Silver halide color photographic materials

A silver halide color photographic material comprising a support having thereon at least one blue sensitive silver halide emulsion layer, at least one green sensitive silver halide emulsion layer and at least one red sensitive silver halide emulsion layer, wherein at least one type of acylacetamide type yellow coupler in which the acyl group represented by formula [I] indicated below is included in said blue sensitive silver halide emulsion layer and at least one type of magenta coupler represented by formula [M] indicated below is included in said green sensitive silver halide emulsion layer, ##STR1## wherein R.sub.1 represents a univalent group, Q represents a group of non-metal atoms which, together with C, is required to form a three to five membered hydrocarbon ring or a three to five membered heterocyclic ring which has within the ring at least one hetero atom selected from the group consisting of N, O, S and P, with the proviso with R.sub.1 is not a hydrogen atom and is not linked to Q and does not form a ring, ##STR2## wherein R.sub.20 represents a hydrogen atom or a substituent group, Z represents a group of non-metal atoms which is required to form a five membered azole ring which contains 2 to 4 nitrogen atoms, said azole rings may have substituent groups including condensed rings, and X represents a hydrogen atom or a coupling-off group.

FIELD OF THE INVENTION 
The present invention relates to silver halide color photographic materials 
and, more precisely, the present invention relates to photographic 
materials which have excellent color reproduction properties and excellent 
stability during photographic processing. 
BACKGROUND OF THE INVENTION 
In recent years, progress has been made by increasing the speed and 
improving the image quality of color photographic photographic materials 
in response to the requirements of the user. With respect to the 
improvement of picture quality, progress has been made in the main with 
improvement of color reproduction, improvement of sharpness and 
improvement of graininess. These factors are of great importance when 
comparing the performance cf photographic materials, and it is clear that 
further improvement will be required in the future. 
The dyes which are formed with the yellow, magenta and cyan couplers which 
have been used in silver halide color photographic materials in the past 
have tended to impair color reproduction because of unwanted auxiliary 
absorbances. Hence, couplers which form colored images with little 
auxiliary absorption have been subject to research as a means of improving 
color reproduction. 
With magenta dyes, improvement of the magenta hue has been achieved by the 
use of pyrazoloazole based magenta couplers in place of the conventional 
5-pyrazolone type magenta couplers. The azomethine dyes formed by reaction 
between these couplers and the oxidation products of color developing 
agents have a high saturation because there is little auxiliary absorption 
in the region of 430 nm which is deleterious with respect to color 
reproduction and it is known that these are desirable from the viewpoint 
of color reproduction. Such couplers have been disclosed, for example, in 
U.S. Pat. No. 3,725,067, JP-A-60-172982, JP-A-60-33552, JP-A-61-72238, 
U.S. Pat. Nos. 4,500,630 and 4,540,654. (The term "JP-A" as used herein 
signifies an "unexamined published Japanese patent application".) 
Furthermore, in the past the yellow couplers have provided low saturation 
and improvement by sharpening the spectral absorption is very desirable. 
On the other hand, reduction of the film thickness of photographic 
materials is required to improve sharpness, but this requires the use of 
couplers which have good color forming properties in the emulsion layers 
and their emulsification and dispersion in a stable manner with a reduced 
quantity of high boiling point organic solvent. The yellow couplers from 
which the dyes are formed have a sharp absorption spectrum, they have 
excellent color reproduction and there is little variation in the color 
forming properties with changes in the pH of the color developer disclosed 
in JP-A-63-123047, for example, can be cited as couplers of this type. 
However, according to observations made by the present inventors, the 
formation of the respective colored dyes when the above mentioned yellow 
couplers and pyrazoloazole based magenta couplers are used conjointly 
varies greatly depending on slight fluctuations in the pH of the color 
developer and color mixing and color staining occurs as a result of 
interlayer mixing of the oxidized developing agent into other layers. The 
resolution of these problems is desirable. 
SUMMARY OF THE INVENTION 
Hence, the first object of the present invention is to provide color 
photographic materials which have a high color saturation, with which 
there is little color mixing or color staining, and which have excellent 
color reproduction properties. 
The second object of the present invention is to provide excellent color 
photographic materials having no fluctuation in photographic properties 
depending on the pH of the color developer. 
As a result of thorough research, the inventors have discovered that the 
objects of the invention can be realized by the means indicated below. 
Thus, the objects of the invention have been realized by means of a silver 
halide color photographic material comprising a support having thereon at 
least one blue sensitive silver halide emulsion layer, at least one green 
sensitive silver halide emulsion layer and at least one red sensitive 
silver halide emulsion layer, wherein at least one type of acylacetamide 
type yellow coupler in which the acyl group represented by formula [I] 
indicated below is included in said blue sensitive silver halide emulsion 
layer and at least one type of magenta coupler represented by formula [M] 
indicated below is included in said green sensitive silver halide emulsion 
layer, 
##STR3## 
wherein R.sub.1 represents a univalent group, Q represents a group of 
non-metal atoms which, together with C, is required to form a three to 
five membered hydrocarbon ring or a three to five membered heterocyclic 
ring which has within the ring at least one hetero atom selected from the 
group consisting of N, O, S and P, with the proviso that R.sub.1 is not a 
hydrogen atom and is not linked to Q and does not form a ring, 
##STR4## 
wherein R.sub.20 represents a hydrogen atom or a substituent group, Z 
represents a group of non-metal atoms which is required to form a five 
membered azole ring which contains 2 to 4 nitrogen atoms, said azole rings 
may have substituent groups (including condensed rings), and X represents 
a hydrogen atom or a coupling-off group (a group which can be eliminated 
at the time of a coupling reaction with the oxidized form of a developing 
agent). 
DETAILED DESCRIPTION OF THE INVENTION 
Silver halide color photographic materials which contain yellow couplers 
and pyrazoloazole based magenta couplers which have sharp absorption 
spectra and which provide excellent color reproduction have been disclosed 
in JP-A-63-231451, but there is no mention whatsoever of yellow couplers 
of the present invention and no disclosure of the same is made. 
The acylacetamide type yellow couplers of the present invention are 
preferably represented by formula [Y] indicated below. 
##STR5## 
In formula [Y], R.sub.1 represents a univalent group other than hydrogen, Q 
represents a group of non-metal atoms which is required, together with C, 
to form a three to five membered hydrocarbon ring or a three to five 
membered heterocyclic ring which contains within the ring at least one 
hetero atom selected from among N, S, O and P, R.sub.2 represents a 
hydrogen atom, a halogen atom (F, Cl, Br, I; same in formula [Y] described 
hereinafter), an alkoxy group, an aryloxy group, an alkyl group or an 
amino group, R.sub.3 represents a group which can be substituted onto a 
benzene ring, Y represents a hydrogen atom or a group which can be 
eliminated by a coupling reaction with the oxidized form of a primary 
aromatic amine developing agent (referred to hereinafter as a coupling-off 
group) and l represents an integer from 0 to 4. Moreover, when l 
represents 2 or more the R.sub.3 groups may be the same or different. 
Examples of R3 include halogen atoms, alkyl groups, aryl groups, alkoxy 
groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, 
carbonamido groups, sulfonamido groups, carbamoyl groups, sulfamoyl 
groups, alkylsulfonyl groups, ureido groups, sulfamoylamino groups, 
alkoxycarbonylamino groups, alkoxysulfonyl groups, acyloxy groups, nitro 
groups, heterocyclic groups, cyano groups, acyl groups, alkylsulfonyloxy 
groups and arylsulfonyloxy groups. Examples of coupling-off group include 
heterocyclic groups which are bonded to the coupling position with a 
nitrogen atom, aryloxy groups, arylthio groups, acyloxy groups, 
alkylsulfonyloxy groups, arylsulfonyloxy groups, heterocyclic oxy groups 
and halogen atoms. 
When the substituent groups in formula [Y] are alkyl groups or contain 
alkyl groups, and no particular limitation is imposed, the term alkyl 
group signifies linear chain, branched chain or cyclic alkyl groups which 
may be substituted and which may contain unsaturated bonds (for example, 
methyl, isopropyl, tert-butyl, cyclopentyl, tert-pentyl, cyclohexyl, 
2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 
3-cyclohexenyl, olel, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, 
ethoxycarbonylmethyl, phenoxyethyl). 
When the substituent groups in formula [Y] are aryl groups or contain aryl 
groups, and no particular limitation is imposed, the term aryl groups 
signifies single ring or condensed ring aryl groups which may have 
substituent groups (for example, phenyl, 1-naphthyl, p-tolyl, o-tolyl, 
p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, 
pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 
2,4-di-tert-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl). 
When the substituent groups in formula [Y] are heterocyclic groups or 
contain heterocyclic rings, and no particular limitation is imposed, the 
term heterocyclic group signifies a three to eight membered single ring or 
condensed ring heterocyclic group which may be substituted and which 
contains at least one hetero atom selected from among O, N, S, P, Se and 
Te (for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 
1 benzotriazolyl, 2-benzotriazolyl, succinimido, phthalimido, 
1-benzyl-2,4-imidazolidinedione-3-yl). 
The substituent groups preferably used in formula [Y] are described below. 
In formula [Y], R.sub.1 is preferably a halogen atom, a cyano group or a 
univalent group which has a total of 1 to 30 carbon atoms (referred to 
hereinafter as the C-number) (for example, alkyl, alkoxy) or a univalent 
group of C-number from 6 to 30 (for example aryl, aryloxy), which may be 
substituted, and examples of substituent groups include halogen atoms, 
alkyl groups, alkoxy groups, nitro groups, amino groups, carbonamido 
groups, sulfonamido groups and acyl groups. 
In formula [Y], Q preferably represents a group of non-metal atoms which is 
required, along with C, to form a three to five membered hydrocarbyl ring 
of C-number from 3 to 30 or a three to five membered heterocyclic ring of 
C-number from 2 to 30 which contains within the ring at least one hetero 
atom selected from among N, S, O and P, which may be substituted. 
Furthermore, the ring which is formed by Q together with C may contain 
unsaturated bonds within the ring. Cyclopropane, cyclobutane, 
cyclopentane, cyclopropene, cyclobutene, cyclopentene, oxethane, oxolane, 
1,3-dioxolane, thiethane, thiolane and pyrrolidine rings are examples of 
rings formed by Q together with C. Examples of substituent groups include 
halogen atoms, hydroxyl groups, alkyl groups, aryl groups, acyl groups, 
alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, 
alkylthio groups and arylthio groups. 
In formula [Y], R.sub.2 is preferably a halogen atom or an alkoxy group of 
C-number from 1 to 30, an aryloxy group of C-number from 6 to 30, an alkyl 
group of C-number from 1 to 30 or an amino group of C-number from 0 to 30, 
and these may be substituted, and examples of substituent groups include 
halogen atoms, alkyl groups, alkoxy groups and aryloxy groups. R.sub.2 is 
more preferably a halogen atom. 
In formula [Y], R.sub.3 is preferably a halogen atom, or an alkyl group of 
C-number from 1 to 30, an aryl group of C-number from 6 to 30, an alkoxy 
group of C-number from 1 to 30, an alkoxycarbonyl group of C-number from 2 
to 30, an aryloxycarbonyl group of C-number from 7 to 30, a carbonamido 
group of C-number from 1 to 30, a sulfonamido group of C-number 1 to 30, a 
carbamoyl group of C-number 1 to 30, a sulfamoyl group of C-number from 0 
to 30, an alkylsulfonyl group of C-number from 1 to 30, an arylsulfonyl 
group of C-number from 6 to 30, a ureido group of C-number from 1 to 30, a 
sulfamoylamino group of C number from 0 to 30, an alkoxycarbonylamino 
group of C-number from 2 to 30, a heterocyclic group of C-number from 1 to 
30, an acyl group of C-number from 1 to 30, an alkylsulfonyloxy group of 
C-number from 1 to 30 or an arylsulfonyloxy group of C-number from 6 to 
30, and these groups may be substituted. Examples of substituent groups 
include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, 
alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthio groups, 
arylthio groups, heterocyclic thio groups, alkylsulfonyl groups, 
arylsulfonyl groups, acyl groups, carbonamido groups, sulfonamido groups, 
carbamoyl groups, sulfamoyl groups, alkoxycarbonylamino groups, 
sulfamoylamino groups, ureido groups, cyano groups, nitro groups, acyloxy 
groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylsulfonyloxy 
groups and arylsulfonyloxy groups. R.sub.3 is more preferably a 
carbonamido group or sulfonamido group. 
In formula [Y], l preferably represents an integer value of 1 or 2, and the 
substitution position of R.sub.3 is preferably meta or para with respect 
to the 
##STR6## 
In formula [Y], Y preferably represents a heterocyclic group which is 
bonded to the coupling position with a nitrogen atom or an aryloxy group. 
When Y represents a heterocyclic group it is preferably a five to seven 
membered single ring or condensed ring heterocyclic group which may be 
substituted, and examples include succinimido, maleimido, phthalimido, 
diglycolimido, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, 
indole, indazole, benzimidazole, benzotriazole, imidazolidin-2,4-dione, 
oxazolidin-2,4-dione, thiazolidin-2,4-dione, imidazolidin-2-one, 
oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one, 
benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 
2-imidazolin-5-one, indolin-2,3-dione, 2,6-dioxypurine, parabanic acid, 
1,2,4-triazolidin-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 
6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine and 
2-imino-1,3,4-thiazolidin-4-one, and these heterocyclic rings may be 
substituted. Examples of substituent groups for these heterocyclic rings 
include halogen atoms, hydroxyl groups, nitro groups, cyano groups, 
carboxyl groups, sulfo groups, alkyl groups, aryl groups, alkoxy groups, 
aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, 
arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl 
groups, acyloxy groups, amino groups, carbonamido groups, sulfonamido 
groups, carbamoyl groups, sulfamoyl groups, ureido groups, 
alkoxycarbonylamino amino groups and sulfamoylamino groups. When Y 
represents an aryloxy group it is preferably an aryloxy group of C-number 
from 6 to 30, and this may be substituted with groups selected from among 
the substituent groups given in the case where Y is a heterocyclic group 
as described above. The preferred substituent groups for an aryloxy group 
are halogen atoms, a cyano group, a nitro group, a carboxyl group, a 
trifluoromethyl group, alkoxycarbonyl groups, a carbonamido group, 
sulfonamido groups, a carbamoyl groups, sulfamoyl groups, alkylsulfonyl 
groups, arylsulfonyl groups or a cyan group. 
The substituent groups used most desirably in formula [Y] are described 
below. 
R.sub.1 is more desirably a halogen atom, or an alkyl group, and most 
desirably a methyl group. Q is most desirably a group of non-metal atoms 
wherein the ring which is formed together with C is a three to five 
membered hydrocarbon ring, for example 
##STR7## 
is most desirable). Here, R represents a hydrogen atom, a halogen atom or 
an alkyl group. Moreover, the R groups may be the same or different. 
R.sub.2 is more desirably a chlorine atom, a fluorine atom, an alkyl group 
of C-number from 1 to 6 (for example methyl, trifluoromethyl, ethyl, 
isopropyl, tert-butyl), an alkoxy group of C-number from 1 to 8 (for 
example, methoxy, ethoxy, methoxyethoxy, butoxy) or an aryloxy group of 
C-number from 6 to 24 (for example phenoxy, p-tolyloxy, p-methoxyphenoxy), 
and it is most desirably a chlorine atom, a methoxy group or a 
trifluoromethyl group. 
R.sub.3 is more desirably a halogen atom, an alkoxy group, an 
alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a 
sulfonamido group, a carbamoyl group or a sulfamoyl group, and it is most 
desirably an alkoxy group, an alkoxycarbonyl group, a carboxnmido group or 
a sulfonamido group. 
Y is most desirably a group which can be represented by formula [Y-1], 
[Y-2] or [Y-3] indicated below. 
##STR8## 
In formula [Y-1], Z.sub.1 represents 
##STR9## 
Here, R.sub.4, R.sub.5, R.sub.8 and R.sub.9 represent hydrogen atoms, 
alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio 
groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups or 
amino groups, R.sub.6 and R.sub.7 represent hydrogen atoms, alkyl groups, 
aryl groups, alkylsulfonyl groups, arylsulfonyl groups or alkoxycarbonyl 
groups, and R.sub.10 and R.sub.11 represent hydrogen atoms, alkyl groups 
or aryl groups. R.sub.10 and R.sub.11 may be joined together to form a 
benzene ring. R.sub.4 and R.sub.5, R.sub.5 and R.sub.6, R.sub.6 and 
R.sub.7, or R.sub.4 and R.sub.8 may be joined together to form a ring (for 
example, a cyclobutane, cyclohexane, cycloheptane, cyclohexene, 
pyrrolidine or piperidine ring). 
The most desirable of the heterocyclic groups represented by formula [Y-1] 
are those in which Z.sub.1 in formula [Y-1] is 
##STR10## 
The C-number of the heterocyclic group represented by formula [Y-1] is 
from 2 to 30, preferably from 4 to 20 and most desirably from 5 to 16. 
##STR11## 
In formula [Y-2], at least one of R.sub.12 and R.sub.13 is selected from 
the group consisting of a halogen atom, a cyano group, a nitro group, a 
trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a 
carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl 
group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and 
the other may be a hydrogen atom, an alkyl group or an alkoxy group. 
R.sub.14 represents a group having the same meaning as R.sub.12 or 
R.sub.13, and m represents an integer from 0 to 2. The C-number of the 
aryloxy groups represented by formula [Y-2] is from 6 to 30, preferably 
from 6 to 24, and most desirably from 6 to 15. 
##STR12## 
In formula [Y-3], W represents a group of non-metal atoms which is 
required, together with N, to form a pyrrole ring, a pyrazole ring, an 
imidazole ring or a triazole ring. Here, the ring represented by 
##STR13## 
may have substituent groups, and halogen atoms, a nitro group, a cyano 
group, an alkoxycarbonyl group, an alkyl group, an aryl group, an amino 
group, an alkoxy group, an aryloxy group and a carbamoyl group are 
examples of preferred substituent groups. The C-number of the heterocyclic 
group represented by formula [Y-3] is from 2 to 30, preferably from 2 to 
24, and most desirably from 2 to 16. 
Y is most desirably a group which can be represented by formula [Y-1]. 
The couplers represented by formula [Y] may form dimers or larger oligomers 
with bonding between groups of valency two or more in the substituent 
groups R.sub.1, Q, Y or 
##STR14## 
In such a case, the number of carbon atoms may be outside the range shown 
for each of the aforementioned substituent groups. 
Actual examples of yellow couplers which can be represented by formula [Y] 
are indicated below. 
##STR15## 
Yellow couplers of the present invention which represented by formula [Y] 
can be prepared using the synthetic route indicated below. 
##STR16## 
The compound a can be prepared using the methods disclosed, for example, in 
J. Chem. Soc. (C), 1968, 2548, J. Am. Chem. Soc., 1934, 56, 2710, 
Synthesis, 1971, 258, J Org. Chem., 1978 43, 1729 and CA, 1960, 66, 
18533y. 
The compounds b, c, d, e and f can be prepared using known methods. 
Examples of the synthesis of couplers of the present invention are 
described below.

EXAMPLE OF SYNTHESIS 1: THE PREATION OF ILLUSTRATIVE COMPOUND Y-28 
Oxalyl chloride (38.1 gram) was drip fed over a period of 30 minutes at 
room temperature into a mixture comprising 25 grams of 
1-methylcyclopropane carboxylic acid which had been prepared using the 
method disclosed by Gotkis, D., et al., J. Am. Chem. Soc., 1934, 56, 2710, 
100 ml of methylene chloride and 1 ml of N,N-dimethylformamide. After the 
drip feed had been completed the reaction was continued for 2 hours at 
room temperature and then the methylene chloride and the excess oxalyl 
chloride were removed under reduced pressure with an aspirator and 1 
methylcyclopropanecarbonyl chloride was obtained as an oily substance. 
Methanol (100 ml) was drip fed over a period of 30 minutes at room 
temperature into a mixture comprising 6 grams of magnesium and 2 ml of 
carbon tetrachloride. After subsequently heating the mixture for 2 hours 
under reflux, 32.6 grams of ethyl 3-oxobutanoate was added dropwise over a 
period of 30 minutes while heating under reflux. After the drip feed had 
been completed, the mixture was heated under reflux for a period of 2 
hours and then the methanol was distilled off completely under low 
pressure using an aspirator. Tetrahydrofuran (100 ml) was added to the 
mixture and dispersed, and the 1-methylcyclopropanecarbonyl chloride 
prepared earlier was added dropwise at room temperature. After reacting 
for a period of 30 minutes, the mixture was extracted with 30 ml of ethyl 
acetate and dilute aqueous sulfuric acid and, after being washed with 
water, the organic layer was dried over anhydrous sodium sulfate and then 
the solvent was removed and 55.3 grams of ethyl 
2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate was obtained as an oily 
substance. 
A solution comprising 55 grams of ethyl 
2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate and 160 ml of ethanol was 
stirred at room temperature and 60 ml of a 30% aqueous ammonia solution 
was added dropwise to this solution over a period of 10 minutes. 
Subsequently, the mixture was stirred for 1 hour and extracted with 300 ml 
of ethyl acetate and dilute aqueous hydrochloric acid. After 
neutralization and washing with water, the organic layer was dried over 
anhydrous sodium sulfate. The solvent was then removed and 43 grams of 
ethyl (1-methylcyclopropanecarbonyl)acetate was obtained as an oily 
material. 
Ethyl (1-methylcyclopropanecarbonyl)acetate (34 grams) and 44.5 grams of 
N-(3-amino-4-chlorophenyl)-2-(2,4-di-tert-pentylphenoxy)butanamide were 
heated under reflux at an internal temperature from 100.degree. C. to 
120.degree. C. under reduced pressure using an aspirator. After reacting 
for 4 hours, the reaction mixture was refined using column chromatography 
with an n-hexane/ethyl acetate mixed solvent and 49 grams of illustrative 
compound Y-28 were obtained as a sticky oily material. The structure of 
the compound was confirmed by MS spectroscopy, NMR spectroscopy and 
elemental analysis. 
EXAMPLE OF SYNTHESIS 2 : THE PREATION OF ILLUSTRATIVE COMPOUND Y-1 
Illustrative compound Y-28 (22.8 grams) was dissolved in 300 ml of 
methylene chloride and 5.4 grams of sulfuryl chloride was added dropwise 
over a period of 10 minutes with ice cooling. After reacting for 30 
minutes, the reaction mixture was washed thoroughly with water and dried 
over anhydrous sodium sulfate and then concentrated whereupon the chloride 
of illustrative compound Y-28 was obtained. The chloride of illustrative 
compound Y-28 which had been prepared beforehand was dissolved in 50 ml of 
N,N-dimethylformaldehyde and added dropwise at room temperature over a 
period of 30 minutes to a solution of 18.7 grams of 
1-benzyl-5-ethoxyhydantoin, 11.2 ml of triethylamine and 50 ml of 
N,N-dimethylformamide. 
Subsequently, after reacting for 4 hours at 40.degree. C., the reaction 
mixture was extracted with 300 ml of ethyl acetate and, after washing with 
water, the extract was washed with 300 ml of 2% aqueous triethylamine 
solution and then it was neutralized with dilute hydrochloric acid. The 
organic layer was dried over anhydrous sodium sulfate and then the solvent 
was distilled off and the oily material which was obtained was 
crystallized from an n-hexane/ethyl acetate mixed solvent. The crystals 
which precipitated out were recovered by filtration and, after washing 
with n-hexane/ethyl acetate mixed solvent, the crystals were dried and 
22.8 grams of crystals of illustrative compound Y-1 were obtained. 
The structure of this compound was confirmed by MS spectrosropy, NMR 
spectroscopy and elemental analysis. Furthermore, the melting point was 
132-133.degree. C. 
The yellow couplers of the present invention may be used independently, or 
mixtures of two or more types can be used conjointly, and they can also be 
used in the form of mixtures with known yellow couplers. 
The yellow couplers of the present invention can be used in a blue 
sensitive silver halide emulsion layer or a layer adjacent thereto, and 
they are desirably used in a blue sensitive silver halide emulsion layer. 
The amount of yellow coupler of the present invention used in a 
photographic material is from 1.times.10.sup.-5 to 1.times.10.sup.-2 mol, 
preferably from 1.times.10.sup.-4 to 5.times.10.sup.-3 mol, and most 
desirably from 2.times.10.sup.-4 to 2.times.10.sup.-3 mol, per square 
meter. 
The couplers represented by formula [M] are described in detail below. 
R.sub.20 represents a hydrogen atom or a substituent group which is the 
same as R.sub.21 in formulae [M-I], [M-II], [M-III] and [M-IV] described 
below. 
Z represents a group of non-metal atom which is required to form a five 
membered azole ring which contains 2 to 4 nitrogen atoms. Z preferably 
represents a triazole ring. 
X represents a hydrogen atom or a coupling-off group (a group which can be 
eliminated at the time of coupling reaction with the oxidized form of a 
developing agent), which is the same as X in formulae [M-I], [M-II], 
[M-III] and [M-IV] described below. 
The preferred skeleton from among the coupler skeletons are 
1H-imidazo[1,2-b]pyrazole, 1H-pyrazolo[1,5-b][1,2,4]triazole, 
1H-pyrazolo[5,1-c][1,2,4]triazole and 1H-pyrazolo[1,5-d]tetrazole, and 
these can be presented by formulae [M-I], [M-II], [M-III] and [M-IV]. 
##STR17## 
The substituent groups R.sub.21, R.sub.22, R.sub.23 and X in these formulae 
are described in detail below. 
R.sub.21 represents a hydrogen atom, a halogen atom, an alkyl group, an 
aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro 
group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, 
an acylamino group, an alkylamino group, an anilino group, a ureido group, 
a sulfamoylamino group, an alkylthio group, an arylthio group, an 
alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a 
sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic 
oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a 
silyloxy group, an aryloxycarbonylamino group, an imido group, a 
heterocyclic thio group, a sulfinyl group, a phosphonyl group, an 
aryloxycarbonyl group, an acyl group or an azolyl group, and dimers may be 
formed with R.sub.21 as a divalent group. 
More precisely, the R.sub.21 groups each represent a hydrogen atom, a 
halogen atom (for example, chlorine, bromine), an alkyl group (for 
example, a linear chain or branched chain alkyl group, aralkyl group, 
alkenyl group, alkynyl group, cycloalkyl group or cycloalkenyl group which 
has from 1 to 32 carbon atoms and, more precisely, for example, methyl, 
ethyl, propyl, isopropyl, tert-butyl, tridecyl, 2-methanesulfonylethyl, 
3-(3-pentadecylphenoxy)propyl, 
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propyl, 
2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 
3-(2,4-di-tert-amylphenoxy)propyl), an aryl group (for example, phenyl, 
4-tert-butylphenyl, 2,4-di-tert-amylphenyl, 4-tetradecanamido-phenyl), a 
heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 
2-benzothiazolyl), a cyano group, a hydroxy group, a nitro group, a 
carboxy group, an amino group, an alkoxy group (for example, methoxy, 
ethoxy, 2-methoxyethoxy, 2-dodecyl-ethoxy, 2-methanesulfonylethoxy), an 
aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 
3-nitrophenoxy, 3-tert-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), an 
acylamino group (for example, acetamido, benzamido, tetradecanamido, 
2-(2,4-di-tert-amylphenoxy)-butanamido, 
4-(3-tert-butyl-4-hydroxyphenoxy)butanamido, 
2-{4-(4-hydroxyphenylsulfonyl)phenoxy} decanamido), an alkylamino group 
(for example, methylamino, butylamino, dodecylamino, diethylamino, 
methylbutylamino), an anilino group (for example, phenylamino, 
2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 
2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 
2-chloro-5-{.alpha.-(3-tert-butyl-4-hydroxyphenoxy)dodecanamido]-anilino), 
a ureido group (for example, phenylureido, methylureido, 
N,N-dibutylureido), a sulfamoylamino group (for example, 
N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkylthio 
group (for example, methylthio, octylthio, tetradecylthio, 
2-phenoxyethylthio, 3-phenoxypropylthio, 
3-(4-tert-butylphenoxy)propylthio), an arylthio group (for example, 
phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 
2-carboxyphenylthio, 4-tetradecanamidophenylthio), an alkoxycarbonylamino 
group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), a 
sulfonamido group (for example, methanesulfonamido, 
hexadecane-sulfonamido, benzenesulfonamido, p-toluenesulfonamido, 
octadecanesulfonamido, 2-methyloxy-5-tert-butylbenzene-sulfonamido), a 
carbamoyl group (for example, N-ethylcarbamoyl, N,N-dibutylcarbamoyl, 
N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, 
N-[3-(2,4-di-tert-amylphenoxy)propyl}-carbamoyl), a sulfamoyl group (for 
example, N-ethylsulfamoyl, N,N-dipropylsulfamoyl, 
N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, 
N,N-diethylsulfamoyl), a sulfonyl group (for example, methanesulfonyl, 
octanesulfonyl, benzenesulfonyl, toluenesulfonyl), an alkoxycarbonyl group 
(for example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, 
octadecyloxycarbonyl), a heterocyclic oxy group (for example, 
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for 
example, phenylazo, 4-methoxyphenylazo, 4-pivaloylamino-phenylazo, 
2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy), 
a carbamoyloxy group (for example, N-methylcarbamoyloxy, 
N-phenylcarbamoyloxy), a silyloxy group (for example, trimethylsilyloxy, 
dibutylmethylsilyloxy), an aryloxycarbonylamino group (for example, 
phenoxycarbonylamino), an imido group (for example, N-succinimido, 
N-phthalimido, 3-octadecenylsuccinimido), a heterocyclic thio group (for 
example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazolyl-6-thio, 
2-pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 
3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group 
(for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an 
aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group (for 
example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxobenzoyl) or an 
azolyl group (for example, imidazolyl, pyrazolyl, 3-chloropyrazol-1-yl, 
triazolyl). Those of these substituent groups which can have further 
substituent groups may have organic substituent groups or halogen atoms 
bonded to a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. 
From among these substituent groups, the alkyl groups, aryl groups, alkoxy 
groups, aryloxy groups, alkylthio groups, ureido groups, urethane groups 
and acylamino groups are preferred for R.sub.21. 
R.sub.22 is a group which is the same as the substituent groups described 
in connection with R.sub.21, and it is preferably a hydrogen atom, an 
alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, 
a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group or a 
cyano group. 
Furthermore, R.sub.23 is a group which is the same as the substituent 
groups described in connection with R.sub.21, and it is preferably a 
hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an 
alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an 
alkoxycarbonyl group, a carbamoyl group or an acyl group, and it is most 
desirably an alkyl group, an aryl group, a heterocyclic group, an 
alkylthio group or an arylthio group. 
X represents a hydrogen atom or a coupling-off group (a group which can be 
eliminated in a reaction with the oxidized form of a primary aromatic 
amine color developing agent) and more precisely the coupling-off group 
is, for example, a halogen atom, an alkoxy group, an aryloxy group, an 
acyloxy group, an alkyl or aryl sulfonyloxy group, an acylamino group, an 
alkyl or aryl sulfonamido group, an alkoxycarbonyloxy group, an 
aryloxycarbonyloxy group, an alkyl, aryl or heterocyclic thio group, a 
carbamoylamino group, a five or six membered nitrogen containing 
heterocyclic group, an imido group or an arylazo group, and these groups 
may be further substituted with the groups which are permitted as 
substituent groups for R.sub.21. 
More precisely, these groups include halogen atoms (for example, fluorine, 
chlorine, bromine), alkoxy groups (for example, ethoxy, dodecyloxy, 
methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, 
ethoxycarbonylmethoxy), aryloxy groups (for example, 4-methylphenoxy, 
4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 
3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy 
groups (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl 
sulfonyloxy groups (for example, methanesulfonyloxy, toluene-sulfonyloxy), 
acylamino groups (for example, dichloroacetylamino, 
pentafluorobutyrylamino), alkyl or aryl sulfonamido groups (for example, 
methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonamino), 
alkoxycarbonyloxy groups (for example, ethoxycarbonyloxy, 
benzyloxycarbonyloxy), aryloxycarbonyloxy groups (for example, 
phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (for example, 
dodecylthio, 1-carboxydodecylthio, phenylthio, 
2-butoxy-5-tert-octylphenylthio, tetrazolylthio), carbamoylamino groups 
(for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), five or six 
membered nitrogen containing heterocyclic groups (for example, imidazolyl, 
pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imido 
groups (for example, succinimido, hydantoinyl) and arylazo group (for 
example, phenylazo, 4-methoxyphenylazo). There are also cases in which the 
form of a dimeric coupler for which four equivalent couplers are condensed 
with an aldehyde or a ketone with X as a coupling-off group which is 
bonded via a carbon atom is adopted rather than these forms. Furthermore, 
X may contain a photographically useful group such as a development 
inhibitor or a development accelerator. X is preferably a halogen atom, an 
alkoxy group, an aryloxy group, an alkyl or aryl thio group or a five or 
six membered nitrogen containing heterocyclic group which is bonded to the 
coupling position via a nitrogen atom. 
Of the magenta couplers represented by the formulae [M-I], [M-II], [M-III] 
and [M-IV], the couplers represented by the formula [M-II] or [M-III] are 
preferred. 
Illustrative examples of magenta couplers which can be represented by the 
formula [M] are indicated below, but these compounds are not limited to 
these examples. 
##STR18## 
Literature in which methods for the preparation of couplers which can be 
represented by formula [M] have been disclosed is indicated below. 
Compounds of formula [M-I] can be prepared using the method disclosed, for 
example, in U.S. Pat. No. 4,500,630. Compounds of formula [M-II] can be 
prepared using the methods disclosed, for example, in U.S. Pat. Nos. 
4,540,654 and 4,705,863, JP-A-61-65245, JP-A-62-209457 and JP-A-62-249155. 
Compounds of formula [M-III] can be prepared using the methods disclosed, 
for example, in JP-B-47-27411 and U.S. Pat. No. 3,725,067. Compounds of 
formula [M-IV] can be prepared using the methods disclosed, for example, 
in JP-A-60-33552. (The term "JP-B" as used herein signifies an "examined 
Japanese patent publication".) 
The layers in which the couplers represented by formula [M] of the present 
invention are added are preferably green sensitive emulsion layers or 
non-photosensitive intermediate layers which are adjacent thereto. 
Furthermore, the couplers represented by formula [M] are preferably used 
in the form of mixtures provided that there is no loss of the effect of 
the invention. The couplers of formula [M] are generally used in amounts 
from 0.01 mmol to 1 mmol, and preferably in amounts from 0.1 mmol to 0.5 
mmol, per square meter of photographic material. 
The various additives aforementioned can be used in a photographic 
materials which involves the present technique, but various other 
additives can also be used for various purposes. 
These additives have been disclosed in more detail in Research Disclosure 
Item 17643 (December 1978) and Research Disclosure Item 18716 (November 
1979), and the locations of said disclosures are indicated in the 
following Table. 
______________________________________ 
Type of Additives 
RD 17643 RD 18716 
______________________________________ 
1. Chemical Sensitizers 
Page 23 Page 648, 
right column 
2. Speed Increasing Agents As above 
3. Spectral Sensitizers 
Pages 23 Page 648, right 
and Supersensitizers 
to 24 column to page 
649, right column 
4. Whiteners Page 24 
5. Antifoggants and 
Pages 24 Page 649, 
Stabilizers to 25 right column 
6. Light-Absorbers, 
Pages 25 Page 649, right 
Filter Dyes and UV 
to 26 column to page 
Absorbers 650, left column 
7. Antistaining Agents 
Page 25, Page 650, left- 
right right column 
column 
8. Dye Image Stabilizers 
Page 25 
9. Film Hardening Agents 
Page 26 Page 651, 
left column 
10. Binders Page 26 As above 
11. Plasticizers, Page 27 Page 650, 
Lubricants right column 
12. Coating aids, Pages 26 Page 650, 
Surfactants to 27 right column 
13. Antistatic Agents 
Page 27 As above 
______________________________________ 
Furthermore, addition of the compounds which can react with and fix 
formaldehyde disclosed in U.S. Pat. Nos. 4,411,987 and 4,435,503 to the 
photographic material is desirable for preventing the deterioration of 
photographic performance due to formaldehyde gas. 
The addition to a color photographic material of the present invention of 
various fungicides and biocides such as 1,2-benzisothiazolin-3-one, 
n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 
2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole, for example, as 
disclosed in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941, is 
desirable. 
Suitable supports which can be used in the present invention have been 
disclosed, for example, on page 28 of the aforementioned Research 
Disclosure No. 17643, and from the right hand column of page 647 to the 
left hand column of page 648 of Research Disclosure No. 18716. 
The photographic materials in which photographic emulsions of the present 
invention are used are such that the total film thickness of all the 
hydrophilic colloid layers on the side where the emulsion layers are 
located is preferably not more than 28 .mu.m, more desirably not more than 
23 .mu.m, and most desirably not more than 20 .mu.m. Furthermore, the film 
swelling rate T.sub.1/2 is preferably not more than 30 seconds and most 
desirably not more than 20 seconds. Here, the film thickness signifies the 
film thickness measured under conditions of 25.degree. C., 55% relative 
humidity (2 days) and the film swelling rate T.sub.1/2 is that measured 
using the methods well known to those in the industry. For example, 
measurements can be made using a swellometer of the type described by A. 
Green in Photogr. Sci. Eng., Volume 19, Number 2, pages 124-129. T.sub.1/2 
is defined as the time taken to reach half the saturated film thickness, 
taking 90% of the maximum swollen film thickness reached on processing the 
material for 3 minutes 15 seconds in a color developer at 30.degree. C. as 
the saturated film thickness. 
The film swelling rate T.sub.1/2 can be adjusted by adding film hardening 
agents for the gelatin which is used as a binder, or by changing the aging 
conditions after coating. Furthermore, the swelling factor is preferably 
from 150% to 400%. The swelling factor can be calculated from the maximum 
swollen film thickness obtained under the conditions described above using 
the expression (maximum swollen film thickness minus film thickness)/film 
thickness. 
Color photographic materials which are in accordance with the present 
invention can be developed and processed using the usual methods disclosed 
on pages 28-29 of the aforementioned Research Disclosure No. 17643 and 
from the left hand column to the right hand column of page 651 of the 
aforementioned Research Disclosure No. 18716. 
Furthermore, color development is carried out after a normal black and 
white development in the case of reversal processing. Known black and 
white developing agents including dihydroxybenzenes such as hydroquinone, 
3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as 
N-methyl-p-aminophenol, for example, can be used individually, or in 
combinations, in the black and white developer. 
The silver halide color photographic materials in which photographic 
emulsions of the invention have been used are generally subjected to a 
water washing process and/or stabilization process after the desilvering 
process. The amount of wash water used in the washing process can be fixed 
within a wide range, depending on the application and the nature (the 
materials such as couplers which have been used for example) of the 
photographic material, the wash water temperature, the number of water 
washing tanks (the number of water washing stages) and the replenishment 
system, i.e. whether a counter flow or a sequential flow system is used, 
and various other conditions. The relationship between the amount of water 
used and the number of washing tanks in a multi-stage counter-flow system 
can be obtained using the method outlined on pages 248-253 of the Journal 
of the Society of Motion Picture and Television Engineers, Volume 64 (May 
1955). 
The amount of wash water used can be greatly reduced by using the 
multi-stage counter-flow system noted in the aforementioned literature, 
but bacteria proliferate due to the increased residence time of the water 
in the tanks and problems arise with the suspended matter which is 
produced becoming attached to the photographic material. The method in 
which the calcium ion and magnesium ion concentrations are reduced, as 
disclosed in JP-A-62-288388, is very effective as a means of overcoming 
this problem when processing color photographic materials of the present 
invention. Furthermore, the isothiazolone compounds and thiabendazoles 
disclosed in JP-A-57-8542, the chlorine based disinfectants such as 
chlorinated sodium isocyanurate, and benzotriazole, for example, and the 
disinfectants disclosed in The Chemistry of Biocides and Fungicides by 
Horiguchi, (1986, Sankyo Shuppan), in Killing Microorganisms, Biocidal and 
Fungicidal Techniques (1982) published by the Health and Hygiene 
Technology Society, and in A Dictionary of Biocides and Fungicides (1986) 
published by the Japanese Biocide and Fungicide Society, can also be used 
in this connection. 
The pH value of the washing water when processing photographic materials of 
the present invention is from 4 to 9, and preferably from 5 to 8. The 
washing water temperature and the washing time can be set variously in 
accordance with the characteristics and application of the photographic 
material but, in general, washing conditions from 20 seconds to 10 minutes 
at a temperature from 15.degree. C. to 45.degree. C., and preferably from 
30 seconds to 5 minutes at a temperature from 25.degree. C. to 40.degree. 
C., are selected. Moreover, the photographic materials of this invention 
can be processed directly in a stabilizing bath instead of being subjected 
to a water wash as described above. The known methods disclosed in 
JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can all be used for a 
stabilization process of this type. 
Furthermore, these are also cases in which a stabilization process is 
carried out following the aforementioned water washing process, and the 
formalin baths which are used as final baths with camera color 
photographic materials are an example of such a process. 
ILLUSTRATIVE EXAMPLES 
The invention is described in practical terms below by means of 
illustrative examples, bu the invention is not limited by these examples. 
Unless otherwise indicated, all parts, percents, ratios and the like are 
by weight. 
EXAMPLE 1 
Preparation of Sample 101 
A multi-layer color photographic material comprising the following layers 
containing the compositions indicated below was prepared on a cellulose 
triacetate film support having a thickness of 127 .mu.m on which a subbing 
layer had been established, and this was taken as sample 101. The numbers 
indicate the amounts added per square meter. Moreover, the effect of the 
compounds added is not limited to application disclosed. 
______________________________________ 
First Layer Anti-halation Layer 
Black colloidal silver 0.25 gram 
Gelatin 1.9 grams 
Ultraviolet absorber U-1 
0.04 gram 
Ultraviolet absorber U-2 
0.1 gram 
Ultraviolet absorber U-3 
0.1 gram 
Ultraviolet absorber U-4 
0.1 gram 
Ultraviolet absorber U-6 
0.1 gram 
High boiling point organic solvent Oil-1 
0.1 gram 
Second Layer Intermediate Layer 
Gelatin 0.40 gram 
Compound Cpd-D 10 mg 
High boiling point organic solvent Oil-3 
0.1 gram 
Dye D-4 0.4 mg 
Third Layer Intermediate Layer 
A fine grain silver iodobromide 
0.05 gram 
emulsion in which the surface 
as silver 
and interior had been fogged 
(average gain size 0.06 .mu.m, 
variation coefficient 18%, 
AgI content 1 mol %) 
Gelatin 0.4 gram 
Fourth Layer Low Speed Red Sensitive 
Emulsion Layer 
Emulsion A as silver 0.2 gram 
Emulsion B as silver 0.3 gram 
Gelatin 0.8 gram 
Coupler C-1 0.15 gram 
Coupler C-2 0.05 gram 
Coupler C-9 0.05 gram 
Compound Cpd-D 10 mg 
High boiling point organic solvent Oil-2 
0.1 gram 
Fifth Layer Medium Speed Red Sensitive 
Emulsion Layer 
Emulsion B as silver 0.2 gram 
Emulsion C as silver 0.3 gram 
Gelatin 0.8 gram 
Coupler C-1 0.2 gram 
Coupler C-2 0.05 gram 
Coupler C-3 0.2 gram 
High boiling point organic solvent Oil-2 
0.1 gram 
Sixth Layer High Speed Red Sensitive 
Emulsion Layer 
Emulsion D as silver 0.4 gram 
Gelatin 1.1 grams 
Coupler C-1 0.3 gram 
Coupler C-3 0.7 gram 
Additive P-1 0.1 gram 
Seventh Layer Intermediate Layer 
Gelatin 0.6 gram 
Compound M-1 0.3 gram 
Anti-color mixing agent Cpd-K 
2.6 mg 
Ultraviolet absorber U-1 
0.1 gram 
Ultraviolet absorber U-6 
0.1 gram 
Dye D-1 0.02 gram 
Eighth Layer Intermediate Layer 
A fine grain silver iodobromide 
0.02 gram 
emulsion in which the surface and 
as silver 
interior had been fogged (average 
grain size 0.06 .mu.m, variation 
coefficient 16%, AgI content 0.3 mol %) 
Gelatin 1.0 gram 
Anti-color mixing agent Cpd-L 
0.2 gram 
Ninth Layer Low Speed Green Sensitive 
Emulsion Layer 
Emulsion E as silver 0.3 gram 
Emulsion F as silver 0.1 gram 
Emulsion G as silver 0.1 gram 
Gelatin 0.5 gram 
Coupler C-4 0.25 gram 
Compound Cpd-B 0.03 gram 
Compound Cpd-D 10 mg 
Compound Cpd-E 0.02 gram 
Compound Cpd-F 0.02 gram 
Compound Cpd-G 0.02 gram 
Compound Cpd-H 0.02 gram 
High boiling point organic solvent Oil-1 
0.1 gram 
High boiling point organic solvent Oil-2 
0.1 gram 
Tenth Layer Medium Speed Green Sensitive 
Emulsion Layer 
Emulsion G as silver 0.3 gram 
Emulsion H as silver 0.1 gram 
Gelatin 0.6 gram 
Coupler C-4 0.25 gram 
Compound Cpd-B 0.03 gram 
Compound Cpd-E 0.02 gram 
Compound Cpd-F 0.02 gram 
Compound Cpd-G 0.05 gram 
Compound Cpd-H 0.05 gram 
High boiling point organic solvent Oil-2 
0.01 gram 
Eleventh Layer High Speed Green Sensitive 
Emulsion Layer 
Emulsion I as silver 0.5 gram 
Gelatin 1.0 gram 
Coupler C-4 0.35 gram 
Compound Cpd-B 0.08 gram 
Compound Cpd-E 0.02 gram 
Compound Cpd-F 0.02 gram 
Compound Cpd-G 0.02 gram 
Compound Cpd-H 0.02 gram 
High boiling point organic solvent Oil-1 
0.02 gram 
High boiling point organic solvent Oil-2 
0.02 gram 
Twelfth Layer Intermediate Layer 
Gelatin 0.6 gram 
Dye D-1 0.1 gram 
Dye D 2 0.05 gram 
Dye D-3 0.07 gram 
Thirteenth Layer Yellow Filter Layer 
Yellow colloidal silver as silver 0.1 gram 
Gelatin 1.1 gram 
Anti-color mixing agent Cpd-A 
0.01 gram 
High boiling point organic solvent Oil-1 
0.01 gram 
Fourteenth Layer Intermediate Layer 
Gelatin 0.6 gram 
Fifteenth Layer Low Speed Blue Sensitive 
Emulsion Layer 
Emulsion J as silver 0.4 gram 
Emulsion K as silver 0.1 gram 
Emulsion L as silver 0.1 gram 
Gelatin 0.8 gram 
Coupler C-5 0.6 gram 
Sixteenth layer Medium Speed Blue 
Sensitive Emulsion Layer 
Emulsion L as silver 0.1 gram 
Emulsion M as silver 0.4 gram 
Coupler C-5 0.6 gram 
Seventeenth Layer High Speed Blue 
Sensitive Emulsion Layer 
Emulsion N as silver 0.4 gram 
Gelatin 1.2 grams 
Coupler C-5 0.7 gram 
Eighteenth Layer First Protective Layer 
Gelatin 0.7 gram 
Ultraviolet absorber U-1 
0.04 gram 
Ultraviolet absorber U-2 
0.01 gram 
Ultraviolet absorber U-3 
0.03 gram 
Ultraviolet absorber U-4 
0.03 gram 
Ultraviolet absorber U-5 
0.05 gram 
Ultraviolet absorber U-6 
0.05 gram 
High boiling point organic solvent Oil-1 
0.02 gram 
Formalin scavengers 
pd-C 0.2 gram 
Cpd-1 0.4 gram 
Dye D-3 0.05 gram 
Nineteenth Layer Second Protective Layer 
Colloidal silver as silver 0.1 mg 
Fine grain silver iodobromide 
0.1 gram 
emulsion (average grain size 
as silver 
0.06 .mu.m, AgI content 1 mol %) 
Gelatin 0.4 gram 
Twentieth Layer Third Protective Layer 
Gelatin 0.4 gram 
Poly(methyl methacrylate) (average 
0.1 gram 
particle size 1.5.mu.) 
Methyl methacrylate/acrylic acid 
0.1 gram 
(4:6 by mol) copolymer (average 
particle size 1.5.mu.) 
Silicone oil 0.03 gram 
Surfactant W-1 3.0 mg 
Surfactant W-2 0.03 gram 
______________________________________ 
Furthermore, additives F-1 to F-8 were added to all of the emulsion layers 
in addition to the components indicated above. Moreover, the gelatin 
hardening agent H-1 and the surfactants W-3 and W-4 for coating purposes 
and emulsification purposes were added to each layer in addition to the 
components indicated above. 
Moreover, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and 
phenethyl alcohol were added as biocides and fungicides. 
The silver iodobromide emulsions used in sample 101 are indicated below. 
__________________________________________________________________________ 
Average 
Variation 
Grain Size 
Coefficient 
AgI Content 
Emulsion (.mu.m) 
(%) (%) 
__________________________________________________________________________ 
A Mono-disperse tetradecahedral grains 
0.25 16 3.7 
B Mono-disperse cubic internal latent 
0.30 10 3.3 
image type grains 
C Mono-disperse tetradecahedral grains 
0.30 18 5.0 
D Poly-disperse twinned crystal grains 
0.60 25 2.0 
E Mono-disperse cubic grains 
0.17 17 4.0 
F Mono-disperse cubic grains 
0.20 16 4.0 
G Mono-disperse cubic internal latent 
0.25 11 3.5 
image type grains 
H Mono-disperse cubic internal latent 
0.30 9 3.5 
image type grains 
I Poly-disperse tabular grains, average 
0.80 28 1.5 
aspect ratio 4.0 
J Mono-disperse tetradecahedral grains 
0.30 18 4.0 
K Mono-disperse tetradecahedral grains 
0.37 17 4.0 
L Mono-disperse cubic internal latent 
0.46 14 3.5 
image type grains 
M Mono-disperse cubic grains 
0.55 13 4.0 
N Poly-disperse tabular grains, average 
1.00 33 1.3 
aspect ratio 7.0 
__________________________________________________________________________ 
Spectral Sensitization of Emulsions A to N 
Sensitizing 
Amount Added per 
Emulsion 
Dye Added 
Mol Silver Halide 
Time At Which Sensitizing Dye Was Added 
__________________________________________________________________________ 
A S-1 0.025 Immediately after chemical sensitization 
S-2 0.25 Immediately after chemical sensitization 
B S-1 0.01 Immediately after the end of grain formation 
S-2 0.25 Immediately after the end of grain formation 
C S-1 0.02 Immediately after chemical sensitization 
S-2 0.25 Immediately after chemical sensitization 
D S-1 0.01 Immediately after chemical sensitization 
S-2 0.10 Immediately after chemical sensitization 
S-7 0.01 Immediately after chemical sensitization 
E S-3 0.5 Immediately after chemical sensitization 
S-4 0.1 Immediately after chemical sensitization 
F S-3 0.3 Immediately after chemical sensitization 
S-4 0.1 Immediately after chemical sensitization 
G S-3 0.25 Immediately after the end of grain formation 
S-4 0.08 Immediately after the end of grain formation 
H S-3 0.2 During grain formation 
S-4 0.06 During grain formation 
I S-3 0.3 Immediately before start of chemical sensitization 
S-4 0.07 Immediately before start of chemical sensitization 
S-8 0.1 Immediately before start of chemical sensitization 
J S-6 0.2 During grain formation 
S-5 0.05 During grain formation 
K S-6 0.2 During grain formation 
S-5 0.05 During grain formation 
L S-6 0.22 Immediately after the end of grain formation 
S-5 0.06 Immediately after the end of grain formation 
M S-6 0.15 Immediately after chemical sensitization 
S-5 0.04 Immediately after chemical sensitization 
N S-6 0.22 Immediately after the end of grain formation 
S-5 0.06 Immediately after the end of grain 
__________________________________________________________________________ 
formation 
##STR19## 
Preparation of Samples 102-118 
Samples 102 to 118 were prepared in the same way as sample 101 except that 
the couplers added to the ninth, tenth, eleventh and fifteenth, sixteenth 
and seventeenth layers of sample 101 were replaced with equimolar amount 
of the comparative compounds and coupler compounds of the present 
invention shown in table 1. 
The samples 101 to 118 which had been prepared in this way were processed 
for 35 mm size magazines and used as camera materials. The subject used 
was a color chicker made by the Macbeth Co. and development processing was 
carried out using the color developer A indicated below. The samples 
obtained were evaluated in terms of color reproduction by a number of 
evaluators. The yellow color reproduction in particular was compared. 
Furthermore, after cutting samples 101 to 118 into strips, they were 
subjected to a graded exposure through an optical wedge and then developed 
and processed using the color developer A indicated below. The processed 
strips were subjected to density measurements and the magenta density at 
the point which had a yellow density of fog+2.0 was measured and this is 
shown in table 1 as the degree of color mixing. 
Moreover, samples 101 to 1158 were subjected to a graded exposure through 
an optical wedge and then developed and processed using the color 
developer A indicated below. Furthermore, samples were exposed in the same 
way as above and developed and processed using the color developer B 
indicated below. The magenta and yellow maximum image densities 
(D.sub.max) and minimum image densities (D.sub.min) of these processed 
strips were measured. 
The results obtained are shown in table 1. 
______________________________________ 
Processing Operations 
Tank Replen- 
Processing Time Temp. Capacity 
ishment Rate 
Operation (min) (.degree.C.) 
(liters) 
(l/m.sup.2) 
______________________________________ 
Black & White 
6 38 12 2.2 
Development 
First Water Wash 
2 38 4 7.5 
Reversal 2 38 4 1.1 
Color Development 
6 38 12 2.2 
Conditioning 2 38 4 1.1 
Bleaching 6 38 12 0.22 
Fixing 4 38 8 1.1 
Second Water Wash 
4 38 8 7.5 
Stabilization 
1 25 2 1.1 
______________________________________ 
______________________________________ 
Black and White Developer 
Parent Bath Replenisher 
______________________________________ 
Nitrilo-N,N,N-trimethyl- 
2.0 grams 2.0 grams 
enephosphonic acid 
pentasodium salt 
Sodium sulfite 30.0 grams 30.0 grams 
Hydroquinone monosulfonic 
20.0 grams 20.0 grams 
acid potassium salt 
Potassium carbonate 
33.0 grams 33.0 grams 
1-Phenyl-4-methyl-4- 
2.0 grams 2.0 grams 
hydroxymethyl-3- 
pyrazolidone 
Potassium bromide 
2.5 grams 1.4 grams 
Potassium thiocyanate 
1.2 grams 1.2 grams 
Potassium iodide 2.0 mg 
Water to make up to 
1,000 ml 1,000 
ml 
pH 9.60 9.60 
______________________________________ 
The pH was adjusted with hydrochloric acid or potassium hydroxide. 
______________________________________ 
Reversal Bath Parent Bath Replenisher 
______________________________________ 
Nitrilo-N,N,N-trimethyl- 
3.0 grams Same as 
enephosphonic acid penta- Parent Bath 
sodium salt 
Stannous chloride 
1.0 gram 
di-hydrate 
p-Aminophenol 0.1 gram 
Sodium hydroxide 
8 grams 
Glacial acetic acid 
15 ml 
Water to make up to 
1,000 ml 
pH 6.00 
______________________________________ 
The pH was adjusted with hydrochloric acid or sodium hydroxide. 
______________________________________ 
Color Developer A 
Parent Bath Replenisher 
______________________________________ 
Nitrilo-N,N,N-trimethyl- 
2.0 grams 2.0 grams 
enephosphonic acid penta- 
sodium salt 
Sodium sulfite 7.0 grams 7.0 grams 
Tri-sodium phosphate 
36 grams 36 grams 
dodeca-hydrate 
Potassium bromide 
1.0 gram -- 
Potassium iodide 
90 mg -- 
Sodium hydroxide 
3.0 grams 3.0 grams 
Citrazinic acid 
1.5 grams 1.5 grams 
N-Ethyl-(.beta.-methanesul- 
11 grams 11 grams 
fonamidoethyl)-3-methyl- 
4-aminoaniline sulfate 
3,6-Dithia-1,8-octanediol 
1.0 grams 1.0 grams 
Water to make up to 
1,000 ml 1,000 ml 
pH 11.80 12.00 
______________________________________ 
The pH was adjusted with hydrochloric acid or potassium hydroxide. 
______________________________________ 
Conditioner Parent Bath Replenisher 
______________________________________ 
Ethylenediamine tetra- 
8.0 grams Same as 
acetic acid di-sodium Parent Bath 
salt di-hydrate 
Sodium sulfite 12 grams 
1-Thioglycerine 0.4 ml 
Sorbitane ester* 0.1 gram 
Water to make up to 
1,000 ml 
pH 6.20 
______________________________________ 
pH adjusted with hydrochloric acid or sodium hydroxide.*: Sorbitane Ester: 
##STR20## 
______________________________________ 
Bleaching Bath Parent Bath Replenisher 
______________________________________ 
Ethylenediamine tetra- 
2.0 grams 4.0 grams 
acetic acid di-sodium 
salt di-hydrate 
Ethylene diamine tetra- 
120 grams 240 grams 
acetic acid ferric ammonium 
salt di-hydrate 
Potassium bromide 
100 grams 200 grams 
Ammonium nitrate 10 grams 20 grams 
Water to make up to 
1,000 ml 1,000 
ml 
pH 5.70 5.50 
______________________________________ 
The pH was adjusted with hydrochloric acid or sodium hydroxide. 
______________________________________ 
Fixer Parent Bath Replenisher 
______________________________________ 
Ammonium thiosulfate 
8.0 grams Same as 
Parent Bath 
Sodium sulfite 5.0 grams 
Sodium bisulfite 
5.0 grams 
Water to make up to 
1,000 ml 
pH 6.60 
______________________________________ 
The pH was adjusted with hydrochloric acid or aqueous ammonia. 
______________________________________ 
Stabilizer Parent Bath 
Replenisher 
______________________________________ 
Formalin (37%) 5.0 ml Same as 
Parent Bath 
Polyoxyethylene p-mono 
0.5 ml 
nonylphenyl ether (average 
degree of polymerization 10) 
Water to make up to 
1,000 ml 
pH Not Adjusted 
______________________________________ 
Color Developer B 
The amount of sodium hydroxide in color developer A was changed and the pH 
was adjusted from 11.80 to 12.00. 
TABLE 1 
__________________________________________________________________________ 
Degree 
Processing Dependence 
Processing Dependence 
Color reproduction.sup.1) 
of of the Magenta Image 
of the Yellow Image 
Magenta 
Yellow 
Ma- color 
D.sub.max 
D.sub.min 
D.sub.max 
D.sub.min 
Sample Coupler 
Coupler 
genta 
Yellow 
Red 
Green 
Mixing 
A.sup.2) 
B.sup.2) 
A B A B A B 
__________________________________________________________________________ 
101 
Comparative 
C-4 C-5 .DELTA. 
.DELTA. 
.DELTA. 
.DELTA. 
0.46 
3.78 
3.74 
0.16 
0.15 
3.62 
3.57 
0.16 
0.15 
Example 
102 
Comparative 
C-7 " .DELTA. 
.DELTA. 
.DELTA. 
.DELTA. 
0.45 
3.85 
3.81 
0.17 
0.15 
3.62 
3.54 
0.17 
0.15 
Example 
103 
Comparative 
" Y-15 .DELTA. 
.largecircle. 
.DELTA. 
.largecircle. 
0.45 
3.85 
3.81 
0.17 
0.15 
3.64 
3.57 
0.18 
0.15 
Example 
104 
Comparative 
C-8 C-5 .largecircle. 
.DELTA. 
.DELTA. 
.DELTA. 
0.46 
3.90 
3.82 
0.18 
0.15 
3.62 
3.55 
0.17 
0.15 
Example 
105 
Comparative 
" C-6 .largecircle. 
.DELTA. 
.DELTA. 
.DELTA. 
0.45 
3.91 
3.82 
0.18 
0.15 
3.64 
3.57 
0.18 
0.15 
Example 
106 
This " Y-15 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.89 
3.86 
0.17 
0.15 
3.64 
3.61 
0.16 
0.15 
Invention 
107 
This M-1 Y-1 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.88 
3.86 
0.16 
0.15 
3.63 
3.59 
0.16 
0.15 
Invention 
108 
This M-5 Y-3 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.92 
3.86 
0.16 
0.15 
3.62 
3.59 
0.16 
0.15 
Invention 
109 
This M-5 Y-10 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.90 
3.87 
0.16 
0.15 
3.64 
3.60 
0.16 
0.15 
Invention 
110 
This C-8 Y-20 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.89 
3.85 
0.16 
0.15 
3.63 
3.60 
0.16 
0.15 
Invention 
111 
This M-20 Y-23 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.91 
3.86 
0.16 
0.15 
3.65 
3.62 
0.16 
0.15 
Invention 
112 
This M-26 Y-15 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.42 
3.91 
3.87 
0.16 
0.15 
3.64 
3.60 
0.15 
0.15 
Invention 
113 
This " Y-10 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.91 
3.87 
0.16 
0.15 
3.64 
3.61 
0.16 
0.15 
Invention 
114 
This M-27 Y-3 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.89 
3.85 
0.16 
0.15 
3.62 
3.58 
0.16 
0.15 
Invention 
115 
This M-21 Y-23 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.92 
3.89 
0.16 
0.15 
3.64 
3.60 
0.16 
0.15 
Invention 
116 
This M-6 Y-15 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.92 
3.88 
0.16 
0.15 
3.63 
3.59 
0.16 
0.15 
Invention 
117 
This M-6 Y-10 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.43 
3.90 
3.87 
0.16 
0.15 
3.63 
3.60 
0.16 
0.15 
Invention 
118 
This M-26 Y-20 .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
0.42 
3.92 
3.88 
0.16 
0.15 
3.63 
3.60 
0.16 
0.15 
Invention 
__________________________________________________________________________ 
.sup.1) Color reproduction .DELTA.: Slight deterioration .largecircle.: 
Excellent 
.sup.2) Type of color developer 
It is clear from the results shown in Table 1 that in comparison to the 
comparative examples there is no great change in the maximum image density 
(D.sub.max) and the minimum image density (D.sub.min) with a change in the 
pH of color developer with the present invention, the color forming 
properties are good and color reproduction is also improved. 
EXAMPLE 2 
Sample 201 was prepared in the following manner. 
Preparation of Sample 201 
Coated weights are shown in units of grams Ag/m.sup.2 in the case of silver 
halides and colloidal silver, in units of g/m.sup.2 in the case of 
couplers, additives and gelatin, and in units of mol per mol of silver 
halide in the same layer in the case of the sensitizing dyes. 
______________________________________ 
First Layer Anti-halation Layer 
Black colloidal silver 0.15 
Gelatin 1.90 
Second Layer Intermediate Layer 
Gelatin 2.10 
ExM-8 2.0 .times. 10.sup.-2 
UV-1 3.0 .times. 10.sup.-2 
UV-2 6.0 .times. 10.sup.-2 
UV-3 7.0 .times. 10.sup.-2 
ExF-1 4.0 .times. 10.sup.-3 
Solv-2 7.0 .times. 10.sup.-2 
Third Layer Low Speed Red Sensitive 
Emulsion Layer 
Silver iodobromide emulsion 
0.50 
(AgI 2 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 0.3 .mu.m, variation 
coefficient of corresponding 
sphere diameter 29%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/ 
thickness ratio 2.5) 
Gelatin 1.50 
ExS-1 1.0 .times. 10.sup.-4 
ExS-2 3.0 .times. 10.sup.-4 
ExS-3 1.0 .times. 10.sup.-4 
ExC-3 0.22 
ExC-4 3.0 .times. 10.sup.-3 
Solv-1 7.0 .times. 10.sup.-3 
Fourth Layer (Intermediate Speed Red Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.85 
(AgI 4 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 0.55 .mu.m, variation 
coefficient of corresponding 
sphere diameter 20%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/thickness 
ratio 1.0) 
Gelatin 2.00 
ExS-1 1.0 .times. 10.sup.-4 
ExS-2 3.0 .times. 10.sup.-4 
ExS-3 1.0 .times. 10.sup.-5 
ExC-2 8.0 .times. 10.sup.-2 
ExC-3 0.33 
ExY-13 2.0 .times. 10.sup.-2 
ExY-14 1.0 .times. 10.sup.-2 
Cpd-10 1.0 .times. 10.sup.-4 
Solv-1 0.10 
Fifth Layer (High Speed Red Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.70 
(AgI 10 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 0.7 .mu.m, variation 
coefficient of corresponding 
sphere diameter 30%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/ 
thickness ratio 2.0) 
Gelatin 1.60 
ExS-1 1.0 .times. 10.sup.-4 
ExS-2 3.0 .times. 10.sup.-4 
ExS-3 1.0 .times. 10.sup.-5 
ExC-5 7.0 .times. 10.sup.-2 
ExC-6 8.0 .times. 10.sup.-2 
Solv-1 0.15 
Solv-2 8.0 .times. 10.sup.-2 
Sixth Layer (Intermediate Layer) 
Gelatin 1.10 
P-2 0.17 
Cpd-1 0.10 
Cpd-4 0.17 
Solv-1 5.0 .times. 10.sup.-2 
Seventh Layer (Low Speed Green Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.30 
(AgI 2 mol %, high internal AgI 
as silver 
type, corresponding sphere 
diameter 0.3 .mu.m, variation 
coefficient of corresponding 
sphere diameter 28%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/thickness 
ratio 2.5) 
Gelatin 0.50 
ExS-4 5.0 .times. 10.sup.-4 
ExS-5 2.0 .times. 10.sup.-4 
ExS-6 0.3 .times. 10.sup.-4 
ExM-8 0.20 
ExY-13 3.0 .times. 10.sup.-2 
Cpd-11 7.0 .times. 10.sup.-3 
Solv-1 0.20 
Eigth Layer (Intermediate Speed Green Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.70 
(AgI 4 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 0.55 .mu.m, variation 
coefficient of corresponding 
sphere diameter 20%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/thickness 
ratio 4.0) 
Gelatin 1.00 
ExS-4 5.0 .times. 10.sup.-4 
ExS-5 2.0 .times. 10.sup.-4 
ExS-6 3.0 .times. 10.sup.-5 
ExM-8 0.25 
ExM-10 1.5 .times. 10.sup.-2 
ExY-13 4.0 .times. 10.sup.-2 
Cpd-11 9.0 .times. 10.sup.-3 
Solv-1 0.20 
Ninth Layer (High Speed Green Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.50 
(AgI 10 mol %, high interal 
as silver 
AgI type, corresponding sphere 
diameter 0.7 .mu.m, variation 
coefficient of corresponding 
sphere diameter 30%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/thickness 
ratio 2.0) 
Gelatin 0.90 
ExS-4 2.0 .times. 10.sup.-4 
ExS-5 2.0 .times. 10.sup. -4 
ExS-6 2.0 .times. 10.sup.-5 
ExS-7 3.0 .times. 10.sup.-4 
ExM-8 0.10 
ExM-12 2.0 .times. 10.sup.-2 
Cpd-2 1.0 .times. 10.sup.-2 
Cpd-9 2.0 .times. 10.sup.-4 
Cpd-10 2.0 .times. 10.sup.-4 
Solv-1 0.20 
Solv-2 5.0 .times. 10.sup.-2 
Tenth Layer (Yellow Filter Layer) 
Gelatin 0.90 
Yellow colloidal silver 5.0 .times. 10.sup.-2 
Cpd-1 0.20 
Solv-1 0.15 
Eleventh Layer (Low Speed Blue Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.40 
(AgI 4 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 0.5 .mu.m, variation 
coefficient of the corresponding 
sphere diameter 15%, octahedral 
grains) 
Gelatin 1.00 
ExS-8 2.0 .times. 10.sup.-4 
ExY-15 0.90 
Solv-1 0.30 
Cpd-2 1.0 .times. 10.sup.-2 
Twelfth Layer (High Speed Blue Sensitive 
Emulsion Layer) 
Silver iodobromide emulsion 
0.50 
(AgI 10 mol %, high internal 
as silver 
AgI type, corresponding sphere 
diameter 1.3 .mu.m, variation 
coefficient of the corresponding 
sphere diameter 25%, regular 
crystal grain/twinned crystal 
grain mixture, diameter/ 
thickness ratio 4.5) 
Gelatin 0.60 
ExS-8 1.0 .times. 10.sup.-4 
ExY-15 0.12 
Cpd-2 1.0 .times. 10.sup.-3 
Solv-1 4.0 .times. 10.sup.-2 
Thirteenth Layer (First Protective Layer) 
Fine grain silver iodobromide 
0.20 
(average grain size 0.07.mu., 
AgI 1 mol %) 
Gelatin 0.80 
UV-2 0.10 
UV-3 0.10 
UV-4 0.20 
Solv-3 4.0 .times. 10.sup.-2 
P-2 9.0 .times. 10.sup.-2 
Fourteenth Layer (Second Protective Layer) 
Gelatin 0.90 
B-1 (Diameter 1.5 .mu.m) 0.10 
B-2 (Diameter 1.5 .mu.m) 0.10 
B-3 2.0 .times. 10.sup.-2 
H-1 0.40 
______________________________________ 
Moreover, Cpd-3, Cpd-5, Cpd-6, Cpd-7, Cpd-8, P-1, W-1, W-2 and W-3 
indicated below were added in order to improve storage properties, 
processing properties and pressure resistance, for biocidal and fungicidal 
purposes, for anti-static purposes and for improving the coating 
properties. 
n-Butyl p-hydroxybenzoate was added in addition to the above mentioned 
compounds. Moreover, B-4, F-1, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11 
and F-13, and iron salts, lead salts, gold salts, platinum salts, iridium 
salts and rhodium salts were included. 
The structural formulae or chemical names of the compounds used in the 
present invention are indicated below. 
##STR21## 
Preparation of Samples 202-218 
Samples 202 to 218 were prepared in the same way as sample 101 except that 
the couplers which were added to the seventh, eighth and ninth, and 
eleventh and twelfth layers of sample 201 were replaced with equimolar 
amount of the comparative compounds and coupler compounds of the present 
invention shown in Table 2. The samples prepared were tested with 
development processing as indicated below as in example 1, and the results 
obtained were the same as those obtained in Example 1. 
After exposing the color photographic materials in the way described above, 
they were processed in accordance with the procedure outlined below in an 
automatic processor (until the cumulative replenishment of the baths 
reaches three times the parent bath capacity). 
__________________________________________________________________________ 
Color Development Processing 
Replenishment 
Process Processing Time 
Processing Temp. 
Rate* Tank Capacity 
__________________________________________________________________________ 
Color development 
3 min. 15 sec. 
38.degree. C. 
33 ml 20 liters 
Bleach 6 min. 30 sec. 
38.degree. C. 
25 ml 40 liters 
Water Wash 
2 min. 10 sec. 
24.degree. C. 
1200 ml 20 liters 
Fixing 4 min. 20 sec. 
38.degree. C. 
24 ml 30 liters 
Water Wash (1) 
1 min. 05 sec. 
24.degree. C. 
Note 1 10 liters 
Water Wash (2) 
1 min. 00 sec. 
24.degree. C. 
1200 ml 10 liters 
Stabilization 
1 min. 05 sec. 
38.degree. C. 
25 ml 10 liters 
Drying 4 min. 20 sec. 
55.degree. C. 
__________________________________________________________________________ 
Replenishment rate per meter of 35 mm wide material 
Note 1: 
A counterflow system from (2) to (1) 
The composition of each processing bath is as indicated below. 
______________________________________ 
Parent Bath 
Replenisher 
(grams) (grams) 
______________________________________ 
Color Developer A 
Diethylenetriamine penta- 
1.0 1.1 
acetic acid 
1-Hydroxyethylidene-1,1-di- 
3.0 3.2 
phosphonic acid 
Sodium sulfite 4.0 4.4 
Potassium carbonate 
30.0 37.0 
Potassium bromide 1.4 0.7 
Potassium iodide 1.5 mg -- 
Hydroxylamine sulfate 
2.4 2.8 
4-[N-ethyl-N-.beta.-hydroxyethyl- 
4.5 5.5 
amino]-2-methylaniline sulfate 
Water to make up to 
1.0 liter 1.0 liter 
pH 10.05 10.10 
Bleach 
Ethylenediamine tetra-acetic 
100.0 120.0 
acid ferric sodium salt 
tri-hydrate 
Ethylenediamine tetra-acetic 
10.0 10.0 
acid di-sodium salt 
Ammonium bromide 140.0 160.0 
Ammonium nitrate 30.0 35.0 
Aqueous ammonia (27%) 
6.5 ml 4.0 ml 
Water to make up to 
1.0 l 1.0 l 
pH 6.0 5.7 
Fixing 
Ethylenediamine tetra-acetic 
0.5 0.7 
acid, di-sodium salt 
Sodium sulfite 7.0 8.0 
Sodium bisulfite 5.0 5.5 
Aqueous ammonium thio- 
170.0 ml 200.0 ml 
sulfate solution (70 wt/vol %) 
Water to make up to 
1.0 l 1.0 l 
pH 6.7 6.6 
Stabilizer 
Formalin (37%) 2.0 ml 3.0 ml 
Polyoxyethylene p-mono- 
0.3 0.45 
nonylphenyl ether (average 
degree of polymerization 10) 
Ethylenediamine tetra-acetic 
0.05 0.08 
acid di-sodium salt 
Water to make up to 
1.0 l 1.0 l 
pH 5.0-8.0 5.0-8.0 
______________________________________ 
Color Developer B 
The amount of potassium carbonate in color developer A was changed and the 
pH was adjusted from 10.05 to 9.60. 
TABLE 2 
______________________________________ 
Sample Magenta Coupler 
Yellow Coupler 
______________________________________ 
201 (Comparative Example) 
ExM-8 ExY-15 
202 (Comparative Example) 
ExM-8 Y-15 
203 (Comparative Example) 
ExM-9 Y-15 
204 (Comparative Example) 
M-1 ExY-15 
205 (Comparative Example) 
M-5 ExY-13 
206 (This Invention) 
M-1 Y-15 
207 (This Invention) 
M-5 Y-1 
208 (This Invention) 
M-12 Y-20 
209 (This Invention) 
M-17 Y-15 
210 (This Invention) 
M-17 Y-10 
211 (This Invention) 
M-26 Y-15 
212 (This Invention) 
M-27 Y-3 
213 (This Invention) 
M-6 Y-10 
214 (This Invention) 
M-6 Y-23 
215 (This Invention) 
M-26 Y-20 
216 (This Invention) 
M-8 Y-3 
217 (This Invention) 
M-8 Y-15 
218 (This Invention) 
M-10 Y-8 
______________________________________ 
EXAMPLE 3 
Sample A is prepared in the same way as in Example 2 of JP-A-2-158431 
except that the total number of mol of the magenta couplers (ExM-1 and 
ExM-2) and the yellow coupler (ExY-1) added to the sixth, seventh, 
eleventh and twelfth layers disclosed in the example are replaced with 
equimolar amounts of couplers of the present invention. Sample A is 
exposed and processed in the same way as described in Example 1 and 
results similar to those of Example 1 are obtained. 
EXAMPLE 4 
Sample B is prepared in the same way as in Example 2 of European Patent EP 
0,355,660A2 except that the total number of mol of yellow coupler (ExY), 
magenta coupler (ExM) and cyan coupler (ExC) in the multi-layer color 
paper sample number 214 disclosed in the example are replaced with 
equimolar amounts of couplers of the present invention. Sample B is 
exposed and processed in the same way as described in Example 1 and 
results similar to those of example 1 are obtained. 
EFFECT OF THE INVENTION 
Silver halide color photographic materials which have excellent color 
reproduction and which exhibit no fluctuation in D.sub.max and D.sub.min 
as a result of fluctuations in the pH of the color developer are obtained 
by means of the present invention. 
While the invention has been described in detail and with reference to 
specific embodiments 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.