitting-off type described in Japanese Patent 
Publication No. 10739/83, U.S. Pat. Nos. 4,401,752 and 4,326,024, RD No. 
18053 (April, 1979), British Pat. No. 1,425,020, German Patent 
Applications (OLS) Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812, and 
so on. .alpha.-Pivaloylacetoanilide couplers can produce dyes excellent in 
fastness, especially in light fastness, upon color development. On the 
other hand, .alpha.-benzoylacetoanilide couplers can provide high color 
density of the developed image. 
Magenta couplers which can be used in the present invention are oil 
protected indazolone or cyanoacetyl couplers, preferably pyrazoloazole 
couplers such as those of 5-pyrazolone type, pyrazolotriazole type, and 
the like. Of 5-pyrazolone couplers, those which are substituted by an 
arylamino or acylamino group at the 3-position are more desirable from the 
viewpoints of hue and color density of the developed image, and the 
representatives thereof are described in U.S. Pat. Nos. 2,311,082, 
2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015, and 
so on. Further, two-equivalent 5-pyrazolone couplers are preferred because 
they can bring about high color density of the developed image and high 
photographic speed even when the silver coverage is reduced. In 
particular, those containing an eliminable group of the nitrogen atom 
splitting-off type described in U.S. Pat. No. 4,310,619 and those 
containing as an eliminable group an arylthio group described in U.S. Pat. 
No. 4,351,897 can be used to advantage. Also, the ballast groups described 
in European Pat. No. 73,636 have a developed color density-increasing 
effect on the 5-pyrazolone couplers. Examples of pyrazoloazole couplers 
include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,897, 
preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 
3,725,067, pyrazolotetrazoles described in RD No. 24220 (June, 1984), and 
pyrazolopyrazoles described in RD No. 24230 (June, 1984). From the 
viewpoints that the developed dyes have little side-absorption in the 
yellow region and great fastness to light, imidazo[1,2-b]pyrazoles 
described in European Pat. No. 119,741 are preferred, and 
pyrazolo[1,5-b][1,2,4]triazoles described in European Pat. No. 119,860 are 
particularly preferred. 
Cyan couplers which can be used in the present invention include those of 
the oil-protected naphthol and phenol types Representatives of naphthol 
couplers are those described in U.S. Pat. No. 2,474,293, and preferable 
two-equivalent naphthol couplers of the oxygen atom splitting-off type are 
described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200. 
Specific examples of phenol couplers are described in U.S. Pat. Nos. 
2,369,929, 2,801,171, 2,772,162, 2,895,826, and so on. Cyan couplers fast 
to moisture and heat are used to advantage in the present invention, and 
typical examples thereof include phenol type cyan couplers described in 
U.S. Pat. No. 3,772,002, 2,5-diacylamino substituted phenol type couplers 
described in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 
4,327,173, German Patent Application (OLS) No. 3,329,729, Japanese Patent 
Application No. 42671/83, and so on, and phenol couplers which have a 
phenylureido group at the 2-position and an acylamino group at the 
5-position, as described in U.S. Pat. Nos. 3,446,622, 4,333,999, 
4,451,559, and 4,427,767, and so on. 
The couplers of the present invention and couplers as described above may 
be incorporated in the same layer as a combination of two or more thereof 
for the purpose of satisfying characteristics required of the 
photosensitive material. Of course, the same coupler may be added to two 
or more different layers. 
In order to correct unnecessary absorption which developed dyes of magenta 
and cyan couplers show in shorter wave length regions, combined use with 
colored couplers is desirable in color photosensitive materials for 
photographic use. Typical examples of such couplers include yellow-colored 
magenta couplers described in U.S. Pat. No. 4,163,670, Japanese Patent 
Publication No. 39413/82, etc.; magenta-colored cyan couplers described in 
U.S. Pat. Nos. 4,004,929 and 4,138,258, British Pat. No. 1,146,368, etc.; 
and so on. 
These color couplers may form a polymer including a dimer. Typical examples 
of polymeric couplers are described in U.S. Pat. Nos. 3,451,820 and 
4,080,211. Specific examples of polymeric magenta couplers are described 
in British Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282. 
The combined use with couplers of the kind which can produce diffusible 
dyes upon color development can effect an improvement in granularity of 
developed images. Specific examples of magenta couplers of the 
above-described type are described in U.S. Pat. No. 4,366,237 and British 
Pat. No. 2,125,570, and those of yellow, magenta and cyan couplers of the 
above-described type are described in European Pat. No. 96,873 and German 
Patent Application (OLS) No. 3,324,533. 
Dye forming couplers are used in an amount of from 0.002 to 0.5 mol per mol 
of light-sensitive silver halide present in the layer in which they are to 
be incorporated. In typical color photosensitive materials for 
photographic use, yellow, magenta, and cyan couplers are used in amounts 
of from 0.01 to 0.5 mol, from 0.003 to 0.25 mol and from 0.002 to 0.12 
mol, respectively, per mol of light-sensitive silver halide. On the other 
hand, in many of color photosensitive materials for printing use, such as 
color paper, etc., each of yellow, magenta and cyan couplers is used in an 
amount of from 0.1 to 0.5 mol per mol of light-sensitive silver halide. Of 
course, it is possible to design photosensitive materials beyond the 
above-described ranges. 
Gelatin is employed to advantage as a binder or a protective colloid to 
constitute emulsion layers and interlayers of the photosensitive material 
of the present invention. Hydrophilic colloids other than gelatin can also 
be used independently or in combination with gelatin. 
Silver halides usable in photographic emulsion layers of the photosensitive 
material of the present invention include silver bromide, silver 
iodobromide, silver iodochlorobromide, silver chlorobromide and silver 
chloride. Preferred silver halides are silver iodobromides containing 15 
mol% or less of silver iodide. Particularly preferred silver halides are 
silver iodobromides containing from 2 to 12 mol% of silver iodide. 
The silver halide grains in the photographic emulsions may have a regular 
crystal form, such as that of a cube, an octahedron, a tetradecahedron, 
and so on; an irregular crystal form, such as that of a sphere, and so on; 
or a composite form thereof. In addition, tabular grains having a 
thickness of 0.5 .mu.m or less, a diameter of at least 0.6 .mu.m, and a 
mean aspect ratio of 5 or more may be contained in a photographic emulsion 
in a fraction of 50 mol% or more, based on the total projected area of all 
grains present therein. 
A crystal form of the silver halide grains may be uniform throughout, or 
the interior and the surface of the silver halide grains may differ in 
crystal form. The silver halide grains may have a layer structure, or 
silver halide grains having different halide compositions may be fused 
together by an epitaxial junction. A mixture of various crystal forms of 
silver halide grains may also be present in a photographic emulsion. 
In addition, either silver halide grains of the kind which form latent 
images predominantly at the surface of the grains, or grains of the kind 
which mainly form latent images inside the grains may be used. 
Either fine silver halide grains having diameters of 0.1 micron or less, 
based on projection area, or coarse ones having diameters up to 3 microns, 
based on projection area, may be employed, and either a monodisperse 
emulsion having a narrow size distribution or a polydisperse emulsion 
having a broad size distribution may be used. 
The photographic emulsions employed in the present invention can be 
prepared using various methods, as described, for example, in P. 
Glafkides, Chimie et Phisique Photographique, Paul Montel, Paris (1967), 
G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London 
(1966), V. L. Zelikmann et al, Making and Coating Photographic Emulsion, 
The Focal Press, London (1964), and so on. More specifically, the acid 
process, the neutral process, the ammonia process and so on can be 
employed, and suitable methods for reacting a water-soluble silver salt 
with a water-soluble halide include a single jet method, a double jet 
method and a combination thereof. 
A method in which silver halide grains are produced in the presence of 
excess silver ion (the so-called reversal mixing method) can also be 
employed. On the other hand, the so-called controlled double jet method, 
in which the pAg is maintained constant, can also be employed in the 
present invention. According to this method, silver halide emulsions 
having a regular crystal form and an almost uniform grain size can be 
obtained. 
Two or more of silver halide emulsions prepared separately may be used as a 
mixture thereof. 
In a process for forming silver halide grains or allowing the formed grains 
to ripen physically, cadmium salts, zinc salts, lead salts, thallium 
salts, iridium salts or complexes, rhodium salts or complexes, iron salts 
or complexes, and/or so on may be present. 
The silver halide emulsions are usually chemically sensitized. Chemical 
sensitization can be carried out using processes described in H. Frieser, 
Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden, pp. 
675-734, Akademische Verlagsgesellschaft (1968), and so on. 
More specifically, sulfur sensitization using compounds contaning sulfur 
capable of reacting with silver ion or active gelatin (e.g., thiosulfates, 
thioureas, mercapto compounds, rhodanines and so on), reduction 
sensitization using reducing materials (e.g., stannous salts, amines, 
hydrazine derivativesm formamidine sulfinic acid, silane compounds and so 
on), sensitization with noble metal compounds (e.g., gold metal complexes, 
and Group VIII metal complexes such as those of platinum, iridium, 
palladium, etc.), and so on can be employed individually or as a 
combination thereof. 
The photographic emulsions of the present invention can contain a wide 
variety of compounds for purposes of preventing fog or stabilizing 
photographic functions during production, storage, or photographci 
processing, with specific examples including azoles such as 
benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, 
chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, 
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, 
aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles 
(especially 1-phenyl-5-mercaptotetrazole), and so on; mercaptopyrimidines; 
mercaptotriazines; thioketo compounds like oxazolidinethiones; azaindenes 
such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted 
(1,3,3a,7) -tetraazaindenes), pentaazaindenes, and so on; and compounds 
which have been known as antifoggants or stabilizers, such as 
benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid 
amide, and so on. 
The photographic emulsion layers of the photographic material of the 
present invention may contain, for example, polyalkylene oxides and 
derivatives thereof, such as ethers, esters and amines thereof, thioether 
compounds. thiomorpholines, quaternary ammonium salt compounds, urethane 
derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and 
so on in order to increase the photographic speed and the contrast, or in 
order to accelerate the developing rate. 
The photographic emulsion layers and other hydrophilic colloid layers to 
constitute the photographic material of the present invention can contain 
a dispersion of water insoluble or slightly soluble synthetic polymers for 
the purpose of improvements in dimensional stability and so on. 
The photographic emulsions to be used in the present invention may be 
spectrally sensitized using methine dyes or other dyes. Specific spectral 
sensitizing dyes which can be employed include cyanine dyes, merocyanine 
dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine 
dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Especially useful 
dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any 
nuclei usually present in cyanine dyes can be the basic heterocyclic 
nuclei of these dyes. 
These sensitizing dyes may be employed individually or in combination. 
Combinations of sensitizing dyes are often employed for the purpose of 
supersensitization. 
Substances which can exhibit a supersensitizing effect in a combination 
with a certain sensitizing dyes although they themselves do not spectrally 
sensitize silver halide emulsions or do not absorb light in the visible 
region may be incorporated into the silver halide emulsions. For example, 
aminostyryl compounds substituted with nitrogen-containing heterocyclic 
groups (for instance, as described in U.S. Pat. Nos. 2,933,390 and 
3,653,721), aromatic organic acid-formaldehyde condensates (for instance, 
as described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene 
compounds and so on can be employed. 
The present invention can also be applied to a multilayer multicolor 
photographic material having at least two different color sensitivities on 
a support. A multilayer color photographic material has, in general, at 
least one red-sensitive emulsion layer, at least one green-sensitive layer 
and at least one blue-sensitive layer on a support. The order of these 
layers can be varied as desired. Usually cyan-, magenta- and 
yellow-forming couplers are incorporated in red-, green- and 
blue-sensitive emulsion layers, respectively. However, different 
combinations can be employed, if desired. 
The photographic emulsion layers or other hydrophilic colloid layers which 
constitute the photographic material of the present invention may contain 
inorganic or organic hardeners. Examples of hardeners which can be used 
include active vinyl compounds (e.g., 
1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, 
etc.), active halogen containing compounds (e.g., 
2,4-dichloro-6-hydroxy-s-triazine, etc.), halogeno carboxyaldehydes such 
as mucochloric acid, mucophenoxychloric acid, etc.), and so on. These 
hardeners may be used alone or as a combination of two or more thereof. 
The photographic material prepared in accordance with the present invention 
may contain as a color fog inhibitor a hydroquinone derivative, an 
aminophenol derivative, a gallic acid derivative, an ascorbic acid 
derivative and so on. 
Hydrophilic colloid layers of the photographic material prepared in 
accordance with the present invention may contain an ultraviolet absorbing 
agent. For examples, aryl-substituted benzotriazole compounds (e.g., those 
described in U.S. Pat. Nos. 3,533,794 and 4,236,013, Japanese Patent 
Publication No. 6540/76, European Pat. No. 57,160, etc.), butadiene 
compounds (e.g., those described in U.S. Pat. Nos. 4,045,229 and 
4,195,999), cinnamate compounds (e.g., those described in U.S. Pat. Nos. 
3,705,805 and 3,707,375), benzophenones (e.g., those described in U.S. 
Pat. No. 3,215,530 and British Pat. No. 1,321,355) and polymers containing 
ultraviolet absorbing residues (e.g., those described in U.S. Pat. Nos. 
3,761,272 and 4,431,726) may be used. Also, ultraviolet absorbing 
brightening agents described in U.S. Pat. Nos. 3,499,762 and 3,700,455 may 
be employed. Typical examples of ultraviolet absorbing agents are 
described in RD No. 24239 (June, 1984) and so on. 
The photographic material prepared in accordance with the present invention 
may contain water-soluble dyes as filter dyes, anti-halation dyes or dyes 
for various other purposes in its hydrophilic colloid layers. Examples of 
dyes useful for the above-described purposes include oxonol dyes, 
hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo 
dyes. Of these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes 
are used to greater advantage. 
In the present invention, known discoloration inhibitors can be used. Color 
image stabilizers which can be used in the present invention can be used 
alone or in combinations of two or more thereof. Specific examples of 
known discoloration inhibitors include hydroquinone derivatives, gallic 
acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and 
bisphenols. 
Color photographic emulsion layers which comprise the dye image forming 
layers constituted in accordance with the present invention are coated on 
a conventionally used flexible support, such as plastic films, paper, 
cloth or the like. Suitable examples of flexible supports include films 
made of semi-synthetic or synthetic polymers such as cellulose acetate, 
cellulose acetate butyrate, polystyrene, polyethylene terephthalate, 
polycarbonate and so on, paper coated or laminated with a baryta layer or 
an .alpha.-olefin polymer (e.g., polyethylene, polypropylene, etc.), and 
so on. Such a support may be colored with dyes or pigments. Also, it may 
be rendered black for the purpose of screening light. 
When a support is used for a reflection type photographic material, it is 
desirable to incorporate white pigments into the support or a laminated 
layer. Suitable examples of white pigments include titanium dioxide, 
barium sulfate, zinc oxide, zinc sulfate, calcium carbonate, antimony 
trioxide, silica white, alumina white, titanium phosphate, and so on. Of 
these pigments, titanium dioxide, barium sulfate, and zinc oxide are 
particularly useful. 
Surfaces of these supports are generally submitted to a subbing treatment 
in order to increase adhesiveness to photographic emulsion layers and so 
on. After or before the subbing treatment, the support surface may be 
subjected to corona discharge, irradiation with ultraviolet light, flame 
treatment and so on. 
When these supports are used in reflection type photographic materials, a 
hydrophilic colloid layer containing a white pigment in high density may 
be provided between the support and an emulsion layer. Thereby, whiteness 
and sharpness of the photographic image can be enhanced. 
In many of reflection type photographic materials containing magenta 
couplers of the present invention, a polymer laminated paper sheet is used 
as support. However, it is particularly preferred to employ a synthetic 
resin film into which a white pigment is kneaded in advance, because 
photographic images which are not only improved in smoothness, glossiness 
and sharpness but also excellent in saturation and depiction capability in 
dark areas can be obtained. In this case, a suitable raw material for the 
synthetic resin film is polyethylene terephthalate or cellulose acetate, 
and a white pigment which is used to particular advantage in kneading with 
such a raw material as described above is barium sulfate or titanium 
oxide. 
The color photographic materials produced in accordance with the present 
invention can contain various photographic additives known in this art in 
addition to the above-described agents. For example, stabilizers, 
antifoggants, surface active agents, antistatic agents, developing agents 
and so on can be added as occasion calls. Specific examples of these 
additives are described in RD No. 17643 (December 1978). 
Moreover, a fine-grained silver halide emulsion which has substantially no 
sensitivity to light (for example, silver chloride, silver bromide or 
silver chlorobromide emulsion having a mean grain size of 0.20 micron or 
less) may optionally be added to light-sensitive silver halide emulsion 
layers or other hydrophilic colloid layers. 
A color developing solution which can be used in the present invention is 
an alkaline aqueous solution containing preferably an aromatic primary 
amine color developing agents as a main component. Typical examples of 
color developing agents of the above-described type include 
4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfoamidoethylaniline, 
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline, and the like. 
Besides color developing agents as described above, the color developing 
solution can contain a pH buffering agent such as sulfites, carbonates, 
borates and phosphates of alkali metals, a development inhibitor or an 
antifoggant such as bromides, iodides and organic antifoggants, and so on. 
Optionally, a water softener, a preservative such as a hydroxyamine, etc., 
an organic solvent such as benzyl alcohol, diethylene glycol, etc., a 
development accelerator such as polyethylene glycols, quaternary ammonium 
salts, amines, etc., dye-forming couplers, competing couplers, a fogging 
agent such as sodium borohydride, etc., an auxiliary developer such as 
1-phenyl-3-pyrazolidone, etc., a viscosity imparting agent, chelating 
agents of polycarboxylic acid type described in U.S. Pat. No. 4,083,723, 
an antioxidant described in German Patent Application (OLS) No. 2,622,950, 
and so on may be contained in the color developing solution. 
The photographic emulsion layers which have been color 
development-processed are generally subjected to a bleach processing. The 
bleach processing may be carried out either simultaneously with or 
separately from a fix processing. Suitable examples of bleaching agents 
which can be used include compounds of polyvalent metals such as 
iron(III), cobalt(IV), chromium(VI), copper(II), etc., peroxy acids, 
quinones, nitroso compounds, and so on. 
More specifically, ferricyanides, dichromates, organic complex salts of 
Fe(III) or Co(III) such as complex salts of aminopolycarboxylic acids, 
e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 
1,3-diamino-2-propanoltetraacetic acid, etc., or those of organic acids, 
e.g., citric acid, tartaric acid, malic acid, etc., persulfates, 
permanganates, nitrosophenol, and so on, can be employed as bleaching 
agent. Of these compounds, potassium ferricyanide, sodium 
ethylenediaminetetraacetatoferrate(III), and ammonium 
ethylenediaminetetraacetatoferrate(III) are especially useful. In 
particular, (ethylenediaminetetraacetato)iron(III) complexes are used to 
advantage in both an independent bleaching bath and a combined bleaching 
and fixing bath. 
After the color development or the bleach-fix processing, the 
photosensitive material may be washed with water. The color development is 
generally carried out in a temperature range of from about 18.degree. C. 
to about 55.degree. C., preferably at 30.degree. C. or higher, and 
particularly preferably at 35.degree. C. or higher. The time required for 
color development is generally in the range of from about 3.5 minutes to 
about 1.sup.- minute, and a short developing time is preferable to long 
one within this range. In the continuous development processing, it is 
desired that a replenisher should be supplemented. A suitable amount of 
the replenisher ranges from 330 ml to 160 ml, preferably 100 ml or less, 
per square meter of the processed area. A suitable content of benzyl 
alcohol in the developing solution is generally 20 ml/l or less, and 
preferably 10 ml/l or less. The bleach-fix processing can be effected at a 
temperature ranging from about 18.degree. C. to about 50.degree. C., 
preferably not lower than 30.degree. C. When the processing temperature is 
set at 35.degree. C. or above, the processing time can be reduced to 1 
minute or less and that, the amount of the replenisher can be diminished. 
The time required for the washing step after the color development or the 
bleach-fix processing is generally 3 minutes or less, and it can also be 
reduced to 1 minute or less if a stabilizing bath is used in combination 
therewith. 
The developed dyes are deteriorated not only by exposure to light, heat or 
moisture but also by the growth of mold upon storage to undergo 
discoloration. In particular, cyan dye images are subjected to greate 
deterioration due to mold. Therefore, it is desired that an antimold agent 
should be used. Suitable examples of antimold agents include 
2-thiazolylbenzimidazoles, as described in Japanese patent Application 
(OPI) No. 157244/82. The antimold agent may be incorporated in the 
photographic material or added externally in the process of development, 
that is, it can be incorporated into the photographic material in an 
arbitrary process, provided that it is present in the processed material. 
The present invention can be applied to silver halide color photosensitive 
materials for general use, for example, color negative films, color 
papers, color positive films, color reversal slide films, color reversal 
motion picture films, color reversal TV films and so on. In particular, 
the present invention can have remarkable effects on improvements in 
sharpness and granularity when utilized in color negative films in which 
high photographic speed and high image quality are required, and 
particularly in color reversal films. 
The present invention can be applied to both the black color-forming 
coupler process and the three-color process. Detailed descriptions of the 
black color-forming coupler process are described in U.S. Pat. Nos. 
3,622,629, 3,734,735, and 4,126,461, and Japanese Patent Applications 
(OPI) Nos. 105247/80, 42725/77, and 105248/80. On the other hand, the 
three-color process is described in detail, for example, in RD No. 1712 
(July, 1978). 
EXAMPLE 1 
On a cellulose triacetate film support having thereon a subbing layer, were 
coated the emulsion layers and auxiliary layers described below in the 
order listed to prepare Sample (1). 
(1) Low-speed, Red-sensitive Emulsion Layer 
100 g of 
2-(heptafluorobutylamido)-5-[2'-(2",4"-di-t-amylphenoxy)butylamido]phenol 
(Coupler(1)), which functions as cyan coupler, was dissolved in a mixed 
solvent composed of 100 ml of tricresyl phosphate and 100 ml of ethyl 
acetate, and mixed with 1 kg of a 10% aqueous solution of gelatin and 10 g 
of sodium dodecylbenzenesulfonate (surface active agent) under high speed 
stirring to prepare an emulsion. To a 500 g portion of the emulsion were 
added 1 kg of a red-sensitive, low speed, silver iodobromide emulsion 
(having a mean grain size of 0.3 micron and a silver iodide content of 3 
mol%, and containing 70 g of silver and 60 g of gelatin), gelatin, water, 
a stabilizer, a coating aid and so on. The resulting emulsion was coated 
in a layer having a dry thickness of 2 microns (silver coverage: 0.6 
g/m.sup.2). 
(2) Medium-Speed, Red-sensitive Emulsion Layer 
A 1 kg portion of the same cyan coupler emulsion as used in the first layer 
was admixed with 1 kg of a red-sensitive, medium-speed, silver iodobromide 
emulsion (having a mean grain size of 0.5 micron and a silver iodide 
content of 3 mol%, and containing 70 g of silver and 60 g of gelatin), 
gelatin, water, a stabilizer, a coating aid and so on. The resulting 
emulsion was coated so as to have a dry thickness of 1 micron (silver 
coverage: 0.4 g/m.sup.2). 
(3) High-speed, Red-sensitive Emulsion Layer 
A 1 kg portion of the same coupler emulsion as used in the first layer was 
admixed with 1 kg of a red-sensitive, high speed, silver iodobromide 
emulsion (having a mean grain size of 0.6 micron and a silver iodide 
content of 3 mol%, and containing 70 g of silver and 60 g of gelatin), 
gelatin, water, a stabilizer, a coating aid and so on. The resulting 
emulsion was coated in a layer having a dry thickness of 1 micron (silver 
coverage: 0.4 g/m.sup.2). 
(4) Interlayer 
An emulsion prepared by dissolving 200 g of 2,5-di-secoctylhydroquinone in 
200 ml of ethyl acetate, and mixing the solution with 1 kg of a 10% 
aqueous solution of gelatin and 20 g of sodium dodecylbenzenesulfonate 
under high speed stirring was mixed with gelatin, water, a coating aid and 
so on. The resulting emulsion was coated in a layer having a dry thickness 
of 1 micron. 
(5) Low-speed, Green-sensitive Emulsion Layer 
An emulsion was prepared in the same manner as the emulsion of the first 
layer except that the magenta coupler, 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert-amylphenoxyacetoamido)benzamid 
o]-5-pyrazolone was employed in place of the cyan coupler. A 500 g portion 
of this emulsion was admixed with 1 kg of a green-sensitive, low-speed, 
silver iodobromide emulsion (having a mean grain size of 0.3 micron and a 
silver iodide content of 3 mol%, and containing 70 g of silver and 60 g of 
gelatin), gelatin, water, a stabilizer and a coating aid. The resulting 
emulsion was coated in a layer having a dry thickness of 2 microns (silver 
coverage: 0.7 g/m.sup.2). 
(6) Medium-speed, Green-sensitive Emulsion layer 
A 1 kg portion of the same magenta coupler emulsion as used in the fifth 
layer was admixed with 1 kg of a green-sensitive, medium-speed, silver 
iodobromide emulsion (having a mean grain size of 0.5 micron and a silver 
iodide content of 3 mol%, and containing 70 g of silver and 60 g of 
gelatin), gelatin, water, a stabilizer, a coating aid and so on. The 
resulting emulsion was coated in a layer having a dry thickness of 1 
micron (silver coverage: 0.4 g/m.sup.2). 
(7) High-speed, Green-sensitive Emulsion Layer 
A 1 kg portion of the same magenta coupler emulsion as used in the fifth 
layer was admixed with 1 kg of a green-sensitive, high-speed, silver 
iodobromide emulsion (having a mean grain size of 0.7 micron and a silver 
iodide content of 3 mole%, and containing 70 g of silver and 60 g of 
gelatin), gelatin, water, a stabilizer, a coating aid and so on. The 
resulting emulsion was coated in a layer having a dry thickness of 1 
micron (silver coverage: 0.4 g/m.sup.2). 
(8) Interlayer 
A 1 kg portion of the same emulsion as used in the fourth layer, gelatin, 
water and a coating aid were mixed, and coated in a layer having a dry 
thickness of 0.5 micron. 
(9) Yellow Filter Layer 
Yellow colloidal silver and gelatin were mixed, and coated in a layer 
having a dry thickness of 1 micron. 
(10) Low-speed, Blue-sensitive Emulsion layer 
An emulsion was prepared in the same manner as the emulsion used in the 
first layer except that the yellow coupler, 
.alpha.-(pivaloyl)-.alpha.-(1-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-do 
decyloxycarbonylacetoanilide, was employed in place of the cyan coupler, 
and both the amount of tricresyl phosphate and that of ethyl acetate were 
changed to 120 ml. A 1 kg portion of this emulsion was admixed with 1 kg 
of a blue-sensitive, low-speed, silver iodobromide emulsion (having a mean 
grain size of 0.5 micron and a silver iodide content of 3 mol%, and 
containing 70 g of silver and 60 g of gelatin), gelatin, water, a 
stabilizer and a coating aid. The resulting emulsion was coated in a layer 
having a dry thickness of 2 microns (silver coverage: 0.6 g/m.sup.2). 
(11) Medium-speed, Blue-sensitive Emulsion Layer 
A 1 kg portion of the same yellow coupler emulsion as used in the tenth 
layer was admixed with 1 kg of a medium-speed, blue-sensitive, silver 
iodobromide emulsion (having a mean grain size of 0.6 micron and a silver 
iodide content of 3 mol%, and containing 70 g of silver and 60 g of 
gelatin), gelatin, water, a stabilizer, a coating aid and so on. The 
resulting emulsion was coated in a layer having a dry thickness of 1 
micron (silver coverage: 0.4 g/m.sup.2). 
(12) High-speed, Blue-sensitive Emulsion Layer 
A 1 kg portion of the same yellow coupler emulsion as used in the tenth 
layer was admixed with 1 kg of a high-speed, blue-sensitive, silver 
iodobromide emulsion (having a mean grain size of 0.7 micron and a silver 
iodide content of 3 mol%, and containing 70 g of silver and 60 g of 
gelatin), gelatin, water, a stabilizer, a coating aid and so on. The 
resulting emulsion was coated in a layer having a dry thickness of 1 
micron (silver coverage: 0.4 g/m.sup.2). 
(13) Second Protective Layer 
UV absorbents, 15 g of 
5-chloro-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 30 g of 
2-(2-hydroxy-5-t-butylphenyl)-2H-abenzotriazole, 35 g of 
2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole and 100 g of 
dodecyl-5-(N,N-diethylamino)-2-benzenesulfonyl-2,4-pentadienoate, were 
dissolved in a mixed solvent composed of 200 m of tricresyl phosphate and 
200 ml of ethyl acetate, and mixed with 20 g of sodium 
dodecylbenzenesulfonate and 2 kg of a 10% aqueous solution of gelatin 
under high speed stirring to prepare an emulsion. A 1 kg portion of this 
emulsion was mixed with gelatin, water, a coating aid and so on, and 
coated in a layer having a dry thickness of 2 microns (total coverage of 
UV absorbents: 0.5 g/m.sup.2). 
(14) First Protective Layer 
A chemically unsensitized fine-grained silver iodobromide emulsion (having 
a mean grain size of 0.1 micron and a silver iodide content of 1 mol%, and 
containing 70 g of silver and 60 g of gelatin) was mixed with gelatin, 
water, a stabilizer, a coating aid and so on, and coated in a layer having 
a dry thickness of 1 micron (silver coverage: 0.3 g/m.sup.2). 
The thus obtained multilayer film was designated as Sample (1). 
Similarly, other cyan coupler emulsions were prepared exchanging one half 
the amount of the cyan coupler employed in the first to third layers for 
the compounds of the present invention or the comparison compounds (in 
equimolar amounts) listed in the following table, respectively. Samples 
(2) to (26) were prepared using these emulsions, respectively, in the same 
manner as employed in the preparation of Sample (1). 
TABLE 1 
______________________________________ 
Sam- 
ple Cyan Coupler in First to Third Layer 
Remark 
______________________________________ 
(1) Coupler (1) 100 g Comparison 
(2) Coupler (1) 50 g + 
Compound (1) 
62.5 g 
Invention 
(3) Coupler (1) 50 g + 
Compound (2) 
58.0 g 
(containing 
(4) Coupler (1) 50 g + 
Compound (3) 
62.2 g 
Compound 
(5) Coupler (1) 50 g + 
Compound (6) 
42.1 g 
represented 
(6) Coupler (1) 50 g + 
Compound (7) 
46.9 g 
by Formula 
(7) Coupler (1) 50 g + 
Compound (8) 
48.0 g 
(Ia)) 
(8) Coupler (1) 50 g + 
Compound (11) 
63.3 g 
(9) Coupler (1) 50 g + 
Compound (27) 
70.8 g 
Invention 
(10) Coupler (1) 50 g + 
Compound (28) 
60.9 g 
(containing 
(11) Coupler (1) 50 g + 
Compound (29) 
57.6 g 
Compound 
(12) Coupler (1) 50 g + 
Compound (30) 
56.7 g 
represented 
(13) Coupler (1) 50 g + 
Compound (31) 
63.4 g 
by Formula 
(14) Coupler (1) 50 g + 
Compound (32) 
65.4 g 
(Ib)) 
(15) Coupler (1) 50 g + 
Compound (33) 
82.3 g 
(16) Coupler (1) 50 g + 
Compound (53) 
63.0 g 
Invention 
(17) Coupler (1) 50 g + 
Compound (54) 
70.1 g 
(containing 
(18) Coupler (1) 50 g + 
Compound (55) 
56.5 g 
Compound 
(19) Coupler (1) 50 g + 
Compound (57) 
73.4 g 
represented 
(20) Coupler (1) 50 g + 
Compound (58) 
79.5 g 
by Formula 
(21) Coupler (1) 50 g + 
Compound (59) 
61.5 g 
(Ic)) 
(22) Coupler (1) 50 g + 
Compound (60) 
66.8 g 
(23) Coupler (1) 50 g + 
Comparison 65.5 g 
Compar- 
Compound (1) ison 
(24) Coupler (1) 50 g + 
Comparison 50.2 g 
Compar- 
Compound (2) ison 
(25) Coupler (1) 50 g + 
Comparison 57.7 g 
Compar- 
Compound (3) ison 
(26) Coupler (1) 50 g + 
Comparison 46.9 g 
Compar- 
Compound (4) ison 
______________________________________ 
##STR11## 
(Comparison compounds (2) and (4) are disclosed in Japanese Patent 
Application (OPI) No. 138636/82). 
Each of Samples (1) to (26) was exposed to light through a pattern for 
granularity measurement, and subjected to color reversal processing. The 
thus processed samples were examined for R.M.S. granularity through the 
density measurement using a microdensitometer, according to Photographic 
Science and Engineering, vol. 19, p. 235 (1975). Granularities at the 
image densities of 1.0 and 2.0, respectively, are shown in Table 2. 
Separately, each of Samples (1) to (26) was exposed to light through a 
pattern for MTF measurement, and submitted to the color reversal 
processing. The thus processed samples were measured with a 
microdensitometer, and MTF values of these samples were calculated. The 
"MTF value" is described in Theory of the Photographic Process, 4th 
edition, p. 604, Macmillan Publishing Co., Inc. (1977). Sharpness was 
represented by MTF value of 10 line/mm and 20 line/mm. 
TABLE 2 
______________________________________ 
Sam- R.M.S. Granularity* 
Sharpness MTF Re- 
ple Density 1.0 
Density 2.0 
10 line/mm 
20 line/mm 
mark 
______________________________________ 
(1) 23 31 0.79 0.58 Com- 
par- 
ison 
(2) 18 23 0.92 0.66 Inven- 
tion 
(3) 19 24 0.91 0.65 Inven- 
tion 
(4) 20 24 0.87 0.63 Inven- 
tion 
(5) 21 25 0.85 0.62 Inven- 
tion 
(6) 19 23 0.91 0.65 Inven- 
tion 
(7) 19 23 0.90 0.64 Inven- 
tion 
(8) 18 22 0.89 0.63 Inven- 
tion 
(9) 19 25 0.91 0.65 Inven- 
tion 
(10) 21 26 0.88 0.63 Inven- 
tion 
(11) 20 25 0.89 0.63 Inven- 
tion 
(12) 19 24 0.91 0.64 Inven- 
tion 
(13) 21 26 0.85 0.62 Inven- 
tion 
(14) 20 25 0.90 0.65 Inven- 
tion 
(15) 20 25 0.87 0.63 Inven- 
tion 
(16) 20 26 0.89 0.63 Inven- 
tion 
(17) 20 25 0.88 0.62 Inven- 
tion 
(18) 20 24 0.91 0.65 Inven- 
tion 
(19) 18 24 0.91 0.64 Inven- 
tion 
(20) 19 25 0.89 0.62 Inven- 
tion 
(21) 19 24 0.90 0.63 Inven- 
tion 
(22) 19 25 0.89 0.62 Inven- 
tion 
(23) 22 31 0.82 0.53 Com- 
par- 
ison 
(24) 23 30 0.79 0.57 Com- 
par- 
ison 
(25) 24 31 0.81 0.58 Com- 
par- 
ison 
(26) 22 29 0.83 0.60 Com- 
par- 
ison 
______________________________________ 
*Values obtained by multiplying the R.M.S. data by 1,000 
Samples (2) to (22) in which the compounds of the present invention were 
used were greatly improved in both granularity and sharpness. 
______________________________________ 
Photographic Processing: 
______________________________________ 
Time 
Step (min) Temperature 
______________________________________ 
First Development 
6 38.degree. C. (.+-.0.3) 
Washing 2 38.degree. C. (.+-.0.3) 
Reversal 2 38.degree. C. (.+-.0.3) 
Color Development 
6 38.degree. C. (.+-.0.3) 
Compensation 2 38.degree. C. (.+-.0.3) 
Bleaching 6 38.degree. C. (.+-.0.3) 
Fixing 4 38.degree. C. (.+-.0.3) 
Washing 4 38.degree. C. (.+-.0.3) 
Stabilizing 1 room temperature 
Drying 
______________________________________ 
First Development 
Water 700 ml 
Sodium Tetrapolyphosphate 2 g 
Sodium Sulfite 20 g 
Hydroquinone Monosulfonate 30 g 
Sodium Carbonate (monohydrate) 
30 g 
1-Phenyl-4-methyl-4-hydroxymethyl-3- 
2 g 
pyrazolidone 
Potassium Bromide 2.5 g 
Potassium Thiocyanate 1.2 g 
Potassium Iodide (0.1% solution) 
2 ml 
Water to make 1000 ml 
Reversal 
Water 700 ml 
Hexasodium Nitrilo-N,N,N--trimethylene- 
3 g 
phosphonate 
Stannous Chloride (dihydrate) 
1 g 
p-Aminophenol 0.1 g 
Sodium Hydroxide 8 g 
Glacial Acetic Acid 15 ml 
Water to make 1000 ml 
Color Development 
Water 700 ml 
Sodium Tetrapolyphosphate 2 g 
Sodium Sulfite 7 g 
Sodium Tertiary Phosphate (dihydrate) 
36 g 
Potassium Bromide 1 g 
Potassium Iodide (0.1% solution) 
90 ml 
Sodium Hydroxide 3 g 
Citrazinic Acid 1.5 g 
N--Ethyl-N--(.beta.-methanesulfonamidoethyl)-3- 
11 g 
methyl-4-aminoaniline Sulfate 
Ethylenediamine 3 g 
Water to make 1000 ml 
Compensation 
Water 700 ml 
Sodium Sulfite 12 g 
Sodium Ethylenediaminetetraacetate (dihydrate) 
8 g 
Thioglycerine 0.4 ml 
Glacial Acetic Acid 3 ml 
Water to make 1000 ml 
Bleaching 
Water 800 ml 
Sodium Ethylenediaminetetraacetate (dihydrate) 
2.0 g 
Ammonium Ethylenediaminetetraacetatoferrate(II) 
(dihydrate) 120.0 g 
Potassium Bromide 100.0 g 
Water to make 1000 ml 
Fixing 
Water 800 ml 
Ammonium Thiosulfate 80.0 g 
Sodium Sulfite 5.0 g 
Sodium Hydrogen Sulfite 5.0 g 
Water to make 1000 ml 
Stabilizing 
Water 800 ml 
Formaldehyde (37 wt % aq. soln.) 
5.0 ml 
Fuji Dri Wel (surface active agent soln.) 
5.0 ml 
Water to make 1000 ml 
______________________________________ 
EXAMPLE 2 
On a transparent cellulose triacetate film support, were coated the layers 
described below in the order listed to prepare a multilayer color 
photosensitive material (101). 
(1) Antihalation layer containing 0.15 g/m.sup.2 of black colloidal silver, 
0.08 g/m.sup.2 of Ultraviolet Absorbent U-1, 0.12 g/m.sup.2 of Ultraviolet 
Absorbent U-2, and gelatin. 
(2) Interlayer containing 0.18 g/m.sup.2 of 
2,5-di-t-pentadecylhydroquinone, 0.11 g/m.sup.2 of Coupler C-1, and 
gelatin. 
(3) First red-sensitive emulsion layer containing 1.2 g/m.sup.2 of a silver 
iodobromide emulsion (having a silver iodide content of 4 mol% and a mean 
grain size of 0.4 micron), 1.4.times.10.sup.-4 mol/mol silver of 
Sensitizing Dye I, 0.4.times.10.sup.-4 mol/mol silver of Sensitizing Dye 
II, 5.6.times.10.sup.-4 mol/mol silver of Sensitizing Dye III, 
4.0.times.10.sup.-4 mol/mol silver of Sensitizing Dye IV, 0.45 g/m.sup.2 
of Coupler C-2, 0.035 g/m.sup.2 of Coupler C-3, 0.025 g/m.sup.2 of Coupler 
C-4, and gelatin. 
(4) Second red-sensitive emulsion layer containing 1.0 g/m.sup.2 of a 
silver iodobromide emulsion (having a silver iodide content of 8 mol% and 
a mean grain size of 0.8 micron), 5.2.times.10.sup.-5 mol/mol silver of 
Sensitizing Dye I, 1.5.times.10.sup.-5 mol/mol silver of Sensitizing Dye 
II, 2.1.times.10.sup.-4 mol/mol silver of Sensitizing Dye III, 
1.5.times.10.sup.-5 mol/mol silver of Sensitizing Dye IV, 0.050 g/m.sup.2 
of Coupler C-2, 0.070 g/m.sup.2 of Coupler C-5, 0.035 g/m.sup.2 of Coupler 
C-3, and gelatin. 
(5) Interlayer containing 0.08 g/m.sup.2 of 
2,5-di-t-pentadecylhydroquinone, and gelatin. 
(6) First green-sensitive emulsion layer containing 0.80 g/m.sup.2 of 
silver iodobromide (having a silver iodide content of 4 mol% and a mean 
grain size of 0.4 micron), 4.0.times.10.sup.-4 mol/mol silver of 
Sensitizing Dye V, 3.0.times.10.sup.-5 mol/mol silver of Sensitizing Dye 
VI, 1.0.times.10.sup.-4 mol/mol silver of Sensitizing Dye VII, 0.45 
g/m.sup.2 of Coupler C-6, 0.13 g/m.sup.2 of Coupler C-7, 0.02 g/m.sup.2 of 
Coupler C-8, 0.04 g/m.sup.2 of Coupler C-4, and gelatin. 
(7) Second green-sensitive emulsion layer containing 0.85 g/m.sup.2 of 
silver iodobromide (having a silver iodide content of 8 mol% and a mean 
grain size of 0.8 micron), 2.7.times.10.sup.-4 mol/mol silver of 
Sensitizing Dye V, 1.8.times.10.sup.-5 mol/mol silver of Sensitizing Dye 
VI, 7.5.times.10.sup.-5 mol/mol silver of Sensitizing Dye VII, 0.095 
g/m.sup.2 of Coupler C-6, 0.015 g/m.sup.2 of Coupler C-7, and gelatin. 
(8) Yellow filter layer containing 0.08 g/m.sup.2 of yellow collidal 
silver, 0.090 g/m.sup.2 of 2,5-di-t-pentadecylhydroquinone, and gelatin. 
(9) First Blue-sensitive emulsion layer containing 0.37 g/m.sup.2 of a 
silver iodobromide emulsion (having a silver iodide content of 5 mol% and 
a mean grain size of 0.3 micron), 4.4.times.10.sup.-4 mol/mol silver of 
Sensitizing Dye VIII, 0.71 g/m.sup.2 of Coupler C-9, 0.07 g/m.sup.2 of 
Coupler C-4, and gelatin. 
(10) Second blue-sensitive emulsion layer containing 0.55 g/m.sup.2 of a 
silver iodobromide emulsion (having a silver iodide content of 7 mol% and 
a mean grain size of 0.9 micron), 3.0.times.10.sup.-4 mol/mol silver of 
Sensitizing Dye VIII, 0.23 g/m.sup.2 of Coupler C-9, and gelatin. 
(11) First protective layer containing 0.14 g/m.sup.2 of Ultraviolet 
Absorbent U-1, 0.22 g/m.sup.2 of Ultraviolet Absorbent U-2, and gelatin. 
(12) Second protective layer containing 0.25 g/.sup.2 of a silver 
iodobromide emulsion (having a silver iodide content of 2 mol% and a mean 
grain size of 0.07 micron), 0.10 g/m.sup.2 of polymethacrylate particles 
(having a diameter of 1.5 micron), and gelatin. 
Each of the above-described layers contained additionally Gelatin Hardener 
H-1 and a surface active agent. 
Samples (102) to (110) were prepared in the same manner as Sample (101) 
except that 50 mol% of Coupler C-2 contained in the third layer was 
replaced by equimolar amounts of the couplers of the present invention, 
Compounds (13), (14), (27), (32), (51), (52), (56), (62), and (64), 
respectively. 
Each of these samples was exposed to light emitted from a light source for 
sensitometry through a red filter and then, subjected to the color 
development processing described below. Separately, optical exposure for 
conventional R.M.S. granularity measurement was carried out and 
subsequently, the same color development processing as above was run. The 
photographic characteristics and the granularities of the thus processed 
samples were examined through the red filter. In the granularity 
measurement, an aperture measureing 48 microns in diameter was used. The 
results obtained are shown in Table 3. 
The development processing employed herein had the following steps, and was 
carried out at a temperature of 38.degree. C. 
______________________________________ 
1. Color Development 3 min. 15 sec. 
2. Bleaching 6 min. 30 sec. 
3. Washing 3 min. 15 sec. 
4. Fixing 6 min. 30 sec. 
5. Washing 3 min. 15 sec. 
6. Stabilizing 3 min. 15 sec. 
______________________________________ 
Compositions of the processing solutions used in the above-described steps, 
respectively, are described below. 
______________________________________ 
Color Developing Solution 
Sodium Nitrilotriacetate 1.0 g 
Sodium Sulfite 4.0 g 
Sodium Carbonate 30.0 g 
Potassium Bromide 1.4 g 
Hydroxylamine Sulfate 2.4 g 
4-(N--ethyl-N--.beta.-hydroxyethylamino)-2-methyl- 
4.5 g 
aniline Sulfate 
Water to make 1 l 
Bleaching Solution 
Ammonium Bromide 160.0 g 
Aqueous Ammonia (28%) 25.0 ml 
Sodium Ethylenediaminetetraacetato- 
130.0 g 
ferrate(III) 
Glacial Acetic Acid 14.0 ml 
Water to make 1 1 
Fixing Solution 
Sodium Tetrapolyphosphate 2.0 g 
Sodium Sulfite 4.0 g 
Ammonium Thiosulfate (70% aq. soln.) 
175.0 ml 
Sodium Hydrogen Sulfite 4.6 g 
Water to make 1 l 
Stabilizing Solution 
Formaldehyde (37 wt % aq. soln.) 
8.0 ml 
Water to make 1 l 
______________________________________ 
TABLE 3 
______________________________________ 
Coupler of Red Image 
Present Relative 
Sample Invention Fog Sensitivity* 
Granularity** 
______________________________________ 
10l -- 0.14 100 0.041 
(Comparison) 
102 (13) 0.14 99 0.034 
103 (14) 0.14 100 0.033 
104 (27) 0.14 103 0.035 
105 (32) 0.14 98 0.034 
106 (51) 0.14 96 0.035 
107 (52) 0.14 98 0.038 
108 (56) 0.14 100 0.040 
109 (62) 0.14 98 0.037 
110 (64) 0.14 100 0.038 
______________________________________ 
*Relative Sensitivity: Standard point of the optical density to determine 
the sensitivity was fog + 0.2, and the standard sensitivity of Sample 
(101) was set at 100. 
**Granularity: Value at a density of 0.8. 
Structural formulae of the compounds employed in Example 2 are illustrated 
below. 
##STR12## 
While the invention has been described in detail and with reference to 
specific embodiment thereof, it will be apparent to one skilled in the art 
that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.