Silver halide photographic materials and method producing thereof

A silver halide photographic material having at least one light-sensitive silver halide emulsion layer coated on a support, wherein the silver halide emulsion layer contains silver chlorobromide grains comprising silver chlorobromide containing 90 mol % or more of silver chloride, having at least one region in which the silver bromide content is high at the vicinity of the corner of the grains, and with not more than 15 mol % of average silver bromide content at the surface of the grains. A method producing the silver halide photographic materials is also disclosed.

FIELD OF THE INVENTION 
This invention relates to novel silver halide photographic materials and to 
a method for producing such. Moreover, the invention relates to high-speed 
and stable silver halide photographic materials and capable of being 
quickly processed, and more particularly to high-speed and stable color 
photographic materials using silver chlorobromide emulsion and giving high 
utilization efficiency of silver halide. 
BACKGROUND OF THE INVENTION 
With the increasing growth of color photographic light-sensitive materials, 
color processing of color photographic materials is more and more 
simplified and quickened. On the other hand, high quality color images and 
uniformity of finished image quality have been required. It is known that 
a silver iodobromide emulsion containing from 4 to 20 mol % silver iodide 
is generally used for photographing color photographic materials and a 
silver chlorobromide emulsion is generally used for color photographic 
papers for printing. It is also known that a silver chlorobromide is 
reluctant to give images having high quality at high speed as compared to 
a silver iodobromide emulsion. 
Silver chlorides or silver chlorobromide of, in particular, cubic grains 
having a (100) crystal plane are very useful for rapid simple processing. 
However, they have the disadvantages that the sensitivity thereof is low, 
chemical sensitization and spectral sensitization are not easily achieved, 
the sensitivity obtained is unsuitable, and the silver halide grains have 
a tendency to produce fog. 
Various methods for solving these problems have been proposed. For example, 
a method of adding water-soluable bromide ions or iodide ions to the 
silver halide emulsion after adding sensitizing dye(s) thereto is 
described in Japanese Patent Application (OPI) No. 51627/73 (The term 
"OPI" as used herein means an "unexamined published application".), 
Japanese Patent Publication No. 46932/74, etc.; a method of simultaneously 
adding bromide ions and silver ions to silver halide grains having a high 
content of silver chloride to form a silver bromide region of more than 60 
mol % on the surface of the grains or of similarly forming a layer of 10 
mol % to 50 mol % silver bromide on the surface of the grains is described 
in Japanese Patent Application (OPI) Nos. 108533/83, 222845/85, etc.; and 
a method of adding bromide ions or simultaneously adding bromide ions and 
silver ions to silver halide grains having a high content of silver 
chloride to form, thus, multiphase structure grains such as double layer 
grains or junction structure grains is described in Japanese Patent 
Publication Nos. 36978/75, 240772/83, U.S. Pat. No. 4,471,050, West German 
Patent Application (OLS) No. 3,229,999, etc. 
However, all of the aforesaid methods have been found to have various 
defects in terms of sensitivity and have stability thereof, in particular, 
a reduction in sensitivity by the addition of color couplers to the silver 
halide grains, and on the tightness of gradation at shadow portions. Also, 
it is known that these silver halide emulsions are unstable and thus the 
production thereof is difficult. This matter is described, for example, in 
Zuckerman Journal of Photographic Science, 24, 142(1976), etc. 
SUMMARY OF THE INVENTION 
An object of this invention is to provide a color photographic 
light-sensitive material having high speed and providing in a stable 
manner processed products having improved uniformity using silver chloride 
or silver chlorobromide emulsion useful for rapid and simple processing 
and a method of producing such. 
Another object of this invention is to provide a color photographic 
light-sensitive material providing good gradation of shadowed portions and 
having high utilization efficiency of silver halide, which can reduce the 
coating amount of silver, and a method of producing such. 
As the result of various investigations, it has now been discovered that 
the above-described objects can be effectively attained by the present 
invention as set forth hereinbelow. 
That is, the invention is a silver halide photographic material having at 
least one light-sensitive silver halide emulsion layer coated on a 
support, wherein said silver halide emulsion layer contains silver 
chlorobromide grains comprising silver chlorobromide containing 90 mol % 
or more of silver chloride, having at least one region in which the silver 
bromide content is high at the vicinity of at least one of the corners of 
the grains, and with not more than 15 mol % of average silver bromide 
content at the surface of the grains. 
DETAILED DESCRIPTION OF THE INVENTION 
The term "the vicinity of the corners" as used in this invention means the 
area is within the area of a regular square having the side length of 
about 1/3, preferably about 1/5, of the diameter of a circle having the 
same area as the projected area of a normal crystal silver chlorobromide 
grain such as a cubic grain and the like with the corner (an intersecting 
point of sides of normal crystal grains such as a cubic grain or the like) 
as one corner of the square. 
Silver chlorobromide grains are present in an amount of 70 mol % or more 
based on total silver halide grains in the same silver halide emulsion 
layer. 
As a conventional method for preferentially causing halogen conversion from 
the corners of silver halide host grains or the vicinity of the corners, 
the forms and photographic properties of silver halide grains in 
performing halogen displacement by immersing a coated material of a silver 
bromide emulsion in an aqueous potassium iodide solution and in performing 
halogen displacement by immersing a coated material of a silver chloride 
emulsion in an aqueous potassium bromide solution are reported by Klein et 
al, Photographishe Korrespondenz, 102, 59(1966). They found that by the 
immersion of a coated material of an octahedral grain silver bromide 
emulsion in an aqueous potassium iodide solution, silver iodide was 
jointed to the corner portions and the edge portions of the silver bromide 
grains in projected form as reported therein but the displacement was 
random displacement having, in particular, no site selectivity in using a 
cubic grain silver bromide or silver chloride emulsion. 
Furthermore, it is reported by Shiozawa in Bulletin of Society of 
Photographic Science and Technology of Japan, 22, 14(1972) that by 
immersing a coated layer of a cubic grain silver chloride emulsion in a 
solution of 0.1N potassium bromide saturated with silver bromide for 64 
minutes, silver bromide is joined to the corner portions and edge portions 
of the cubic silver chloride grains. 
However, since it is impossible to produce a large quantity of photographic 
light-sensitive materials by these methods, they are unsuitable for 
practical photographic light-sensitive materials. 
The preferred method for preparing silver halide emulsions in this 
invention is explained below in detail. 
(1) The host silver halide crystals which are used for preparing the Corner 
Development Grain ("CDG") emulsion of this invention are cubic or 
tetradecahedral crystal grains (which may have roundish corners and higher 
order planes) substantially having a (100) plane, the halogen composition 
thereof is silver chlorobromide, or silver chloride containing 90 mol % of 
silver chloride and containing no silver iodide or less than 2 mol % 
silver iodide, and particularly preferably silver halide crystals 
containing at least 95 mol %, or more preferably at least 99 mol % silver 
chloride or pure silver chloride crystals. The mean grain size of the host 
silver halide grains is preferably from 0.2 .mu.m to 2 .mu.m and the 
distribution state thereof is preferably monodisperse. 
The monodisperse silver halide emulsion for use in this invention is a 
silver halide emulsion having a grain size distribution of less than 0.25 
in the coefficient of variation (S/r) on the grain sizes of the silver 
halide grains, wherein r is a mean grain size and S is a standard 
deviation of grain sizes. 
That is, if the grain size of each silver halide grain is r.sub.i and the 
number of the grains is n.sub.i, the mean grain size r is defined as 
follows; 
##EQU1## 
and the coefficient of variation S is defined as follows; 
##EQU2## 
Each grain size in this invention is the diameter of a circle having an 
area corresponding to the projected area of the silver halide grain as 
viewed by a well-known method in this field (usually, electron 
micro-photography) as described in T. H. James et al "The Theory of the 
photographic Process", 3rd edition, pages 36-43, published by McMillan 
Co., 1966. Accordingly, when silver halide grains have other forms than 
that of a sphere (e.g., cube, octahedron, tetradecahedron, tabular form, 
potato form, etc.), the mean grain size r and the standard deviation S can 
be obtained as described above. 
The coefficient of variation of the grain sizes of silver halide grains is 
0.25 or less, preferably 0.20 or less, more preferably 0.15 or less, and 
most preferably 0.10 or less. 
2) Then, bromide ion or fine grains having a high content of silver bromide 
are supplied to the host silver halide grains described above to 
precipitate a new silver halide phase which contains higher content of 
silver bromide at the surface of host silver halide grains. The process 
proceeds by an exchange reaction between the bromide ions and halogen ions 
at the surface of the host silver halide grains where bromide ions are 
supplied, the so-called "halogen conversion", and proceeds by "a 
recrystallization reaction" between the fine grains of high silver bromide 
content and host silver halide grains to produce crystals having a more 
stabilized composition where fine grains or high silver bromide content 
are supplied, which is considered to be different from the typical 
"halogen conversion". In the recrystallization reaction, the reaction is 
promoted by an increased entropy, which is a different reaction than 
Ostwald ripening. This is disclosed, for example, in H. C. Yutzy Journal 
of American Chemical Society, Vol. 59, page 916 (1937); etc: 
It is astonishing matter that a new phase which is rich in silver bromide 
content is formed at the vicinity of the corner in both reactions which 
are quite different reactions. 
3) CR compounds can be used to attain more effectively the objects of the 
present invention, i.e., to attain an extraordinarily high sensitivity by 
concentration of the latent image or development nucleus. 
The CR compound is generally a material which function to delay or 
completely obstruct the initiation of the halogen conversion as compared 
to crystal planes having no such compound adsorbed thereto by selectively 
adsorbing onto specific crystal planes and in particular a material which 
is mainly (selectively) adsorbed on the (100) planes and of the 
recrystalization of silver halide grains, and functions to restrain the 
initiation of the conversion on the (100) planes and the recrystalization. 
Suitable CR compounds which can be used in this invention, are cyanine 
dyes, merocyanine dyes, mercaptoazoles (specific examples of which are the 
compounds shown formulae (XXI), (XXII) or (XXIII) as described hereinafter 
in detail), and nucleic acid decomposition products (e.g., intermediate 
decomposition products of deoxyribonucleic acids or ribonucleic acids, 
adenine, quanine, uracil, cytocil, thymine, etc.). 
In particular, compounds shown by following formulae (I), (II) or (III) 
described below are preferred in this invention. 
##STR1## 
In the above formula, Z.sub.101 and Z.sub.102 each represents an atomic 
group necessary for forming a heterocyclic nucleus. 
Example of suitable heterocyclic nuclei include, 5- or 6-membered cyclic 
nuclei containing a nitrogen atom and an other atom such as a sulfur atom, 
an oxygen atom, a selenium atom, or a tellurium atom as the hetero atoms 
(these rings may have a condensed ring bonded thereto or may be 
substituted) are preferred. 
Specific examples of the aforesaid heterocyclic nuclei are thiazole nuclei, 
benzothiazole nuclei, naphthothiazole nuclei, selenazole nuclei, 
benzoselenazole nuclei, naphthoselenazole nuclei, oxazole nuclei, 
benzoxazole nuclei, naphthoxazole nuclei, imidazole nuclei, benzimidazole 
nuclie, naphthimidazole nuclei, 4- quinoline nuclei, pyrroline nuclei, 
pyridine nuclei, tetrazole nuclei, indolenine nuclei, benzindolenine 
nuclei, indole nuclei, tellurazole nuclei, benzotellurazole nuclei, 
naphthotellurazole nuclei, etc. 
In formula (I), R.sub.101 and R.sub.102 each represents an alkyl group, an 
alkenyl group, an alkynyl group, or an aralkyl group. These groups may be 
unsubstituted or substituted. For example, the alkyl group included 
unsubstituted alkyl groups and substituted alkyl groups and these groups 
may be straight chain, branched, or cyclic groups. The carbon atom number 
of the alkyl group is preferably from 1 to 8. 
Specific examples of substituents for the substituted alkyl groups are a 
halogen atom (e.g., chlorine, bromine, fluorine, etc.), a cyano group, an 
alkoxy group, a substituted or unsubstituted amino group, a carboxylic 
acid group, a sulfonic acid group, a hydroxy group, etc., and the alkyl 
group may have one substituent or a plurality of substituents. 
Specific examples of the alkenyl group are a vinyl-methyl group, etc. 
Specific examples of the aralkyl group are a benzyl group, a phenethyl 
group, etc. 
In formula (I) described above, m.sub.101 represents an integer of 1, 2 or 
3. 
When m.sub.101 is 1, R.sub.103 represents a hydrogen atom, a lower alkyl 
group, an aralkyl group, or an aryl group and R.sub.104 represents a 
hydrogen atom. Specific examples of the aforesaid aryl group are a 
substituted or unsubstituted phenyl group. 
When m.sub.101 is 2 or 3, R.sub.103 represents a hydrogen atom and 
R.sub.104 represents a hydrogen atom, a lower alkyl group, or an aralkyl 
group or further may combine with R.sub.102 to form a 5-membered or 
6-membered ring. 
Also, when m.sub.101 is 2 or 3 and R.sub.104 is a hydrogen atom, R.sub.103 
may combine with the other R.sub.103 to form a hydrocarbon ring or a 
heterocyclic ring. These rings are preferably a 5- or 6-membered ring. 
In formula (I), j.sub.101 and k.sub.101 represent 0 or 1, X.sub.101 
represents an acid anion, and n.sub.101 represents 0 or 1. 
##STR2## 
In formula (II), Z.sub.201 and Z.sub.202 have the same significance as 
Z.sub.101 or Z.sub.102. Also, R.sub.201 and R.sub.202 have the same 
significance as R.sub.101 or R.sub.102. R.sub.203 represents an alkyl 
group, an alkenyl group, an alkynyl group, or an aryl group (e.g., a 
substituted or unsubstituted phenyl group). 
In formula (II), m.sub.201 represents 0, 1 or 2. R.sub.204 represents a 
hydrogen atom, a lower alkyl group, or an aryl group and also when 
m.sub.201 is 2, R.sub.204 and R.sub.204 may combine with each other to 
form a hydrocarbon ring or a heterocyclic ring. These rings are preferably 
a 5- or 6-membered ring. 
In formula (II), Q.sub.201 represents a sulfur atom, an oxygen atom, a 
selenium atom or 
##STR3## 
wherein R.sub.205 has the same significance as R.sub.203 and k.sub.201, 
R.sub.201, X.sup.-.sub.201, and n.sub.201 have the same significance as 
j.sub.101, k.sub.101, X.sup.-.sub.101, and n.sub.101, respectively, in 
formula (I). 
##STR4## 
In formula (III), Z.sub.301 represents an atomic group necessary for 
forming a heterocyclic ring. 
Examples of suitable heterocyclic rings are the nuclei described above 
Z.sub.101 Z.sub.102 in formula (I) and specific examples of other nuclei 
are thiazoliadine nuclei, thiazoline nuclei, benzothiazoline nuclei, 
naphthothiazoline nuclei, selenazolidine nuclei, selenazoline nuclei, 
benzoselenazoline nuclei, naphthoselenazoline nuclei, benzoxazoline 
nuclei, naphthoxazoline nuclei, dihydropyridine nuclei, dihydroquinoline 
nuclei, benzimidazoline nuclei, naphthimidazoline nuclei, etc. 
In formula (III) described above, Q.sub.301 has the same significance as 
Q.sub.201 in formula (II), R.sub.301 has the same significance as 
R.sub.101 or R.sub.102 in formula (I), and R.sub.302 has the same 
significance as R.sub.203 in formula (II). 
Also, R.sub.303 has the same significance as R.sub.204 in formula (II), and 
when m.sub.301 is 2 or 3, R.sub.303 may combine with other R.sub.303 to 
form a hydrocarbon ring or a heterocyclic ring, preferably a 5 to 
7-membered ring containing nitrogen atom as a hetero atom. 
In formula (III), j.sub.301 has the same significance as j.sub.101 in 
formula (I). 
The detailes of the above formulac are described in Japanese Patent 
Application (OPI) NO. 215272/87, pages 22 to 26. 
The CR compounds promote selectivity in the first place to produce the new 
phase which is richer in silver bromide content than the host grains, and 
promote the formation and the maintenance of the new phase rich in silver 
bromide content, which is grown epitaxially at only the vicinity of the 
corner of the host grains preventing a reaction that the new phase firstly 
produced repeats a recrystallization reaction with the surface of the host 
grains to form a new uniform layer covering the entire surface of the host 
grains. 
Further, it is surprising that an extraordinarily high sensitization which 
is one of the objects of this invention, is obtained by a preparation of 
the new phase formed at this limited region. 
This high sensitization of this invention tends to provide pressure 
desensitization, simultaneously. Pressure desensitization is a phenomenon 
where sensitivity at a pressed region is reduced when pressure is exerted 
on a photosensitive material before exposure. Pressure desensitization 
tends to be degraded as silver bromide content in the new phase which is 
richer in silver bromide content than the host grains increases. 
Therefore, the silver bromide content in the new phase is preferably 90 
mol % or less, and more preferably 60 mol % or less. 
A method of supplying bromide ions, the so-called conversion method, tends 
to form a phase having a high content of silver bromide to cause a 
degraded pressure desensitization, to cause non-uniform conversion between 
grains because of a too high reaction speed thereof, and especially to 
problems of a production on a large commercial scale, since 
recrystallization reaction proceeds more slowly than the conversion 
reaction during ripening of the mixture of the host grains and the fine 
grains having high silver bromide content, the recrystallization reaction 
has the advantage that reaction uniformity is high and the reaction is 
easily controllable. In addition, in the recrystallization reaction, 
silver bromide content in the new phase is widely controllable by varying 
the silver bromide content of the fine grains having high silver bromide 
content, grain size, concentration of chloride ions during the 
recrystallization reaction, etc. 
The silver halide grains of this invention contain 90 mol % or more of 
silver chloride, and have a new phase which is grown epitaxially at the 
vicinity of the corner of the host grains and have a higher silver bromide 
content than the host grains, wherein a transition region with a gentle 
variation of halogen composition may be present between the new phase and 
the host grains. 
Such a grain structure is observed by various analysis methods. Using an 
electron microscope, a new phase is observed to be joined at the vicinity 
of the corner of the grains by observing the variation in grain form. By 
X-ray diffractiometry, the halogen compositions of the host grain and the 
new phase can be determined. The average halogen composition of the 
surface is measured by a XPS (X-ray Photoelectron Spectroscopy) method 
using, for example, ESCA 750 type spectrograph (made by Shimazu 
Corporation--Du Pont Co., Ltd.). the details of the measurement method are 
disclosed in Someno and Amoi, Hyomen Bunseki (Surface Analysis) published 
by Kodansha (1977). 
The proportion of the area of the new phase in the entire surface area of 
the grain is determined from the halogen compositions of the new phase and 
the host grain obtained by X-ray diffractiometry and the average halogen 
composition of the surface of the grain by XPS method. 
Further, the position of the new phase which is richer in silver bromide 
content than the host grain, is identified and the proportion of the area 
of the new phase at the vicinity of the corner of the grain is measured by 
the above described electron microscope EDX (Energy Dispersive X-ray 
Analysis) method, using an EDX spectrometer set on a transmission electron 
microscope. The details of the measurement as disclosed in Keiji Eukushima 
Electron-ray Micro Analysis published by Nikkan Kogyo (1987). 
The preferred grain sizes of the high bromide content silver halide grains 
of the fine grain silver halide emulsion for use in this invention depend 
upon the grain sizes of the host grains and the halogen composition 
thereof but are usually not larger than 0.3 .mu.m, and preferably not 
larger than 0.1 .mu.m. 
In regard to the halogen composition of the fine grain and high bromide 
content silver halide emulsion for use in this invention, it is necessary 
that the silver bomide content of the emulsion be higher than that of the 
host silver halide grains and the silver bromide content of the silver 
halide emulsion is preferably at least 50 mol %, and more preferably at 
least 70 ml %. 
If desired, the high bromide content fine grain silver halide emulsion for 
use in this invention can contain silver iodide and also it can contain 
the ions or a compound of a heavy metal such as iridium, rhodium, 
platinum, etc. 
The fine grain silver halide emulsion is mixed with the host silver halide 
in the range of from 0.1 to 50 mol % as silver, preferably from 0.2 to 20 
mol %, and particularly preferably from 0.2 to 8 mol %. The temperature of 
mixing can vary but generally is in the range of from 30.degree. C. to 
80.degree. C. 
The new phase is preferably present partially. In the average halogen 
proportion of the surface of the grain, silver bromide is preferably not 
more than 15 mol %, more preferably not more than 10 mol %, and most 
preferably from about 1 mol % to 10 mol %. An increase of the average 
silver bromide content of the surface of the grains leads to a decrease of 
uneven distribution near the vicinity of the corners of the new phase and 
causes a decrease of sensitivity. It is observed using electron microscope 
that the new phase obtained by the preferable process of the present 
invention is epitaxially connected and grown at the corners. 
In the CDG emulsion for use in this invention, the development center is 
concentrated and very high speed is obtained, and further the stability of 
the emulsion is greatly improved and thus excellent stability can be 
obtained with less fog and without reducing the rapid developing property. 
Also, the CDG emulsion has astonishingly high contrast and has the 
advantages that the occurrence of pressure desentization is less and the 
formation of fog at the unexposed portions is less. 
The CR compounds for use in this invention can be selected from sensitizing 
dyes. In particular, the CR compounds useful for the (100) plane can be 
selected from the compounds shown by formulae (I), (II), and (III) 
described above and since these compounds have a function as sensitizing 
dyes, the use of these compounds is advantageous for increasing the 
spectral sensitivity and, in particular, the spectral sensitivity of the 
emulsion can be stabilized further by the partial recrystalization at the 
surface. The discovery of such an excellent combination of the CR 
compounds and the excellent merits thereof is astonishing. 
Furthermore, the CR compounds(s) may be combined with other sensitizing 
dye(s) or super color sensitizer(s) to increase further the sensitivity 
and stability of the silver halide emulsion. 
For example, the CR compounds may be combined with aminostilbene compounds 
substituted by a nitrogen-containing heterocyclic nucleus group (e.g., the 
compounds of formula (I), in particular, specifically illustrate compounds 
(I-1) to (I-17) described in the specification of Japanese Patent 
Application (OPI) No. 174738/87 filed by the same applicant as herein and 
the compounds described in U.S. Pat. Nos. 2,933,390 and 3,635,721), 
aromatic organic acid-formaldehyde condensation products (as described in 
U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc. The 
combinations described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295, 
and 3,635,721 are particularly useful. 
Then, specific examples of the CR compounds shown by formulae (I), (II), 
and (III) are illustrated below although the CR compounds in this 
invention are not limited to these compounds. 
##STR5## 
Of the processes to prepare silver halide grains such as a process to add a 
silver nitrate aqueous solution to an alkali halide aqueous solution, a 
process of the opposing addition order thereof and a process of the 
simultaneous addition thereof, preferable process is the simultaneous 
addition process, more preferably under a control of pAg, to prepare mixed 
silver halide for obtaining host grains. 
The silver halide emulsions for use in this invention are produced by 
controlling the pH and addition time of silver nitrate and alkali halides. 
First, a preferred pH for forming the host silver halide grains in this 
invention is from 2 to 10. In this case, doping can be applied to the 
emulsion by using rhodium complex salts, iridium complex salts, lead 
salts, etc., or a noble metal sensitization (gold sensitization, etc.,) 
can be applied thereto. As the case may be, sulfur sensitization using a 
thiosulfate, allylthiocarbamide, cystein, etc., or reduction sensitization 
using a polyamine, stannous chloride, etc., can be applied to the 
emulsion. 
Then, the aforesaid CR compound is dissolved in a water-miscible organic 
solvent such as an alcohol (e.g., methanol, etc.), ethyl acetate, etc. or 
a mixture of such with water and added to the above-described host silver 
halide emulsion as a solution thereof. Also, the CR compound may be added 
to the emulsion as a dispersion thereof in an aqueous gelatin solution or 
an aqueous solution of a surface active agent. The addition amount thereof 
is preferably from 10.sup.-6 mol % to 10.sup.-2 mol %, and more preferably 
from 10.sup.-5 mol % to 10.sup.-3 mol % per mol of the host silver halide. 
Then, the host silver halide emulsion is mixed with a fine grain high 
bromide content emulsion as described above and the mixture is ripened 
while properly controlling the temperature and pAg in the range of from 
30.degree. C. to 80.degree. C. and the silver ion concentration range of 
pAg 5 to 10, respectively. 
Thereafter, if necessary, sensitizing dye(s) or super color sensitizer(s) 
may be added thereto for spectral sensitization. 
It is preferred to apply the chemical sensitization as described above to 
the silver halide emulsion during or after ripening the mixture. 
Also, fog inhibitors such as mercaptotriazoles, mercaptotetrazoles, 
benzotriazoles, etc., can be used the silver halide emulsion for use in 
this invention. 
For rapid processing, a silver chlorobromide emulsion containing a high 
content of silver chloride is preferably used and for the emulsion, fog 
inhabitors or stabilizers strongly adsorbing to the silver halide grains, 
such as mercapto compounds, nitrobenzotriazole compounds, benzotriazole 
compounds, etc., are used. Also, development accelerators, halation 
preventing agents, irradiation preventing agents, optical whitening 
agents, etc., may be used for the silver halide emulsions. 
Most preferred stabilizers which are used for the silver halide emulsions 
in this invention are those represented by following formula (XXI), (XXII) 
or (XXIII): 
##STR6## 
wherein R represents an alkyl group, an alkenyl group or an aryl group and 
X represents a hydrogen atom, an alkali metal atom, an ammonium group or a 
precursor thereof. 
Examples of alkali metal atoms are a sodium atom, a potassium atom etc., 
and examples of the ammonium group are a tetramethylammonium group, a 
triemthylbenzylammonium group, etc. Also, the precursor is a group capable 
of becoming a hydrogen atom or an alkali metal atom under alkaline 
conditions and examples thereof are an acetyl group, a cyanoethyl group, a 
methanesulfonylethyl group, etc. 
In the above-described groups shown by R, the alkyl group and alkenyl group 
include unsubstituted groups and substituted groups as well as alicyclic 
groups. 
Examples of substituents for the substituted alkyl group are a halogen 
atom, a nitro group, a cyano group, a hydroxy group, an alkoxy group, an 
aryl group, an acylamino group, an alkoxycarbonylamino group, a ureido 
group, an amino group, a heterocyclic group, an acyl group, a sulfamoyl 
group, a sulfonamido group, a thioureido group, a carbamoyl group, an 
alkylthio group, an arylthio group, a heterocyclic thio group, a 
carboxylic acid group, a sulfonic acid group, or the salts of these acids. 
The above-described ureido group, thioureido group, sulfamoyl group, 
carbamoyl group, and amino group each includes unsubstituted groups, 
N-alkyl-substituted group, and N-aryl-substituted groups. 
Examples of aryl group are a phenyl group and a substituted phenyl group 
and examples of substituents are an alkyl group and the substituents 
described above as to the substituent for the alkyl group. 
##STR7## 
wherein Y represents a sulfur atom or an oxygen atom; L represents a 
divalent linking group; R represents a hydrogen atom, an alkyl group, an 
alkenyl group, or an aryl group; X has the same significance as X in 
formula (XXI) described above; and n represents 0 or 1. 
The alkyl group and the alkenyl group shown by R, and X have the same 
significance as defined above as to R and X of formula (XXI). 
Specific examples of the divalent linking group shown by L are 
##STR8## 
wherein R.sup.0, R.sup.1, and R.sup.2 each represents a hydrogen atom, an 
alkyl group, or an aralkyl group) or a combination thereof. 
##STR9## 
wherein R and X have the same significance as defined above for formula 
(XXI); L has the same significance as defined above for formula (XXII); 
R.sup.3 has the same significance as defined R. 
The compound shown by formula (XXI), (XXII), or (XXIII) described above can 
be incorporated in any of the layers of a silver halide color photographic 
material of this invention and/or in a color developer. The term "any of 
the layers of silver halide color photographic material" means 
light-sensitive emulsion layer(s) and/or the light-insensitive hydrophilic 
colloid layer(s) of the color photographic material. 
The addition amount of the compound shown by formula (XXI), (XXII), OR 
(XXIII) is preferably from 1.times. 10.sup.-5 mol to 5.times.10.sup.-2 
mol, and more preferably from 1.times.10.sup.-4 mol to 1.times.10.sup.-2 
mol per mol of silver halide where such is incorporated in the silver 
halide color photographic material and is preferably from 
1.times.10.sup.-6 mol/liter to 1.times.10.sup.-3 mol/liter, and more 
preferably from 5.times.10.sup.-6 mol/liter to 5.times.10.sup.-4 
mol/liter, where such is incorporated in a color developer. 
Specific examples of the compounds shown by formulae (XXI), (XXII), and 
(XXIII) are illustrated below but the invention is not to be construed as 
being limited to them. In addition, the compounds shown below are 
described at pages 11 to 30-1 of the specification of Japanese Patent 
Application No. 114276/86. 
##STR10## 
Color couplers which are used in this invention are explained below. 
In addition to general requirements such as color hues and high extinction 
coefficient for the color couplers, since the CDG emulsion shown 
particularly high development progress, the color couplers must have high 
activity so that the coupling coloring reaction of the couplers with the 
oxidation product of a color developing agent such as a p-phenylenediamine 
derivative does not become the rate determining step. From this view 
point, use of the couplers represented by following formula (IV), (V), 
(VI), or (VII) is preferred in this invention. 
##STR11## 
wherein R.sub.1, R.sub.4, and R.sub.5 each represents an aliphatic group, 
an aromatic group, a heterocyclic group, an aromatic amino group, or a 
heterocyclic amino group; R.sub.2 represents an aliphatic group; R.sub.3 
and R.sub.6 each represents a hydrogen atom, a halogen atom, an aliphatic 
group, an aliphatic oxy group, or an acylamino group; R.sub.7 and R.sub.9 
each represents a substituted or unsubstituted phenyl group; R.sub.8 
represents a hydrogen atom, an aliphatic acyl group, an aromatic acyl 
group, an aliphatic sulfonyl group, or an aromatic sulfonyl group; 
R.sub.10 represents a hydrogen atom or a substituent; Q represents a 
substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb each 
represents methine, substituted methine, or .dbd.N--; Y.sub.1, Y.sub.2, 
and Y.sub.4 each represents a halogen atom or a group capable of releasing 
on coupling with the oxidation product of a color developing agent 
(hereinafter, referred to as releasing group); Y.sub.3 represents a 
hydrogen atom or a releasing group; and Y.sub.5 represents a releasing 
group. 
In formulae (IV) and (V) described above R2 and R3 or R5 and R6 may combine 
and form a 5-, 6-, or 7-membered ring. 
Furthermore, the compound shown by formula (IV), (V), (VI), (VII), or 
(VIII) described above may form a dimer or higher polymer at R.sub.1, 
R.sub.2, R.sub.3, or Y.sub.1 ; R.sub.4, R.sub.5, R.sub.6, or Y.sub.2 ; 
R.sub.7, R.sub.8, R.sub.9, or Y.sub.3 ; R.sub.10, Z.sub.a, Z.sub.b, or 
Y.sub.4 ; or Q or Y.sub.5. 
Details of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, 
R.sub.8, R.sub.9, R.sub.10, Z.sub.a, Z.sub.b, Q.sub.1, Y.sub.1, Y.sub.2, 
Y.sub.3, and Y.sub.4 in formulae (IV), (V), (VI), (VII), and (VIII) are 
same as those described in regard to formulae (I), (II), (III), (IV), and 
(V) described in pages 17-3 to 34 of the specification of Japanese Patent 
Application No. 175233/86. 
Specific examples of these couplers are couplers (C-1) to (C-40), couplers 
(M-1) to (M-42), and couplers (Y-1) to (Y-46) described in pages 36 to 
78-3 of the specification of Japanese Patent Application No. 175233/86 and 
more preferable examples of the couplers are as follows. 
##STR12## 
The generally used amount of the color coupler described above is in the 
range of from 0.001 to 1 mol per mol of light-sensitive silver halide, and 
preferably is from 0.01 to 0.5 mol for a yellow coupler, from 0.003 to 0.3 
mol for a magenta coupler, and from 0.002 to 0.3 mol for a cyan coupler, 
per mol of light-sensitive silver halide. 
In the silver halide color photographic material of this invention using 
the color couplers shown by formula (IV), (V), (VI), (VII) or (VIII) 
described above, the preferred amount of silver halide coated is not more 
than 3 g/m.sup.2, preferably from 2 g/m.sup.2 to 0.1 g/m.sup.2 in the case 
of using a reflection support and preferably from 7 g/m.sup.2 to 0.2 
g/m.sup.2 in the case of using a transparent support, calculated as 
silver. 
These couplers are incorporated in silver halide emulsion layers as a 
dispersion in at least one high-boiling organic solvent. In this case, 
high-boiling organic solvents represented by following formula (A) to (E) 
are preferably used. 
##STR13## 
wherein W.sub.1, W.sub.2, and W.sub.3 each represents a substituted or 
unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl 
group, a substituted or unsubstituted alkenyl group, a substituted or 
unsubstituted aryl group or a substituted or unsubstituted heterocyclic 
group; W.sub.4 represents W.sub.1, OW.sub.1, or S--W.sub.1 ; and n 
represents an integer of from 1 to 5; when n is an integer of 2 or more 
W.sub.4 S may be the same or different; and in formula (E), said W.sub.1 
and W.sub.2 may combine and form a condensed ring. 
The color photographic emulsions of this invention may further contain 
hydroquinone derivatives, aminophenol derivatives, amines, gallic acid 
derivatives, catechol derivatives, ascorbic acid derivatives, non-coloring 
couplers, sulfonamidophenol derivatives, etc., as color fogging preventing 
agentor color mixing preventing agents. 
For the color photographic materials of this invention, fading preventing 
agents can be used. Typical examples of organic fading preventing agents 
are hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, 
p-alkoxyphenols, hindered phenols such as bisphenols, gallic acid 
derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the 
ether or ester derivatives obtained by silyling or alkylating the phenolic 
hydroxy groups of these compounds. Also, metal complexes such as 
(bissalicylaldoxymate) nickel complexes and 
(bis-N,N-dialkyldithiocarbamate) nickel complexes can be used. 
Compounds having both moiety structures of hindered amine and hindered 
phenol in the same molecule as described in U.S. Pat. No. 4,268,593 can be 
used with good results for the prevention of the deterioration of yellow 
color images formed by heat, moisture and light. Also, spiroindanes 
described in Japanese Patent Application (OPI) No. 159644/81 and 
chouromans substituted by hydroquinone diether or monoether as described 
in Japanese Patent Application No. 89835/80 can be used with good results 
for preventing the deterioration of magenta dye images formed by, in 
particular light. 
Furthermore, the image stabilizers described in Japanese Patent Application 
(OPI) No. 125732/84 can be particularly advantageously used for 
stabilizing magenta images formed using pyrazolotriazole type magenta 
couplers. 
For improving storage stability, in particular light fastness of the cyan 
images formed, benzotriazole series ultraviolet absorbents are preferably 
used together. The ultraviolet absorbent may be co-emulsified with the 
cyan coupler. 
The coating amount of the ultraviolet absorbent may be that sufficient for 
imparting light stability to cyan dye images but since if the amount 
thereof is too high, unexposed portions (background portions) of the color 
photographic material are sometimes yellowed, the amount thereof is 
usually in their range of from 1.times.10.sup.-4 mol/m.sup.2 to 
2.times.10.sup.-3 mol/m.sup.2, and in particular, from 5.times.10.sup.-4 
mol/m.sup.2 to 1.5.times.10.sup.-3 mol/m.sup.2. 
Ultraviolet absorbents are incorporated in one of both layers adjacent cyan 
coupler-containing red-sensitive emulsion layer or, preferably in both the 
layers, in a conventional layer construction of color photographic paper. 
When ultraviolet absorbents are incorporated in an interlayer between a 
green-sensitive silver halide emulsion layer and a red-sensitive silver 
halide emulsion layer, the ultraviolet absorbents may be co-emulsified 
with color mixing preventing agents. Also, when ultraviolet absorbents are 
incorporated in a protective layer, another protective layer may be formed 
thereon as the outermost layer. The outermost protective layer may contain 
a matting agent with an optional particle size or a mixture of latexes 
having different particle sizes. 
In the color photographic material of this invention, ultraviolet 
absorbents may be incorporated in hydrophilic colloid layer(s) as well. 
When a reflection support, which can be used in this invention, is 
employed, it is preferred for color images formed in the silver halide 
emulsion layers to be viewed clearly and this is achieved by increasing 
the reflectivity of the support, examples of such supports include a 
support coated with a hydrophobic resin containing a light reflecting 
material such as titanium oxide, zinc oxide, calcium carbonate, calcium 
sulfate, etc., and a support composed of a vinyl chloride resin having a 
light reflective material dispersed therein. For example, there are 
haryta-coated papers, polyethylene-coated paper, poly-propylene series 
synthetic papers, transparent supports having formed thereon a reflective 
layer or containing therein a reflective material, this transparent 
support being polyester films such as polyethylene terephthalate films, 
triacetyl cellulose films, cellulose nitrate films, etc., polyamide films, 
polycarbonate films, polystyrene films, etc. These supports may be 
appropriately selected depending on use. Also, the supports having a 
mirror plane reflective surface or a second class diffusion reflective 
surface as described in Japanese Patent Application (OPI) No. 210346/85, 
Japanese Patent Application Nos. 168800/86 and 168801/86, etc. 
Transparent supports can also be used in this invention. Transmittance of 
light of the transparent support is preferably not more than 50%. 
This invention can be applied to a multilayer multicolor photographic 
light-sensitive material having at least two different spectral 
sensitivities on a support. A multilayer natural color photographic 
material usually has at least one red-sensitive silver hade emulsion 
layer, at least one green-sensitive silver halide emulsion layer, and at 
least one blue-sensitive silver halide emulsion layer on a support. The 
order of these layers can be optionally selected as desired. Also, each of 
the above-described silver halide emulsion layers may be composed of two 
or more silver halide emulsion layers having different light sensitivity 
or a light-insensitive layer may be present between two or more silver 
halide emulsion layers having the same color sensitivity. 
It is preferred that the color photographic light-sensitive material of 
this invention has auxiliary layers such as protective layer(s), 
interlayers, a filter layer, antihalation layer(s), a backing layer, etc., 
in addition to silver halide emulsion layers on a support. 
As a binder or a protective colloid which can be used for the emulsion 
layers and other hydrophilic colloid layers of the color photographic 
light-sensitive material of this invention, gelatin is advantageously used 
but other hydrophilic colloids can be also used. 
Examples of suitable protective colloids are proteins such as gelatin 
derivatives, graft polymers of gelatin and other polymers, albumin, casein 
etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl 
cellulose, cellulose sulfuric acid ester, etc.; saccharose derivatives 
such as sodium alginate, starch derivatives, etc.; and synthetic 
hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial 
acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, 
polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. 
Lime gelatin as well as acid-treated gelatin and enzyme-treated gelatin as 
described in Bull, Soc. Sci. Phot. Japan, No. 16, 30(1966) may be used as 
the gelatin and further the hydrolyzed products and the enzyme 
decomposition products of gelatin can be also used. 
The color photographic materials of this invention may further contain 
various additives such as stabilizers, stain preventing agents, developing 
agents or precursors thereof, development accelerators or the precursors 
therefor, lubricants, mordants, matting agents, antistatic agents, 
plasticizers, and other photographically useful additives in addition to 
the above-described additives. Typical examples of these additives are 
described in Research Disclosure, No. 17643 (December, 1978) and ibid, No. 
18716 (November, 1979). 
The color photographic materials of this invention may further contain 
water-soluble dyes in the hydrophilic colloid layers as filter dyes or for 
irradiation prevention, halation prevention, and other various purposes. 
Also, the color photographic materials of this invention may further 
contain stilbene series, triazine series, oxazole series, or coumarine 
series whitening agents in the photographic emulsion layers or other 
hydrophilic colloid layers. These whitening agents may be water-soluble or 
water-insoluble whitening agents may be used as the form of dispersion. 
Another feature of this invention is quick stabilization of the color 
development process and in a color development process shorter than 3 
minutes and 40 seconds, preferably shorter than 3 minutes, more preferably 
shorter than 2 minutes and 30 seconds. The reduced coating amount of 
silver halide is very useful not only for color development but also to 
improve the desilvering step. 
An aromatic primary amino color developing agent which is used for a color 
developer in the case of developing the color photographic materials of 
this invention includes various color developing agents widely used in 
various color photographic processes. These color developing agents 
include aminophenol series derivatives and p-phenylenediamine series 
delivatives. Preferred examples of color developing agents are 
p-phenylenediamine derivatives and specific examples thereof are 
illustrated below without limiting, however, the color developing agents 
which can be used in this invention. 
D-1: N,N-Diethyl-p-phenylenediamine 
D-2: 2-Amino-5-diethylaminotoluene 
D-3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene 
D-4: 4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]aniline 
D-5: 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]-aniline 
D-6: N-Ethyl-N-(.beta.-methanesulfonamidoethyl)-3-methyl-4-aminoaniline 
D-7: N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide 
D-8: N,N-Dimethyl-p-phenylenediamine 
D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline 
D-10: 4-Amino-3-methyl-N-ethyl-N-.beta.-ethyoxyethylaniline 
D-11: 4-Amino-3-methyl-N-ethyl-N-.beta.-ethyoxyethylaniline. 
Also, these p-phenylenediamine derivatives may be salts thereof, such as 
sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc. The 
above-described compounds are described in U.S. Pat. Nos. 2,193,015, 
2,552,241, 2,566,271, 2,592,364, 3,656,950, 3,698,525, etc. 
The amount of the aromatic primary amine color developing agent used is 
from about 0.1 g to about 20 g, and preferably from about 0.5 g to about 
10 g, per liter of color developer. 
The color developer which is used in this invention may contain 
hydroxylamines. 
The hydroxylamine may be used in the form of the free amine in the color 
developer but is generally used in the form of a water-soluble acid salt 
thereof. Examples of such salts are the sulfates, oxalates, 
hydrochlorides, phosphates, carbonates, acetates, etc. Hydroxylamines may 
be substituted or unsubstituted hydroxylamines, for example, the nitrogen 
atom of the hydroxylamine may be substituted with an alkyl group. 
The addition amount of hydroxylamine is preferably from 0 to 10 g, and more 
preferably from 0 to 5 g, per liter of color developer. If the stability 
of color developer is maintained, the addition amount thereof preferably 
is as small as possible. 
Also, it is preferred that the color developer contains sulfite such as 
sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, 
sodium metasulfite, potassium metasulfite, or a carbonyl sulfuric acid 
addition product as a preservative. The addition amount thereof is 
preferably from 0 to 20 g/liter, and more preferably from 0 to 5 g/liter. 
The amount thereof preferably is as small as possible such that the 
stability of the color developer is maintained. 
Other preservatives which can be used are aromatic polyhydroxy compounds 
described in Japanese Patent Application (OPI) Nos. 49828/77, 47038/81, 
32140/81, 160142/84, and U.S. Pat. No. 3,746,544; hydroxyacetones 
described in U.S. Pat. No. 3,615,503 and British Patent 1,306,176; 
.alpha.-aminocarbonyl compounds described in Japanese Patent Application 
(OPI) Nos. 143020/77 and 89425/78; various metals described in Japanese 
Patent Application (OPI) Nos. 44148/82 and 53749/82; various saccharides 
described in Japanese Patent Application (OPI) No. 102727/77; 
.alpha.-.alpha.'-dicarbonyl compounds described in Japanese Patent 
Application (OPI) No. 160141/84; salicylic acids described in Japanese 
Patent Application (OPI) No. 180588/84; alkanolamines described in 
Japanese Patent Application (OPI) No. 3532/79; poly(alkyleneimines) 
described in Japanese Patent Application (OPI) No. 04349/81; gluconic acid 
derivatives described in Japanese Patent Application (OPI) No. 75647/81, 
etc. 
These preservatives may be used as a mixture thereof if desired. 
Particularly preferred preservatives are 4,5-dihydroxy-m-benzenedisulfonic 
acid, poly(ethyleneimine), and triethanolamine. 
The pH of the color developer which is used for developing the color 
photographic materials of this invention is preferably form 9 to 12, and 
more preferably from 9 to 11.0. The color developer may further contain 
other compounds known as components for color developers. 
To maintain aforesaid pH, a buffer is preferred, suitable buffers are 
carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine 
salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine 
salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 
2-amino-2-methyl-1, 3-propanediol salts, valine salts, proline salts, 
trishydroxyaminomethane salts, lysine salts, etc. In particular, 
carbonates, phosphates, tetraborates, and hydroxybenzoates have the 
advantages that they have excellent solubility and also buffer action at 
high pH region of higher than 910, they are added to color developer 
without adversely influencing (fog, etc.,) photographic properties, and 
they are available at low cost and hence these buffers is particularly 
preferred. 
Specific examples of these buffers are sodium carbonate, potassium 
carbonate, sodium bicarbonate, potassium bicarbonate, sodium 
tertiaryphosphate, potassium tertiary phosphate, sodium secondary 
phosphate, potassium secondary phosphate, sodium borate, potassium borate, 
sodium tetraborate (borax), potassium tetraborate, sodium 
o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 
5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 
5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. However, the 
buffers for use in this invention are not limited to these compounds. 
The addition amount of the buffer to the color developer is preferably more 
than 0.1 mol/liter, and particularly preferably from 0.1 mol/liter to 0.4 
mol/liter. 
Furthermore, color developers of this invention may contain various 
chelating agents as a precipitation preventing agent for calcium or 
magnesium, or for improving the stability of the color developers. 
Suitable chelating agents are preferably organic acid compounds and 
examples thereof are aminopolycarboxylic acids described in Japanese 
Patent Publication Nos. 30496/73 and 30232/69, organic sulfonic acids 
described in Japanese Patent Application (OPI) No. 96347/81, Japanese 
Patent Publication No. 39359/81, and West German Patent 2,227,639, 
phosphonocarboxylic acids described in Japanese Patent Application (OPI) 
Nos. 102726/77, 42730/78, 121127/79, 126241/80, and 65956/80, and the 
compounds described in Japanese Patent Application (OPI) Nos. 195845/83, 
203440/83, and Japanese Patent Publication No. 40900/78. Specific examples 
of chelating agents are illustrated below without limiting the chelating 
agents for use in this invention: 
nitrilotriacetic acid, 
diethyleneaminopentaacetic acid, 
ethylenediaminetetraacetic acid, 
triethylenetetraminehexaacetic acid, 
N,N,N-trimethylenephosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 
1,3-diamino-2-propnaol-tetraacetic acid, 
trans-cyclohexanediaminctetraacetic acid, 
nitrilotripropionic acid, 
1,2-diaminopropanetetraacetic acid, 
hydeoxethyliminodiacetic acid, 
glycol ether diaminetetraacetic acid, 
hydroxyethylenediaminetriacetic acid, 
ethylenediamine-o-hydroxyphenylacetic acid, 
2-phosphonobutane-1,2-4-tricarboxylic acid, 
1-hydroxyethane-1,1-diphopshonic acid, and 
N,N'-bis(2-hydroxubenzyl)ethylenediamine-N,N'-diacetic acid. 
These chelating agents may be, if desired, used as a mixture of two or 
more. The addition amount of the chelating agent may be that sufficient 
for blocking metal ions in the color developer and, for example, from 0.1 
g to 10 g per liter of the color developer is a suitable amount. 
The color developer may further contain, if described, a development 
accelerator. 
Examples of development accelerator are thioether series compounds 
described in Japanese Patent Publications 16088/52, 5987/52, 7826/63, 
12380/69, 9019/70, and U.S. Patent 3,813,247, p-phenylenediamine series 
compounds described in Japanese Patent Application (OPI) Nos. 49829/77 and 
15554/75, quaternary ammonium salts described in Japanese Patent 
Application (OPI) Nos. 137726/75, 156826/81, and 43429/77, and Japanese 
Patent Publication No. 30074/69, p-aminophenols described in U.S. Pat. 
Nos. 2,610,122 and 4,119,462, amino series compounds described in U.S. 
Pat. Nos. 2,494,903 3,128,182, 4,230,796, 3,253,919, 2,482,546, 2,596,926, 
and 3,582,346, and Japanese Patent Publication No. 11431/66, polyalkylene 
oxides described in Japanese Patent Publication Nos. 16088/62, 25201/67, 
11431/66, and 23882/67, and U.S. Pat. Nos. 3,128,183 and 3,532,501, and, 
further, 1-phenyl-3-pyrazolidones, hydrazines, meso-ion type compounds, 
thione type compounds, imidazoles, etc. 
In particular, thioether series compounds and 1-phenyl-3-pyrazlidones are 
preferred. 
The color developer used in this invention may further contain, if desired, 
optionally an antifoggant. 
Suitable antifoggants are alkali metal halide such as potassium bromide, 
sodium chloride, potassium iodide, etc., or other organic antifoggants may 
be used on combination with the above-described compound shown by formula 
(XXI), (XXII), or (XXIII). Specific examples of organic antifoggants are 
nitrogen-containing heterocyclic compounds such as benzotriazole, 
6-nitrobenzimidazole, 5-nitroisoindazole, 5methylbenzotriazole, 
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 
2-thiazolylmethyl-benzimidazole, hydroxyazaindrizine, etc.; other 
mercapto-substituted heterocyclic compounds than those shown by formula 
(XXI), (XXII), or (XXIII) described above, such as 2-mercatobenzimidazole, 
2-mercaptobenzothiazole, etc.; adenine; and further mercapto-substituted 
aromatic compounds such as thiosalicylic acid. 
These antifoggants may be dissolved from the color photographic materials 
during processing and accumulated in the color developer but the 
accumulated amount is preferably less from the stand point of reducing the 
amount to be discharged. 
It is also preferred for the color developer in this invention to contain 
an optical whitening agent. Examples of optical whitening agents are 
4,4-diamino-2,2'-disulfostilbene series compounds and these preferred. The 
addition amount thereof is from 0 to 5 g/liter, and preferably from 0.1 
g/liter to 2 g/liter. 
Also, if desired, the color developer may contain a surface active agent 
such as an alkylsulfonic acid, an aryl-sulfonic acid, the aliphatic 
carboxylic acid, an aromatic carboxylic acid, etc. 
The temperature of use of the color developer for developing the color 
photographic materials of this invention is preferably from 30.degree. C. 
to 50.degree. C., and more preferably from 30.degree. C. to 42.degree. C. 
The replenishing amount for the color developer is less than 2,000 ml, and 
preferably less than 1,500 ml, per square meter of color photographic 
material but the replenishing amount is preferably less from the 
standpoint of reducing the amount of waste solution. For instance, the 
replenishing amount of color printing photographic material is generally 
400 ml or less, more preferably 150 ml or less. 
In this invention, for increasing the speed of the processing by a color 
developer without any benzyl alcohol, which is disadvantageous in the 
points of environmental contamination, storage stability of color images, 
and occurrence of stains, being present, it is preferred to use in the 
color development system a restoring agent for the oxidation product of a 
color developing agent and a trapping agent for the oxidation product of 
the restoring agent as described in Japanese Patent Application No. 
259799/86. 
Suitable bleaching agents for the bleach solution or blix (bleach-fix) 
solution which can be used for processing the color photographic materials 
after color development include ferric ion complexes. i.e., the complexes 
of ferric ions and a chelating agent such as an aminopolycarboxylic acid, 
an aminopolyphopshoric acid, or the salts thereof. 
The aminopolycarboxyaltes or aminopolyphosphates are the salts of 
aminopolycarboxylic acids or aminopolyphosphoric acids and an alkali salt, 
ammonium salt, or a water-soluble amine salt are suitable. 
Examples of alkali metal salts are sodium, potassium, lithium, etc., and 
examples of the water-soluble amine salts are salts of alkylamines such as 
methylamine, diethylamine, triethylamine, butrylamine, etc., alicyclic 
amines such as alkylamine, cyclohexylamine, etc., arylamines such as 
aniline, m-toluidine, etc., and heterocyclic amines such as pyridine, 
morpholine, piperidine, etc. 
Typical examples of these aminopolycarboxylic acids, aminopolyphosphoric 
acids, and the salts thereof useful as chelating agents are; 
ethylenediaminetetraacetic acid, 
ethylenediaminetetraacetic acid disodium salt, 
ethylenediaminetetraacetic acid diammonium salt, 
ethylenediaminetetraacetic acid tetra(trimethyl-ammonium) salt, 
ethylenediaminetetraacetic acid tetra-potassium salt, 
ethylenediaminetetraacetic acid tetra-sodium salt, 
ethylenediaminetetraacetic acid tri-sodium salt, 
ethylenediaminetetraacetic acid 
diethylenetriaminepentaacetic acid, 
diethylenetriaminepentaacetic acid penta-sodium salt, 
ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid, 
ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid tri-sodium salt, 
ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic tri-ammonium salt, 
propylenediaminetetraacetic acid, 
propylenediaminetetraacetic acid disodium salt, 
nitrilotriacetic acid, 
nitrilotriacetic acid trisodium salt, 
cyclohexanediaminetetraacetic acid, 
cyclohexanediaminetetraacetic acid disodium salt, 
iminodiacetic acid, 
dihydroxyethylglycine, 
ethyl ether diaminetetraacetic acid, 
glycol ether diaminetetraacetic acid, 
ethylenediaminetetrapropionic acid, 
phenylenediaminetetraacetic acid, 
1,3-diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephoshonic acid, 
1,3-propylenediamine-N, N', N'-tetramethylenephoshonic acid etc. 
tetramethylenephoshonic acid etc. 
The ferric ion complex may be used in the form of a complex salt or may be 
formed in a solution using a ferric salt such as ferric sulfate, ferric 
chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., 
and a chelating agent such as aminopolycarboxylic acid, 
aminopolyphosphoric acid, phosphonocarboxylic acid, etc. In the case of 
use in the form of a complex salt, the complexes may be used along or as a 
mixture of two or more complexes. On the other hand, where the complex 
salts(s) are formed in solution using a ferric salt and a chelating agent, 
the ferric salts may be used alone or as a mixture of two or more kinds of 
ferric salts. Furthermore, the chelating agents may be used alone or as a 
mixture of two or more thereof. Also, in any cases, the chelating agent(s) 
may be used in an excessive amount to the amount of ferric ion complex 
formed. As the ferric complexes, aminopolycarboxylic acid ferric complexes 
are preferred and the addition amount thereof is from 0.01 to 1.0 
mol/liter, and preferably from 0.05 to 0.50 mol/liter. 
The bleach solution or the blix solution may, if desired, contain a bleach 
accelerator. Specific examples of useful bleach accelerators are compounds 
having a mercapto group or a disulfide group as described in U.S. Pat. No. 
3,893,858, West German Patents 1,290,812, and 2,059,988, and Japanese 
Patent Application (OPI) Nos. 32736/78, 57831/78, 37418/78, 65732/78, 
72623/78, 95630/78, 95631/78, 104232/78, 124424/78, 141623/78, 28426/78, 
Research Disclosure, No. 17129 (July, 1978), etc.; thiazolidine 
derivatives as described in Japanese Patent Application (OPI) No. 
140129/75, thiourea derivatives described in Japanese Patent Publication 
No./8506/70Japanese Patent Application (OPI) Nos. 20832/77 and 32735/78, 
and U.S. Pat. No. 3,706,561; iodides described in West German Patent 
1,127,715, and Japanese Patent Application (OPI) No. 16235/83; 
polyethylene oxides described in West German Patents 966,410 and 
2,748,430; polyamine compounds described in Japanese Patent Publication 
No. 8836/70; the compounds described in Japanese Patent Application (OPI) 
Nos. 42434/74, 59644/74, 94927/78, 35727/79, 26506/80, and 163940/83; and 
iodide ions, bromide ions, etc. 
Of the aforesaid compounds, the compounds having a mercapto group or a 
disulfide group are preferred from the standpoint providing a large 
acceleration effect and the compounds described in U.S. Pat. No. 
3,893,858, West German Patent 3,893,858, West German Patent 1,290,812, and 
Japanese Patent Application (OPI) No. 95630/78 are particularly preferred. 
Furthermore, the bleach solution or the blix solution used in this 
invention may contain a re-halogenating agent such as a bromide (e.g., 
potassium bromide, sodium bromide, ammonium bromide, etc.), a chloride 
(e.g., potassium chloride, sodium chloride, ammonium chloride, etc.), or 
an iodide (e.g., ammonium iodide). Also, the bleach solution or blix 
solution may further contain, if desired, a corrosion preventing agent, 
e.g., inorganic acids, organic acids, and alkali metal or ammonium salts 
thereof each having a pH buffer capability, such as boric acid, borax, 
sodium metaborate, acetic acid, sodium acetate, sodium carbonate, 
potassium carbonate, phopshorous acid, phosphoric acid, sodium phosphate, 
citric acid, sodium citrate, tartaric acid, ammonium nitrate, etc., or 
guanidine, etc. 
Suitable fixing agents for the blix solution or the fix solution which is 
used in this invention are thiosulfates such as sodium thiosulfate, 
ammonium thiosulfate, etc.; thiocyanates such as sodium thiocyanate, 
ammonium thiocyanate, etc.; thioether compounds such as 
ethylenebis-thioglycolic acid, 3,6-diethia-1,8-octanediol, etc.; and 
water-soluble silver halide solvents such as thioureas, etc. They can be 
used alone or as a mixture thereof. 
Also, a specific blix solution containing fixing agent and a large amount 
of a halide such as potassium iodide described in Japanese Patent 
Application (OPI) No. 155354/80 can be used. In this invention, the use of 
a thiosulfate, in particular ammonium thiosulfate is preferred. 
The amount of the fixing agent is preferably from 0.3 mol/liter to 2 
mols/liter, and more preferably from 0.5 mol/liter to 1.0 mol/liter. 
The pH range of the blix solution or fix solution used in this invention is 
preferably 3 to 10, and more preferably from 4 to 9. If the pH is lower 
than the aforesaid range, the deterioration of the solution and the 
formation of leuco compound from cyan dyes are accelerated although 
desilvering may be improved. Also, if the pH is higher than the range, 
desilvering is delayed and stain tends to form. 
To control the pH, sulfuric acid, nitric acid, acetic acid (glacial acetic 
acid), bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium 
carbonate, potassium carbonate, etc., may be added thereto to control the 
pH. 
Also, the blix solution may further contain an optical whitening agent, a 
defoaming agent, a surface active agent, and an organic solvent such as 
polyvinylpyrrolidone, methanol, etc. 
Furthermore, the blix solution or fix solution in this invention contains a 
sulfite ion-releasing compound such as a sulfite (e.g., sodium sulfite, 
potassium sulfite, and ammonium sulfite), a bisulfite (e.g., ammonium 
bisulfite, sodium bisulfite, and potassium bisulfite), a metabisulfite 
(e.g., potassium metabisulfite, sodium metabisulfite, and ammonium 
bisulfite), etc., as a preservative. The amount of the preservative is 
preferably from about 0.02 mol/liter to 0.05 mol/liter, and more 
preferably from about 0.04 to 0.40 mol/liter calculated as sulfide ions. 
As the preservative, a sulfite is generally used but ascorbic acid, a 
carbonyl bisulfurous acid addition product, a carbonyl compound, etc., may 
be used together with the sulfite. 
Furthermore, the blix solution or the fix solution may contain, if 
necessary, a buffer agent, an optical whitening agent, a chelating agent, 
an antifungal agent, etc. 
It is preferred to use at least one of ion (III) complex salts of 
ethylenediaminetetraacetic acid, ion (III) complex salts of 
diethylenetriaminepentaacetic acids, and ion (III) complex salts of 
cyclohexanediaminetetraacetic acids for the blix solution or the bleach 
solution in this invention. 
The wash step in this invention is explained below. 
In this invention, a simple "stabilization processing" only without 
substantially employing wash step in place of ordinary "wash processing" 
can be employed. Thus, "wash processing" in this invention is used in the 
broad meaning as described above. 
The amount of washing water is not easily defined since the amount depends 
upon the number of tanks for multistage countercurrent washing and the 
amount of the bleaching component carried by the color photographic 
materials from prior baths but the bleach and fix components may be 
carried to the final wash bath or tank. For example, in the case of a 
3-tank countercurrent washing, the amount of wash water is preferably more 
than about 1,000 ml, more preferably more than 5,000 ml, per square meter 
of color photographic material. Also, in the case of water saving 
processing, it is better to use water in an amount of from 100 ml to 1,000 
ml per square meter of color photographic material. 
The washing temperature is usually from 15.degree. C. to 45.degree. C., and 
preferably from 20.degree. C. to 35.degree. C. 
Wash water from the wash step may contain various compounds for preventing 
precipitation and stabilizing wash water. For example, chelating agents 
such as inorganic phosphonic acids, aminopolycarboxylic acids, organic 
phosphoric acids, etc., antibacterial or antifungal agents for preventing 
the growth of various bacteria, algae, and molds, such as the compounds 
described in Journal of Antibacterial and Antifungal Agents, Vol. 11, No. 
5, 207-223(1983) and the compounds described in Hiroshi Horiguchi, Bokin 
Bobai no Kagaku (Antibacterial and Antifungal Chemistry), metal salts such 
as magnesium salts and aluminum salts, alakali metal salts, ammonium 
salts, and surface active agents can be present. Moreover, the compounds 
described in Journal of Photographic Science and Engineering. Vol. 6, 
344-359(1065) may be added thereto. 
Further, water from which calcium compounds and magnesium compounds are 
deleted, which is described in Japanese Patent Application No. 133632/61, 
may be used as a wash water instead of antifungal. 
This invention is particularly effective in greatly saving the amount of 
wash water by adding a chelating agent, an antibacterial agent, and an 
antifungal agent to the wash water and by employing multistage 
countercurrent washing using two or more tanks. Also, the invention is 
effective in practicing multistage countercurrent stabilization processing 
(so-called stabilization processing) as described in Japanese Patent 
Application (OPI) No. 8543/82 in place of an ordinary wash step. In these 
cases, the blix component in the final bath may be 5.times.10.sup.-2 or 
less, and preferably 1.times.10.sup.-2. 
The stabilization solution in this invention contains various compounds for 
stabilizing color images formed. For example, various additives such as 
various buffers for controlling the pH (e.g., pH 3 to 8) of the 
photographic layers (e.g., borates, metaborates, borax, phosphates, 
carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, 
monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc., as a 
combination thereof) and an aldehyde such as form aldehyde can be present. 
Other additives for the stabilizing solution are chelating agents (e.g., 
inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphonic 
acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc.), 
sterilizers (e.g., thiazole series sterilizers, isothiazole series 
sterilizers, halogenated phenols, sulfonylamide, benzotriazole, etc.), 
surface active agents, optical whitening agents, hardening agents, etc. 
They may be used as a mixture two or more of the same kind or different 
kinds of additives. 
Also, it is preferred to improve the storage stability of the color images 
obtained to add various ammonium salts such as ammonium chloride, ammonium 
nitrate, ammonium sulfate, ammonium phoshate, ammonium sulfite, ammonium 
thiosulfate, etc., to the stabilization solution as a pH controlling agent 
for the processor. 
In greatly saving the amount of wash water as described above, it is 
preferred to reduce the amount of waste solution that a part or all of the 
overflow solution of the wash water is supplied to a blix bath or fix 
bath, which is a pre-bath. 
In continuously performing the process step in this invention, a constant 
finish is obtained by preventing a change in the composition of each 
processing solution using a replenisher for each processing solution. The 
amount of each replenisher can be reduced to a half or less than a half of 
the standard amount of the replenisher for a reduction in cost. 
Each processing bath may be, if desired, equipped with a heater, a 
temperature sensor, a liquid level sensor, a circulation pump, a filter, a 
floating lid, a squeegee a nitrogen gas stirrer, an air stirrer, etc. 
For the color photographic materials of this invention can be applied any 
processing using color developer. For example, photographic processing for 
color photographic papers, color reversal photographic papers, color 
positive photographic films, color negative photographic films, color 
reversal photographic film, etc., can be employed.

The following examples serve to illustrate this invention more practically 
without limiting, however, the scope of the invention. Unless otherwise 
indicated, all parts, percents, ratios and the like are by weight. 
EXAMPLE 1 
Silver halide emulsion (A) was prepared by the following manner. 
______________________________________ 
Solution 1 
Water 1,000 ml 
Sodium Chloride 5.5 g 
Gelatin 32 g 
Solution 2 
Sulfuric Acid (1N) 24 ml 
Solution 3 
Compound A shown below (aq. 1% soln.) 
3 ml 
##STR14## 
Solution 4 
Sodium Chloride 11.00 g 
Water to make 200 ml 
Solution 5 
Silver Nitrate 32.00 g 
Water to make 200 ml 
Solution 6 
Sodium chloride 44.00 g 
K.sub.2 IrCl.sub.6 (0.001% soln.) 
2.3 ml 
Water to make 560 ml 
Solution 7 
Silver Nitrate 128 g 
Water to make 560 ml 
______________________________________ 
After heating Solution 1.degree. to 52.degree. C., Solution 2 and Solution 
3 were added to the solution. 
Thereafter, Solution 4 and Solution 5 were simultaneously added to the 
mixture thus formed over a period of 14 minutes. After furthermore 10 
minutes, Solution 6 and Solution 7 were simultaneously added to the 
mixture obtained over a period of 15 minutes. Five minutes after the 
addition, the temperature of the system was lowered and desalting was 
carried out. Then, water and a gelatin dispersion were added thereto and 
the pH thereof was adjusted to 6.2 to provide a monodisperse cubic grain 
silver chloride emulsion having a mean grain size of 0.48 .mu.m and a 
variation coefficient of 0.10 (a value obtained by dividing a standard 
deviation by an average grain size). 
After adding to the emulsion sodium thiosulfate and applying thereto 
optimum chemical sensitization at 58.degree. C. the above described CR 
compound (CR-24) was added to the emulsion at 4.times.10.sup.-4 mol per 
mol of silver halide to achieve spectral sensitization. Also, a stabilizer 
[(XXI)-(7)] was added thereto at 5.times.10.sup.-4 mol per mol of silver 
halide. Thus, Emulsion (A) was prepared. 
By following the same procedure as the case of preparing Emulsion (A) 
except that after the addition of Solution 6 and Solution 7, Solution 8 
shown below was added to the mixture over a period of 10 minutes and after 
5 minutes since then, the temperature of the system was lowered, Emulsion 
(B) was obtained. 
______________________________________ 
Solution 8 
______________________________________ 
Potassium Bromide 5.60 g 
Water to make 280 ml 
______________________________________ 
By following the same procedure as the case of preparing Emulsion (A) 
except that Solution 9 and Solution 10 shown below were added over a 
period of 15 minutes in place of adding Solution 6 and Solution 7, after 
10 minutes after the addition, Solution 11 and Solution 12 shown below 
were further added to the mixture over a period of 5 minutes, and after 5 
minutes since then, the temperature of the system was lowered, Emulsion 
(C) was obtained. 
______________________________________ 
Solution 9 
Sodium Chloride 41.28 g 
K.sub.2 IrCl.sub.6 (0.001% soln.) 
2.3 ml 
Water to make 525 ml 
Solution 10 
Silver Nitrate 120 g 
Water to make 525 ml 
Solution 11 
Potassium Bromide 5.60 g 
Water to make 100 ml 
Solution 12 
Silver Nitrate 8.00 g 
Water to make 100 ml 
______________________________________ 
Then, by following the same procedure as the case of preparing Emulsion (C) 
except that Solution 13 and Solution 14 shown below were used in place of 
Solution 11 and Solution 12, Emulsion (D) was obtained. 
______________________________________ 
Solution 13 
Potassium Bromide 4.48 g 
Sodium Chloride 0.55 g 
Water to make 100 ml 
Solution 14 
Silver Nitrate 8.00 g 
Water to make 100 ml 
______________________________________ 
Then, by following the same procedure as the case of preparing Emulsion (A) 
except that the super fine grain silver bromide emulsion (having mean 
grain size of 0.05 .mu.m) described above was added to the mixed emulsion 
in an amount of containing 1 mol % of silver bromide to silver chloride 
before applying the chemical sensitization to the emulsion and then the 
resultant emulsion was ripened for 10 minutes at 58.degree. C., Emulsion 
(E) was obtained. 
Furthermore, by following the same procedure as the case of preparing 
Emulsion (E) except that the CR compound (CR-24) was added at 
4.0.times.10.sup.-4 mol per mol of silver halide before adding the super 
fine grain silver bromide emulsion, Emulsion (F) was obtained. 
The characteristics of the emulsion (A) to (F) are shown in the Table 
below. 
Then, 100 g of a magneta coupler (M-(1) described hereinbefore) was 
dissolved in a mixed solvent of 130 ml of a solvent (Solv-2) and 100 ml of 
ethyl acetate together with 80 g of a color image stabilizer (Cpd-3) and 
38 g of a color image stabilizer (Cpd-4) and the solution was dispersed by 
emulsification in 1200 g of a aqueous 10% gelatin solution containing 4.0 
g of sodium dodecylbenzenesulfonate to provide an emulsified dispersion 
(I-1). 
The chemical structures of the compounds used are as follows. 
##STR15## 
TABLE 1 
__________________________________________________________________________ 
Average Halogen 
Proportion 
AgBr AgCl Average AgBr 
Maximum Content* 
Emulsion 
(mol %) 
(mol %) 
(Content) 
of AgBr Position** 
__________________________________________________________________________ 
A 0 100 0 0 Not present 
B 5 95 14 about 70 mol % 
Corner of the cubic 
C 5 95 15 about 50 mol % 
" 
D 4 96 14 about 40 mol % 
" 
E 1 99 12 about 50 mol % 
" 
F 1 99 5 about 50 mol % 
" 
__________________________________________________________________________ 
*Maximum content of AgBr contained in a phase of high content of AgBr. 
**Position where a phase of high content of AgBr is present. 
Average surface halogen proportion, maximum AgBr content in the AgBr 
containing layer and the position of the phase of high content of AgBr, 
was each obtained by XPS method, Xray diffraction method, and electron 
microscope and EDX method, respectively. 
TABLE 2 
__________________________________________________________________________ 
Green sensitive emulsion layer 
Emulsion Emulsified Protective 
Sample 
Support 
(Ag: 400 mg/m.sup.2) 
dispersion layer 
__________________________________________________________________________ 
Sample 101 
Paper support 
Emulsion (A) 
Emulsion dispersion I-1 
Gelatin 
Comparison 
Sample 102 
laminiated 
Emulsion (B) 
Magenta coupler (E .times. M.sub.1) 
coverage 
Present Invention 
Sample 103 
with Emulsion (C) 
350 mg/m.sup.2 Fading preventing 
1500 mg/m.sup.2 
" 
Sample 104 
polyethylene 
Emulsion (D) 
agent (Cpd-3) 280 mg/m.sup.2 
" 
Sample 105 
on both 
Emulsion (E) 
(Cpd-4) 133/m.sup.2 Coupler solvent 
" 
Sample 106 
surfaces 
Emulsion (F) 
(Solv-2) 0.455 ml/m.sup.2 Gelatin 
" 
was added so as to obtain 
gelatin coverage of 1500 mg/m.sup.2. 
__________________________________________________________________________ 
Thus, 6 kinds of samples shown in Table 2 below were prepared. 
In this case, the polyethylene layer on the support at the emulsion layer 
carrying side contained titanium dioxide and a slight amount of 
ultramarine blue. Also, 1-oxy-3,5-dichloro-s-triazine sodium salt was used 
for each layer as a hardening agent. 
For determining the photographic properties of the coated samples thus 
obtained, the following experiment was carried out. 
First, each sample was subjected to a sensitometric gradation exposure 
through a green filter using an actionmeter (FWF type, made by Fuji Photo 
Film Co., Ltd., color temperature of light source 3200.degree. K.). The 
light exposure in this case was applied at an exposure time of 1/10 sec. 
and at an exposure amount of 250 CMS. 
Thereafter, the samples thus exposed were processed as follows (Processing 
1) 
______________________________________ 
Processing Step Temperature 
Time 
______________________________________ 
Color Development 
35.degree. C. 
45 sec. 
Blix 35.degree. C. 
45 sec. 
Wash 28 to 35.degree. C. 
45 sec. 
______________________________________ 
The compositions of the processing solutions used were as follows. 
______________________________________ 
Color Developer 
Triethanolamine 8.12 ml 
N,N-Diethylhydroxylamine 4.93 ml 
Optical Whitening agent 2.80 g 
4,4'-diaminostilbene, 
(UVITEX CK trade name, 
made by Ciba-Geigy 
Corporation) 
4-Amino-3-methyl-N-ethyl-N-[.beta.- 
4.96 g 
(methanesulfonamido)ethyl]-p- 
phenylenediamine Sulfate 
Sodium, Sulfite 0.13 g 
Sodium, Carbonate 18.40 g 
Potassium Hydrogen Carbonate 
4.85 g 
EDTA.2Na.2H.sub.2 O 2.20 g 
Sodium Chloride 1.36 g 
Water to make 1,000 ml 
pH = 10.05 
Blix Solution 
Ammonium Thiosulfate (54 wt. %) 
103.0 ml 
NH.sub.4 [EDTA.Fe] 54.10 g 
EDTA.2Na.2H.sub.2 O 3.41 g 
Sodium Sulfite 16.71 g 
Glacial Acetic acid 8.61 g 
Water to make 1000 ml 
pH = 5.44 
______________________________________ 
After processing the color density of each sample was measured and the 
sensitivity and gradation thereof were determined. The sensitivity was 
defined as the reciprocal of the exposure amount of giving a coloring 
density of fog density +0.5 and was shown by the relative value with the 
sensitivity of Sample 101 being defined as 100. Also, the gradation was 
shown by the difference between the logarithm of the exposure amount of 
giving a coloring density of 0.5 and the logarithm of the exposure amount 
of giving a coloring density of 2.0. 
The results are shown in Table 3 below. 
TABLE 3 
______________________________________ 
Sample Sensitivity Gradation Notes 
______________________________________ 
101 100 0.56 Comparison 
102 235 1.55 Present Invention 
103 342 1.32 " 
104 331 1.28 " 
105 370 1.11 " 
106 398 1.57 " 
______________________________________ 
From the results shown in Table 3 above, it can be clearly seen that by 
using the silver halide emulsions of this invention, high-speed 
photographic materials are obtained as compared with the case of using 
comparison emulsions, especially Sample 106 provides high-sensitivity and 
hard contrast. 
EXAMPLE 2 
A multilayer color photographic paper having the layer structure shown 
below on a paper support, both surfaces of which were coated with 
polyethylene, was prepared. 
Each coating solution was prepared by mixing each silver halide emulsion, 
various chemicals, and an emulsified dispersion of coupler. The 
preparation methods are shown below. 
Preparation of Coupler Emulsified Dispersion 
In mixture of 27.2 ml of ethyl acetate and 7.7 ml of a solvent (Solv-1) 
were dissolved 19.1 g of a yellow coupler (ExY) and 4.4 g of a color image 
stabilizer (Cpd-1) and the solution was dispersed by emulsification in 185 
ml of an aqueous 10% gelatin solution containing 8 ml of a solution of 10% 
sodium dodecylbenzenesulfonate. 
By the similar manner as above, the emulsified dispersion for each of a 
magenta coupler, a cyan coupler, and an intermediate layer was prepared. 
The compounds used for each emulsion were as follows. 
##STR16## 
A Stabilizer [(XXI)-(7) described above] at 2.5.times.10.sup.-4 mol per mol 
of silver halide for the blue-sensitive emulsion layer was used. 
For each layer 1-oxy-3-5-dichloro-s-triazine sodium salt was used as a 
hardening agent. 
Also, the following dyes were added to the emulsion layers for irradiation 
prevention. 
##STR17## 
Also, the following compound was added to the red-sensitive emulsion layer 
at 2.6.times.10.sup.-3 mol per mol of silver halide. 
##STR18## 
The preparation methods for the silver halide emulsions used in this 
example are explained below. 
For the blue-sensitive emulsion, Emulsion (G) prepared according to the 
following procedure was used as the emulsion of this invention. 
For the green-sensitive emulsion, Emulsion (A) and (F) prepared in Example 
(1) were used. 
For the red-sensitive emulsion, the following Emulsions (I) and (J) were 
used. That is, by following the same procedure as the cases of preparing 
Emulsions (A) and (F) for the green-sensitive emulsion except that the 
sensitizing dye used as the CR compound was changed to CR-32 and the 
addition amount was 1.5.times.10.sup.-4 mol per mol of silver halide. 
The emulsion was mixed with each emulsified dispersion of coupler and the 
mixture was coated as shown in Table 4. Thus, Samples 201 to 208 were 
prepared. In this case, the couplers were replaced with each other on an 
equimolar basis. 
The preparation of emulsions (G) and (H) were carried out as follows. 
Formation of host silver chloride grains: 
______________________________________ 
Solution 1 
Water 1,000 ml 
Sodium Chloride 5.5 g 
Gelatin 32 g 
Solution 2 
Sulfuric Acid (1N) 24 ml. 
Solution 3 
Compound A shown below (aq. 1% soln.) 
3 ml 
Solution 4 
Sodium Chloride 1.7 g 
Water to make 200 ml 
Solution 5 
Silver Nitrate 5 g 
Water to make 200 ml 
Solution 6 
Sodium Chloride 41.3 g 
K.sub.2 IrCl.sub.6 (0.001% soln.) 
0.5 ml 
Water to make 600 ml 
Solution 7 
Silver Nitrate 120 g 
Water to make 600 ml 
______________________________________ 
After heating Solution 1.degree. to 76.degree. C., Solution 2 and Solution 
3 were added to the solution. 
Thereafter, Solution 4 and Solution 5 were simultaneously added to the 
mixture thus formed over a period of 10 minutes. 
Ten minutes later, Solution 6 and Solution 7 were simultaneously added to 
the mixture over a period of 35 minutes and 5 minutes after the addition, 
the temperature of the system was lowered and desalting was carried out. 
Then, water and a gelatin dispersion was added to the mixture and the pH 
thereof was adjusted to 6.3 to provide a monodisperse cubic grain silver 
chloride emulsion having a mean grain size of 1.1 .mu.m and a variation 
coefficient of 0.10. 
The emulsion thus formed was split into two equal-volume portions. To one 
of them were added a 0.6% solution of a blue spectral sensitizing dye 
(CR-7 described above) in an amount of 1.26 ml as the CR compound and 
further a fine grain silver bromide emulsion having a mean grain size of 
0.05 .mu.m in an amount of 0.5 mol % to the host silver chloride emulsion, 
and the mixed emulsion was ripened for 10 minutes at 58.degree. C. 
Thereafter, sodium thiosulfate was added to the emulsion to apply thereto 
optimum chemical sensitization and the aforesaid stabilizer [(XXI)-(7)] 
was added thereto at 10.sup.-4 mol/mol-Ag to provide Emulsion (G). The 
remaining portion of the emulsion containing no CR compound nor AgBr 
super-fine grain emulsion, etc., was defined as Emulsion (H). 
TABLE 4 
______________________________________ 
First layer Third layer* Fifth layer 
Sam- Emul- Emul- Emul- 
ple sion Coupler sion Coupler 
sion Coupler 
______________________________________ 
201 (H) E .times. Y 
(A) E .times. M.sub.1 
(I) E .times. C.sub.1 
and 
C.sub.2 (1:1) 
202 (G) E .times. Y 
(F) E .times. M.sub.1 
(J) E .times. C.sub.1 
and 
C.sub.2 (1:1) 
203 (G) E .times. Y 
(F) E .times. M.sub.2 
(J) E .times. C.sub.4 
204 (G) E .times. Y 
(F) E .times. M.sub.3 
(J) E .times. C.sub.4 
205 (G) E .times. Y 
(F) E .times. M.sub.4 
(J) E .times. C.sub.4 
206 (G) E .times. Y 
(F) E .times. M.sub.3 
(J) E .times. C.sub.3 
207 (G) E .times. Y 
(F) E .times. M.sub.3 
(J) E .times. C.sub.5 
208 (G) E .times. Y 
(F) E .times. M.sub.3 
(J) E .times. C.sub.1 
______________________________________ 
*Silver halide emulsion coverage of the third layer is controlled so as t 
be 0.18 g/m.sup.2, when couplers used in the third layer are those other 
than E .times. M.sub.1. 
Layer Structure 
The composition of each layer on Sample 201 is shown below. The numerals 
show coated amounts in g/m.sup.2 but shown the coated amount (g/m.sup.2) 
as silver for silver halide emulsion layer. 
In addition, the support was a paper support, both surfaces of which were 
coated with polyethylene wherein titanium dioxide as white pigment and 
blue dye (ultramarine) were contained in polyethylene having the first 
layer thereon. The hardening agent used in each layer was sodium 
1-oxy-3,5-dichloro-s-triazine. 
______________________________________ 
Layer 1 (Blue-Sensitive Layer) 
Silver Halide Emulsion 0.30 
Gelatin 1.86 
Yellow Coupler (ExY) 0.82 
Color Image Stabilizer (Cpd - 1) 
0.19 
Solvent (Solv - 1) 0.35 
Layer 2 (Color mixing Preventing Layer) 
Gelatin 0.99 
Color Mixing Preventor (Cpd - 2) 
0.08 
Layer 3 (Green-Sensitive Layer) 
Silver Chlorobromide Emulsion 
0.36 
Gelatin 1.24 
Magenta Coupler (ExM - 1) 
0.31 
Color Image Stabilizer (Cpd - 3) 
0.25 
Color Image Stabilizer (Cpd - 4) 
0.12 
Solvent (Solv - 2) 0.42 
Layer 4 (Ultraviolet Absorptive Layer) 
Gelatin 1.58 
Ultraviolet Absorbent (UV - 1) 
0.62 
Color Mixing Preventor (Cpd - 5) 
0.05 
Solvent (Solv - 3) 0.24 
Layer 5 (Red-Sensitive Layer) 
Silver Chlorobromide Emulsion 
0.23 
Cyan Couplers (blend of ExC - 1 
0.34 
and ExC - 2 at 1:1) 
Color Image Stabilizer (Cpd - 6) 
0.17 
Polymer (Cpd - 7) 0.40 
Solvent (Solv - 4) 0.23 
Layer 6 (Ultraviolet Absorptive Layer) 
Gelatin 0.53 
Ultraviolet Absorbent (UV - 1) 
0.21 
Solvent (Solv - 3) 0.08 
Layer 7 (Protective Layer) 
Gelatin 1.33 
Acryl-Modified Copolymer of Poly- 
0.17 
vinyl Alcohol (modified degree 17%) 
Liquid Paraffin 0.03 
______________________________________ 
Each of the coated sample 201 to 208 thus prepared was exposed and 
processed as shown in processing 1 and then the sensitivities of each of 
blue sensitive layers, green-sensitive layers, and red-sensitive layers 
were compared. The results obtained are shown in Table 5. 
TABLE 5 
______________________________________ 
Blue- Green- Red- 
sensitive sensitive sensitive 
Sample 
Layer Layer Layer Notes 
______________________________________ 
201 100 100 100 Comparison 
202 415 401 370 Present Invention 
203 410 411 411 " 
204 409 405 410 " 
205 411 410 410 " 
206 409 404 330 " 
207 414 406 411 " 
208 415 405 371 " 
______________________________________ 
As is clear from the results shown in Table 5 above, it can be seen that 
the coated samples of this invention have very high sensitivity as 
compared with the comparison sample. 
The following processings (2) and (3) are applied in the same manner as 
Example 2, and the same results as in Table 5 were obtained to ascertain 
the effects of the present invention. 
______________________________________ 
Processing (2) 
Processing Step Temperature 
Time 
______________________________________ 
Color Development 
35.degree. C. 
45 sec. 
Blix 30 to 35.degree. C. 
45 sec. 
Wash 1 30 to 35.degree. C. 
20 sec. 
Wash 2 30 to 35.degree. C. 
20 sec. 
Wash 3 30 to 35.degree. C. 
20 sec. 
Wash 4 30 to 35.degree. C. 
30 sec. 
Drying 70 to 80.degree. C. 
60 sec. 
______________________________________ 
Counter-current system using 3 tanks from wash step 4 to 1 was applied. 
The compositions of the processing solutions used were as follows. 
______________________________________ 
Color Developer 
Water 800 ml 
Ethylenediamine-N,N,N',N'- 
tetiamethylene phosphonic Acid 
Methyltriethylene diamine 1.5 g 
(1,4-diaza-bicyclo[2,2,2]octane) 
5.0 g 
Sodium Chloride 1.4 g 
Potassium, Carbonate 25.0 g 
N-ethyl-N-(.beta.-methanesulphoneamidoethyl)- 
5.0 g 
3-methyl-4-aminoaniline sulfate 
N,N-diethylhydroxylamine 5.0 g 
Fluorescent Blightening Agent 
2.0 g 
(UVITEX CK trade name, 
made by Ciba-Geigy 
Corporation) 
Water to make 1,000 ml 
pH (25.degree. C.) 10.10 
Blix 
Water 400 ml 
Ammonium Thiosulfate (70%) 
100 ml 
Sodium Sulfite 18 g 
NH.sub.4 [EDTA.Fe(III)] 55 g 
EDTA.2Na 3 g 
Ammonium Bromide 40 g 
Sodium Sulfite 16.71 g 
Glacial Acetic Acid 8 g 
Water to make 1000 ml 
pH (25.degree. C.) 5.5 
______________________________________ 
Washing Liquid 
Ion Exchange Water (Ca ion and Mg ion each is contained in an amount of 
less than 3 ppm or less). 
Processing (3) 
The same processing step, Blix and Washing Liquid as in Processing (2) were 
used. 
______________________________________ 
Color Developer 
______________________________________ 
Water 800 ml 
Ethylenediamine-N,N,N',N'- 
tetiamethylene phosphonic Acid 
Methyltriethylene diamine 1.5 g 
(1,4-diaza-bicyclo[2,2,2]octane) 
5.0 g 
Sodium Chloride 1.4 g 
Potassium, Carbonate 25.0 g 
N-ethyl-N-(.beta.-methanesulphoneamidoethyl)- 
5.0 g 
3-methyl-4-aminoaniline sulfate 
N,N-dicarboxyhydrazine 5.0 g 
Fluorescent Blightening Agent 
2.0 g 
(UVITEX CK trade name, 
made by Ciba-Geigy 
Corporation) 
Water to make 1,000 ml 
pH (25.degree. C.) 10.10 
______________________________________ 
EXAMPLE 3 
By following the same procedure except that the support, the disposition of 
layers, the coated amounts of each layer were different and each emulsion 
was gold and sulfur-sensitized, Samples 301 to 308 were prepared. The 
combinations are shown in Table 6 below. 
Layer Structure 
The composition of each layer in Sample 301 is shown below. The numerals 
show the coated amount g/m.sup.2, which is, however, shown as silver for 
the silver halide emulsions. 
Support 
Polyethylene Terephthalate Film (thickness 180 .mu.m, having a layer of 
gelatin containing titanium dioxide as white pigment so that the white 
light transmittance becomes 30% at the emulsion layer coated side). 
______________________________________ 
Layer 1 (Green-sensitive Layer) 
Silver Halide Emulsion 0.82 
Gelatin 2.80 
Magenta Coupler (ExM 1) 0.69 
Color Image Stabilizer (Cpd - 3) 
0.56 
Color Image Stabilizer (Cpd - 4) 
0.27 
Solvent (Solv - 2) 0.95 
Layer 2 (Ultraviolet Absorptive Layer) 
Gelation 1.58 
Ultraviolet Absorbent (UV - 1) 
0.62 
Color Mixing Preventor (Cpd - 5) 
0.05 
Solvent (Solv - 3) 0.24 
Layer 3 (Red-sensitive Layer) 
Silver Halide Emulsion 0.54 
Gelatin 1.98 
Cyan Coupler (1:1 blend of ExC - 1 
0.69 
and ExC - 2) 
Color Image Stabilizer (Cpd - 6) 
0.36 
Polymer (Cpd - 7) 0.84 
Solvent (Solv - 4) 0.48 
Layer 4 (Color Mixing Preventing Layer) 
Gelation 0.99 
Color Mixing Preventor (Cpd - 2) 
0.08 
Layer 5 (Blue-sensitive Layer) 
Silver Halide Emulsion 0.52 
Gelatin 3.66 
Yellow Coupler (ExY) 1.66 
Color Image Stabilizer (Cpd - 1) 
0.38 
Solvent (Solv - 1) 0.70 
Layer 6 (Ultraviolet Absorptive Layer) 
Gelatin 0.53 
Ultraviolet Absorbent (UV - 1) 
0.21 
Solvent (Solv - 3) 0.08 
Layer 7 (Protective Layer) 
Gelatin 1.33 
Acryl-Modified Copolymer of Poly- 
0.17 
vinyl Alcohol (modified degree 17%) 
Matting Agent (polymethyl methacry- 
0.04 
late) 
______________________________________ 
The silver halide emulsions used in this example were prepared as follows. 
By following the same procedures as the cases of preparing Emulsions (H), 
(G), (A), (F), (I), and (J) in Example 2 except that each emulsion was 
subjected to optimum gold and sulfure sensitizations with chloroauric acid 
and sodium thiosulfate, Emulsions (L), (M), (N), (O), (P), and (Q) were 
obtained. 
Using the combinations of these emulsions and the couplers as shown in 
Table 6 below, Samples 301 to 308 were also prepared by the same manner as 
above. 
TABLE 6 
______________________________________ 
First layer Third layer* Fifth layer 
Sam- Emul- Emul- Emul- 
ple sion Coupler sion Coupler sion Coupler 
______________________________________ 
301 (N) E .times. M.sub.1 
(p) Mixture of 
(L) E .times. Y 
E .times. C.sub.1 
and C.sub.2 (1:1 
by weight) 
302 (O) E .times. M.sub.1 
(Q) Mixture of 
(M) E .times. Y 
E .times. C.sub.1 
and C.sub.2 (1:1 
by weight) 
303 (O) E .times. M.sub.2 
(Q) E .times. C.sub.4 
(M) E .times. Y 
304 (O) E .times. M.sub.3 
(Q) B .times. C.sub.4 
(M) E .times. Y 
305 (O) E .times. M.sub.4 
(Q) E .times. C.sub.4 
(M) E .times. Y 
306 (O) E .times. M.sub.3 
(Q) E .times. C.sub.3 
(M) E .times. Y 
307 (O) E .times. M.sub. 3 
(Q) E .times. C.sub.5 
(M) E .times. Y 
308 (O) E .times. M.sub.3 
(Q) E .times. C.sub.1 
(M) E .times. Y 
______________________________________ 
*Silver halide emulsion coverage of the third layer is controlled so as t 
be 0.29 g/m2, when couplers used in the first layer are those other than 
.times. M.sub.1. 
Each of coated samples 301 to 308 thus obtained was exposed and subjected 
to Processing 2 shown below, and then the sensitivities of each of the 
green-sensitive layers, red-sensitive layers, and blue-sensitive layers 
were compared. The results obtained are shown in Table 7 below. 
______________________________________ 
Processing A 
Processing Step 
Temperature 
Time 
______________________________________ 
Color Development 
33.degree. C. 
3 min. 30 sec. 
Blix 33.degree. C. 
1 min. 30 sec. 
Wash 24 to 34.degree. C. 
3 min. 30 sec. 
______________________________________ 
The compositions of the processing solutions used as follows. 
______________________________________ 
Color Developer 
Water 800 ml 
1-Hydroxyethylidene-1,1-diphosphonic 
2.0 g 
Acid (60%) 
Triethanolamine 11 ml 
Benzyl Alcohol 15 ml 
Diethylene Glycol 0.2 ml 
Potassium Sulfite 1.8 g 
Potassium Bromide 0.6 g 
Potassium Carbonate 28 g 
N-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 
4.5 g 
3-methyl-4-aminoaniline Sulfate 
Hydroxylamine Sulfate 3.0 g 
Optical Whitening Agent (4,4'-diamino- 
0.5 g 
stilbene series) 
Lithium Chloride 2.0 g 
Water to make 1000 ml 
pH (25.degree. C.) 10.10 
Blix Solution 
Water 400 ml 
Ammonium Thiosulfate (70% aq. soln) 
120 ml 
Sodium sulfite 18 g 
Ethylenediaminetetracetic Acid 
60 g 
Iron(III) Ammonium 
Ethylenediaminetetraacetic Acid 
5 g 
Disodium 
Water to make 1000 ml 
pH (25.degree. C.) 
______________________________________ 
TABLE 7 
______________________________________ 
Green- Red- Blue- 
sensitive sensitive sensitive 
Sample 
Layer Layer Layer Remarks 
______________________________________ 
301 100 100 100 Comparison 
302 398 355 400 Present Invention 
303 395 391 391 " 
304 385 385 390 " 
305 389 390 390 " 
306 389 305 385 " 
307 396 386 381 " 
308 380 355 392 " 
______________________________________ 
As is clear from the results shown in Table 7 above, it can be seen that 
the samples of this invention having the combinations in this invention 
show very high speed or sensitivity as compared with the comparison sample 
using the comparison combination. 
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 modification can be made therein without 
departing from the spirit and scope thereof.