Silver halide color photographic light-sensitive material

A silver halide color photographic light-sensitive material containing a phenol cyan coupler having an ureido group in the 2-position dispersed in a phthalic ester.

BACKGROUND OF THE INVENTION 
The invention relates to a silver halide color photographic light-sensitive 
material and, more particularly, to a silver halide color photographic 
light-sensitive material which is excellent in the absorption spectra of 
cyan dyes produced by a coupling reaction with oxidants of a color 
developing agent. 
Still more detailedly, the invention relates to a silver halide color 
photographic light-sensitive material in which ortho-positioned ureido 
type hydrophobic phenol couplers are dispersed by making use of a specific 
phthalic acid ester and thus obtained dispersed matter is contained stably 
in silver halide emulsions, and in which the absorption spectra of cyan 
dyes produced by the color development of the couplers are of long wave 
length and less in the secondary absorption of green spectrum, that is, 
the absorption spectra of the cyan dyes are preferable for color 
reproduction. 
Heretofore, naphthol couplers have been used for cyan couplers of highly 
light-sensitive color negative photographic materials. These cyan couplers 
have been put into practice because they are characterized in that the 
absorption spectra of cyan dyes produced by a reaction with the oxidants 
of a color developing agent are of long wave length and less in the 
secondary absorption of green spectrum, that is, the absorption spectra of 
the cyan dyes are preferable for color reproduction. 
However, in the recent years, the general tendency is being directed to the 
resource-saving from the viewpoint of silver shortage and the like, and 
the current types of color negative photographic light-sensitive materials 
are being shifted to those in an extremely small format of the picture 
size from, for example, 135 mm size to 110 size and further most recently 
to a disk film size of 8.times.10 mm that has most recently been put on 
the market. These light-sensitive materials of such a small format must, 
however, record a lot of information onto the much smaller area thereof 
than the areas of conventional types of light-sensitive materials, and 
eventually the print magnification becomes larger. It is therefore 
indispensable to apply technics for improving image quality such as 
graininess and sharpness. 
In disk films, it has been reported that the technic for improving image 
sharpness was achieved by making use of DIR couplers which can display an 
excellent edge-effect and by thinning the coated layer on the film, and it 
may be indicated that the graininess thereof has been achieved by 
increasing the amount of silver coated. None the less, there is a serious 
disadvantage in these achievements that conventional types of naphthol 
cyan dyes cause a reduction discoloration by a large amount of ferrous 
ions produced in the course of a bleach or a bleach-fix process for 
developed silver in a processing liquid, that has made such naphthol cyan 
couplers difficult to use. 
As mentioned above, it is necessary to increase the amount of silver to be 
coated if required for improving the graininess of small-format 
light-sensitive materials. In such a light-sensitive material, it must 
note that it is itself necessary to have a coupler not causing any 
reduction discoloration by ferrous ions of cyan dye but having a spectral 
absorption characteristics equivalent to those of conventional types of 
naphthol cyan dyes. 
As for the couplers not causing any reduction discoloration of cyan dyes in 
course of a bleach or a bleach-fix process, there are known couplers each 
substituted by an acylamino radical at the ortho and the meta positions of 
phenol as disclosed in U.S. Pat. No. 2,895,826, Japanese Patent 
Publication Open to the Public Inspection (hereinafter referred to as 
Japanese Patent O.P.I. Publication) Nos. 112038/1975, 109630/1978 and 
163537/1980, and the like. In the absorption spectra of the color 
developable dyes of everyone of these couplers, there are the respective 
maximum absorption in the wave-length range shorter than the red spectral 
range and there are many absorption in the green spectral range, and that 
has not therefore been preferable from the viewpoint of color 
reproduction. Phenol couplers each having an ureido radical in the ortho 
position thereof are described in British Pat. No. 1,011,940, and U.S. 
Pat. Nos. 3,446,622, 3,996,253, 3,758,308 and 3,880,661. In these 
couplers, similar to the aforementioned couplers, there are the absorption 
in the wavelength range shorter than the red spectral range of the 
absorption spectra of the color developable dyes and the absorption are 
broad. They are consequently not preferable for color reproduction, and 
besides there are some couplers which cause color fading in a bleach 
process, that has been a problem. 
On the other hand, phenol couplers each having an ureido radical in the 
ortho position thereof as described in Japanese Patent O.P.I. Publication 
No. 65134/1981 will not cause any color fading of the cyan dyes in a 
bleach process and the respective absorption maximum of the phenol 
couplers are in a relatively longer wavelength portion of the red spectral 
range of the absorption spectre thereof, and the green spectral absorption 
is also less, so that they can display the absorption characteristics 
closer to those of the naphthol couplers. However, the absorption maximum 
of the wavelength and the green spectral range (i.e.; sharp-cut of the 
short wave side) are still not fully satisfied. 
In these couplers, there have been few changes in absorption spectra of 
color developing dyes even if there have used therein with a variety of 
solvents such as phthalic acid esters, phosphoric esters and the like 
which have ordinary been used as high-boiling solvents for an oil-soluble 
additive for photographic use such as antioxidants for couplers, and 
therefore, absorption spectra have hardly been improved by utilizing the 
changes of the high boiling solvents used. 
SUMMARY OF THE INVENTION 
Based on the technical background as mentioned above, the inventors have 
devoted themselves to study the usage of couplers each not being caused 
therein any color fading in a bleach process and having absorption 
spectral characteristics of the color developing dyes thereof equivalent 
to those of naphthol dyes and the usage of the high boiling solvents to be 
used with the couplers, and resultantly, they have found out the amazing 
effect that the objects of the invention can be achieved in the process 
that couplers each having an ureido radical in the ortho position given in 
Formula [I] are dispersed by making use of a specific high boiling solvent 
of phthalic acid esters having Formula [II] and the dispersed matter is 
contained in a silver halide emulsion layer. 
OBJECTS OF THE INVENTION 
It is an object of the invention to provide a silver halide color 
light-sensitive material in which the absorption maximum is in the long 
wave-length portion of the red spectral range and by which a cyan dye 
image having less absorption in green spectral range can be obtained. 
Another object of the invention is to provide a silver halide color 
light-sensitive material in which the cyan dyes thereof are not faded by 
ferrous ions in the course of a bleaching process. 
It is a further object of the invention to provide a silver halide color 
light-sensitive material in which the graininess thereof is improved. 
Abovementioned object of the invention can be achieved with a silver halide 
color photographic light-sensitive material comprising a support provided 
thereon a hydrophilic colloidal layer containing at least one kind of 
phenol cyan coupler having the Formula [I] in which an ureido radical is 
2-position and being dispersed by making use of a phthalic ester having 
the Formula [II]: 
##STR1## 
wherein R.sub.1 represents a straight or branched alkyl, cycloalkyl 
radical, R.sub.2 represents a hydrogen atom, a halogen atom or a 
monovalent organic radical, R.sub.3 represents a straight or branched 
alkyl radical, R.sub.4 and R.sub.5 each represents a branched alkyl 
radical, Z represents a hydrogen atom or a radical capable of eliminating 
in a coupling reaction with an oxidation product of a color developing 
agent, n represents an integer of 0 to 3, preferably 0 or 1. 
##STR2## 
Wherein R.sub.6 and R.sub.7 each represent an alkyl, alkenyl, aryl or 
cycloalkyl radical. 
In the Formula [I] as for the halogen represented by R.sub.2, chlorine and 
bromine are preferable. As for the monovalent organic radicals, for 
example, the following are given; an alkyl radical and inter alia 
preferably a straight or branched alkyl radical having 1 to 4 carbon atoms 
and more preferably methyl or tert-butyl, an aryl radical and inter alia 
preferably a substituted or unsubstituted phenyl radical, a heterocyclic 
radical and inter alia preferably a nitrogen-containing heterocyclic 
radical and more preferably pyrrolidine or piperidine, a hydroxy radical, 
an alkoxy radical and inter alia preferably a susbstituted or 
unsubstituted alkoxy radical having 1 to 8 carbon atoms and more 
preferably a methoxy, tert-butyloxy, or methoxycarbonyl methoxy radical or 
the like, an aryloxy radical and inter alia preferably a substituted or 
unsubstituted phenoxy radical, an acyloxy radical and inter alia 
preferably a substituted or unsubstituted alkylcarbonyloxy radical, 
arylcarbonyloxy radical or the like, a mercapto radical, an alkylthio 
radical or the like, a mercapto radical, an alkylthio radical and inter 
alia preferably a substituted or unsubstituted alkyl radical having 1 to 8 
carbon atoms and more preferably a methylthio radical, a nitro radical, a 
cyano radical, an acyl radical and inter alia preferably an alkylcarbonyl 
radical having 1 to 8 carbon atoms and more preferably an acetyl radical 
or pivaloyl radical, an amino radical, an alkylamino radical and inter 
alia preferably a straight or branched alkylamino radical having 1 to 4 
carbon atoms and more preferably a methylamino radical, ethylamino radical 
or tert-butylamino radical, or a dialkylamino radical and inter alia 
preferably dimethylamino radical or diethylamino radical. 
As the monovalent organic radical, an acyloxy radical such as an acetoxy or 
benzoyloxy radical, a nitro radical and a cyano radical are more 
preferable. 
R.sub.1 represents preferably an alkyl radical having 1 to 20 carbon atoms, 
such as a methyl, ethyl, n-propyl, Sec-propyl, n-butyl, tert-octyl, 
n-dodecyl, or benzyl radical and the like; a cycloalkyl radical such as a 
cyclohexane radical or the like. 
Rhd 4 and R.sub.5 each preferably represent a branched alkyl radical having 
3 to 20 carbon atoms, such as a tert-butyl, tert-pentyl, or tert-octyl 
radical, and R.sub.4 and R.sub.5 may be the same with or the different 
from each other and preferably be the same. 
In the Formula [I], as for the radicals represented by Z capable of 
eliminating in the course of a coupling reaction with oxidation products 
of a color developing agent, the following radicals may be given as a 
halogen atom such as chlorine, bromine, fluorine, an aryloxy, 
carbamoyloxy, carbamoylmethoxy, acyloxy, sulfonamide or succinimide 
radical wherein oxygen atom or nitrogen atom is directly coupled in the 
coupling position, and more concretely the examples thereof are described 
respectively in U.S. Pat. No. 3,471,563, Japanese Patent O.P.I. 
Publication Nos. 37425/1972, 10135/1975, 117422/1975, 130441/1975, 
108841/1976, 120334/1975, 18315/1977, 52423/1978 and 105226/1978, and 
Japanese Patent Examined Publication No. 36894/1973. 
Couplers of the invention can be synthesized in the processes described 
respectively in Japanese Patent Application Nos. 90334/1981, 90335/1981, 
90336/1981 and the like. 
Cyan couplers of the invention having Formula [I] are exemplified as 
follows and it is however to be understood that they shall not be limited 
to the cyan couplers hereby exemplified: 
##STR3## 
Phenol cyan couplers relating to the invention and having the Formula [I] 
may be prepared in such a synthesizing process as described in Japanese 
Patent O.P.I. Publication No. 204545/1982. 
Next, phthalic acid ester high boiling solvents to be used in the invention 
are formularized in the aforegiven Formula [II], and the particularly 
preferably phthalic acid esters for the invention are those in which 
R.sub.6 and R.sub.7 each represent, in the Formula [II], a straight or 
branched alkyl radical having 4 to 12 carbon atoms, such as an n-butyl, 
Sec-butyl, n-hexyl, Sec-octyl, or n-dodecyl radical and the like, or, a 
substituted or unsubstituted aryl radical having 6 to 12 carbon atoms, 
such as a phenyl, or, tolyl radical and the like. Further preferable ones 
thereof are those in which both of R.sub.6 and R.sub.7 are a straight or 
branched alkyl radical having 4 to 12 carbon atoms. 
Phthalic acid ester compounds to be used of the invention may be 
exemplified below, and it is however understood that they shall not be 
limited thereto: 
##STR4## 
The abovementioned high boiling solvents are available from the market as a 
merchandise. 
The invention displays the amazing effects that the spectral absorption 
characteristics equivalent to those of naphthol cyan dyes are obtainable 
and that any discoloration cannot be occurred in a bleaching process, in 
the manner that a cyan coupler having Formula [I] are dispersed to and 
contained in a hydrophilic colloidal layer by making use of a high boiling 
solvent having Formula [II]. 
It is also allowed to use two or more kinds of these high boiling solvents 
in combination. And, if occasion demands, these high boiling solvents may 
be used in combination with the other high boiling solvents or low boiling 
solvents on condition that the effects of the invention shall not be 
spoiled. 
The amount of the abovementioned high boiling organic solvent used in the 
invention is 0.05 to 15 parts by weight and more preferably 0.1 to 6.0 
parts by weight to one part of the aforesaid cyan couplers. 
In the invention, as mentioned above, cyan couplers relating to the 
invention are dispersed by making use of high boiling solvents relating to 
the invention and are then contained in a hydrophilic colloidal layer, 
however, in general, a silver halide color photographic light-sensitive 
material has a multi-layered constitution and comprises a support bearing 
thereon a plurality of color dye image forming component unit layers being 
spectrally sensitized in each of the spectral regions and if necessary 
bearing thereon, besides the abovementioned unit layers, such a 
non-light-sensitive auxiliary layer as a protective layer, inter layer 
including, e.g., a non-sensitized emulsion layer, a filter layer, 
irradiation layer, an antihalation layer and the like, and such layers 
constituting a color light-sensitive material ordinarily comprise 
hydrophilic colloidal layers. 
Cyan couplers having Formula [I] which are to be used in the invention may 
also be applied with the processes and techniques to be applied for an 
ordinary cyan dye forming coupler. 
In the invention, cyan couplers relating to the invention are compounded in 
a light-sensitive silver halide emulsion layer which is preferably one of 
the hydrophilic colloidal layers, and the emulsion layer is coated over to 
the support, and thus, a color photographic light-sensitive material is 
formed. In a multi-color photographic light-sensitive material, cyan dye 
forming couplers relating to the invention are contained ordinarily in a 
red-sensitive silver halide emulsion layer. However, in the invention, 
cyan couplers relating to the invention may also be contained in a silver 
halide emulsion layer having the light-sensitivity thereof in a different 
spectral region from that of the above-mentioned red-sensitive silver 
halide emulsion layer, and in addition thereto, they may further be 
contained in the other constitutional layers. In a silver halide color 
photographic light-sensitive material of the invention, each of the 
abovementioned constitutional unit layers may comprise a single emulsion 
layer or a multi-layered emulsion layer which is light-sensitive to a 
certain region of a spectrum. The layers of the abovementioned 
light-sensitive material including an image forming unit layer may be 
arranged in a variety of the orders being well-known in the art. Typical 
multi-color photographic light-sensitive materials comprise a support 
bearing thereon a cyan dye image forming unit comprising at least one 
red-sensitive silver halide emulsion containing at least one cyan dye 
forming coupler in which at least one of the cyan dye forming couplers is 
a coupler of the invention, a magenta dye image forming unit comprising at 
least one green-sensitive silver halide emulsion layer containing at least 
one magenta dye forming coupler, and a yellow dye image forming unit 
comprising at least one blue-sensitive silver halide emulsion layer 
containing at least one yellow dye forming coupler, and the material may 
have additional layers such as the aforementioned filter layer, an 
interlayer, a protective layer, and besides, a subbing layer and the like. 
A conventional process having hitherto been publicly known may be used for 
containing the couplers relating to the invention into an emulsion. For 
example, a silver halide emulsion to be used for the invention may be 
prepared in such a process that couplers of the invention may be prepared 
in such a process that couplers of the invention are dissolved 
independently or in combination in a high boiling solvent relating to the 
invention or, if required, in a mixed solution of the abovementioned 
solvent and a low boiling solvent such as butyl acetate, butyl propionate 
or the like, and the solution obtained is then mixed with an aqueous 
gelatin solution containing a surface active agent, and next, the mixture 
is emulsified by means of a high-speed rotary mixer or a colloid mill, and 
the emulsion obtained is added to silver halide. In the case of adding the 
couplers relating to the invention into silver halide emulsion, 
preferably, approximately 0.07 to 0.7 mole of the couplers per mole of 
silver halide, and more preferably, 0.1 to 0.4 mole are normally added. 
As for the silver halide to be used in silver halide emulsions of silver 
halide color photographic light-sensitive materials of the invention, 
there are included any arbitrary silver halide to be used in such a normal 
silver halide emulsion as silver bromide, silver chloride, silver 
iodobromide, silver chlorobromide, silver chloroiodobromide and the like. 
As for the binders for hydrophilic colloidal layers forming the silver 
halide emulsion layers or the other constitutional layers of the 
abovementioned light-sensitive materials of the invention, there have so 
far been used the well-known ones, for example, gelatin and such a gelatin 
derivative as phenylcarbamylated gelatin, acylated gelatin, phthalated 
gelatin and the like. These binders are allowed to use if occasion demands 
as a compatible mixture of not less than two kinds thereof. 
It is possible to prepare a silver halide emulsion which is to be used in 
the invention in a variety of the preparation processes including 
processes being usually used, for example, such processes as described in 
Japanese Patent Examined Publication No. 7772/1971, namely, the so-called 
conversion emulsion preparation process in which a silver salt particle 
emulsion comprising at least one part of silver salt whose solubility is 
greater than that of silver bromide is formed and at least one part of 
these silver salt particles is then converted into silver bromide or 
silver iodobromide and the like processes, a preparation process for 
Lippmann emulsion comprising a fine grain silver halide having the average 
grain size of no larger than 0.1.mu., or the like. 
Further, silver halide emulsion in the invention may be chemically 
sensitized by making suitable use independently or in combination of a 
sulphur sensitizer such as allylthio carbamide, thio urea, cystine, or the 
like; an active or inactive selenium sensitizer; a reduction sensitizer 
such as stannous salt, polyamine or the like; a noble metal sensitizer 
such as a gold sensitizer and, more concretely, potassium aurithiocyanate, 
potassium chloraurate, 2-aurosulfobenzothiazole methyl chloride or the 
like; or a water-soluble salt sensitizer such as a salt of ruthenium, 
rhodium, iridium or the like and more concretely, ammonium chloropalladate 
potassium chloroplatinate, sodium chloropalladite or the like. 
The abovementioned silver halide emulsions may also contain a variety of 
photographic additives which have publicly been known. For example, there 
is such a photographic additive as described in "Research Disclosure", 
Article No. 17643, Dec., 1978. 
Silver halide which is to be used in a silver halide color photographic 
light-sensitive material of the invention is spectrally sensitized by 
making use of a suitably selected sensitizing dye with the purpose of 
endowing with the light-sensitivity to a light-sensitive spectral region 
necessary for a red-sensitive emulsion. 
As for the spectrally sensitizing dyes, a variety thereof may be used 
independently or in combination. As for the spectrally sensitizing dyes 
which are to be used advantageously in the invention, the examples thereof 
may be typically given as a cyanine dye, merocyanine dye or conjugated 
cyanine dye described in U.S. Pat. Nos. 2,269,234, 2,270,378, 2,442,710, 
2,454,620, 2,776,280, and the like. 
The abovementioned light-sensitive material of the invention may be 
developed, after it is exposed to light, in a well-known process having 
popularly been used. For example, it may be color developed in a color 
developing process having popularly been used. 
Color developing liquids which are preferably usable for color-developing 
the abovementioned photographic light-sensitive material of the invention 
principally comprise an aromatic primary amine color developing agent of 
which the concrete examples are typically given as those of p-phenylene 
diamine such as diethyl-p-phenylene diamine chloride, 
monomethyl-p-phenylene diamine chloride, dimethyl-p-phenylene diamine 
chloride, 2-amino-5-diethylamino toluene chloride, 
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 
2-amino-5-(N-ethyl-N-.beta.-methanesulfonamide ethyl)aminotoluene sulfide, 
4-(N-ethyl-N-.beta.-methanesulfonamide ethylamino)aniline, 
4-(N-ethyl-N-.beta.-hydroxyethylamino)aniline, 
2-amino-5-(N-ethyl-N-.beta.-methoxy ethyl)aminotoluene, and the like. 
After a development is completed, a series of normal processes of 
bleaching, fixing or bleach-fix, washing and drying is carried out for 
removing silver and silver halide.

The invention will be more concretely described by the following examples; 
however, these examples are not to be constructed to limit the embodiments 
of the invention. 
EXAMPLE 1 
Coupler of the invention and control couplers (A), (B), (C) and (D) shown 
in Table 1 were taken respectively in the amount of 10 mol% to Ag, and 
each of the couplers taken was added to the respective mixture of such a 
high boiling solvent as shown in Table 1 in one-half of the amount by 
weight of the couplers and ethyl acetate in three times the amount by 
weight of the couplers, and then heat was applied thereto to dissolve 
completely. Thus obtained solutions each were mixed with 200 ml of aqueous 
solution of 5% gelatin containing 20 ml of aqueous solution of 5% alkanol 
B (i.e., alkyl naphthalene sulfonate, mfd. by Du Pont), and an 
emulsification-dispersion of each mixture was made by means of a colloid 
mill, and thus each emulsified matter was obtained. 
After then, the dispersed solutions were added respectively to 1 kg of 
red-sensitive silver iodobromide emulsion containing 6 mol% of silver 
iodide, and thereto 20 ml of solution of 2% 1,2-bis-(vinyl sulfonyl)ethane 
(of which the proportion was water: methanol=1:1) were added, and the 
mixtures each thus obtained were coated onto a sublayered transparent 
polyethylene terephthalate base and were dried up, and thus, Samples (1-1) 
through (1-10) were prepared. (Silver amounts coated each: 20 mg/dm.sup.2) 
##STR5## 
Thus prepared Samples (1-1) through (1-10) were exposed to light in a 
conventional method and then developed in the following process. The 
results obtained are shown in Table 1. 
______________________________________ 
[Developing Process](at 38.degree. C.) 
Processing Time 
______________________________________ 
Color developing 3 min. 15 sec. 
Bleaching 6 min. 30 sec. 
Washing 3 min. 15 sec. 
Fixing 6 min. 30 sec. 
Washing 3 min. 15 sec. 
Stabilizing 1 min. 30 sec. 
______________________________________ 
Composition of each processing liquid used in the abovementioned processes 
was as follows: 
______________________________________ 
[Color developing liquid composition] 
4-amino-3-methyl-N--ethyl-N-- 
4.75 g 
(.beta.-hydroxy ethyl)-aniline sulfate 
Sodium sulfite, anhydrous 
44.25 g 
Hydroxyamine 1/2 sulfate 
2.0 g 
Potassium carbonate, anhydrous 
37.5 g 
Sodium bromide 1.3 g 
Nitrilotriacetic acid 3 sodium 
2.5 g 
salt (monohydrate) 
Potassium hydroxide 1.0 g 
Add water to make 1.0 ltr. 
Adjust pH value by making use of 
pH 10.0 
potassium hydroxide to 
[Bleaching liquid composition] 
Ethylenediamine tetraacetic 
100.0 g 
acid iron ammonium salt 
Ethylenediamine tetraacetic 
10.0 g 
acid 2 ammonium salt 
Ammonium bromide 150.0 g 
Glacial acetic acid 10.0 ml 
Add water to make 1.0 ltr. 
Adjust pH value by making use of 
pH 60.0 
aqueous ammonia to 
[Fixing liquid composition] 
Ammonium thiosulfate 162 ml 
(50% aqueous solution) 
Sodium sulfite, anhydrous 
12.4 g 
Add water to make 1.0 ltr. 
Adjust pH value by making use of 
pH 6.5 
acetic acid to 
[Stabilizing liquid composition] 
Formalin (37% aqueous solution) 
5.0 ml 
Koniducks (mfd. by Konishiroku 
7.5 ml 
Photo Ind. Co., Ltd.) 
Add water to make 1.0 ltr. 
______________________________________ 
In Table 1, .lambda.-max value indicates the respective absorption maximum 
values when a cyan color image density is at 1.0, and .DELTA..lambda.S 
indicates the respective values obtained by the formula below and it 
expresses that the smaller the value is, the sharper the short-wave side 
is and the smaller the green-spectral region is absorbed: 
.DELTA..lambda.S(nm)=(.lambda.-max. value when D=1.0)-(.lambda..sub.0 
value when D=0.2, on the short-wave side from .lambda.-max. point). 
TABLE 1 
______________________________________ 
Sample .lambda.-max 
No. Coupler High boiling solvent 
(nm) .DELTA..lambda.S (nm) 
______________________________________ 
1 - 1 Control Invention P - 1 
695 120 
1 - 2 Control - B 
" 662 123 
1 - 3 Control - C 
" 692 130 
1 - 4 Control - C 
TCP 688 128 
1 - 5 Control - C 
DELA 684 128 
1 - 6 Control - D 
Invention P - 1 
684 132 
1 - 7 Control - D 
TCP 683 133 
1 - 8 Invention-1 
Invention P - 1 
696 123 
1 - 9 Invention-1 
TCP 682 125 
1 - 10 
Invention-1 
DELA 676 122 
______________________________________ 
From Table 1, it may be understood that the .lambda.-max. of Control 
Coupler B apparently shows a short wave. Control Coupler C has 
substantially smaller changes of the .lambda.-max according to the changes 
of the high boiling solvent, however, the .lambda.-max. value thereof is 
not better than that of Control Coupler A, and the gradient on the short 
wave side is also broad. On the other hand, the .lambda.-max. values of 
the couplers of the invention were of the short-wave when the other high 
boiling solvents than those of the invention were used, but when the high 
boiling solvents of the invention were used with the couplers of the 
invention, the .lambda.-max. value thereof was drastically shifted to the 
long wave side and the dominant wave length thereof becomes equivalent to 
that of Control Coupler A, and the gradient on the short wave side was 
also sharp. It is therefore understood that the invention is preferable 
for color reproduction. 
EXAMPLE 2 
By making use of the couplers of the invention and high boiling solvents of 
the invention each shown in Table 2, Samples (2-1) through (2-4) were 
respectively prepared by dispersing and coating in the similar manner to 
that taken in the case of Example 1. 
Thus prepared Sample (2-1) through (2-4) were respectively exposed to light 
and were then developed in the similar manner to that taken in the case of 
Example 1, and the results were obtained as shown in Table 2. In Table 2, 
the spectral absorption values were obtained in the similar manner to that 
taken in Example 1. 
TABLE 2 
______________________________________ 
Sample High boiling 
No. Coupler solvent Dmax .lambda.max (nm) 
.DELTA..lambda.S 
______________________________________ 
(nm) 
2 - 1 1 P - 10 2.20 695 124 
2 - 2 2 P - 2 2.23 696 124 
2 - 3 5 P - 11 2.18 693 123 
2 - 4 8 P - 13 2.50 694 124 
______________________________________ 
It is understood from Table 2 that when the couplers of the invention were 
respectively dispersed by making use of the high boiling solvents each, 
the excellent spectral absorption characteristics displayed. 
EXAMPLE 3 
Samples (3-1) through (3-4) were prepared in the manner that control 
coupler (A) and the coupler of the invention as shown in Table 3 were 
taken respectively in the amounts each indicated in Table 3 to the amount 
of Ag, and each of the couplers taken was added to the respective mixture 
of dibutyl phthalate (P-1) in one half of the amount by weight of the 
couplers and ethyl acetate in three times the amount by weight of the 
couplers, and thus obtained solutions were dispersed, coated and then 
dried up in the similar manner to that taken in Example 1. 
Thus prepared samples were exposed to light and were then processed in the 
similar manner to that taken in Example 1, and the graininess of each dye 
image was measured in RMS (Root mean square) method by means of red-light. 
The measurement results of RMS graininess in the vicinity of color dye 
density at 0.7 are respectively shown in Table 3. 
RMS value is defined as a value 1000 times as many as the standard 
deviation value of a density variation which may occur when a scanning is 
made by means of a micro-densitometer whose circular scanning aperture 
diameter is 25.mu.. 
TABLE 3 
______________________________________ 
Amount of 
coupler Amount of Ag. 
Sample 
Coupler added* coated (mg/dm.sup.2) 
.gamma.2 
RMS 
______________________________________ 
3 - 1 Control 10 20 0.73 50 
coupler (A) 
3 - 2 Control 5 30 0.70 42 
coupler (A) 
3 - 3 Invention 6 
10 20 0.70 48 
3 - 4 Invention 6 
5 30 0.68 41 
______________________________________ 
It is understood from Table 3 that the graininess of both couplers of the 
invention and Control Coupler (A) were improved by increasing the amounts 
of Ag added and by lowering the mole % of the couplers. 
Next, coated Samples (3-1) through (3-4) thus obtained as mentioned above 
were respectively exposed to light in the similar manner to that taken in 
Example 1, and every Sample was processed for development in the similar 
manner to that taken in Example 1 except that one group of the Samples 
were normally processed in the similar manner to that taken in Example 1 
and the other group of the samples were processed with the bleaching 
liquid of which the composition was as follows in place of the bleaching 
liquid used in Example 1, and then the reduction discoloration of their 
cyan dyes were inspected. 
______________________________________ 
[Bleaching liquid composition] 
Ethylenediamine tetraacetic acid 
100 g 
iron-ammoniun salt 
Ethylenediamine tetraacetic acid 
10 g 
2-ammonium salt 
Ammonium bromide 150 g 
Hydrosulfite 5 g 
Glacial acetic acid 10 ml 
Add water to make 1 ltr. 
Adjust pH value by making use of 
pH 5.5 
10NH.sub.2 SO.sub.4 to 
______________________________________ 
In the table, each value is expressed as a percentage of residual color 
dyes provided the value of the D-max. in processing the samples with a 
bleaching liquid having an ordinary composition is regarded as 100. 
TABLE 4 
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Amt. of Amt. of Ag. 
coupler coated Residual 
Sample 
Coupler added* (mg/dm.sup.2) 
color dye (%) 
______________________________________ 
3 - 1 Control - A 
10 20 65 
3 - 2 Control - A 
5 30 50 
3 - 3 Invention-1 
10 20 99 
3 - 4 Invention-1 
5 30 100 
______________________________________ 
*Amt. of Coupler added: (mole of Coupler/mole of Ag) .times. 100 
From Table 4, it is understood that Control Coupler A apparently causes a 
reduction discoloration in the cyan dyes, and that the couplers of the 
invention have no problem at all.