Silver halide photographic materials

A silver halide photographic material comprising at least one photosensitive emulsion layer contains silver halide grains on a support. In the silver halide photographic material, (1) the silver halide grains are prepared in the presence of iridium compounds, (2) the silver halide grains consist of silver chlorobromide which is essentially free of silver iodide, (3) at least 90 mol% of all silver halide from which the silver halide grains are made is silver chloride, (4) the silver halide grains have localized phase in which the silver bromide content exceeds at least 20 mol%, (5) the localized phase is precipitated together with at least 50% of all the iridium which is added during the preparation of the silver halide grains, and (6) the surface of the silver halide grains is chemically sensitized to the extent that the grains are essentially of the surface latent image type.

FIELD OF THE INVENTION 
This invention concerns silver halide photographic materials and, more 
precisely, it concerns silver halide photographic materials which have 
excellent rapid processing characteristics, high speed and high contrast, 
which exhibit little reciprocity law failure and which, moreover, have 
excellent handling properties. 
BACKGROUND OF THE INVENTION 
The silver halide photographic materials and methods for forming images 
using these materials which are available at the present time are useful 
in many and various fields. The halogen composition of the silver halide 
emulsions used in many of these photosensitive materials often include 
silver iodobromide, silver chloroiodobromide or silver bromochloride, and 
other silver halides based principally on silver bromide, in order to 
achieve the required high speeds. 
On the other hand, with the products which are used in markets where there 
is a great demand for finishing large numbers of prints in a short period 
of time, such as the color printing paper type photosensitive materials, 
silver bromide or silver chlorobromide which is substantially silver 
iodide free is used because of the need to realize high processing speeds. 
In recent years, the demand for increased processing speeds in connection 
with color printing papers has increased, and much research has been done 
in this connection. Thus it is well known that the development rate can be 
greatly increased by raising the silver chloride content of the silver 
halide emulsion which is being used. 
However, silver halide emulsions which have a high silver chloride content 
are liable to fogging and it is difficult to achieve high speeds with 
normal chemical sensitization with these emulsions. Further, they are 
known to suffer from problems with reciprocity law failure which causes, 
for example, changes in speed and gradation depending on the exposure 
luminance. 
Various techniques have been developed with a view to overcoming the 
disadvantages of the silver halide emulsions which have a high silver 
chloride content as described above. 
Thus it is indicated in JP-A-58-95736, U.S. Pat. No. 4,564,591 
(JP-A-58-108533), JP-A-61-222844 and U.S. Pat. No. 4,590,155 
(JP-A-60-222845) (the term "JP-A" as used herein means an "unexamined 
published Japanese patent application") that the provision of silver 
halide grain structures such that there is a layer or phase which has a 
high silver bromide content is effective for overcoming the disadvantages 
of silver halide emulsions which have a high silver chloride content. 
Thus, the introduction of a layer or phase which has a high silver bromide 
content has various effects on the photographic performance of a silver 
halide emulsion which has a high silver chloride content, but it has 
little improving effect in terms of reciprocity law failure. 
It is also known that the doping of silver halide grains with iridium is 
effective for improving a silver halide emulsion in respect of reciprocity 
law failure. For example, in JP-B-43-4935 (the term "JP-B" as used herein 
means "examined Japanese patent publication") it is indicated that images 
which have almost constant gradation can be obtained over a wide range of 
exposure times with photographic materials in which a trace amount of an 
iridium compound has been added during the precipitation or ripening of 
the silver halide emulsion. However, it is indicated on page 201 of volume 
33 of the Journal of Photographic Science by Twikkey that latent image 
intensification occurs during a comparatively short interval of time from 
15 seconds to about 2 hours after exposure in the case of iridium doped 
silver halide emulsions which have a high silver chloride content. For 
example, changes inevitably occur in the photographic performance as a 
result of changing the time interval between exposure and processing as a 
result of this effect and this is undesirable in practice with 
photosensitive materials which are to be used as color printing papers. 
Examples of the iridium doping of silver chloroiodobromide emulsions which 
have a comparatively high silver chloride content have been disclosed in 
U.S. Pat. No. 4,126,472 (JP-A-50-116025), JP-A-56-25727, U.S. Pat. No. 
4,469,783 (JP-A-58-211753), JP-A-58-215641, U.S. Pat. No. 4,621,041 
(JP-A60-19141) and JP-A-61-47941, but in none of these cases is the 
aforementioned problem of reciprocity law failure overcome. 
SUMMARY OF THE INVENTION 
Hence, the first aim of the invention is to provide silver halide 
photographic materials which have excellent high speed processing 
characteristics and which have a high contrast at high speed. 
The second aim of the invention is to provide silver halide photographic 
materials in which the variation in speed and gradation due to changes in 
the exposure luminance is slight. 
The third aim of the invention is to provide silver halide photographic 
materials in which the variation in speed and gradation due to the time 
interval between exposure and processing is slight. 
The aims of the invention are achieved by providing a silver halide 
photographic material comprising at least one photosensitive emulsion 
layer which contains silver halide grains on a support, wherein: 
(1) the silver halide grains are prepared in the presence of iridium 
compounds, 
(2) the silver halide grains consist of silver chlorobromide which is 
substantially free of silver iodide, 
(3) at least 90 mol% of all silver halide from which the silver halide 
grains are made is silver chloride, 
(4) the silver halide grains have a localized phase in which the silver 
bromide content exceeds at least 20 mol%, 
(5) the localized phase is precipitated together with at least 50% of all 
the iridium which is added during the preparation of the silver halide 
grains, and 
(6) the surface of the silver halide grains is chemically sensitized to the 
extent that the grains are substantially of the surface latent image type.

DETAILED DESCRIPTION OF THE INVENTION 
Water soluble iridium compounds can be used as the iridium compounds which 
are used in the invention. For example, it is possible to use iridium(III) 
halides, iridium(IV) halides, iridium complex salts which have halogens, 
amines or oxalates etc. as ligands, for example hexachloroiridium(III) or 
(IV) complex salts, hexa-ammineiridium(III) or (IV) complex salts, 
trioxalatoiridium(III) or (IV) complex salts etc. Combinations of the (III 
and (IV) valent compounds selected arbitrarily from among these compounds 
can be used in this invention. These iridium compounds can be dissolved in 
water or in a suitable solvent for use, but steps are usually taken to 
stabilize the solution of iridium compounds, which is to say that methods 
in which hydrogen halide solutions (for example hydrochloric acid, 
hydrobromic acid, hydrofluoric acid etc.) or alkali halides (for example 
KCl, NaCl, KBr, NaBr etc.), are added can be used. Moreover, separate 
silver halide grains which have been doped with iridium previously can be 
added and dissolved during the manufacture of silver halide grains in 
accordance with this invention instead of using water soluble iridium 
compounds. 
The total amount of iridium compound added during the manufacture of the 
silver halide grains in accordance with this invention is suitably from 
5.times.10-9 to 1.times.10-4 mol, preferably from 1.times.10-8 to 
1.times.10-4 mol, and most desirably from 5.times.10-8 to 5.times.10-6 
mol, per mol of silver halide which is ultimately formed. 
The halogen composition of the silver halide grains in this invention must 
be such that the grains consist of substantially silver iodide free silver 
chlorobromide in which at least 90 mol% of all of the silver halide from 
which the silver halide grains are made is silver chloride. Here, the term 
"substantially silver iodide free" signifies a silver iodide content not 
exceeding 1.0 mol%. The preferred halogen composition of the silver halide 
grains is that of an substantially silver iodide free silver chlorobromide 
in which at least 95 mol% of all of the silver halide from which the 
silver halide grains are made is silver chloride. 
The silver halide grains in this invention must have a localized phase in 
which the silver bromide content exceeds at least 20 mol%. A term of a 
"localized phase" in the present invention means a phase having higher 
silver bromide content in the silver bromide grains comparing with those 
in other phase. The location of this localized phase which has a high 
silver bromide content can be selected freely according to the intended 
purpose of the grains, and it may take the form of a surface phase or a 
sub-surface phase, or it may be divided between an internal and a surface 
or sub-surface phase. Furthermore, the localized phase may have a 
layer-like structure such as to enclose the silver halide grain, 
internally or at the surface, or it may have a discontinuous, isolated 
structure. In a preferred example of the arrangement of the localized 
phase which has a high silver bromide content, the localized phase in 
which the silver bromide content exceeds at least 20 mol% is grown 
epitaxially on the surfaces of silver halide grains. 
The silver bromide content of the localized phase must exceed 20 mol%, but 
if it is too high the photosensitive material may become liable to 
desensitization on the application of pressure, and this can result in the 
appearance of undesirable characteristics in photographic materials in 
that the speed and gradation may be affected and vary as a result of 
fluctuations in the composition of the processing baths. In consideration 
of these points, the silver bromide content of the localized phase is 
preferably within the range from 20 to 60 mol%, and most desirably it is 
within the range from 30 to 50 mol%. The silver bromide content of the 
localized phase can be analyzed using X-ray diffraction methods (for 
example see the Japanese Chemical Society publication "New Experimental 
Chemistry Series 6, Structural Analysis", published by Maruzen) or using 
the XPS method (for example, see "Surface Analysis,--The Application of 
IMA, Auger Electron--Photoelectron Spectra", published by Kodansha). The 
localized phase is preferably made using from 0.1 to 20 mol% of all of the 
silver used to form the silver halide grains of this invention, and it is 
most desirably made using from 0.5 to 7 mol% of the total amount of 
silver. 
The interface between the localized phase which has a high silver bromide 
content and any other phase may consist of a distinct phase boundary, or 
there may be a short transition zone in which the halogen composition 
changes gradually. 
Various methods can be employed to form a localized phase which has a high 
silver bromide content of this type. For example, the local phase can be 
formed by reacting a soluble silver salt with a soluble halide salt using 
either the one side mixing method or the simultaneous mixing method. 
Moreover, the local phases can be formed using the so-called conversion 
method which includes a process in which a silver halide which has been 
formed already is converted to a silver halide which has a lower 
solubility product. Alternatively, the local phase can be formed by adding 
fine silver bromide grains or fine silver chlorobromide grains and 
carrying out a recrystallization on the surface of silver chloride grains. 
The localized phase must be precipitated together with at least 50% of all 
of the iridium which is added during the preparation of the aforementioned 
silver halide grains. Here, the statement that "the localized phase is 
precipitated together with the iridium" means that the iridium compound is 
supplied at the same time as the silver or halogen is being supplied to 
form the localized phase, immediately before the supply of the silver or 
halogen, or immediately after the supply of the silver or halogen. The 
iridium compound(s) may be present during the formation of phases other 
than the localized phase which has a high silver bromide content, but the 
localized phase must be precipitated together with at least 50% of all of 
the iridium which is added. Cases in which the localized phase is 
precipitated together with at least 80% of all the iridium added are 
preferred, and cases in which the localized phase is precipitated together 
with all of the iridium added are most desirable. 
In more detail, the localized phase of the silver halide grains is 
preferably formed by adding other silver halide grains, for example, fine 
silver chlorobromide grains which have been doped with iridium. 
The silver halide grains in this invention must have the surface sensitized 
chemically to such an extent that they are substantially of the surface 
latent image type. The chemical sensitization can be carried out using the 
sulfur sensitization methods in which compounds which contains sulfur 
which can react with active gelatin and silver (for example thiosulfates, 
thioureas, mercapto compounds, rhodanines) are used, the reduction 
sensitization methods in which reducing substances (for example stannous 
salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane 
compounds) are used, or the precious metal sensitizing methods in which 
metal compounds (for example, complex salts of metals of group VIII of the 
periodic table, such as Pt, Ir, Pd, Rh, Fe etc., as well as gold) are 
used, and these methods may be used individually or in combination. Of 
these methods the sulfur sensitization method is preferred. 
Photosensitive materials made from silver halide grains which have been 
prepared in this way have excellent rapid processing characteristics, high 
speed and contrast, little reciprocity law failure and, moreover, the 
latent image stability is high and they ave excellent handling properties. 
These features are different from the normal features of conventional 
silver chloride emulsions and the findings are therefore surprising. 
The silver halide grains in this invention preferably have the (100) 
surface or the (111) surface as the outer surface, or they may have both 
of these surfaces as the outer surface, and the use of silver halide 
grains which have higher order surfaces is especially desirable. The 
silver halide grains in this invention may have a regular crystalline form 
such as a cubic, octahedral, dodecahedral or tetradecahedral form, or they 
may have an irregular form such as spherical form, or they may be tabular 
grains, and emulsions in which tabular grains of which the 
length/thickness ratio is at least 5, and preferably at least 8, account 
for at least 50% of the total projected area of the grains are the best. 
The size of the silver halide grains in this invention may be within the 
range normally used, but grains of which the average grain size is from 
0.1 .mu.m to 1.5 .mu.m are preferred. The grain size distribution may be 
poly-disperse or mono-disperse, but mono-dispersions are preferred. The 
grain size distribution feature which represents the extent of 
mono-dispersion is the ratio of the statistical standard deviation (s) and 
the average grain size (d), i.e., (s/d), and the value of this ratio is 
preferably not more than 0.2, and most desirably not more than 0.15. 
Cadmium salts, zinc salts, thallium salts, lead salts, rhodium salts or 
complex salts thereof, iron salts or complex salts thereof etc. can also 
be present during the formation or physical ripening processes of the 
silver halide grains of this invention. 
Various compounds can be included in the photographic emulsions used in the 
invention with a view to preventing the occurrence of fogging during the 
manufacture, storage or processing of the photosensitive material or with 
a view to the stabilization of photographic characteristics. Thus many 
compounds which are known as anti-fogging agents or stabilizers, such as 
the azoles (for example benzothiazolium salts, niroimidazoles, 
nitrobenzimidazoles, chlorobemzimidazoles, bromobenzimidazoles, 
mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, 
mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, 
mercaptotetrazoles, (especially 1-phenyl-5-mercaptotetrazoles etc.), 
mercaptopyrimidines, mercaptotriazoles etc., thioketone compounds such as 
oxazolinethione for example, azaindenes such as triazaindenes, 
tetra-aza-indenes (especially 4-hydroxy substituted 
(1,3,3a,7)-tetra-azaindene), penta-azaindenes etc. for example, and 
benzenethiosulfonic acid, benzenesulfinic acid and benzene sulfonic acid 
amide etc. 
Of these, the addition of the mercaptoazoles which can be represented by 
the general formulae [I], [II] or [III] given below to the silver halide 
coating liquids is preferred. The amounts added are preferably within the 
range of from 1.times.10-5 to 5.times.10-2, and most desirably within the 
range from 1.times.10-4 to 1.times.10-2 mol, per mol of silver halide. 
##STR1## 
In this formula, R represents an alkyl group, alkenyl group or an aryl 
group. X represents a hydrogen atom, an alkali metal atom, an ammonium 
group or a precursor. The alkali metal atom is, for example, a sodium 
atom, potassium atom etc., and the ammonium group is, for example, a 
tetramethylammonium group or a trimethylbenzylammonium group. Furthermore 
the precursor is a group which is such that X=H or an alkali metal under 
alkaline conditions, being for example an acetyl group, cyanoethyl group, 
methanesulfonylethyl group etc. 
The alkyl groups and alkenyl groups included among the groups represented 
by R may be unsubstituted or substituted groups, and they may also be 
alicyclic groups. Possible substituent groups for the substituted alkyl 
groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, 
alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, 
ureido groups, amino groups, heterocyclic groups, acyl groups, sulfamoyl 
groups, sulfonamido groups, thioureido groups, carbamoyl groups, alkylthio 
groups, arylthio groups, heterocyclic thio groups, or carboxylic acid 
groups, sulfonic acid groups or the salts of these groups, etc. 
The above mentioned ureido groups, thioureido groups, sulfamoyl groups, 
carbamoyl groups and amino groups may be unsubstituted groups or they may 
be N-alkyl substituted groups or N-aryl substituted groups. A phenyl group 
and substituted phenyl groups are examples of aryl groups represented by R 
and the alkyl groups and the substituent groups for the alkyl groups 
indicated above can be present as substituent groups. 
##STR2## 
In this formula, L represents a divalent linking group and R.sup.4 
represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl 
group and X is as defined in formula [1]. The alkyl groups, alkenyl groups 
and aryl groups for R.sup.4 are the same as those described for R in 
connection with formula [I]. 
Typical examples of divalent linking groups include: 
##STR3## 
Groups consisting of combinations of these groups are also included. 
Here n has a value of 0 or 1 and R.sup.0, R.sup.1 and R.sup.2 each 
represents a hydrogen atoms, an alkyl group having 1 to 8 carbon atoms or 
an aralkyl group such as benzyl group, phenetyl group, etc. 
##STR4## 
In this formula, R and X have the same meaning as in formula [I], and L has 
the same meaning as in formula [II]. R.sup.3 has the same meaning as R and 
these groups may be the same or different. 
Actual examples of compounds which can be represented by the formulae [I], 
[II]and [III]are indicated below, but the invention is not limited by 
these examples. 
##STR5## 
The invention can be applied to black and white photosensitive materials, 
but it is preferably applied to multi-layer multi-color photographic 
materials which have at least two layers of different spectral 
sensitivities on a support. Multi-layer natural color photographic 
materials normally have at least one red sensitive emulsion layer, at 
least one green sensitive emulsion layer and at least one blue sensitive 
emulsion layer on a support. The order in which these layers are 
established can be chosen arbitrarily, as required. A cyan forming coupler 
is normally included in the red sensitive emulsion layer, a magenta 
forming coupler is normally included in the green sensitive emulsion layer 
and a yellow forming coupler is normally included in the blue sensitive 
layer, but different combinations can be adopted according to the 
particular case. 
The methine dyes such as the cyanine dyes and merocyanine dyes etc. 
normally used for photographic purposes can be used as spectrally 
sensitizing dyes, but the use of the cyanine dyes which can be represented 
by the formula [IV] below is especially desirable in this invention. These 
dyes are added during the manufacture of the silver halide emulsion, and 
preferably before the washing of the emulsion or before chemical 
sensitization. 
##STR6## 
In this formula, Z.sub.101 and Z.sub.102 each represents a group of atoms 
which is required to form a heterocyclic nucleus. 
The heterocyclic nuclei are preferably five or six membered rings (which 
may be linked to a condensed ring) which contain, as well as nitrogen 
atoms, sulfur atoms, oxygen atoms, selenium atoms or thallium atoms as 
heterocyclic atoms. 
Actual examples of the aforementioned heterocyclic nuclei include a 
thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, 
selenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole 
nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole 
nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, 
tetrazole nucleus, indolenine nucleus, benzimidolenine nucleus, indole 
nucleus, tetrazole nucleus, benzotetrazole nucleus, naphthotetrazole 
nucleus etc. 
R.sub.101 and R.sub.102 each represents an alkyl group, alkenyl group, 
alkynyl group or an aralkyl group. These groups and the groups mentioned 
below are used in the sense that they include the respective substituted 
groups. For example, in the case of the alkyl groups, these include 
unsubstituted and substituted alkyl groups, and the groups may have a 
linear or branched chain or they may be cyclic groups. The alkyl groups 
preferably have from 1 to 8 carbon atoms and are, for example, methyl 
group, ethyl group, pentyl group, 3-sulfopropyl group. 
Furthermore, actual examples of the substituent groups of the substituted 
alkyl groups include halogen atoms (chlorine atoms, bromine atoms, 
fluorine atoms etc.), cyano groups, alkoxy groups, substituted and 
unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, 
hydroxyl groups etc., and these groups may be substituted in combinations 
of the same group or as a plurality of different groups. 
Actual examples of alkenyl groups include a vinylmethyl group. 
Actual examples of aralkyl groups include a benzyl group and a phenethyl 
group. 
Moreover, m.sub.101 represents 0 or an integer of value 1, 2 or 3. When 
m.sub.101 represents 1 then R.sub.103 represents a hydrogen atom, lower 
alkyl group, aralkyl group or aryl group. 
Actual examples of the aforementioned aryl groups include substituted and 
unsubstituted phenyl groups. 
When m.sub.101 represents 1, 2 or 3, then R.sub.104 represents a hydrogen 
atom, lower alkyl group or aralkyl group. Moreover, when m.sub.101 
represents 2 or 3, R.sub.103 represents a hydrogen atom, and R.sub.104 
represents a hydrogen atom, lower alkyl group or aralkyl group, or it may 
be linked to R.sub.102 to form a five or six membered ring. Furthermore, 
when m.sub.101 represents 2 or 3 and R.sub.104 represents a hydrogen atom, 
R.sub.103 may be connected to another R.sub.103 to form a carbocyclic or 
heterocyclic ring. These rings are preferably five or six membered rings. 
Moreover, 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. 
Of these dyes, the compounds which have a reduction potential of -1.23 (V 
vs S.C.E.) or more negative are preferred as red sensitizing dyes, and 
those of these dyes which have a reduction potential of -1.27 or more 
negative are especially desirable. In terms of chemical structure, the 
benzothiadicarbocyanine dyes in which two methine groups of the 
pentamethine linking groups are linked together to form a ring are 
preferred. Electron donor groups, such as alkyl groups and alkoxy groups, 
may be bonded onto the benzene ring of the benzothiazole nucleus of the 
dye. 
Measurement of the reduction potential is carried out using phase 
discrimination type second harmonic alternating current polarography. A 
mercury dropping electrode is used for the measuring electrode, a 
saturated calomel electrode is used for the reference electrode and 
platinum is used for the counterelectrode. 
Measurement of reduction potentials using phase discrimination type second 
harmonic alternating current polarography with platinum for the measuring 
electrode has been described on pages 27 to 35 of volume 30 of the Journal 
of Imaging Science (1986). 
Typical examples of red sensitizing dyes which can be used in the invention 
are given below. 
##STR7## 
Yellow couplers, magenta couplers and cyan couplers which form the colors 
yellow, magenta and cyan respectively on coupling with the oxidized form 
of a primary aromatic amine are normally used in color photosensitive 
materials. 
Of the yellow couplers which can be used in this invention, the 
acylacetamideerivatives such as benzoylacetanilide and pivaloylacetanilide 
etc. are preferred. 
Among these, the couplers represented by the formulae [Y-1] and [Y-2] below 
are ideal as yellow couplers. 
##STR8## 
In these formulae, X.sup.2 represents a hydrogen atom or a coupling 
elimination group. R.sub.21 represents a non-diffusible group which has a 
total number of from 8 to 32 carbon atoms, and R.sub.22 represents a 
hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower 
alkoxy group or a non-diffusible group which has a total of from 8 to 32 
carbon atoms. R.sub.23 represents a hydrogen atom or a substituent group. 
When there are two or more R.sub.23 groups they may be the same or 
different. 
Details of pivaloylacetanilide type yellow couplers have been disclosed in 
the specifications of U.S. Pat. No. 4,622,287 (from column 3, line 15, to 
column 8, line 39) and U.S. Pat. No. 4,623,616 (from column 14, line 50, 
to column 19, line 41). 
Details of benzoylacetanilide type yellow couplers have been disclosed in 
U.S. Pat. Nos. 3,408,194, 3,933,501, 4,046,575, 4,133,958 and 4,401,752 
etc. 
Actual examples of pivaloylacetanilide type yellow couplers include the 
illustrative compounds (Y-1) to (Y-39) disclosed in columns 37 to 54 of 
the specification of the aforementioned U.S. Pat. No. 4,622,287, and of 
these compounds those designated as (Y-1), (Y-4), (Y-6), (Y-7), (Y-15), 
(Y-21), (Y-22), (Y23), (Y-26), (Y-35), (Y-36), (Y-37), (Y-38) and (Y-39) 
etc. are preferred. 
There are also the illustrative compounds (Y-1) to (Y-33) disclosed in 
columns 19 to 24 of the specification of the aforementioned U.S. Pat. No. 
4,623,616, and of these, those designated as (Y-2), (Y-7), (Y-8), (Y-12), 
(Y-20), (Y-21), (Y-23) and (Y-29) etc. are preferred. 
Other desirable compounds include the typical example (34 disclosed in 
column 6 of the specification of U.S. Pat. No. 3,408,194, illustrative 
compounds (16) and (19) disclosed in column 8 of the specification of U.S. 
Pat. No. 3,933,501, illustrative compound (9) disclosed in columns 7 and 8 
of the specification of U.S. Pat. No. 4,046,575, illustrative compound (1) 
disclosed in columns 5 and 6 of the specification of U.S. Pat. No. 
4,133,958, illustrative compound 1 disclosed in column 5 of the 
specification of U.S. Pat. No. 4,401,752, and the compounds a) to g) shown 
below. 
__________________________________________________________________________ 
##STR9## 
Compound 
R.sub.22 X.sup.3 
__________________________________________________________________________ 
##STR10## 
##STR11## 
b 
##STR12## As above 
c 
##STR13## 
##STR14## 
d As above 
##STR15## 
e As above 
##STR16## 
f NHSO.sub.2 C.sub.12 H.sub.25 
##STR17## 
g NHSO.sub.2 C.sub.16 H.sub.23 
##STR18## 
__________________________________________________________________________ 
Those among the above mentioned couplers whichhave a nitrogen atom for the 
elimination atom are especially desirable. 
Furthermore, the oil protected type, indazolone based and cyanoacetyl based 
couplers, and especially the 5-pyrazolone based and the pyrazoloazole 
based couplers such as the 5-pyrazolotriazoles can be used for the magenta 
couplers which are used in the invention. The 5-pyrazolone based couplers 
which are substituted with an arylamino group or an acylamino group in the 
3-position are preferred from the point of view of the hue of the colored 
dye and the color density, and typical examples of these have been 
disclosed in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 
3,062,653, 3,152,896 and 3,936,015 etc. The nitrogen atom elimination 
groups disclosed in U.S. Pat. No. 4,310,619 and the arylthio groups 
disclosed in U.S. Pat. No. 4,351,897 or WO 88/04795 are the preferred 
elimination groups for the two equivalent 5-pyrazolone based couplers. 
Furthermore, high color densities can be obtained with the 5-pyrazolone 
based couplers which have ballast groups as disclosed in European Patent 
73,636. 
The benzolobenzimidazoles disclosed in U.S. Pat. No. 3,369,879, and 
preferably the pyrazolo[5,1-c]-[1,2,4]triazoles disclosed in U.S. Pat. No. 
3,725,067, the pyrazolotetrazoles disclosed in Research Disclosure, 24220 
(June 1984) and the pyrazolopyrazoles disclosed in Research Disclosure, 
24230 (June 1984) can be used as pyrazoloazole based couplers. All of the 
couplers described above may take the form of a polymeric coupler. 
Typical examples of these compounds can be represented by the formulae 
[M-1], [M-2]or [M-3] indicated below. 
##STR19## 
Here R.sub.31 represents a non-diffusible group which has a total of from 8 
to 32 carbon atoms, and R.sub.32 represents a phenyl group or a 
substituted phenyl group. R.sub.33 represents a hydrogen atom or a 
substituent group. Z represents a group of non-metal atoms which is 
required to form a five membered azole ring which contains from 2 to 4 
nitrogen atoms, and the azole ring may have substituent groups (including 
condensed rings). 
X.sup.4 represents a hydrogen atom or an elimination group. Details of the 
substituent groups of R.sub.33 and the substituent groups of the azole 
ring have been disclosed for example in the specifications of U.S. Pat. 
No. 4,540,654, from line 41 of column 2 to line 27 of column 8. 
Among the pyrazoloazole based couplers, the imidazo[1,2-b]pyrazoles 
disclosed in U.S. Pat. No. 4,500,630 are preferred in view of the small 
absorbance on the yellow side of the colored dye and their light fastness, 
and the pyrazolo[1,5-b][1,2,4]triazoles disclosed in U.S. Pat. No. 
4,540,654 are especially desirable. 
Moreover, the use of the pyrazolotriazole couplers which have a branched 
alkyl group bonded directly in the 2-, 3- or 6-position of the 
pyrazolotriazole ring as disclosed in JP-A-61-65245, the pyrazoloazole 
couplers in which a sulfonamido group is included in the molecule as 
disclosed in JP-A-61-65246, the pyrazoloazole couplers which have an 
alkoxyphenylsulfonamido ballast group as disclosed in JP-A-61-147254 and 
the pyrazolotriazole couplers which have an alkoxy group or an aryloxy 
group in the 6-position as disclosed in European Patent Application 
226,849A is desirable. 
Actual examples of these couplers are given below. 
3 
##STR20## 
Compound R.sub.33 R.sub.34 X.sup.4 
M-1 CH.sub.3 
##STR21## 
Cl 
M-2 As above 
##STR22## 
As above 
M-3 As above 
##STR23## 
##STR24## 
M-4 
##STR25## 
##STR26## 
##STR27## 
M-5 CH.sub.3 
##STR28## 
Cl 
M-6 As above 
##STR29## 
As above 
M-7 
##STR30## 
##STR31## 
##STR32## 
M-8 CH.sub.3 CH.sub.2 O As above As above 
M-9 
##STR33## 
##STR34## 
As above 
M-10 
##STR35## 
##STR36## 
Cl 
M-11 CH.sub.3 
##STR37## 
Cl 
M-12 As above 
##STR38## 
As above M-13 
##STR39## 
##STR40## 
As above 
M-14 
##STR41## 
##STR42## 
As above 
M-15 
##STR43## 
##STR44## 
Cl 
M-16 
##STR45## 
##STR46## 
##STR47## 
The most typical cyan couplers are the phenol based cyan couplers and the 
naphthol based cyan couplers. 
There are phenol based cyan couplers which have an acylamino group in the 
2-position and an alkyl group in the 5-position of the phenol ring 
(including polymerized couplers) as disclosed in U.S. Pat. Nos. 2,369,929, 
4,518,687, 4,511,647, 3,772,002 etc., and typical examples include the 
coupler of Example 2 disclosed in Canadian Patent 625,822, compound (1) 
disclosed in U.S. Pat. No. 3,772,002, compounds (I-4) and (I-5) disclosed 
in U.S. Pat. No. 4,564,590, compounds (1), (2) and (3) disclosed in 
JP-A-61-39045, and the compound (C-2) disclosed in JP-A-62-70846. 
There are the 2,5-diacylaminophenol based couplers disclosed in U.S. Pat. 
Nos. 2,772,162, 2,895,826, 4,334,011 and 4,500,653, and in JP-A-59-164555, 
and typical examples of these include compound (V) disclosed in U.S. Pat. 
No. 2,895,826, compound (17) disclosed in U.S. Pat. No. 4,557,999, 
compounds (2) and (12) disclosed in U.S. Pat. No. 4,565,777, compound (4) 
disclosed in U.S. Pat. No. 4,124,396, and compound (I-19) disclosed in 
U.S. Pat. No. 4,613,564, etc. 
There are the phenol based cyan couplers in which a nitrogen containing 
heterocyclic ring is condensed with the phenol nucleus as disclosed in 
U.S. Pat. Nos. 4,327,173, 4,564,586 and 4,430,423, JP-A-61-390441, and 
JP-A-62-257158 and typical examples include the couplers (1) and (3) 
disclosed in U.S. Pat. No. 4,327,173, compounds (3) and (16) disclosed in 
U.S. Pat. No. 4,564,586, compounds (1) and (3) disclosed in U.S. Pat. No. 
4,430,423, and the compounds shown below. 
##STR48## 
Other phenol based cyan couplers include the ureido based couplers 
disclosed in U.S. Pat. Nos. 4,333,999, 4,451,559, 4,444,872, 4,427,767 and 
4,579,831 and in European Patent (EP) No. 067,689B1 etc., and typical 
examples include the coupler (7) disclosed in U.S. Pat. No. 4,333,999, the 
coupler (1) disclosed in U.S. Pat. No. 4,451,559, the coupler (14) 
disclosed in U.S. Pat. No. 4,444,872, the coupler (3) disclosed in U.S. 
Pat. No. 4,427,767, the couplers (6) and (24) disclosed in U.S. Pat. No. 
4,609,619, the couplers (1) and (11) disclosed in U.S. Pat. No. 4,579,813, 
the couplers (45) and (50) disclosed in European Patent (EP) 67,689B1, and 
the coupler (3) disclosed in JP-A-61-42658, etc. 
As naphthol based cyan couplers there are those which have an 
N-alkyl-N-arylcarbamoyl group in the 2-position of the naphthol nucleus 
(see, for example U.S. Pat. No. 2,313,586), those which have an 
alkylcarbamoyl group in the 2-position (see, for example U.S. Pat. Nos. 
2,474,293 and 4,282,312), those which have an arylcarbamoyl group in the 
2-position (see, for example JP-B-50-14523), those which have a 
carbonamido group or a sulfonamido group in the 5-position (see, for 
example JP-A-60-237448, JP-A-61-145557 and JP-A-61-153640), and those 
which have an aryloxy elimination group (see, for example U.S. Pat. No. 
3,476,563), those which have a substituted alkoxy elimination group (see, 
for example U.S. Pat. No. 4,296,199) and those which have a glycolic acid 
elimination group (see, for example JP-B-60-39217), etc. 
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, 
ascorbic acid derivatives etc. can also be included as anti-color fogging 
agents in photosensitive materials made using this invention. 
The catechol derivatives disclosed for example in the specifications of 
JP-A-59-125732 and JP-A-60-262159 etc. can also be used as dye image 
stabilizers. 
Ultraviolet absorbers may also be included in the hydrophilic colloid 
layers of photosensitive materials made using this invention. For example, 
it is possible to use benzotriazole compounds which are substituted with 
aryl groups (for example those disclosed in U.S. Pat. No. 3,533,794), 
4-thiazolidone compounds (for example those disclosed in U.S. Pat. Nos. 
3,314,794 and 3,352,681), benzophenone compounds (for example, those 
disclosed in JP-A-46-2784), ketoacid ester compounds (for example those 
disclosed in U.S. Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds 
(for example those disclosed in U.S. Pat. No. 4,045,229) or benzo-oxydol 
compounds (for example those disclosed in U.S. Pat. No. 3,700,455). 
Couplers which have ultraviolet absorbing properties (for example the 
.alpha.-naphthol based cyan dye forming couplers) and polymers which have 
ultraviolet absorbing properties can also be used. These ultraviolet 
absorbers may be mordanted in a specified layer. 
Water soluble dyes may be included in the hydrophilic colloid layers of 
photosensitive materials of this invention as filter dyes, with a view to 
preventing the occurrence of irradiation, or for other purposes. 
Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, aniline dyes 
and azo dyes are included among these dyes. Of these dyes, the oxonol 
dyes, the hemioxonol dyes and merocyanine dyes are preferred. 
Gelatin is useful as the binding agent or protective colloid which is used 
in the emulsion layers of photosensitive materials of this invention, but 
other hydrophilic colloids may be used either independently, or in 
conjunction with gelatin. 
The gelatin used in the invention may be a lime treated gelatin or a 
gelatin which as been treated using an acid. Details of methods for the 
manufacture of gelatin have been disclosed in "The Macromolecular 
Chemistry of Gelatin", by Arthur Weiss, (published by Academic Press, 
1964). 
The cellulose nitrate films, cellulose acetate films, cellulose acetate 
butyrate films, cellulose acetate propionate films, polystyrene films, 
polyethyleneterephthalate films, polycarboante films and laminates of 
these materials, thin glass films, paper etc. normally used in 
photographic materials can be used for the support which is used in this 
invention. Good results are obtained with supports such as paper which has 
been coated or laminated with baryta or an .alpha.-olefin polymer, 
especially polymers based on .alpha.-olefins which have from 2 to 10 
carbon atoms, such as polyethylene, polypropylene, ethylene butene 
copolymers etc., vinyl chloride resins which contain a reflecting 
substance such as TiO.sub.2, and plastic films of which the adhesivity 
with other polymeric substances has been improved by roughening the 
surface in the way indicated in JP-B-47-19068. Furthermore, ultraviolet 
hardenable resins can also be used. 
A transparent support or a non-transparent support is selected in 
accordance with the intended purpose of the photographic material. 
Furthermore, the support may be rendered colored and transparent by the 
addition of dyes or pigments. 
As well as truly non-transparent materials such as paper, supports obtained 
by adding dyes or pigments such as titanium oxide to transparent films and 
plastic films which have been surface treated using the method disclosed 
in JP-B-47-19068, and paper are included among the non-transparent 
supports. An undercoating layer is normally established on the support. 
Preliminary treatments such as a coronal discharge treatment, ultraviolet 
irradiation treatment, flaming treatment etc. can also be applied to the 
support surface in order to improve adhesivity. 
The normal color photosensitive materials, especially color photographic 
materials for prints, can be used for making color photographs of this 
invention. 
A black and white development bath and/or a color development bath can be 
used for the development of the photosensitive materials of this 
invention. The color development bath used is preferably an aqueous 
alkaline solution which contains a primary aromatic amine based color 
developing agent as the principal component. Aminophenol based compounds 
are also useful as color developing agents, but the use of 
p-phenylenediamine based compounds is preferred. Typical examples of these 
compounds include 3-methyl-4-amino-N,N-diethylaniline, 
3-methyl-4-amino-N-ethyl-N-8-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-8-methanesulfonamidoethylaniline, 
3-methyl-4-amino-N-ethyl-N-8-methoxyethylaniline and the sulfate, 
hydrochloride and ptoluenesulfonate salts of these compounds. Two or more 
of these compounds can be used in combination, depending on the intended 
purpose. 
The color development baths generally contain pH buffers such as the 
carbonates, borates or phosphates of the alkali metals, and development 
inhibitors or antifogging agents such as bromides, iodides, 
benzimidazoles, benzothiazoles or mercapto compounds etc. They may also 
contain, as required, various preservatives, such as hydroxylamine, 
diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, 
triethanolamine, catechol sulfonic acids, 
triethylenediamine(1,4-diazabicyclo[2,2,2]octane), organic solvents such 
as ethylene glycol and diethylene glycol, development accelerators such as 
benzyl alcohol, poly(ethylene glycol), quaternary ammonium salts and 
amines, color forming couplers, competitive couplers fogging agents such 
as sodium borohydride, auxiliary developing agents such as 
1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating 
agents as typified by the aminopolycarboxylic acids, aminopolyphosphonic 
acids, alkylphosphonic acids and phosphonocarboxylic acids, typical 
examples of which include ethylenediamine tetra-acetic acid, 
nitrilotriacetic acid, diethylenetriamine pentaacetic acid, 
cyclohexanediamine tetra-acetic acid, hydroxyethylimino diacetic acid, 
1-hydroxyethylidene-1,1-diphosphonic acid, 
nitrilo-N,N,N-trimethylenephosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine 
di(o-hydroxyphenylacetic acid), and salts of these compounds. 
Color development is carried out after a normal black and white development 
in the case of reversal processing. The known black and white developing 
agents, for example the dihydroxybenzenes such as hydroquinone etc., the 
3-pyrazolidones such as 1-phenyl-3pyrazolidone etc., and the amino phenols 
such as N-methyl-p-aminophenol etc., can be used individually or in 
combination in the black and white development bath. 
The pH of these color developing baths and black and white developing baths 
is generally within the range from 9 to 12. Furthermore, the replenishment 
rate of the development bath depends on the color photographic material 
which is being processed, but it is generally less than 3 liters per 
square meter of photosensitive material and it is possible, by reducing 
the bromide ion concentration in the replenisher, to use a replenishment 
rate of less than 500 ml per square meter of photosensitive material. The 
prevention of loss of liquid by evaporation, and aerial oxidation, by 
minimizing the contact area with air in the processing tank is desirable 
in cases where the replenishment rate is low. Furthermore, the 
replenishment rate can be reduced by using a means of suppressing the 
accumulation of bromide ion in the developer. 
The photographic emulsion layers are subjected to a normal bleaching 
process after color development. The bleaching process may be carried out 
at the same time as the fixing process (in a bleach-fix process) or it may 
be carried out as a separate process. Moreover, a bleach-fix process can 
be carried out after a bleach process in order to speed up processing. 
Moreover processing can be carried out in two connected bleach-fix baths, 
a fixing process can be carried out before carrying out a bleach-fix 
process, or a bleaching process can be carried out after a bleach-fix 
process, according to the intended purpose of the processing. Compounds of 
a multi-valent metal such as iron(III), cobalt(III), chromium(VI), 
copper(II), etc., peracids, quinones, nitro compounds etc. can be used as 
bleaching agents. Typical bleaching agents include ferricyanides; 
dichromates; organic complex salts of iron(III) or cobalt(III), for 
example complex salts with aminopolycarboxylic acids such as 
ethylenediamine tetraacetic acid, diethylenetriamine penta-acetic acid, 
cyclohexanediamine tetra-acetic acid, methylimino diacetic acid, 
1,3-diaminopropane tetra-acetic acid, glycol ether diamine tetra-acetic 
acid etc. or citric acid, tartaric acid, malic acid etc.; persulfates; 
bromates; permanganates and nitrobenzenes, etc. Of these materials the use 
of the aminopolycarboxylic acid iron(III) complex salts, principally 
ethylenediamine tetra-acetic acid iron(III) complex salts, and persulfates 
is preferred from the points of view of both rapid processing and the 
prevention of environmental pollution. Moreover, the amino polycarboxylic 
acid iron(III) complex salts are especially useful in both bleach baths 
and bleach-fix baths. The pH of bleach or bleach-fix baths in which 
aminopolycarboxylic acid iron(III) complex salts are being used is 
normally from 5.5 to 8, but processing can be carried out at lower pH 
values in order to speed up processing. 
Bleach accelerators can be used, as required, in the bleach baths, 
bleach-fix baths, or bleach or bleach-fix prebaths. Actual examples of 
useful bleach accelerators have been disclosed in the following 
specifications: Thus there are the compounds which have a mercapto group 
or a disulfide group disclosed in U.S. Pat. No. 3,893,858, West German 
Patents 1,290,812, and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A 
53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-04232, 
JP-A-53-124424, JP-A-53-141623 and JP-A-53-28426, and in Research 
Disclosure No. 17,129 (July 1978) etc.; the thiazolidine derivatives 
disclosed in JP-A-50-40129; the thiourea derivatives disclosed in 
JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735, and in U.S. Pat. No. 
3,706,561; the iodides disclosed in West German Patent 1,127,715 and in 
JP-A-58-16235; the polyoxyethylene compounds disclosed in West German 
Patents 966,410 and 2,748,430; the polyamine compounds disclosed in 
JP-B-45-8836; the other compounds disclosed in JP-A-49-42434, 
JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and 
JP-A-58-163940; and bromide ions etc. Among these compounds, those which 
have a mercapto group or a disulfide group are preferred in view of their 
large accelerating effect, and the use of the compounds disclosed in U.S. 
Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 is 
specially desirable. Moreover, the use of the compounds disclosed in U.S. 
Pat. No. 4,552,834 is also desirable. These bleach accelerators may be 
added to the sensitive material. These bleach accelerators are especially 
effective with bleach-fixing color photosensitive materials for 
photographic purposes. 
Thiosulfates, thiocyanates, thioether based compounds, thioureas and large 
quantities of iodides etc. can be used as fixing agents, but thiosulfates 
are generally used for this purpose, and ammonium thiosulfate in 
particular can be used in the widest range of applications. Sulfites or 
bisulfites, or carbonyl-bi-sulfite addition compounds, are the preferred 
preservatives for bleach-fix baths. 
The silver halide color photographic materials of this invention are 
generally subjected to a water washing and/or stabilizing process after 
the desilvering process. The amount of water used in the water washing 
process can be fixed within a wide range according to the nature of the 
photosensitive material (for example the materials, such as the couplers, 
which are being used), the wash water temperature, the number of washing 
tanks (the number of washing stages), the replenishment system, i.e. where 
a counter-flow or a sequential-flow system is used, and various other 
conditions. The relationship between the amount of water used and the 
number of water washing tanks in a multi-stage counter-flow system can be 
obtained using the method outlined on pages 248 to 253 of Journal of the 
Society of Motion Picture and Television Engineers, Volume 64 (May 1955). 
The amount of wash water can be greatly reduced by using the multi-stage 
counter-flow system noted in the aforementioned literature, but bacteria 
proliferate due to the increased residence time of the water in the tanks 
and problems arise as a result of the sediments which are formed becoming 
attached to the photosensitive material. The method in which the calcium 
ion and manganese ion concentrations are reduced as disclosed in 
JP-A-62-288838 can be used very effectively to overcome problems of this 
sort in the processing of color photosensitive materials of this 
invention. Furthermore, the isothiazolone compounds and thiabendazoles 
disclosed in JP-A-57-8542, and the chlorine based disinfectants such as 
chlorinated sodium isocyanurate, and benzotriazoles etc., and the 
disinfectants disclosed in "Chemistry of Biocides and Fungicides" by 
Horiguchi, "Reduction of Micro-organisms, Biocidal and Fungicidal 
Techniques", published by the Health and Hygiene technical Society and in 
"A Dictionary of Biocides and Fungicides", published by the Japanese 
Biocide and Fungicide Society, can be used for this purpose. 
The pH value of the wash water used in the processing of the photosensitive 
materials of the invention is within the range of from 4 to 9, and 
preferably within the range of from 5 to 8. The wash water temperature and 
the washing time can be set according to the nature of the photosensitive 
material and the application etc. but, in general, washing conditions of 
from 20 seconds to 10 minutes at a temperature of from 15.degree. to 
45.degree. C., and preferably of from 30 seconds to 5 minutes at a 
temperature of from 25.degree. to 40.degree. C., are selected. Moreover, 
the photosensitive materials of this invention can be processed directly 
in a stabilizing bath instead of being subjected to a water wash as 
described above. The known methods disclosed in JP-A-57-8543, 
JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose. 
Furthermore, there are cases in which a stabilization process is carried 
out following the aforementioned water washing process and the stabilizing 
baths which contain formalin and surfactant which are used as a final bath 
for color photosensitive materials used for photographic purposes are an 
example of such a process. Various chelating agents and fungicides etc. 
can be added to these stabilizing baths. 
The overflow which accompanies replenishment of the above mentioned wash 
water and/or stabilizer can be reused in other processes such as the 
desilvering process etc. 
A color developing agent may also be incorporated into the silver halide 
color photosensitive materials of this invention in order to simplify and 
speed-up processing. The use of various color developing agent precursors 
is preferred. For example, the indoaniline based compounds disclosed in 
U.S. Pat. No. 3,342,597, the Schiff's base type compounds disclosed in 
U.S. Pat. No. 3,342,599 and in Research Disclosure Nos. 14,850 and 15,159 
the aldol compounds disclosed in Research Disclosure No. 13,924, the metal 
salt complexes disclosed in U.S. Pat. No. 3,719,492, and the urethane 
based compounds disclosed in JP-A-53-135628 can be used for this purpose. 
Various 1-phenyl-3-pyrazolidones can be incorporated, as required, into the 
silver halide color photosensitive materials of this invention with a view 
to accelerating color development. Typical compounds of this type have 
been disclosed in JP-A-56-64339, JP-A-57-44547 and JP-A-58-115438 etc. 
The various processing baths are used at a temperature of from 10.degree. 
to 50.degree. C. in this invention. The standard temperature is normally 
from 33.degree. to 38.degree. C., but processing is accelerated and the 
processing time is shortened at higher temperatures and, conversely, 
higher picture quality and improved stability of the processing baths can 
be achieved at lower temperatures. Furthermore, processes using hydrogen 
peroxide intensification or cobalt intensification as disclosed in West 
German Patent 2,226,770 or U.S. Pat. No. 3,674,499 can be carried out in 
order to economize on silver in the photosensitive material. 
In order to realize to the full extent the distinguishing features of the 
silver halide photographic materials of this invention, the silver halide 
color photographic material which has, on a reflective support, at least 
one photosensitive layer which contains silver halide grains of this 
invention and at least one type of coupler which forms a dye by means of a 
coupling reaction with the oxidized form of a primary aromatic amine 
developing agent is preferably processed for a development time of not 
more than 2 minutes 30 seconds in a color development bath which is 
essentially free of benzyl alcohol and which contains not more than 0.002 
mol/liter of bromide ion. 
The term "essentially free of benzyl alcohol" as used above signifies a 
concentration of benzyl alcohol not exceeding 2 ml per liter of color 
development bath, preferably not exceeding 0.5 ml per liter of development 
bath or, most desirably, the complete absence of benzyl alcohol. 
The present invention will now be described by reference to non-limiting 
examples, unless otherwise specified, all percents, ratios, parts, etc., 
are by weight. 
EXAMPLE 1 
Lime treated gelatin (32 grams) was added to 1000 ml of distilled water 
and, after forming a solution at 40.degree. C, 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 11.0 grams of sodium chloride in 200 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 14 
minutes while maintaining the temperature at 52.degree. C. Moreover, a 
solution obtained by dissolving 128.0 grams of silver nitrate in 560 ml of 
distilled water and a solution obtained by dissolving 44.0 grams of sodium 
chloride in 560 ml of distilled water were added to, and mixed with, the 
above mentioned mixture over a period of 20 minutes while maintaining the 
temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl]-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous sodium chloride solution had been completed. The 
temperature was then maintained at 52.degree. C. for a period of 15 
minutes, after which it was reduced to 40.degree. C. and the mixture was 
desalted and washed with water. Then a further 90.0 grams of lime treated 
gelatin was added and, after adjusting to pAg 7.2 using sodium chloride, 
2.0 mg of triethylthiourea was added and chemical sensitization was 
carried out optimally at 58.degree. C. The silver chloride emulsion so 
obtained was referred to as emulsion A-1. 
An emulsion was prepared in the same way as emulsion A-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion A-2. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 0.27 gram of potassium bromide and 10.9 gram chloride in 200 ml 
of distilled water were added to, and mixed with, the aforementioned 
solution over a period of 14 minutes while maintaining the temperature at 
52.degree. C. Moreover, a solution obtained by dissolving 128.0 grams of 
silver nitrate in 560 ml of distilled water and a solution obtained by 
dissolving 1.08 grams of potassium bromide and 43.5 grams of sodium 
chloride in 560 ml of distilled water were added to, and mixed with, the 
above mentioned mixture over a period of 20 minutes while maintaining the 
temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous alkali halide solution had been completed. The temperature 
was then maintained at 52.degree. C. for a period of 15 minutes, after 
which it was reduced to 40.degree. C. and the mixture was desalted and 
washed with water. Then a further 90.0 grams of lime treated gelatin was 
added and, after adjusting to pAg 7.2 using sodium chloride, 2.0 mg of 
triethylthiourea was added and chemical sensitization was carried out 
optimally at 58.degree. C. The silver chlorobromide (1.2 mol% silver 
bromide) emulsion so obtained was referred to as emulsion B-1. 
An emulsion was prepared in the same way as emulsion B-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous alkali 
halide solution which was added on the second occasion, and this was 
referred to as emulsion B-2. 
Next 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N' dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 29.6 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 8.0 grams of sodium chloride in 146 ml of distilled water were 
added to, and mixed with, the aforementioned solution while maintaining 
the temperature at 52.degree. C., the addition of the two solutions 
starting at the same time, with the addition of the aqueous silver nitrate 
solution taking place over a period of 12 minutes 57 seconds and the 
addition of the aqueous sodium chloride solution taking place over a 
period of 10 minutes 11 seconds. Moreover, a solution obtained by 
dissolving 2.4 grams of silver nitrate in 20 ml of distilled water and a 
solution obtained by dissolving 1.35 grams of potassium bromide and 0.17 
gram of sodium chloride in 20 ml of distilled water were added to, and 
mixed with, the above mentioned mixture over a period of 5 minutes while 
maintaining the temperature at 52.degree. C. Then a solution obtained by 
dissolving 128.0 grams of silver nitrate in 560 ml of distilled water and 
a solution obtained by dissolving 44.0 grams of sodium chloride in 560 ml 
of distilled water were added to, and mixed with, the aforementioned 
mixture over a period of 20 minutes while maintaining the temperature at 
52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-yidenemethy 
l]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous sodium chloride solution had been completed. The 
temperature was then maintained at 52.degree. C. for a period of 15 
minutes, after which it was reduced to 40.degree. C. and the mixture was 
desalted and washed with water. Then a further 90.0 grams of lime treated 
gelatin was added and, after adjusting to pAg 7.2 using sodium chloride, 
2.0 mg of triethylthiourea as added and chemical sensitization was carried 
out optimally at 58.degree. C. The silver chlorobromide (1.2 mol% silver 
bromide) emulsion so obtained was referred to as emulsion C-1. 
An emulsion was prepared in the same way as emulsion C-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the third occasion, and this was 
referred to as emulsion C-2. 
Furthermore, an emulsion was prepared in the same way as emulsion C-1 
except that 0.91 mg of potassium hexachloroiridate (IV) was added to the 
aqueous alkali halide solution which was added on the second occasion, and 
this was referred to as emulsion C-3. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 11.0 grams of sodium chloride in 200 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 14 
minutes, while maintaining the temperature at 52.degree. C. Moreover, a 
solution obtained by dissolving 125.6 grams of silver nitrate in 560 ml of 
distilled water and a solution obtained by dissolving 41.0 grams of sodium 
chloride in 532 ml of distilled water were added to, and mixed with, the 
above mentioned mixture while maintaining the temperature at 52.degree. 
C., the addition of the two solutions being started at the same time, with 
the addition of the silver nitrate solution taking place over a period of 
19 minutes 38 seconds and the addition of the aqueous sodium chloride 
solution taking place over a period of 18 minutes 38 seconds. Then a 
solution obtained by dissolving 2.4 gram of silver nitrate in 20 ml of 
distilled water and a solution obtained by dissolving 1.35 grams of 
potassium bromide and 0.17 gram of sodium chloride in 20 ml of distilled 
water were added to, and mixed with, the aforementioned mixture over a 
period of 5 minutes while maintaining the temperature at 52.degree. C. 
Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-yridenemeth 
yl]-1-butenyl}-3-benzooxazolio]-ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous alkali halide solution had been completed. The temperature 
was then maintained at 52.degree. C. for a period of 15 minutes, after 
which it was reduced to 40.degree. C. and the mixture was desalted and 
washed with water. Then, a further 90.0 grams of lime treated gelatin was 
added and, after adjusting to pAg 7.2 using sodium chloride, 2.0 mg of 
triethylthiourea was added and chemical sensitization was carried out 
optimally at 58.degree. C. The silver chlorobromide (1.2 mol% silver 
bromide) emulsion so obtained was referred to as emulsion D-1. 
An emulsion was prepared in the same way as emulsion D-1 except that 0.046 
mg of potassium hexa-chloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion D-2. 
Furthermore, an emulsion was prepared in the same way as emulsion D-1 
except that 0.91 mg of potassium hexachloroiridate (IV) was added to the 
aqueous alkali halide solution which was added on the third occasion, and 
this was referred to as emulsion D-3. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 11.0 grams of sodium chloride in 200 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 14 
minutes, while maintaining the temperature at 52.degree. C. Moreover, a 
solution obtained by dissolving 125.6 grams of silver nitrate in 560 ml of 
distilled water and a solution obtained by dissolving 41.0 gram of sodium 
chloride in 560 ml of distilled water were added to, and mixed with, the 
above mentioned mixture while maintaining the temperature at 52.degree. C. 
Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl}-3-benzo-oxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous sodium chloride solution had been completed. Then a 
solution obtained by dissolving 2.4 grams of silver nitrate in 20 ml of 
distilled water and a solution obtained by dissolving 1.35 grams of 
potassium bromide and 0.17 gram of sodium chloride in 20 ml of distilled 
water were added to and mixed with the aforementioned mixture over a 
period of 5 minutes while maintaining the temperature at 52.degree. C. 
Subsequently, the temperature was reduced to 40.degree. C. and the mixture 
was desalted and washed with water. Then, a further 90.0 grams of lime 
treated gelatin was added and, after adjusting to pAg 7.2 using sodium 
chloride, 2.0 mg of triethylthiourea was added and chemical sensitization 
was carried out optimally at 58.degree. C. The silver chlorobromide (1.2 
mol% silver bromide) emulsion so obtained was referred to as emulsion E-1. 
An emulsion was prepared in the same way as emulsion E-1 except that 0.046 
mg of potassium hexa-chloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion E-2. 
Furthermore, an emulsion was prepared in the same way as emulsion E-1 
except that 0.91 mg of potassium hexachloroiridate (IV) was added to the 
aqueous alkali halide solution which was added on the third occasion, and 
this was referred to as emulsion E-3. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 1.12 grams of potassium bromide and 10.4 grams of sodium 
chloride in 200 ml of distilled water were added to, and mixed with, the 
aforementioned solution over a period of 14 minutes 50 seconds, while 
maintaining the temperature at 52.degree. C. Moreover, a solution obtained 
by dissolving 128.0 grams of silver nitrate in 560 ml of distilled water 
and a solution obtained by dissolving 4.48 grams of potassium bromide and 
41.8 grams of sodium chloride in 560 ml of distilled water were added to, 
and mixed with, the above mentioned mixture while maintaining the 
temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidene-met 
hyl]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous sodium chloride solution had been completed. The 
temperature was then maintained at 52.degree. C. for a period of 15 
minutes, after which it was reduced to 40.degree. C. and the mixture was 
desalted and washed with water. Then, a further 90.0 grams of lime treated 
gelatin was added and, after adjusting to pAg 7.2 using sodium chloride, 
2.0 mg of triethylthiourea was added and chemical sensitization was 
carried out optimally at 58.degree. C. The silver chlorobromide (5.0 mol% 
silver bromide) emulsion so obtained was referred to as emulsion F-1. 
An emulsion was prepared in the same way as emulsion F-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion F-2. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 11.0 grams of sodium chloride in 200 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 14 
minutes, while maintaining the temperature at 52.degree. C. Moreover, a 
solution obtained by dissolving 118.0 grams of silver nitrate in 520 ml of 
distilled water and a solution obtained by dissolving 38.4 gram of sodium 
chloride in 492 ml of distilled water were added to, and mixed with, the 
above mentioned mixture while maintaining the temperature at 52.degree. 
C., the addition of the two solutions being started at the same time with 
the aqueous silver nitrate solution being added over a period of 18 
minutes 26 seconds and the aqueous sodium chloride solution being added 
over a period of 17 minutes 26 seconds. Then a solution obtained by 
dissolving 10.0 grams of silver nitrate in 60 ml of distilled water and a 
solution obtained by dissolving 5.6 grams of potassium bromide and 0.69 
gram of sodium chloride in 60 ml of distilled water were added to, and 
mixed with, the aforementioned mixture over a period of 20 minutes while 
maintaining the temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous alkali halide solution had been completed. The temperature 
was maintained at 52.degree. C. for 15 minutes, after which it was reduced 
to 40.degree. C. and the mixture was desalted and washed with water. Then, 
a further 90.0 grams of lime treated gelatin was added and, after 
adjusting to pAg 7.2 using sodium chloride, 2.0 mg of triethylthiourea was 
added and chemical sensitization was carried out optimally at 58.degree. 
C. The silver chlorobromide (5.0 mol% silver bromide) emulsion so obtained 
was referred to as emulsion G-1. 
An emulsion was prepared in the same way as emulsion G-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion G-2. 
Furthermore, an emulsion was prepared in the same way as emulsion G-1 
except that 0.91 mg of potassium hexachloroiridate (IV) was added to the 
aqueous alkali halide solution which was added on the third occasion, and 
this was referred to as emulsion G-3. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium, 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolin-2-thione (3.2 ml) was added to 
this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 4.48 grams of potassium bromide and 8.81 grams of sodium 
chloride in 200 ml of distilled water were added to, and mixed with, the 
aforementioned solution over a period of 17 minutes 30 seconds while 
maintaining the temperature at 52.degree. C. Moreover, a solution obtained 
by dissolving 128.0 grams of silver nitrate in 560 ml of distilled water 
and a solution obtained by dissolving 17.9 grams of potassium bromide and 
35.2 grams of sodium chloride in 650 ml of distilled water were added to, 
and mixed with, the above mentioned mixture over a period of 20 minutes 
while maintaining the temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous alkali halide solution had been completed. The temperature 
was maintained at 52.degree. C. for 15 minutes, after which it was reduced 
to 40.degree. C. and the mixture was de-salted and washed with water. 
Then, a further 90.0 grams of lime treated gelatin was added and, after 
adjusting to pAg 7.2 using sodium chloride, 2.0 mg of triethylthiourea was 
added and chemical sensitization was carried out optimally at 58.degree. 
C. The silver chlorobromide (20.0 mol% silver bromide) emulsion so 
obtained was referred to as emulsion H-1. 
An emulsion was prepared in the same way as emulsion H-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion H-2. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 3.3 grams of sodium 
chloride was added and the temperature was raised to 52.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.2 ml) was added 
to this solution. Next, a solution obtained by dissolving 32.0 grams of 
silver nitrate in 200 ml of distilled water and a solution obtained by 
dissolving 11.0 grams of sodium chloride in 200 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 14 
minutes, while maintaining the temperature at 52.degree. C. Moreover, a 
solution obtained by dissolving 88.0 grams of silver nitrate in 385 ml of 
distilled water and a solution obtained by dissolving 28.1 grams of sodium 
chloride in 357 ml of distilled water were added to, and mixed with, the 
above mentioned mixture while maintaining the temperature at 52.degree. 
C., the addition of the two solutions being started at the same time with 
the aqueous silver nitrate solution being added over a period of 13 
minutes 45 seconds and the aqueous sodium chloride solution being added 
over a period of 12 minutes 45 seconds. Then a solution obtained by 
dissolving 40.0 grams of silver nitrate in 60 ml of distilled water and a 
solution obtained by dissolving 22.4 grams of potassium bromide and 2.75 
gram of sodium chloride in 175 ml of distilled water were added to, and 
mixed with, the aforementioned mixture over a period of 40 minutes while 
maintaining the temperature at 52.degree. C. Next 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonatoethyl)benzooxazolin-2-ylidenemeth 
yl]-1-butenyl}-3-benzooxazolio]ethane sulfonic acid, pyridinium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous alkali halide solution had been completed. The temperature 
was maintained at 52.degree. C. for 15 minutes, after which it was reduced 
to 40.degree. C. and the mixture was desalted and washed with water. Then, 
a further 90.0 grams of lime treated gelatin was added and, after 
adjusting to pAg 7.2 using sodium chloride, 2.0 mg of triethylthiourea was 
added and chemical sensitization was carried out optimally at 58.degree. 
C. The silver chloride emulsion so obtained was referred to as emulsion 
I-1. 
An emulsion was prepared in the same way as emulsion I-1 except that 0.046 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion I-2. 
Furthermore, an emulsion was prepared in the same way as emulsion I-1 
except that 0.91 mg of potassium hexachloroiridate (IV) was added to the 
aqueous alkali halide solution which was added on the third occasion, and 
this was referred to as emulsion H-3. 
The forms of the grains, the grain sizes and the grain size distributions 
of the twenty-three silver halide emulsions A-1 to I-3 prepared in this 
way were obtained from electron-micrographs. The silver halide grains in 
all of the emulsions from A-1 to I-3 were of a cubic form. The grain size 
was represented by the average value of the diameters of the circles 
corresponding to the projected areas of the grains, and the value obtained 
on dividing the standard deviation of the grain size by the average grain 
size was used as a measure of the grain size distribution. The results 
obtained were as shown in Table 1. 
The halogen composition of the emulsion grains was then determined by 
measuring X-ray diffraction from the silver halide crystals. A 
monochromatic Cu.sub.k.alpha. beam was used as the source and the 
diffraction angles of the diffraction lines from the (200) surface were 
measured in detail. Whereas the diffraction lines from a crystal which has 
a uniform halogen composition consist of a single peak, the diffraction 
lines from crystals which have local phases of different composition 
consist of a plurality of peaks corresponding to the compositions of the 
phases. The lattice constant can be calculated from the diffraction angle 
of the measured peaks and it is possible to determine the halogen 
composition of the silver halide from which the crystal is made. The 
results obtained were as shown in Table 2. 
TABLE 1 
______________________________________ 
Emulsion Form Grain Size, .mu., and (distribution) 
______________________________________ 
A-1 Cubic 0.51 (0.08) 
A-2 " 0.51 (0.08) 
B-1 " 0.50 (0.09) 
B-2 " 0.50 (0.09) 
C-1 " 0.51 (0.08) 
C-2 " 0.51 (0.08) 
C-3 " 0.51 (0.08) 
D-1 " 0.51 (0.09) 
D-2 " 0.51 (0.09) 
D-3 " 0.51 (0.09) 
E-1 " 0.51 (0.08) 
E-2 " 0.51 (0.08) 
E-3 " 0.51 (0.08) 
F-1 " 0.48 (0.10) 
F-2 " 0.48 (0.10) 
G-1 " 0.51 (0.10) 
G-2 " 0.51 (0.10) 
G-3 " 0.51 (0.10) 
H-1 " 0.50 (0.10) 
H-2 " 0.50 (0.10) 
I-1 " 0.51 (0.11) 
I-2 " 0.51 (0.11) 
I-3 " 0.51 (0.11) 
______________________________________ 
TABLE 2 
__________________________________________________________________________ 
Remarks 
Local silver 
Period at which the iridium was 
Emulsion 
Main Peak Subsidiary Peak 
bromide phase 
Introduced 
__________________________________________________________________________ 
A-1 Cl 100% -- No -- 
A-2 Cl 100% -- No When forming the 100% AgCl phase 
B-1 Cl 98.8% (Br 1.2%) 
-- No -- 
B-2 Cl 98.8% (Br 1.2%) 
-- No When forming the 98.8% AgCl phase 
C-1 Cl 100% Cl 76% to 90% 
Yes -- 
C-2 Cl 100% Cl 76% to 90% 
Yes When forming the 100% AgCl phase 
C-3 Cl 100% Cl 76% to 90% 
Yes When forming the localized phase 
D-1 Cl 100% Cl 68% to 90% 
Yes -- 
D-2 Cl 100% Cl 68% to 90% 
Yes When forming the 100% AgCl phase 
D-3 Cl 100% Cl 68% to 90% 
Yes When forming the localized phase 
E-1 Cl 100% Cl 61% to 90% 
Yes -- 
E-2 Cl 100% Cl 61% to 90% 
Yes When forming the 100% AgCl phase 
E-3 Cl 100% Cl 61% to 90% 
Yes When forming the localized phase 
F-1 Cl 95.0% (Br 5.0%) 
-- No -- 
F-2 Cl 95.0% (Br 5.0%) 
-- No When forming the 95.0% AgCl phase 
G-1 Cl 100% Cl 49% to 85% 
Yes -- 
G-2 Cl 100% Cl 49% to 85% 
Yes When forming the 100% AgCl phase 
G-3 Cl 100% Cl 49% to 85% 
Yes When forming the localized phase 
H-1 Cl 80.0% (Br 20%) 
-- No -- 
H-2 Cl 80.0% (Br 20%) 
-- No When forming the 80.0% AgCl phase 
I-1 Cl 100% Cl 33% to 80% 
Yes -- 
I-2 Cl 100% Cl 33% to 80% 
Yes When forming the 100% AgCl phase 
I-3 Cl 100% Cl 33% to 80% 
Yes When forming the localized 
__________________________________________________________________________ 
phase 
Next 30.0 ml of ethyl acetate and 38.5 ml of solvent (d) were added to 29.6 
grams of the magenta coupler (a) and 5.9 grams and 11.8 grams of the 
colored image stabilizers (b) and (c) respectively, and a solution was 
obtained. This solution was emulsified and dispersed in 320 ml of a 10% 
aqueous gelatin solution which contained 20 ml of 10% sodium 
dodecylbenzenesulfonate. 
The emulsified coupler dispersion and the emulsion, thus obtained, were 
mixed together and were father mixed in coating liquids to prepare coating 
compositions shown in Table 3. The coating composition was coated with the 
layer structure indicated in Table 3 onto paper supports which had been 
laminated on both sides with polyethylene to provide 23 types of 
photosensitive material. 1-Oxy-3,5-dichloro-s-triazine, sodium salt, was 
used as a gelatin hardening agent in each layer. 
TABLE 3 
______________________________________ 
Second Layer 
(Protective layer) 
Gelatin 1.50 g/m.sup.2 
First Layer 
(Green sensitive layer) 
Silver chloride (chloro- 
0.36 g/m.sup.2 
bromide) emulsion (A-1 to I-3) 
Magenta coupler (a) 0.32 g/m.sup.2 
Colored Image Stabilizer (b) 
0.06 g/m.sup.2 
(c) 0.13 g/m.sup.2 
Solvent (d) 0.42 ml/m.sup.2 
Gelatin 1.00 g/m.sup.2 
Support Laminated on Both Sides with Polyethylene 
TiO.sub.2 and ultramarine were included in the 
polyethylene on the same side as the first 
layer. 
______________________________________ 
(a) Magenta Coupler 
##STR49## 
(b) Colored Image Stabilizer 
##STR50## 
(c) Colored Image Stabilizer 
##STR51## 
(d) Solvent 
##STR52## 
Furthermore, 125 mg of the compound indicated below was added per mol 
of silver halide to each coating liquid. 
##STR53## 
The properties of the emulsions prepared were tested using the 23 coated 
samples obtained in this way (these samples were identified using the 
Thus, the samples were exposed for 5 seconds through an optical wedge and a 
green filter and then, after 30 seconds, they were subjected to color 
development processing after using the processing operations and 
development bath indicated below. The luminance of the exposing device was 
then increased by a factor of 50 times, the samples were subjected to a 
0.01 second exposure, and the exposed samples were processed after 30 
seconds in the same way as before in order to investigate the changes 
which occurred when a short exposure was given at a high luminance. 
Furthermore, samples were processed in the same way as before except that 
times of 8 minutes or 60 minutes were allowed to elapse after exposure 
before carrying out development processing (the 0.5 seconds exposure 
conditions were used) in order to investigate the latent image stability 
of the emulsions. 
______________________________________ 
Processing Operation 
Temperature 
Time 
______________________________________ 
Color development 
35.degree. C. 
45 seconds 
Bleach-fixing 30 to 35.degree. C. 
45 seconds 
Rinse (1) 30 to 35.degree. C. 
20 seconds 
Rinse (2) 30 to 35.degree. C. 
20 seconds 
Rinse (3) 30 to 35.degree. C. 
20 seconds 
Rinse (4) 30 to 35.degree. C. 
30 seconds 
Drying 70 to 80.degree. C. 
60 seconds 
______________________________________ 
(Three tank counterflow system from rinse (4) to rinse (1)). 
The compositions of each of the processing baths were as indicated below. 
______________________________________ 
Color Development Bath 
Water 800 ml 
Ethylenediamine-N,N,N,N-tetra- 
1.5 grams 
methylenesulfonic acid 
Triethylenediamine(1,4-diaza- 
5.0 grams 
bicyclo[2,2,2]octane) 
Sodium sulfite 1.4 grams 
Potassium carbonate 25 grams 
N-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 
5.0 grams 
3-methyl-4-aminoaniline sulfate 
N,N-Diethylhydroxylamine 
4.2 grams 
Fluorescent whitener (UVITEX CK, 
2.0 grams 
Ciba Geigy Co.) 
Water to make up to 1000 ml 
pH (25.degree. C.) 10.10 
Bleach-fix Bath 
Water 400 ml 
Ammonium thiosulfate (70%) 
100 ml 
Sodium sulfite 18 grams 
Ethylenediamine tetra-acetic acid 
55 grams 
iron (III) ammonium salt 
Ethylenediamine tetra-acetic acid 
3 grams 
di-sodium salt 
Ammonium bromide 40 grams 
Glacial acetic acid 8 grams 
Water to make up to 1000 ml 
pH (25.degree. C.) 5.5 
Rinse Bath 
Ion exchanged water (Calcium and magnesium contents 
less than 3 ppm) 
______________________________________ 
The reflection densities of each of the processed samples produced in this 
way were measured and the so-called characteristic curves were obtained. 
The reciprocal of the exposure which gave a density 0.5 higher than the 
fog density was taken as a measure of the speed, and the results were 
expressed as relative values taking the speed on exposing sample A-1 for 
0.5 seconds and processing after 30 seconds to be 100. Furthermore, the 
difference between the density corresponding to an exposure increased 0.5 
as log E from the exposure at which the speed was obtained and the density 
at the point where the speed was obtained was taken as a measure of 
contrast. Next, the fall in density on processing 30 seconds after a 0.01 
second exposure at the exposure which gave a density of 2.2 on processing 
each sample 30 seconds after as 0.5 second exposure was obtained and this 
was taken as a measure of reciprocity failure with short exposure times at 
high luminance. Moreover, the densities on processing 8 minutes and 60 
minutes after exposure on giving the exposure which gave a density of 1.5 
when processed 30 seconds after a 0.5 second exposure were obtained for 
each sample. The results obtained in these tests were as shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Performance on processing 
High Luminance 
Latent Image Stability*2 
30" after a 0.5" exposure 
Reciprocity 
Processed after 30' 
Processed after 60' 
Sample 
Relative Speed 
Contrast 
Law Failure* 
to processed after 8' 
to processed after 8' 
Remarks 
__________________________________________________________________________ 
A-1 100 1.45 0.96 0.03 0.04 Comparative Example 
A-2 71 1.39 0.30 0.35 0.52 Comparative Example 
B-1 112 1.41 0.90 0.02 0.04 Comparative Example 
B-2 85 1.35 0.28 0.30 0.48 Comparative Example 
C-1 195 1.29 0.75 0.04 0.05 Comparative Example 
C-2 148 1.23 0.21 0.34 0.46 Comparative Example 
C-3 174 1.33 0.05 0.02 0.02 This Invention 
D-1 200 1.38 0.68 0.03 0.03 Comparative Example 
D-2 151 1.30 0.18 0.35 0.50 Comparative Example 
D-3 173 1.42 0.07 0.02 0.03 This Invention 
E-1 224 1.41 0.61 0.04 0.06 Comparative Example 
E-2 166 1.33 0.16 0.38 0.52 Comparative Example 
E-3 199 1.49 0.04 0.00 0.01 Thsi Invention 
F-1 117 1.34 0.71 0.02 0.02 Comparative Example 
F-2 91 1.20 0.20 0.29 0.34 Comparative Example 
G-1 223 1.27 0.67 0.03 0.04 Comparative Example 
G-2 178 1.20 0.18 0.33 0.46 Comparative Example 
G-3 195 1.35 0.05 0.01 0.01 This Invention 
H-1 126 1.22 0.86 0.01 0.01 Comparative Example 
H-2 105 1.09 0.28 0.32 0.36 Comparative Example 
I-1 228 1.08 0.80 0.02 0.03 Comparative Example 
I-2 190 0.98 0.23 0.36 0.39 Comparative Example 
I-3 204 1.19 0.08 0.03 0.02 This Invention 
__________________________________________________________________________ 
*1, *2: In each case a smaller value is better. 
It is clear from these results that high speeds can be obtained when there 
is a local phase of which the silver bromide content exceeds 20 mol%, but 
there is considerable reciprocity law failure and an adverse effect in 
cases where the exposure is made with a high speed printer etc. On the 
other hand, high luminance reciprocity is improved by doping with iridium, 
but the latent image stability is markedly worsened and it is difficult to 
apply this method in practice. However, it is possible to obtain emulsions 
which have a high speed and high contrast, with which there is no loss of 
latent image stability and which is superior in that the reciprocity law 
failure is improved by means of this invention. 
EXAMPLE 2 
Lime treated gelatin (32 grams) was added to 1000 ml of distilled water 
and, after forming a solution at 40.degree. C., 5.8 grams of sodium 
chloride was added and the temperature was raised to 75.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.8 ml) was added 
to this solution. Next, a solution obtained by dissolving 6.4 grams of 
silver nitrate in 180 ml of distilled water and a solution obtained by 
dissolving 2.2 grams of sodium chloride in 180 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 10 
minutes, while maintaining the temperature at 75.degree. C. Moreover, a 
solution obtained by dissolving 153.6 grams of silver nitrate in 410 ml of 
distilled water and a solution obtained by dissolving 52.8 grams of sodium 
chloride in 410 ml of distilled water were added to, and mixed with, the 
above mentioned mixture over a period of 35 minutes while maintaining the 
temperature at 75.degree. C. Next 172.8 mg of 
3-{2-[5-chloro-3-(3-sulfonatoethyl)benzothiazolin-2ylidenemethyl]-3-naphth 
o[1,2-d]thiazolio.}propanesulfonic acid, triethylammonium salt, was added 1 
minute after the addition of the aqueous silver nitrate solution and the 
aqueous sodium chloride solution had been completed. The temperature was 
maintained at 75.degree. C. for 15 minutes, after which it was reduced to 
40.degree. C. and the mixture was de-salted and washed with water. Then, a 
further 90.0 grams of lime treated gelatin was added and, after adjusting 
to pAg 7.2 using sodium chloride, 1.0 mg of triethylthiourea was added and 
chemical sensitization was carried out optimally at 58.degree. C. The 
silver chloride emulsion so obtained was referred to as emulsion J-1. 
An emulsion was prepared in the same way as emulsion J-1 except that 0.021 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion J-2. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 5.8 grams of sodium 
chloride was added and the temperature was raised to 75.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.8 ml) was added 
to this solution. Next, a solution obtained by dissolving 6.4 grams of 
silver nitrate in 180 ml of distilled water and a solution obtained by 
dissolving 0.054 gram of potassium bromide and 2.18 grams of sodium 
chloride in 180 ml of distilled water were added to, and mixed with, the 
aforementioned solution over a period of 10 minutes while maintaining the 
temperature at 75.degree. C. Moreover, a solution obtained by dissolving 
153.6 grams of silver nitrate in 410 ml of distilled water and a solution 
obtained by dissolving 1.29 grams of potassium bromide and 52.21 grams of 
sodium chloride in 410 ml of distilled water were added to, and mixed 
with, the above mentioned mixture over a period of 35 minutes while 
maintaining the temperature at 75.degree. C. Next 172.8 mg of 3-{2-[ 
5-chloro-3-(3-sulfonatoethyl)benzothiazolin-2-ylidenemethyl]-1-butenyl}-3- 
naphtho[1,2-d]thiazolio}propanesulfonic acid, triethylammonium salt, was 
added 1 minute after the addition of the aqueous silver nitrate solution 
and the aqueous sodium chloride solution had been completed. The 
temperature was maintained at 75.degree. C. for 15 minutes, after which it 
was reduced to 40.degree. C. and the mixture was de-salted and washed with 
water. Then, a further 90.0 grams of lime treated gelatin was added and, 
after adjusting to pAg 7.2 using sodium chloride, 1.0 mg of 
triethylthiourea was added and chemical sensitization was carried out 
optimally at 58.degree. C. The silver chloride emulsion so obtained was 
referred to as emulsion K-1. 
An emulsion was prepared in the same way as emulsion K-1 except that 0.021 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and this was 
referred to as emulsion K-2. 
Next, 32 grams of lime treated gelatin was added to 1000 ml of distilled 
water and, after forming a solution at 40.degree. C., 5.8 grams of sodium 
chloride was added and the temperature was raised to 75.degree. C. A 1% 
aqueous solution of N,N'-dimethylimidazolidin-2-thione (3.8 ml) was added 
to this solution. Next, a solution obtained by dissolving 6.4 grams of 
silver nitrate in 180 ml of distilled water and a solution obtained by 
dissolving 2.2 grams of sodium chloride in 180 ml of distilled water were 
added to, and mixed with, the aforementioned solution over a period of 10 
minutes, while maintaining the temperature at 75.degree. C. Moreover, a 
solution obtained by dissolving 151.2 grams of silver nitrate in 410 ml of 
distilled water and a solution obtained by dissolving 47.4 grams of sodium 
chloride in 410 ml of distilled water were added to, and mixed with, the 
above mentioned mixture over a period of 35 minutes while maintaining the 
temperature at 75.degree. C. Next 172.8 mg of 
3-{2-[5-chloro-3-(3-sulfonatopropyl)-benzothiazolin-2-ylidenemethyl]-3-nap 
htho[1,2d]thiazolio]propanesulfonic acid, triethylammonium salt, was added 
1 minute after the addition of the aqueous silver nitrate solution and the 
aqueous sodium chloride solution had been completed. The temperature was 
maintained at 75.degree. C. for 15 minutes, after which it was reduced to 
52.degree. C. Subsequently, a solution obtained by dissolving 2.4 grams of 
silver nitrate in 20 ml of distilled water and a solution obtained by 
dissolving 1.35 grams of potassium bromide and 0.17 grams of sodium 
chloride in 20 ml of distilled water were added to, and mixed with, the 
aforementioned mixture over a period of 5 minutes while maintaining the 
temperature at 52.degree. C. The temperature was then dropped to 
40.degree. C. and the mixture was de-salted and washed with water. Then, a 
further 90.0 grams of lime treated gelatin was added and, after adjusting 
to pAg 7.2 using sodium chloride, 1.0 mg of triethylthiourea was added and 
chemical sensitization was carried out optimally at 58.degree. C. The 
silver chloride emulsion so obtained was referred to as emulsion L-1. 
An emulsion was prepared in the same way as emulsion L-1 except that 0.240 
mg of potassium hexachloroiridate (IV) was added to the aqueous sodium 
chloride solution which was added on the second occasion, and 0.160 mg of 
potassium pentachloroiridate (IV) was added to the aqueous alkali halide 
solution which was added on the third occasion, and this was referred to 
as emulsion L-2. 
An emulsion was prepared in the same way as emulsion L-1 except that 0.400 
mg of potassium hexachloroiridate (IV) was added to the aqueous alkali 
halide solution which was added on the third occasion, and this was 
referred to as emulsion L-3. 
Next, an emulsion was prepared in the same way as emulsion E-2 in Example 1 
except that 0.546 mg of potassium hexachloroiridate (IV) was added to the 
aqueous sodium chloride solution which was added on the second occasion, 
and 0.364 mg of potassium hexachloroiridate (IV) was added to the aqueous 
alkali halide solution which was added on the third occasion, and this was 
referred to as emulsion E-4. 
Next emulsions M-1, M-2, N-1, N-2, O-1, O-3 and O-4 were prepared in the 
same way as emulsions A-1, A-2, B-1, B-2, E-1, E-3 and the above mentioned 
E-4 respectively except that 60.0 mg of 
2-[2,4-(2,2-dimethyl-1,3-propano)-5-(6-methyl-3-pentylbenzothiazolin-2-yli 
dene)-1,3-pentadienyl]-3-ethyl-6-methylbenzothiazolium iodide was added in 
place of the 286.7 mg of 
2-[5-phenyl-2-{2-[5-phenyl-3-(2-sulfonateoethyl)benzooxazolin-2-ylidenemet 
hyl]-1-butenyl}-3-benzooxazolio]ethanesulfonic acid, pyridinium salt. The 
form of the grains, the grain sizes and the grain size distributions of 
the emulsions J-1, J-2, K-1, K-2, L-1, L-2 and L-3 prepared in this way 
were as shown in Table 5. 
Furthermore, the halogen compositions of the emulsion grains were obtained 
using X-ray diffraction in the same way as in Example 1, and the results 
were as shown in Table 6. 
TABLE 5 
______________________________________ 
Emulsion Form Grain Size, .mu., and (distribution) 
______________________________________ 
J-1 Cubic 1.04 (0.07) 
J-2 " 1.04 (0.07) 
K-1 " 0.99 (0.08) 
K-2 " 0.99 (0.08) 
L-1 " 1.04 (0.08) 
L-2 " 1.04 (0.08) 
L-3 " 1.04 (0.08) 
______________________________________ 
TABLE 6 
__________________________________________________________________________ 
Remarks 
Local silver 
Period at which the iridium was 
Emulsion 
Main Peak Subsidiary Peak 
bromide phase 
Introduced 
__________________________________________________________________________ 
J-1 Cl 100% -- No -- 
J-2 Cl 100% -- No When forming the 100% AgCl phase 
K-1 Cl 98.8% (Br 1.2%) 
-- No -- 
K-2 Cl 98.8% (Br 1.2%) 
-- No When forming the 98.8% AgCl phase 
L-1 Cl 100% Cl 58% to 90% 
Yes -- 
L-2 Cl 100% Cl 58% to 90% 
Yes When forming the 100% AgCl phase 
and the localized phase 
L-3 Cl 100% Cl 58% to 90% 
Yes When forming the localized phase 
E-4 Cl 100% Cl 58% to 90% 
Yes When forming the 100% AgCl phase 
and the localized phase 
__________________________________________________________________________ 
Seven types of color photosensitive material were prepared by multi-layer 
coating using the emulsions obtained in this way in accordance with the 
composition and layer structure, and combinations of emulsions, shown in 
Tables 7 and 8. 
PREATION OF THE FIRST LAYER COATING LIQUIDS 
Ethyl acetate (27.2 ml) and 7.9 ml of solvent (d) were added to 19.1 grams 
of the yellow coupler (e) and 4.4 grams of the colored image stabilizer 
(f) to form a solution, and this solution was emulsified and dispersed in 
10% aqueous gelatin solution which contained 8.0 ml of 10% sodium 
dodecylbenzenesulfonate. 
On the other hand, the above mentioned emulsified dispersion was mixed with 
and dissolved in the silver chloride or silver chlorobromide emulsions 
shown in Table 8 to provide first layer coating liquids which had a 
composition as shown in Table 7. 
The coating liquids for the second to the seventh layers were prepared 
using the same procedure as used for the first layer coating liquids. 
However, the emulsified dispersion used in the fifth layer coating liquids 
was used after the removal of the ethyl acetate under reduced pressure at 
40.degree. C. after emulsification and dispersion. 
The same compound as used in Example 1 was used in each layer as a gelatin 
hardening agent. 
The structural formulae of the couplers etc. used in this example are given 
below. 
##STR54## 
The following compounds were used in each layer as anti irradiation dyes. 
##STR55## 
Furthermore, the compound shown below was added to each coating liquid, at 
the rate of 50 mg per mol of silver halide in the blue sensitive emulsion 
layer and at a rate of 125 mg per mol of silver halide in the green 
sensitive emulsion layer and the red sensitive emulsion layer. 
TABLE 7 
______________________________________ 
##STR56## 
Layer Principal Composition 
Amount Used 
______________________________________ 
Seventh layer 
Gelatin 1.33 grams/m.sup.2 
(Protective 
Acrylic modified poly- 
0.17 gram/m.sup.2 
layer) (vinyl alcohol) copolymer 
(17% modification) 
Sixth layer 
Gelatin 0.54 gram/m.sup.2 
(Ultraviolet 
Ultraviolet absorber (j) 
0.21 gram/m.sup.2 
absorbing Solvent (l) 0.09 ml/m.sup.2 
layer) 
Fifth layer 
Silver halide emulsion 
0.24 gram/m.sup.2 
(Red sensi- 
(see Table 8) 
tive layer) 
Gelatin 0.96 gram/m.sup.2 
Cyan coupler (m) 0.38 gram/m.sup.2 
Colored image stabilizer (n) 
0.17 gram/m.sup.2 
Solvent (d) 0.23 ml/m.sup.2 
Fourth layer 
Gelatin 1.60 grams/m.sup.2 
(Ultraviolet 
Ultraviolet absorber (j) 
0.62 gram/m.sup.2 
absorbing Anti-color mixing agent (k) 
0.05 gram/m.sup.2 
layer) Solvent (l) 0.26 ml/m.sup.2 
Third layer 
Silver halide emulsion 
0.16 gram/m.sup.2 
(Green (see Table 8) 
sensitive Gelatin 1.80 grams/m.sup.2 
layer) Magenta coupler (h) 
0.45 gram/m.sup.2 
Colored image stabilizer (c) 
0.20 gram/m.sup.2 
Solvent (i) 0.45 ml/m.sup.2 
Second Gelatin 0.99 gram/m.sup.2 
layer Anti-color mixing agent (g) 
0.08 gram/m.sup.2 
(Anti-color 
mixing layer 
First layer 
Silver halide emulsion 
0.27 gram/m.sup.2 
(Blue sensi- 
(see Table 8) 
tive layer) 
Gelatin 1.86 grams/m.sup.2 
Yellow coupler (e) 0.74 gram/m.sup.2 
Colored image stabilizer (f) 
0.17 gram/m.sup.2 
Solvent (d) 0.31 ml/m.sup.2 
Support Polyethylene laminated paper (TiO and 
ultramarine were included in the poly- 
ethylene positioned at the first layer side) 
______________________________________ 
The amount of silver halide emulsion indicated is the amount calculated as 
silver. 
TABLE 8 
______________________________________ 
Blue Sensitive 
Green Sensitive 
Red Sensitive 
Sample 
Emulsion Layer 
Emulsion Layer 
Emulsion layer 
______________________________________ 
a J-1 A-1 M-1 
b J-2 A-2 M-2 
c K-1 B-1 N-1 
d K-2 B-2 N-2 
e L-1 E-1 O-1 
f L-2 E-4 O-4 
g L-3 E-3 O-3 
______________________________________ 
Photographic performance was tested using the seven types of samples a to g 
obtained in this way. 
Except that the samples were exposed using three types of filters, namely a 
blue filter, a green filter and a red filter, the samples were exposed and 
processed in the same way as in Example 1, and single layer colored 
samples of each photosensitive layer were prepared. The reflection 
densities of these samples were measured and the relative speed 
immediately after exposure, contrast, reciprocity law failure at high 
luminance and the latent image stability were investigated in each case in 
the same way as in Example 1. The results obtained are shown in Table 9. 
Here, the speed of each photosensitive layer of sample a was taken to be 
100 as the basis for the relative speeds of each of the layers in samples 
b to g (the blue sensitive layers were compared with the blue sensitive 
layer, the green sensitive layers with the green sensitive layer and the 
red sensitive layers with the red sensitive layer). Furthermore, the 
standard density for obtaining reciprocity failure at high luminance was 
1.8 for the blue sensitive layer, 2.0 for the green sensitive layer and 
2.2 for the red sensitive layer. 
TABLE 9 
__________________________________________________________________________ 
Performance on processing 
High Luminance 
Latent Image Stability*2 
Sample 
30" after a 0.5" exposure 
Reciprocity 
Processed after 30' 
Processed after 60' 
*3 Relative Speed 
Contrast 
Law Failure*1 
to processed after 8' 
to processed after 8' 
Remarks 
__________________________________________________________________________ 
a B 100 1.25 0.73 0.02 0.04 Comparative Example 
G 100 1.36 0.85 0.04 0.04 
R 100 1.47 0.98 0.03 0.04 
b B 75 1.21 0.24 0.18 0.36 Comparative Example 
G 71 1.31 0.29 0.30 0.45 
R 69 1.41 0.34 0.36 0.54 
c B 118 1.20 0.73 0.04 0.05 Comparative Example 
G 112 1.34 0.88 0.03 0.03 
R 110 1.43 0.93 0.02 0.04 
d B 88 1.20 0.18 0.17 0.29 Comparative Example 
G 85 1.28 0.23 0.27 0.43 
R 85 1.36 0.27 0.33 0.47 
e B 218 1.24 0.50 0.03 0.07 Comparative Example 
G 224 1.35 0.60 0.02 0.06 
R 210 1.44 0.69 0.03 0.07 
f B 178 1.28 0.02 0.31 0.39 Comparative Example 
G 168 1.40 0.03 0.40 0.52 
R 170 1.48 0.03 0.36 0.50 
g B 195 1.28 0.03 0.02 0.02 This Invention 
G 199 1.39 0.04 0.01 0.03 
R 210 1.50 0.05 0.01 0.02 
__________________________________________________________________________ 
*1, *2: In each case a smaller value is better. 
*3: B: Blue Sensitive Layer, G: Green Sensitive Layer, R: Red Sensitive 
Layer 
It is clear from these results that the invention is also very effective in 
multi-layer color photosensitive materials. Thus, on comparing samples a, 
c and e it is clear that higher speeds are achieved when a localized layer 
which has a silver bromide content of at least 20 mol% is present but that 
there is pronounced reciprocity law failure at high luminance and problems 
would be experienced in practice. Furthermore, on comparing sample b with 
sample a, sample d with sample c and sample f with sample e, it is clear 
that there is an improvement in respect to reciprocity law failure at high 
luminance on doping with iridium in each case but that there is a marked 
deterioration in latent image sensitization. On the other hand, with 
sample g, even though the emulsion has been doped with the same amount of 
iridium as sample e (in terms of the amounts per mol of silver halide), 
there is a considerable improvement in that there is virtually no latent 
image sensitization to be seen. 
EXAMPLE 3 
Tests were carried out in the same way using the coated samples a to g used 
in Example 2 except that the development processing operation and the 
processing baths were changed to those indicated below. 
______________________________________ 
Processing Operation 
Temperature 
Time 
______________________________________ 
Color development 
35.degree. C. 
45 seconds 
Bleach-fixing 30 to 36.degree. C. 
45 seconds 
Stabilizer (1) 30 to 37.degree. C. 
20 seconds 
Stabilizer (2) 30 to 37.degree. C. 
20 seconds 
Stabilizer (3) 30 to 37.degree. C. 
20 seconds 
Stabilizer (4) 30 to 37.degree. C. 
30 seconds 
Drying 70 to 85.degree. C. 
60 seconds 
______________________________________ 
(Four tank counterflow system from stabilizer (4) to stabilizer (1)). 
The composition of each processing bath was as indicated below. 
______________________________________ 
Color Development Bath 
Water 800 ml 
Ethylenediamine tetra-acetic acid 
2.0 grams 
Triethanolamine 8.0 grams 
Sodium chloride 1.4 grams 
Potassium carbonate 25.0 grams 
N-Ethyl-N-(.beta.-methanesulfonamidoethyl)- 
5.0 grams 
3-methyl-4-aminoaniline sulfate 
N,N-Diethylhydroxylamine 
4.2 grams 
5,6-Dihydroxybenzene-1,2,4-trisulfonic 
0.3 gram 
acid 
Fluorescent whitener (4,4'-diamino- 
2.0 grams 
stilbene based) 
Water to make up to 1000 ml 
pH (25.degree. C.) 10.10 
Bleach-fix Bath 
Water 400 ml 
Ammonium thiosulfate (70%) 
100 ml 
Sodium sulfite 18 grams 
Ethylenediamine tetra-acetic acid 
55 grams 
iron (III) ammonium salt 
Ethylenediamine tetra-acetic acid 
3 grams 
di-sodium salt 
Glacial acetic acid 8 grams 
Water to make up to 1000 ml 
pH (25.degree. C.) 5.5 
Stabilizer Bath 
Formalin (37%) 0.1 gram 
Formalin-bisulfite addition compound 
0.7 gram 
5-Cloro-2-methyl-4-isothiazolin-3- 
0.02 gram 
one-2-methyl-4-isothiazolin-3-one 
2-Methyl-4-isothiazolin-3-one 
0.01 gram 
Copper sulfate 0.005 gram 
Water to make up to 1000 ml 
pH 4.0 
______________________________________ 
EXAMPLE 4 
The 10 types of coated sample shown in Table 11 were prepared by 
substituting the compositions shown in Table 10 for the third and fifth 
layers of the multi-layer color photosensitive materials in Example 2. 
The same tests as used in Example 2 were carried out and the effect of the 
invention was confirmed. 
The results showed that in these coated samples the effect of using 
emulsions of this invention, namely a high contrast at high speed, little 
variation due to reciprocity law and excellent latent image stability, was 
pronounced. 
##STR57## 
A 3:4 (by weight) mixture of: 
The same Cyan Coupler as (r) and 
##STR58## 
A polymer as indicated above of number average molecular weight 60,000. 
##STR59## 
TABLE 10 
__________________________________________________________________________ 
Amounts Coated 
Layer Principal Components 
Samples h, i 
Samples j, k 
Samples l, m 
Samples n, o 
Samples p, 
__________________________________________________________________________ 
q 
Fifth Layer 
Silver halide emulsion 
0.24 0.24 0.24 0.24 0.24 
(Red Sensitive 
Gelatin 0.96 0.96 0.96 1.60 1.60 
Layer) Cyan coupler 
(s) 0.37 
(s) 0.37 
(s) 0.37 
(r) 0.35 
(r) 0.35 
Colored image stabilizer 
(n) 0.17 
(n) 0.17 
(n) 0.17 
(n) 0.17 
(n) 0.17 
Compound (t) 
-- -- -- 0.35 0.35 
Solvent (d) 0.23 
(d) 0.23 
(d) 0.23 
(d) 0.23 
(d) 0.23 
Third Layer 
Silver halide emulsion 
0.36 0.20 0.16 0.36 0.16 
(Green Sensitive 
Gelatin 1.20 1.20 1.80 1.20 1.80 
Layer) Magenta coupler 
(a) 0.32 
(o) 0.28 
(u) 0.35 
(a) 0.32 
(u) 0.35 
Colored image stabilizer 
(b) 0.06 
(p) 0.06 
(c) 0.20 
(b) 0.06 
(c) 0.20 
(c) 0.13 
(c) 0.09 (c) 0.13) 
Solvent (d) 0.42 
(q) 0.42 
(i) 0.60 
(d) 0.42 
(i) 0.60 
__________________________________________________________________________ 
The amounts of silver halide emulsion are indicated as the coated amount 
(grams/m.sup.2) calculated as silver. The other numerical values indicate 
the amounts coated in grams/m.sup.2, except in the case of solvents where 
the amounts coated are indicated in terms of volume (ml/m.sup.2). 
TABLE 11 
__________________________________________________________________________ 
Blue Sensitive 
Green Sensitive 
Red Sensitive 
Sample 
Layer Emulsion 
Layer Emulsion 
layer Emulsion 
Remarks 
__________________________________________________________________________ 
h L-2 E-4 O-4 Comparative Example 
i L-2 E-3 O-3 This Invention 
j L-2 E-4 O-4 Comparative Example 
k L-3 E-3 O-3 This Invention 
l L-2 E-4 O-4 Comparative Example 
m L-3 E-3 O-3 This Invention 
n L-2 E-4 O-4 Comparative Example 
o L-3 E-3 O-3 This Invention 
p L-2 E-4 O-3 Comparative Example 
q L-3 E-3 O-3 This Invention 
__________________________________________________________________________ 
It is possible, by means of this invention, to obtain excellent color 
photographic materials which have high speed and high contrast, which 
exhibit little reciprocity law failure and which have good latent image 
stability. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.