Processing solution for silver halide color photographic materials and method for processing the materials with use of the processing solutions

A processing solution for a silver halide color photographic material, said solution containing at least one kind of compound represented by formula (I), (II), or (III); ##STR1## the substituents are defined in the instant specification.

FIELD OF THE INVENTION 
The present invention relates to a processing solution being used for 
processing a silver halide color photographic material, (hereinafter, also 
referred to as a color photographic material or a light-sensitive 
material) and a processing method using it, and more particularly a 
processing solution giving a reduced formaldehyde vapor pressure that is 
excellent in stabilizing dye images, and a method for processing the 
silver halide color photographic material with the processing solution. 
BACKGROUND OF THE INVENTION 
In general, the fundamental steps for processing a color photographic 
material are a color development step and a desilvering step. In the color 
development step, the exposed silver halide is reduced by a color 
developing agent to form silver and at the same time the oxidized color 
developing agent reacts with color forming agents (couplers) to form dye 
images. In the subsequent desilvering step, silver formed in the color 
development step is oxidized by an oxidizing agent called a bleaching 
agent; this oxidized silver is then dissolved by a complex ion forming 
agent of silver ions called a fixing agent. As the result of applying the 
desilvering step, dye images only are formed on the color photographic 
material. 
Usually, after these steps, a wash process removes unnecessary components 
left on the color photographic material from the processing solutions. In 
the case of a color photographic paper and a reversal color photographic 
paper, processing is finished by the above-described steps and then the 
color photographic material is generally subjected to a drying step. In 
the case of a color negative photographic film and a color reversal 
photographic film, however a stabilization step is added to the foregoing 
steps. It is well-known that formalin is used in the stabilizing bath to 
prevent fading of magenta dyes caused by magenta couplers remaining in the 
color photographic material after processing. A certain amount of the 
formaldehyde vapor is generated during preparation of the stabilizing bath 
containing formaline and during drying of color photographic materials 
processed in these baths. 
It is known that the inhalation of formalin is harmful for the human body 
and the Japan Association of Industrial Health that the allowable 
concentration of formaldehyde in a working environment is 0.5 ppm or less. 
Accordingly, efforts to reduce the concentration of formalin in a 
stabilizing bath and replacing formaldehyde with an alternative have been 
made to improve the working environment. 
As an alternative for formalin, hexamethylenetetramine series compounds are 
described in JP-A-63-244036 (the term "JP-A" as used herein means an 
"unexamined published Japanese patent application"). By using these 
compounds, the concentration of formaldehyde, that is, the vapor pressure 
of formaldehyde can be reduced but the ability to prevent fading of 
magenta dye is also reduced. Thus, the essential purpose of using these 
compounds is diminished for when the color images formed are allowed to 
stand, the magenta color fades within few weeks, even at room temperature. 
On the other hand, JP-A-61-75354, JP-A-61-42660, JP-A-62-255948, 
JP-A-1-295258, and JP-A-2-54261 describe 
1-(dihydroxyaminomethyl)benztriazoles, JP-A-1-230043, etc., describes 
N-(morpholinomethyl)heterocyclic thiones and 
N-(piperidinomethyl)heterocyclic thiones, and JP-A-2-153350 describes 
bis(alkylamino)methane and bis(anilino)methane. 
However, although some these compounds reduce vapor pressure of 
formaldehyde (as compared with that formed when using formalin alone), the 
image storage stability is poor. The rest of these compounds that do have 
improved image storage stability produce a vapor pressure of formaldehyde 
similar to that produced when using formalin. Thus, the foregoing 
compounds do not simultaneously improve the image storage stability and 
reduce of the vapor pressure of formaldehyde. 
It has also been found that some of these compounds can improve the image 
storage stability of a magenta dye but form stains; deteriorate the 
storage stability of other dyes contained in the color photographic 
material processed, such as yellow dyes and cyan dyes; show low 
solubility; and attach to the color photographic material which stains the 
color images formed. 
Thus, there has been strong demand for an innovative process to prevent 
magenta dye fading and lower the vapor pressure of formaldehyde. 
SUMMARY OF THE INVENTION 
One object of this invention is to provide a photographic processing 
solution which does not substantially release compounds in amounts harmful 
to the human body. 
A second object of the present invention is to provide a photographic 
processing method which is safe and can give color images having excellent 
image storage stability after processing. 
A third object of the present invention is to provide an excellent 
photographic process which gives color images having an excellent image 
storage stability and causes no problems of staining color photographic 
materials, etc. 
As the result of various investigations, the present inventors have 
discovered that the foregoing objects can be achieved by the present 
invention as described hereinbelow. 
That is, the above objects can be achieved by processing a silver halide 
color photographic material with a processing solution for a silver halide 
color photographic material, said solution containing at least one kind of 
a compound represented by formula (I), (II), or (III); 
##STR2## 
wherein z.sub.1 represents a non-metallic atomic group bonding to each 
nitrogen atom with a carbon atom, an oxygen atom, or a sulfur atom and 
necessary for forming a 4- to 8-membered ring, and R.sub.1 and R.sub.2, 
which may be the same or different, each represents a hydrogen atom, an 
alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an 
acyl group, a sulfonyl group, a sulfinyl group, a hydroxy group, an 
acyloxy group, an alkoxycarbonyl group, an alkoxy group, an aryloxy group, 
an amino group, an alkylamino group, an acylamino group, a sulfonamide 
group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino 
group, a carbamoyl group, or a sulfamoyl group, with the proviso that 
R.sub.1 and R.sub.2 do not form a ring which is formed by bonding R.sub.1 
to R.sub.2, and 
##STR3## 
is not 
##STR4## 
wherein Ar' represents an aryl group, R.sub.d, R.sub.e, R.sub.f and 
R.sub.g each represents a hydrogen atom, an alkyl group or an aryl group: 
##STR5## 
wherein X.sub.1, X.sub.2, X.sub.3, and X.sub.4, which may be the same or 
different, each represents 
##STR6## 
(wherein R.sub.10, R.sub.11, R.sub.12, or R.sub.13, which may be the same 
or different, each represents a hydrogen atom or a substituent); and 
Z.sub.2 and Z.sub.3, which may be the same or different, each represents a 
non-metallic atomic group necessary for forming a 4- to 8-membered ring, 
with the proviso that when the ring formed by Z.sub.2 is a 5-membered ring 
and one of X.sub.1 and X.sub.2 is --CO and another of X.sub.1 and X.sub.2 
is 
##STR7## 
and/or when the ring formed by Z.sub.3 is a 5-membered ring and one of 
X.sub.3 and X.sub.4 is 
##STR8## 
and another of X.sub.3 and X.sub.4 is 
##STR9## 
R.sub.10 is not an aryl group: 
##STR10## 
wherein Z.sub.4 represents non-metallic atomic group necessary for forming 
a 4- to 8-membered ring; Y represents --O-- or --S--; and R.sub.3 
represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic 
group, an acyl group a sulfonyl group, a sulfinyl group, an alkoxycarbonyl 
group, a carbamoyl group, a sulfamoyl group, or an oxalyl group. 
According to other embodiment of the present invention, there is further 
provided a method for processing an imagewise exposed silver halide color 
photographic material comprising a support having thereon at least one 
light-sensitive silver halide emulsion layer, comprising the steps of 
color developing in a color developing solution and bleaching in a 
solution having a bleaching ability, wherein color developing the 
photographic material is processed in a processing solution containing at 
least one compound represented by the above described formula (I), (II) or 
(III). 
DETAILED DESCRIPTION OF THE INVENTION 
The processing solution of the present invention which contains the 
compound represented by formula (I), (II), or (III) described above, 
maintains a safer working environment by reducing formaldehyde vapor 
pressure. Also, the present invention has the additional important 
features of stabilizing the color images formed and not staining color 
photographic materials. The present invention has the additional advantage 
that, any conventional processing solution and conventional color 
photographic materials can be used. 
The compounds shown by formulae (I), (II), and (III) being used in this 
invention are described in detail. 
In formula (I), Z.sub.1 represents a non-metallic atomic group bonding to 
each nitrogen atom with a carbon atom, an oxygen atom, or a sulfur atom 
and necessary for forming a 4- to 8-membered ring. 
Examples of the 4- to 8-membered ring formed with Z.sub.1 and --N--N--, 
include, for example, diazetine, pyrazole, 1,2,4-triazole, indazole, 
pyrazolidine, pyrazoline, pyrazolo[4,3-d]oxazole, maleinhydrazide, 
diazepine, and 1,2-diazacyclooctane. 
The carbon atom or nitrogen atom bonding to each nitrogen atom of the 4- to 
8-membered ring formed by Z.sub.1 may be substituted. Examples of the 
substituent include a halogen atom (e.g., chlorine, bromine, and 
fluorine), a hydroxyl group, a nitro group, a formyl group, a cyano group, 
a sulfo group, a carboxy group, a phospho group, an alkyl group (e.g., 
methyl, ethyl, n-propyl, n-butyl, cyclopropyl, hydroxymethyl, 
hydroxyethyl, methoxymethyl, benzyl, pyrazolylmethyl, and 
1,2,4-triazol-1-yl-methyl), an alkenyl group (e.g., allyl), an aryl group 
(e.g., phenyl and 4-tert-butylphenyl), a heterocyclic group (e.g., 
5-pyrazole and 4-pyrazole ), an acyl group (e.g., acetyl, benzyl, and 
propanoyl ), a sulfonyl group (e.g., methanesulfonyl, octanesulfonyl and 
toluenesulfonyl, benzenesulfonyl), a sulfinyl group (e.g., 
dodecanebenzenesulfonyl, methanesulfinyl, benzenesulfinyl), an acyloxy 
group (e.g., acetoxy), an alkoxycarbonyl group (e.g., methoxycarbonyl and 
butoxycarbonyl), an alkoxy group (e.g., methoxy and ethoxy), an aryloxy 
group (e.g., phenoxy), an amino group, an alkylamino group (e.g., 
methylamino, diethylamino, and N-hydroxyethylamino), an acylamino group 
(e.g., acetylamino, benzamino, and diacetylamino), a sulfonamide group 
(e.g., sulfonamide and benzenesulfonamide), an imido group (e.g., 
succinimido), an ureido group (e.g., methylureido), a sulfamoylamino group 
(e.g., N-methylsulfamoylamino), an alkoxycarbonylamino group (e.g. 
methoxycarbonylamino), a carbamoly group (e.g., carbamoyl and 
N-ethylcarbamoyl, N-methylcarbamoyl ), a sulfamoyl group (e.g., sulfamoyl 
and N-ethylsulfamoyl, N-methylsulfamoyl), an alkylthio group (e.g., 
methylthio and octylthio), and arylthio group (e.g., phenylthio), a 
heterocyclic thio group (e.g., benzoyltriazolylthio), and a heterocyclic 
oxy group (e.g., 1-phenyltetrazol-5-oxy). Among these, a halogen atom, a 
sulfo group, a carboxy group, an alkyl group, an alkoxycarbonyl group, an 
alkoxy group and an acylamino group are preferred. 
In formula (I), R.sub.1 and R.sub.2, which may be the same or different, 
each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl 
group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl 
group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an 
alkoxy group, an aryloxy group, an amino group, an alkylamino group, an 
acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino 
group, an alkoxycarbonylamino group, a carbamoyl group, or a sulfamoyl 
group. In these groups, the groups which can have a substituent may be 
substituted and examples of the substituent include the above-described 
substituents which can be substituted to the carbon atom or nitrogen atom 
bonding to each nitrogen atom of the ring formed by Z.sub.1. 
R.sub.1 and R.sub.2 represent, in more detail, a hydrogen atom, an alkyl 
group [e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, cyclopropyl, 
hydroxymethyl, hydroxyethyl, hydroxypropyl, 2,3-dihydroxypropyl, 
methoxymethyl, methoxyethyl, carboxyethyl, sulfoethyl, cyanomethyl, and 
2-(N-pyrazolyl-N-methylamino)ethyl], an alkenyl group (e.g., allyl), an 
aryl group (e.g., phenyl and 4-tert-butylphenyl), a heterocyclic group 
(e.g., 5-pyrazolyl and 4-pyrazolyl), an acyl group (e.g., acetyl, benzoyl, 
and propanoyl), a sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, 
and toluenesulfonyl, benzenesulfonyl), a sulfinyl group (e.g., 
dodecanebenzenesulfonyl), methanesulfinyl, benzenesulfinyl), a hydroxy 
group, an acyloxy group (e.g., acetoxy), an alkoxycarbonyl group, (e.g., 
methoxycarbonyl and butoxycarbonyl), carbonyl), an alkoxy group (e.g., 
methoxy and ethoxy), an aryloxy group (e.g., phenoxy), an amino group, an 
alkylamino group (e.g., methylamino, diethylamino, and 
N-hydroxyethylamino), an acylamino group (acetylamino, benzamino, and 
diacetylamino), a sulfonamide group (e.g., sulfonamide and 
benzenesulfonamide), a ureido group (e.g., methylureido), a sulfamoylamino 
group (e.g., N-methylsulfamoylamino), an alkoxycarbonylamino group (e.g., 
methoxycarbonylamino), a carbamoyl group (e.g., carbamoyl, 
N-methylcarbamoyl, and N-ethylcarbamoyl), or a sulfamoyl group (e.g., 
sulfamoyl, N-methylsulfamoyl, and N-ethylsulfamoyl). 
In formula (II), X.sub.1, X.sub.2, X.sub.3, and X.sub.4, which may be the 
same or different, each represents 
##STR11## 
.dbd.N--, --O--, 
##STR12## 
(wherein R.sub.10, R.sub.11, R.sub.12, and R.sub.13, which may be the same 
or different, each represents a hydrogen atom or a substituent. 
R.sub.10 is preferably a hydrogen atom, an alkyl group, an alkenyl group, 
an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. 
R.sub.11 and R.sub.12 are preferably a halogen atom, a nitro group, a 
formyl group, a cyano group, a sulfo group, an alkylthio group, an 
arylthio group, a heterocyclicthio group, a heterocyclicoxy group, or each 
of the foregoing groups shown by R.sub.1 and R.sub.2. 
R.sub.13 is preferably each of the foregoing groups shown by R.sub.1 and 
more preferably each of the foregoing preferred groups shown by R.sub.10. 
In these groups, these groups which can have a substituent may be 
substituted, such as those described above as the substituents of the 
groups shown by R.sub.1 and R.sub.2. 
In more detail, R.sub.10 is preferably a hydrogen atom, an alkyl group 
(e.g., methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxymethyl, and 
methoxymethyl), an alkenyl group (e.g., allyl), an aryl group (e.g., 
phenyl and 4-tert-butylphenyl), a heterocyclic group (e.g., 5-pyrazolyl 
and 4-pyrazolyl), an acyl group (e.g., acetyl, benzoyl, and propanoyl), or 
a sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, 
and toluenesulfonyl). 
R.sub.11 and R.sub.12 each is preferably a halogen atom (e.g., chlorine, 
bromine, and fluorine), a nitro group, a formyl group, a cyano group, a 
sulfo group, an alkylthio group (e.g., methylthio and octylthio), an 
arylthio group (e.g., phenylthio), a heterocyclic thio group (e.g., 
benzoyltriazolylthio), a heterocyclic oxy group (e.g., 
1-phenyltetrazol-5-oxy) or each of the groups shown by R.sub.1 and R.sub.2 
described above in detail. 
The preferred group for R.sub.13 is each of the foregoing groups shown by 
R.sub.1. 
With the proviso that R.sub.1 and R.sub.2 do not form a ring which is 
formed by bonding R.sub.1 to R.sub.2, and further 
##STR13## 
is not 
##STR14## 
wherein Ar' represents an aryl group, R.sub.d, R.sub.e, E.sub.f and 
R.sub.g each represents a hydrogen atom, an alkyl group or an aryl group. 
In formula (II), Z.sub.2 and Z.sub.3, which may be the same or different, 
each represents a non-metallic atomic group necessary for forming a 4- to 
8-membered ring together with the nitrogen atom, X.sub.1 and X.sub.2 in 
formula (II) or together with the nitrogen atom, X.sub.3 and X.sub.4 in 
formula (II), with the proviso that when the ring formed by Z.sub.2 is a 
5-membered ring and one of X.sub.1 and X.sub.2 is 
##STR15## 
and another of X.sub.1 and X.sub.2 is 
##STR16## 
and/or when the ring formed by Z.sub.3 is a 5-membered ring and one of 
X.sub.3 and X.sub.4 is 
##STR17## 
and another of X.sub.3 and X.sub.4 is 
##STR18## 
R.sub.10 is not an aryl group. 
In formula (III), Z.sub.4 also represents a non-metallic atomic group 
necessary for forming a 4- to 8-membered ring together with the nitrogen 
atom in formula (III). It is preferred that the ring formed by Z.sub.4, 
##STR19## 
is not 
##STR20## 
wherein Ar' represents an aryl group, R.sub.d, R.sub.e, R.sub.f and 
R.sub.g each represents a hydrogen atom, an alkyl group or an aryl group. 
Examples of the 4- to 8-membered ring formed by Z.sub.2, Z.sub.3 or Z.sub.4 
as described above include azetidine, azetidin-2-one, pyrrole, 
pyrrolidine, pyrazole, imidazole, indole, benzimidazole, 1,2,4-triazole, 
1,2,3-triazole, tetrazole, urazole, pyrazoline, piperazine, piperidine, 
morpholine, purine, azepine, .epsilon.-caprolactam, 7-pentanelactam, and 
S-triazine. 
The carbon atom or the nitrogen atom of the 4- to 8-membered ring thus 
formed may be substituted. Examples of the substituent include the 
above-described substituents which can be substituted to the carbon atom 
or the nitrogen atom bonding to each nitrogen atom of the ring formed by 
Z.sub.1. 
In formula (III), Y represents --O-- or --S--. 
R.sub.3 represents an alkyl group, an alkenyl group, an aryl group, a 
heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, an 
alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, or an oxalyl 
group. These groups each may also be substituted by the above-described 
substituents which can be substituted to the carbon atom or the nitrogen 
atom of the formed by Z.sub.1. 
R.sub.3 represents, in more detail, an alkyl group (e.g., methyl, ethyl, 
n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl, i-propyl, 
n-butyl, hydroxyethyl, hydroxypropyl, methoxyethyl, carboxyethyl, 
sulfoethyl, cyanomethyl, 2-(N-pyrazolyl-N-methylamino)ethyl, and 
2,3-dihydroxypropyl), an alkenyl group (e.g., allyl), an aryl group (e.g., 
phenyl and 4-tertbutylphenyl), a heterocyclic group (e.g., 5-pyrazolyl and 
4-pyrazolyl), an acyl group (e.g., acetyl, benzoyl, and propanoyl), a 
sulfonyl group (e.g., methanesulfonyl and benzenesulfonyl, octanesulfonyl, 
toluenesulfonyl ), a sulfinyl group (e.g., methanesulfinyl and 
benzenesulfinyl, dodecanesulfinyl), an alkoxycarbonyl group (e.g., 
methoxycarbonyl and butoxycarbonyl), a carbamoyl group (e.g., carbamoyl 
N-ethylcarbamoyl and N-methylcarbamoyl), a sulfamoyl group (e.g., 
sulfamoyl N-ethylsulfamoyl and N-methylsulfamoyl), or an oxalyl group 
(e.g., methoxalyl and phenoxyalyl). 
In the compound represented by formula (I), the sum total of carbon atoms 
of R.sub.1 and R.sub.2 is preferably not more than 15, more preferably not 
more than 10, and particularly preferably not more than 6. 
Also, it is preferred that R.sub.1 and R.sub.2 each represent an alkyl 
group. 
As to the ring formed by Z.sub.1, an aromatic ring or a ring capable 
formally forming an aromatic ring as a tautomer (i.e., a tautomer of the 
aromatic ring such as a urazole ring) is preferable, a 5-membered ring is 
more preferable, and a pyrazole ring, a 1,2,4-triazole ring, or a urazole 
ring is most preferred. In particular, the ring represented by following 
formula (Z) is desired. 
##STR21## 
In formula (Z), Za represents --C(Ra).dbd. or --N.dbd. and Ra, Rb, and Rc, 
which may be the same or different, each represents a hydrogen atom, a 
halogen atom, a hydroxy group, an alkyl group having a sum total of carbon 
atoms of from 1 to 3 (e.g., methyl, ethyl, and hydroxymethyl), or an 
alkylacylamino group having a sum total of carbon atoms of from 1 to 3 
(e.g., acetylamino). 
As to one preferred compounds represented by formula (II), at least one of 
the Z.sub.2 or Z.sub.3 is a non-metallic atomic group necessary for 
forming an aromatic ring or a ring capable of formally forming an aromatic 
ring as a tautomer (i.e., a tautomer of the aromatic ring) together with 
the nitrogen atom, X.sub.1 and X.sub.2 or together with the nitrogen atom, 
X.sub.3 and X.sub.4 in formula (II). 
Then, preferred compounds in the compounds represented by formula (II) are 
described in detail. 
As to one preferred compounds represented by formula (II), Z.sub.2 is a 
non-metallic atomic group necessary for forming an aromatic ring or a ring 
capable of formally forming an aromatic ring as a tautomer (i.e., a 
tautomer of the aromatic ring) together with the nitrogen atom, X.sub.1 
and X.sub.2 in formula (II) and Z.sub.3 is a non-metallic atomic group 
necessary for forming a non-aromatic ring together with the nitrogen atom, 
X.sub.3 and X.sub.4 is preferable. 
As the aromatic ring or the ring capable of formally forming an aromatic 
ring as a tautomer (i.e., a tautomer of the aromatic ring) formed by 
Z.sub.2, a 5-membered ring is preferred and a pyrazole ring, a triazole 
ring (e.g., 1,2,4-triazole and 1,2,3-triazole, provided that preferably 
1,2,4-triazole), and a urazole ring are more preferable. Also, as the 
non-aromatic ring formed by Z.sub.3, a pyrrolidine ring, a piperidine 
ring, a morpholine ring, and a piperazine ring are more preferred. 
Among the compounds represented by formula (II), the compounds represented 
by formula (II-1) are preferable. 
##STR22## 
wherein Z.sub.2 ' and Z.sub.2 " which may be the same or different, each 
represents a non-metallic atomic group necessary for forming a 5-membered 
aromatic ring or a ring capable of formally forming a 5-membered aromatic 
ring as a tautomer. 
As the 5-membered aromatic ring or a ring capable of formally forming a 
5-membered aromatic ring as a tautomer formed by Z.sub.2 ' or Z.sub.2 ", a 
pyrazole ring, a 1,2,4-triazole ring, a 1,2,3-triazole ring and a urazole 
ring are preferred. 
As the 5-membered aromatic ring formed by Z.sub.2 ' or Z.sub.2 ", the rings 
represented by formula (Z) described above are preferable. That is, the 
compounds represented by formula (II-1) is preferably 
##STR23## 
In particular, as the 5-membered ring formed by Z.sub.2 ' or Z.sub.2 ", the 
compounds represented by formula (Z), wherein Za represents --C(Ra).dbd. 
or --N.dbd., and Ra, Rb, and Rc, which may be the same or different, each 
represents a hydrogen atom, a halogen atom or an alkyl group having a sum 
total of carbon atoms of from 1 to 3 (e.g., methyl, ethyl, and 
hydroxymethyl) are preferable. 
In the compounds represented by formula (III) described above, the 
compounds wherein the sum total of carbon atoms of R.sub.3 is not more 
than 15 are preferred, the compounds wherein the sum total of carbon atoms 
of R.sub.3 is not more than 10 are more preferred, and the compounds 
wherein the sum total of carbon atoms is not more than 5 are most 
preferred. 
As the ring formed by Z.sub.4 in formula (III), aromatic ring or a ring 
capable of formally forming an aromatic ring as a tautomer is preferred, a 
5-membered ring compound is more preferred, and a pyrazole ring, a 
1,2,4-triazole ring, and a urazole ring are most preferred. In particular, 
the rings represented formula (Z) described above are preferred. 
In formula (III), Y is preferably --O--. 
Among the compounds represented by formula (I), (II), and (III), the 
compounds represented by formula (I) or (II) are preferred, and the 
compounds represented by formula (II) are most preferred. 
Furthermore, it is preferred that the compounds represented by formulae 
(I), (II), and (III) are water-soluble. Also, the sum total of carbon 
atoms in the compound is preferably not more than 30, more preferably not 
more than 20, and particularly preferably not more than 16. 
Then, specific examples of the compounds for use in this invention 
represented by formulae (I), (II), and (III) are illustrated below but the 
invention is not limited to these compounds. 
##STR24## 
Among these, Compounds II-17 and II-18 are preferred. 
The compounds for use in this invention can be synthesized by the methods 
or methods similar to these described in Journal of Americal Pharma. 
Association, 45, 531(1956), Ber., 91, 1432(1958), Journal of Americal 
Chemical Society, 68, 2496(1956), Rev. Prog. Coloration, 17, 7(1987), and 
the literatures cited within these publications.

Typical synthesis of examples of compounds in this invention are shown 
below: 
Synthesis Example 1 (Compound II-17) 
In a 500 ml three-neck flask equipped with a stirrer, a thermometer, and a 
condenser were placed 68 g of pyrazole and 80 ml of methanol. The mixture 
was heated to 50.degree. C. while stirring. To this mixture was added, 
dropwise, a mixture of 31.6 g of 95% paraformaldehyde, 0.67 g of methanol 
containing 28% NaOCH.sub.3, and 70 ml of methanol. The resultant mixture 
was stirred for one hour at 50.degree. C., and then cooled with water. The 
mixture was stirred for one hour after adding 97.1 g of piperazine 
hexahydrate to the mixture little by little. The reaction mixture formed 
was filtrated, the filtrate was concentrated under reduced pressure. The 
concentrate thus obtained was crystallized with a mixed solvent of 300 ml 
of acetic acid ethyl ester and 50 ml of n-hexane to provide 100 g of 
compound (II-17) as colorless crystals having a melting point of from 
about 109.degree. C. to 112.degree. C. Elemental analysis and various 
spectra confirmed the chemical structure of the compound. 
Synthesis Example 2 (Compound II-18) 
In a 500 ml three-neck flask equipped with a stirrer, a thermometer, and a 
condenser were placed 69.1 g of 1,2,4-triazole and 170 ml of methanol. The 
mixture was heated to 50.degree. C. while stirring. To this mixture was 
added, dropwise, a mixture of 31.6 g of 95% paraformaldehyde, 0.67 g of 
methanol containing 28% NaOCH.sub.3, and 67 ml of methanol. The resultant 
mixture was heated to 50.degree. C. for one hour and then cooled with 
water. The mixture was stirred for about one hour after adding thereto 
97.1 g of piperazine hexahydrate little by little. Crystals formed during 
the reaction. After the reaction was over, the reaction mixture was cooled 
with water. Resulting crystals were collected by filtration and washed 
with cooled methanol to provide 103 g of compound (II-18) as colorless 
crystals having a melting point of from about 205.degree. C. to 
209.degree. C. Elemental analysis and varions spectra confirmed the 
chemical structure of the compound. 
Other compounds can be also synthesized similarly. 
The compound for .use in this invention may be used for any step in the 
processing steps of color photographic materials. 
The processing solution of the present invention is a processing solution 
(including the replenisher for the processing solution) having the effect 
for stabilizing the dye images formed by color development (in particular, 
the effect of preventing a magenta dye from fading with the passage of 
time), by containing the compound of the present invention. That is, the 
processing solution of the present invention is an aqueous photographic 
processing solution. Accordingly, the processing solution of the present 
invention is a processing solution for use after color development: 
namely, a bleaching solution, a bleach-fixing solution (blixing solution), 
a fixing solution, a stopping solution, a conditioning solution, a washing 
solution, a rinsing solution, or a stabilizing solution, preferably a 
stabilizing solution, a stopping solution, a conditioning solution, or a 
bleaching solution, more preferably a stabilizing solution, a conditioning 
solution or a bleaching solution and most preferably a stabilizing 
solution. 
The compound for use in this invention represented by formula (I), (II), or 
(III) may be added to the replenisher for each processing solution that is 
a preferred embodiment of this invention. Thus, the processing solution of 
the present invention includes a replenisher. The replenisher in the 
present invention is a solution for replenishing a fresh processing 
solution used for keeping the original composition of a processing 
solution at continuous photographic processing. 
Each replenisher of this invention is prepared to sustain the performance 
of each processing solution by maintaining a constant concentration of 
active compounds through replenishment of these compounds consumed during 
processing of color photographic materials and degraded in an automatic 
processor with the passage of time, while controlling the concentration of 
compounds dissolved out from color photographic materials by processing. 
Accordingly, the concentration of these compounds which are consumed is 
kept higher in the replenisher than the corresponding processing solution. 
Conversely, the concentration of compounds eluted from the photographic 
materials is kept lower in the replenisher than in the processing 
solution. About the same concentration as in the ordinary processing 
solution is used in the corresponding replenisher for those compounds 
which do not tend to change concentration by processing or with the 
passage of time. 
The stabilizing solution in the present invention is a stabilizing solution 
used for the final processing step of a color negative photographic film 
and a color reversal photographic film or a stabilizing solution used in 
place of water-washing solution in a washing step as the final processing 
step. When the final processing step is a washing step or a rinsing step, 
a stabilizing solution used for the stabilizing step as the pre-bath for 
the step or the rinsing step is also another in the processing solution of 
the present invention. The stabilizing solution containing the compound 
for use in this invention is preferably used during the final step. 
Before our innovation, a stabilizing solution and its replenisher used 
during the final processing step was a processing solution containing 
formalin that produced an image stabilization effect. However, in this 
invention, the vapor pressure of formaldehyde caused by the presence of 
formalin in the processing solution can be reduced without losing 
stabilization of color images. Therefore, the stabilizing solution of this 
invention does not substantially contain formalin. The term "not 
substantially contain formalin" means that the solution may contain 
formalin within the range which does not influence the effect of the 
present invention. Practically, it means that the sum of formaldehyde and 
the hydrate of formaldehyde is generally not more than 0.005 mol/liter. 
For reducing the vapor pressure of formaldehyde, the sum of formaldehyde 
and its hydrate is preferably as low as possible and more preferably not 
more than 1.0.times.10.sup.-4 mol/liter. 
The content of the compound represented by formula (I) to (III) in the 
processing solution of this invention is preferably from 
1.0.times.10.sup.-4 to 0.5 mol, more preferably from 0.001 to 0.1 mol, and 
most preferably from 0.001 to 0.03 mol per liter of the processing 
solution. 
The processing solutions to which the discovered compound can be added as 
well as other processing solutions used in conjunction are described next. 
Since the processing solution containing the discovered compound alone 
does not have a stabilization effect of color images, it is technically 
improper to call such this processing solution a stabilizing solution. But 
for convenience, such a processing solution will also be called a 
stabilizing solution. 
First, a stabilizing solution and a conditioning solution are the preferred 
processing solution for containing the compound in this invention. The 
conditioning solution is a processing solution that is sometimes called a 
bleach accelerating bath. 
It is preferable that the stabilizing solution contains various surface 
active agents for preventing water spots during the drying of color 
photographic materials. Appropriate surface active agents include: 
polyethylene glycol type nonionic surface active agents, polyhydric 
alcohol type nonionic surface active agents, alkylbenzenesulfonate type 
anionic surface active agents, higher alcohol sulfate type anionic surface 
active agents, alkylnaphthalenesulfonate type anionic surface active 
agents, quaternary ammonium salt type cationic surface active agents, 
amine salt type cationic surface active agents, amino salt type amphoteric 
surface active agents, and betaine type amphoteric surface active agents. 
Nonionic surface active agents are preferred, and alkylphenol ethylene 
oxide addition products are particularly preferred. The desired 
alkylphenol includes: octylphenol, nonylphenol, dodecylphenol, and 
dinonylphenol. The addition mol number of ethylene oxide is particularly 
preferably from 8 to 14. Furthermore, silicone series surface active 
agents having a high defoaming effect is preferred. 
Also, it is preferred that the stabilizing solution contains various 
antibacterial agents or antifungal agents to prevent the formation of fur 
and fungi in-the color photographic materials. Examples of these 
antibacterial agents and antifungal agents include the 
thiazolylbenzimidazole series compounds as described in JP-A-57-157244 and 
JP-A-58-105145, the isothiazolone series compounds described in 
JP-A-57-8542, chlorophenol series compounds such as trichlorophenol, etc., 
bromophenol series compounds, organotin compounds, organozinc compounds, 
acid amide series compounds, diazine and triazine series compounds, 
thiourea compounds, benzotriazole series compounds, alkylguanidine series 
compounds, quaternary ammonium salts such as benzalkonium chloride, etc., 
antibiotics such as penicillin, etc., and the antifungal agents described 
in Journal of Antibacterial and Antifungal Agents, vol. 1, No. 5, 207-223 
(1983). 
These compounds may be used singly or in combination. Also, the various 
bactericides described in JP-A-48-83820 can be used. 
Also, it is preferred that the stabilizing solution contains various 
chelating agents. As preferred chelating agents, aminopolycarboxylic acids 
such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic 
acid, etc; organic phosphonic acids such as 
1-hydroxyethylidene-1,1-diphosphonic acid, 
diethylenetriamine-N,N,N'N'-tetramethylenephosphonic acid, etc.; and the 
hydrolized products of maleic anhydride polymers described in European 
Patent 345,172A1. 
Also, for the stabilizing solution, other compounds for stabilizing dye 
images than the compounds for use in this invention such as, for example, 
hexamethylenetetramine and the derivatives thereof, hexahydrotriazine and 
the derivatives thereof, dimethylolurea, organic acids, and pH buffers may 
be used single or in combination. Furthermore, it is preferred that the 
stabilizing solution of this invention contains, if desired; an ammonium 
compound such as ammonium chloride, ammonium sulfite, etc.; a metal 
compound such as a Bi compound, an Al compound, etc.; an brightening 
agent, a hardener, the alkanolamine described in U.S. Pat. No. 4,786,583, 
and a preservative which can be used for a fixing solution or a blixing 
solution described below. 
The pH of the stabilizing solution in this invention is in the range of 
usually from 4 to 9, and preferably from 6 to 8. The replenishment amount 
for the stabilizing solution is preferably from 200 to 1500 ml, and more 
preferably from 300 to 600 ml per square of a color photographic material 
being processed. The processing temperature of the stabilizing solution is 
preferably from 30.degree. C. to 45.degree. C. and the processing time is 
preferably from 10 seconds to 2 minutes, and particularly preferably from 
15 seconds to 30 seconds. 
The conditioning solution of this invention can further contain an 
aminopolycarboxylic acid chelating agent such as 
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 
1,3-diaminopropanetetraacetic acid, cyclohexanediaminetetraacetic acid, 
etc.; a sulfite such as sodium sulfite, ammonium sulfite, etc,; and a 
bleaching accelerator such as thioglycol, aminoethanethiol, 
sulfoethanethiol, etc. (These additives will be explained during 
discussion of the bleaching solution.) It is preferred that the 
conditioning solution contains the sorbitan esters of fatty acid 
substituted by ethylene oxide described in U.S. Pat. No. 4,839,262 and the 
polyoxyethylene compounds described in U.S. Pat. No. 4,059,446 and 
Research Disclosure, Vol. 191, 19104, (1980). These compounds can be used 
in the range of from 0.1 g to 20 g, and preferably from 1 g to 5 g per 
liter of the conditioning solution. 
The pH of the conditioning solution is usually in the range of from 3 to 
11, preferably from 4 to 9, and more preferably from 4.5 to 7. 
The processing time of the conditioning solution is preferably from 30 
seconds to 5 minutes. 
Also, the replenishment amount for the conditioning solution is preferably 
from 30 ml to 3000 ml, and more preferably from 50 ml to 1500 ml per 
square meter of a color photographic material being processed. 
The processing temperature of the conditioning solution is preferably from 
20.degree. C. to 50.degree. C., and more preferably from 30.degree. C. to 
40.degree. C. 
A silver halide color photographic material, a negative type color 
photographic material and a direct positive type color photographic 
material are usually subjected to a color development after imagewise 
exposure. A reversal positive type color photographic material is usually 
subjected to a color development after being subjected to a black and 
white development, reversal processing, etc. 
The color developer to be used in this invention is an alkaline aqueous 
solution containing an aromatic primary amine color developing agent as 
its main component. 
A preferred color developing agent is a p-phenylenediamine derivative and 
typical examples are shown below, but the invention is not limited to 
them. 
______________________________________ 
D-1 N,N-Diethyl-p-pheylenediamine 
D-2 2-Methyl-N,N-diethyl-p-phenylenediamine 
D-3 4-[N-Ethyl-N-(.beta.-hydroxyethyl)amino]aniline 
D-4 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)- 
amino]aniline 
D-5 4-Amino-3-methyl-N-ethyl-N-[.beta.-(methane- 
sulfonamido)ethyl]aniline 
D-6 4-Amino-3-methyl-N-ethyl-N-methoxyethyl- 
aniline 
D-7 4-Amino-3-methyl-N-ethyl-N-(4-hydroxy- 
butyl)aniline 
______________________________________ 
Of the above p-phenylenediamine derivatives, D-4 and D-5 are particularly 
preferred. 
These p-phenylenediamine derivatives may be in the form of the salts, such 
as: the sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc. 
The amount of the aromatic primary amine color developing agent is 
preferably from 0.001 to 0.1 mol, and more preferably from 0.01 to 0.06 
mol per liter of the color developer. 
Also, the color developer can contain a sulfite, if desired, a sulfite such 
as sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium 
hydrogensulfite, sodium metasulfite, potassium metasulfite, etc., or a 
carbonylsulfite addition product. The preferred addition amount of the 
preservative is from 0.5 to 10 g, and particularly from 1 to 5 g per liter 
of the color developer. 
As compound can be added preserve the previously discussed aromatic primary 
amine color developing agent. Examples include: various hydroxylamines 
(preferably, the compounds having a sulfo group or carboxy group) 
described in JP-A-63-5341 and JP-A-63-106655; the hydroxamic acids 
described in JP-A-63-43138; the hydrazines and hydrazides described in 
JP-A-63-146041; the phenols described in JP-A-63-44657 and JP-A-63-58443; 
the .alpha.-hydroxyketones and .alpha.-aminoketones described in 
JP-A-63-44656; and various kinds of the sucrose described in 
JP-A-63-36244. 
Additionally, these preservative compounds can be used in combination with: 
the monoamines described in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, 
JP-A-63-146040, JP-A-63-27841, and JP-A-63-25654; the diamines described 
in JP-A-63-30845, JP-A-63-14640, and JP-A-63-43139; the polyamines 
described in JP-A-63-21647, JP-A-63-26655, and JP-A-63-44655; the nitroxy 
radicals described in JP-A-63-53551; the alcohols described in 
JP-A-63-43140 and JP-A-63-53549; the oximes described, in JP-A-63-56654, 
and the tertiary amines described in JP-A-63-239447. 
The color developer may also contain other preservatives. Examples include: 
the various metals described in JP-A-57-44-44148 and JP-A-57-53749; the 
salicylic acids described in JP-A-59-180588; the alkanolamines described 
in JP-A-54-3582; the polyethyleneimines described in JP-A-56-94349; the 
aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, etc. 
Of these compounds, the aromatic polyhydroxy compounds are particularly 
preferred. 
The pH of the color developer being used in this invention is preferably 
from 9 to 12, and more preferably from 9 to 11.0. To maintain the pH 
within these parameters, it is preferable to use various buffers. 
Practical examples of buffers include: sodium carbonate, potassium 
carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium 
tertiary phosphate, potassium tertiary phosphate, sodium secondary 
phosphate, potassium secondary phosphate, sodium borate, potassium borate, 
sodium tetraborate (borax), potassium tetraborate, sodium 
o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 
5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 
5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). 
The addition amount of the buffer is preferably not less than 0.1 mol, and 
particularly preferably from 0.1 to 0.4 mol per liter of the color 
developer. 
It is preferred that the color developer contains various kinds of 
chelating agents to inhibit a precipitation of calcium and magnesium or to 
further improve the stability of the color developer. As the chelating 
agent, organic acid compounds are preferable examples include 
aminopolycarboxylic acids, organic sulfonic acids, and phosphonocarboxylic 
acids. 
Typical examples of these organic acid compounds include 
diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, 
N,N,N-trimethylenephosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 
transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic 
acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic 
acid, ethylenediamine o-hydroxyphenylacetic acid, 
2-phosphonobutane-1,2,4-tricarboxylic acid, 
1-hydroxyethylidene-1,1-diphosphonic acid, and 
N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid. 
Chelating agents may be used single or in combination. A typical amount of 
the chelating agent required to block metal ions in the color developer 
and is about 0.1 g to 10 g per liter of the color developer. 
If desired, an optional developing accelerator can be added to the color 
developer. It is preferred, however, that the color developer in this 
invention contains substantially no benzyl alcohol. Benzyl alcohol 
pollutes the enviroment, worsens the preparing property of the solution, 
and promotes color stains. In this case, the term "contains substantially 
no benzyl alcohol" means that the color developer contains not more than 2 
ml of benzyl alcohol per liter of the color developer and preferably 
contains no benzyl alcohol. 
Examples of the developing accelerator which can be added, if desired, to 
the color developer include the thioether Compounds described in 
JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 
(the term "JP-B" as used herein means an "examined Japanese patent 
publication"), and U.S. Pat. No. 3,818,247; the p-phenylenediamine series 
compounds described in JP-A-52-49829 and JP-A-50-15554; the quaternary 
ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826, 
and JP-A-52-43429; the amine series compounds described in U.S. Pat. Nos. 
2,494,903, 3,128,182, 4,230,796, and 3,253,919, JP-B-41-11431, U.S. Pat. 
Nos. 2,484,546, 2,596,926, and 3,582,346; the polyalkylene oxides 
described in JP-B-37-16088, JP-B-42-25201, U.S. Pat. No. 3,128,183, 
JP-B-41-11431, JP-B-42-23883, and U.S. Pat. No. 3,532,510; as well as 
1-phenyl-3-pyrazolideones, and imidazoles. 
The addition amount of the development accelerator is from about 0.01 g to 
5 g per liter of the color developer. 
In this invention, the color developer can contain, if desired, an optional 
antifoggant. 
Examples of the antifoggants include alkali metal halides, such as sodium 
chloride, potassium bromide, potassium iodide, etc. and organic 
anti-foggants. Examples of the organic antifoggant include 
nitrogen-containing heterocyclic compounds such as benzotriazole, 
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 
5-nitrobenzimidazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 
2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and 
adenine. 
The addition amount of the antifoggant is from about 0.001 g to 1 g per 
liter of the color developer. 
The color developer of this invention may further contain an optical 
brightening agent. The prefened optical brightening agents are 
4,4'-diamino-2,2'-disulfostilbene series compounds. The addition amount of 
the optical brightening agent to be added is preferably from 0 to 5 g, and 
more preferably from 0.1 g to 4 g per liter of the color developer. 
If necessary, the color developer may also contain various surface active 
agents including: alkylsulfonic acids, arylsulfonic acids, aliphatic 
carboxylic acids, aromatic carboxylic acids, etc. 
The replenisher for the color developer contains these compounds found in 
the color developer. One function of the replenisher for the color 
developer is to replenish the compounds which are consumed during 
processing of color photographic materials or by the deterioration in an 
automatic processor with the passage of time. Another founction is to 
maintain a constant rate of development by controlling the concentration 
the compounds released from the color photographic materials during 
processing. Accordingly, the concentrations of consumed compounds are 
higher in the replenisher than in the tank solution of the color 
developer. Conversely the concentration of released compounds is lower in 
the replenisher than in the tank solution. 
The consumed compounds include a color developing agent and a preservative. 
The replenisher contains them in a ratio of from 1.1 to 2 times those in 
the tank solution. Also, the released compound is a development inhibitor 
such as a halide (e.g., potassium bromide); the replenisher contains it in 
a ratio of from 0 to 0.6 times that in the tank solution. The 
concentration of a halide in the replenisher for the color developer is 
usually not more than 0.006 mol/liter, if containing any at all. 
Some, compounds virtually maintain their concentration despite processing 
and/or the passage of time the replenisher has almost same concentrations 
of these condition as those in the tank solution of the color developer. 
Examples of such compounds are chelating agents and buffers. 
Furthermore, the pH of the replenisher for the color developer is higher by 
about 0.05 to 0.5 than that of the tank solution to maintain the pH in the 
tank solution during processing. The degree increased in pH of the 
replenisher is required to increase with the reduction of the 
replenishment amount. The replenishing amount for the color developer is 
preferbly not more than 3000 ml and more preferably from 100 ml to 1500 ml 
per square meter of a color photographic material being processed. 
The proper processing temperature of the color developer is generally from 
20.degree. to 50.degree. C., and preferably form 30.degree. to 45.degree. 
C. The processing time is properly from 20 seconds to 5 minutes, 
preferably from 30 seconds to 3 minutes and 20 seconds, and more 
preferably from 1 minute to 2 minutes and 30 seconds. 
Also, if desired, the color development can be carried out using two or 
more baths. Its replenisher may be added during the first bath or the 
later baths. This shortens the developing time and further decreases the 
replenishing amount. 
The processing method of the present invention is preferably used for color 
reversal photographic processing. In the color reversal process, a color 
development is carried out after black and white development and, if 
desired, applying reversal processing. The black and white developer, is 
usually called the black and white 1st developer, is used for the reversal 
process of a color photographic light-sensitive material and can contain 
various kinds of additives which are used for a black and white developer 
for processing a black and white silver halide photographic materials. 
Typical additives include: a developing agent such as 
1-phenyl-3-pyrazolidone, Metol, hydroquinone, etc.; a preservative such as 
a sulfite, etc.; an accelerator such as sodium hydroxide, sodium 
carbonate, potassium carbonate, etc.; an inorganic or organic inhibitor 
such as potassium bromide, 2-methylbenzimidazole, methylbenzothiazole, 
etc.; a water softener such as a polyphosphate, etc.; and a development 
inhibitor such as a slight amount of iodide, a mercapto compound etc. 
An automatic processor using either black and white developer or color 
developer should have a small opening area. In other words, the contact 
area (opening area) of the developer (the black and white developer or 
color developer) exposed to air should be as small as possible. The 
opening ratio defined the opening area (cm.sup.2) divided by the volume 
(cm.sup.3) of the developer is preferably 0.01 cm.sup.-1 or less, and more 
preferably 0.005 cm.sup.-1 or less. 
The developer can be regenerated for reuse. Regeneration of the used 
developer occurs through treatment with an anion exchange resin, 
electrodialysis, or addition of processing chemicals called regenerating 
agents. The old developer is activated and used again as fresh developer. 
In this case, the generating ratio (the ratio of the overflow solution to 
the replenisher) is preferably 50% or more, and particularly preferably 
70% or more. 
In the regeneration of a developer, the overflow solution of the developer 
is, after regeneration, used as a replenisher for the developer. 
As a method for the regeneration, it is preferred to use an anion exchange 
resin. Particularly preferred compositions of anion exchange resins and 
regenerating method for the anion exchange resins are described in Diaion 
Manual (I), (14th edition, 1986), published by Mitsubishi Chemical 
Industry Co., Ltd. Also, in anion exchange resins, the resins having the 
compositions described in JP-A-2-952 and JP-A-1-281152. 
In the present invention, the color developed photographic material is 
subjected to a desilvering process. The desilvering process is consists of 
a bleaching process and a fixing process carried out simultaneously as 
bleach-fixing process (blixing process) or a combination of them. 
Typical desilvering processing steps are as follows: 
(1) Bleaching-fixing 
(2) Bleaching-blixing 
(3) Bleaching-washing-fixing 
(4) Bleaching-blixing-fixing 
(5) Blixing 
(6) Fixing-blixing 
In the foregoing steps, steps (1), (2), (4), and (5) are preferred. Step 
(2) is disclosed, e.g., in JP-A-61-75352 and step (4) is disclosed, e.g., 
in JP-A-61-143755 and EP 0427204A1 corresponding to Japanese Patent 
Application No. 2-216389. 
Also, the processing baths such as bleaching bath, fixing bath, etc., being 
applied to the foregoing steps each may comprise one bath or two or more 
boths (e.g., 2 to 4 baths, in this case, counter-current replenishing 
system is preferably employed). 
The desilvering step may be carried out via a rinsing bath, a washing bath, 
a stopping bath, etc., after color development. When processing a negative 
type color photographic material, however the desilvering step is 
preferably carried out immediately after color development. During 
reversal process, the desilvering step is preferably carried out in a 
conditioning bath after color development. 
The bleaching solution can contain the compound for use in the present 
invention. Examples of main component of bleaching agents include: 
inorganic compounds, such as potassium ferricyanide, ferric chloride, 
bichromates, persulfates, bromates, etc.; and partial-organic compounds 
such as an aminopolycarboxylic acid ferric complex salt, an 
aminopolyphosphoric acid ferric complex salt, etc. 
In this invention, the use of an aminopolyphosphonic acid ferric complex 
salt is preferred form the view points of environmental preservation, 
safety to handle, and anti-corrosive property to metals. 
Then, practical examples of the aminopolycarboxylic acid ferric complex 
salt in this invention are illustrated below together with their oxidation 
reduction potentials, but the bleaching agents for use in this invention 
are not limited to these compounds. 
______________________________________ 
Oxidation 
Compound Reduction 
No. Potential* 
______________________________________ 
1. N-(2-Acetamido)iminodiacetic Acid 
180 
Ferric Complex Salt 
2. Methyliminodiacetic Acid Ferric 
200 
Complex Salt 
3. Iminodiacetic Acid Ferric Complex Salt 
210 
4. 1,4-Butylenediaminetetraacetic Acid 
230 
Ferric Salt 
5. Diethylene Thioether Diaminetetra- 
230 
acetic Acid Ferric Complex Salt 
6. Glycol Ether Diaminetetraacetic Acid 
240 
Ferric Complex Salt 
7. 1,3-Propylenediaminetetraacetic Acid 
250 
Ferric Complex Salt 
8. Ethylenediaminetetraacetic Acid Ferric 
110 
Complex Salt 
9. Diethylenetriamimepentaacetic Acid 
80 
Ferric Complex Salt 
10. Trans-1,2-cyclohexanediaminetetra- 
80 
acetic Acid Ferric Complex Salt 
______________________________________ 
(*): (mV vs. NHE, pH = 6) 
The oxidation reduction potential of the bleaching agent is defined as the 
oxidation reduction potential obtained by the method described in 
Transactions of the Faraday Society, Vol. 55, (1959), pages 1312-1313. 
In the present invention, from the viewpoints of rapid processing and 
effectively obtaining the effects of this invention, the oxidation 
reduction potential of the bleaching agent is preferably not lower than 
150 mV, more preferably not lower than 180 mV, and most preferably not 
lower than 200 mV. If the oxidation reduction potential of the bleaching 
agent is too high, bleaching fog occurs. Hence, the upper limit is 700 mV, 
and preferably 500 mV. 
In the above-described aminopolycarboxylic acid ferric complex salts, 
compound No. 7, 1,3-propylenediaminetetraacetic ferric complex salt is 
particularly preferred. 
The aminopolycarboxylic acid ferric complex salt is used as the salt of 
sodium, potassium, ammonium, etc., but the ammonium salt is preferred in 
the point of showing fastest bleaching. 
The amount of the bleaching agent for the bleaching solution is preferably 
from 0.01 to 0.7 mol per liter of the bleaching solution and is also 
preferably from 0.15 to 0.7 mol in the points of rapid processing and 
reducing the occurrence of stains with the passage of time. The amount 
thereof is particularly preferably from 0.30 to 0.6 mol. Also, the amount 
of the bleaching agent for the blixing solution is preferably from 0.01 to 
0.5 mol, and more preferably from 0.02 to 0.2 mol per liter of the blixing 
solution. 
In the present invention, the bleaching agents may be used singly or in 
combination. When using two or more in combination, the total 
concentration may be adjusted such that it is within the range described 
above. 
The aminopolycarboxylic acid ferric complex salt for the bleaching solution 
can be used in the form of the complex salt itself or as an 
aminopolycarboxylic acid (complex-forming compound) and ferric salt (e.g., 
ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, 
and ferric phosphate) may coexist in the bleaching solution to form the 
complex salt in the bleaching solution. 
When the complex salt is formed in the bleaching solution as described 
above, the amount of the aminopolycarboxylic acid may be slightly 
excessive to the amount necessary for forming the complex salt with a 
ferric ion and in this case, it is preferably used excessively in the 
range of from 0.01 to 10%. 
The bleaching solution is generally used at pH of from 2 to 7.0. For rapid 
processing, the pH of the bleaching solution is preferably from 2.5 to 
5.0, more preferably from 3.0 to 4.8, and most preferably from 3.5 to 4.5. 
It is preferred that the replenisher for the bleaching solution has a pH 
of from 2.0 to 4.2. 
In this invention, for adjusting the pH in the above-described range, 
conventional acids can be used. The acids used have preferably pKa of from 
2 to 5.5, wherein pKa is defined as the logarithmic value of the 
reciprocal of an acid dissociation constant and is obtained under the 
condition of an ionic strength of 0.1 mol/dm (at 25.degree. C.). 
It is preferred that the bleaching solution contains at least 0.5 mol/liter 
of an acid having pKa in the range of from 2.0 to 5.5 for preventing the 
occurrence of bleaching fog and the precipitation in the replenisher at 
low temperature with the passage of time. 
The acid having pKa of from 2.0 to 5.5, include: inorganic acids such as 
phosphoric acid, etc., and organic acids such as acetic acid, malonic 
acid, citric acid, etc. The acid having pKa from 2.0 to 5.5 effectively 
showing the aforesaid effect is preferably the organic acid. Also, in the 
organic acids, the organic acid having a carboxy group is particularly 
preferred. 
The organic acid having pKa of from 2.0 to 5.5 may be a monobasic acid or a 
polybasic acid. In the case of the polybasic acid, the acid can be used in 
the form of a metal salt (e.g., a sodium salt and a potassium salt) or an 
ammonium salt if the pKa thereof is within the range of from 2.0 to 5.5. 
Also, the organic acids having pKa from 2.0 to 5.0 can be used as a 
mixture of two or more kinds thereof. With proviso that 
aminopolycarboxylic acids, the salts thereof, and the Fe complex salts 
thereof are excluded from the acids described above. 
Preferred practical examples of the organic acid having pKa of from 2.0 to 
5.5, which can be used in this invention, include aliphatic monobasic 
acids such as acetic acid, monochloroacetic acid, monobromic acid, 
glycolic acid, propionic acid, monochloropropionic acid, lactic acid, 
pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivaric acid, 
aminobutyric acid, valeric acid, isovaleric acid, etc.; amino acid series 
compounds such as asparagine, alanine, arginine, ethionine, glycine, 
glutamine, cysteine, serine, methionine, leucine, etc.; aromatic monobasic 
acids such as benzoic acid, mono-substituted benzoic acids (e.g., 
chlorobenzoic acid and hydroxybenzoic acid), nicotinic acid, etc.; 
aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, 
tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, 
glutaric acid, adipic acid, etc.; amino acid series dibasic acids such as 
asparagic acid, glutamic acid, cystine, etc.; aromatic dibasic acids such 
as phthalic acid, terephthalic acid, etc.; and polybasic acids such as 
citric acid, etc. 
Of these acids, the monobasic acids having a hydroxy group or a carboxy 
group are preferred, and glycolic acid and lactic acid are particularly 
preferred. 
The amount of the glycolic acid or lactic acid is preferably from 0.2 to 2 
mols, and more preferably. from 0.5 to 1.5 mols per liter of the bleaching 
solution. These acids are preferred since they remarkably exhibit the full 
effects of this invention, emit no odors, and restrain the occurrence of 
bleaching fog. 
Also, the combination use of acetic acid and glycolic acid or lactic acid 
is preferred since the simultaneously solve the precipitation and 
bleaching fog. The ratio of acetic acid to glycolic acid or lactic acid is 
preferably from 1/2 to 2/1. 
The total amounts of these acids are properly at least 0.5 mol, preferably 
from 1.2 to 2.5 mols, and more preferably from 1.5 to 2.0 mols per liter 
of the bleaching solution. 
In the case of controlling the pH of the bleaching solution in the 
foregoing range, an alkali agent (e.g., aqueous ammonia, potassium 
hydroxide, sodium hydroxide, imidazole, monoethanolamine, and 
diethanolamine) may be used together with the acid(s). Among these alkali 
agents, aqueous ammonia is preferred. 
Also, the preferred alkali agent which is used as a bleaching starer when 
preparing a starting solution of a bleaching solution from a replenisher, 
include: potassium carbonate, aqueous ammonia, imidazole, monoethanolamine 
or diethanolamine. Also, the diluted. replenisher may be used alone 
without the bleaching starter. 
In the present invention, various bleaching accelerators can be added to 
the bleaching solutions or the pre-baths thereof. Examples of the 
bleaching accelerator include the compounds having a mercapto group or a 
disulfido group described in U.S. Pat. No. 3,893,858, German Patent 
1,290,821, British Patent 1,138,842, JP-A-53-95630, and Research 
Disclosure, No. 17129 (July, 1978); the thiazolidine derivatives described 
in JP-A- 50-140129; the thiourea derivatives described in U.S. Pat. No. 
3,706,561; the iodides described in JP-A-58-16235; the polyethylene oxides 
described in German Patent 2,748,430; and the polyamine compounds 
described in JP-B-45-8836. The mercapto compounds described in British 
Patent 1,138,842 and JP-A-2-190856 are particularly preferred. 
The bleaching solution for use in this invention can further contain a 
rehalogenating agent such as bromides (e.g., potassium bromide, sodium 
bromide, and ammonium bromide) and chlorides (e.g., potassium chloride, 
sodium chloride, and ammonium chloride). The concentration of the 
rehalogenating agent is preferably from 0.1 to 5.0 mols, and more 
preferably from 0.5 to 3.0 mols per liter of the bleaching solution. 
Also, it is preferred to use ammonium nitrate for the bleaching solution as 
a metal corrosion inhibitor. 
In the present invention, a replenishing system is preferably used and the 
replenishing amount for the bleach solution is preferably not more than 
600 ml, and more preferably from 100 to 500 ml per square of the color 
photographic material being processed. 
The bleaching processing time is preferably 120 seconds or less, more 
preferably 50 seconds or less, and most preferably 40 seconds or less. 
In addition, at processing, it is preferred that the bleaching solution 
containing an aminopolycarboxylic acid ferric complex salt is subjected to 
aeration to oxidize the aminopolycarboxylic acid ferrous complex salt 
formed, whereby the oxidizing agent (bleaching agent) is regenerated and 
the photographic performance is very stably kept. 
In processing with the bleaching solution in this invention, it is 
preferred to apply a so-called evaporation correction, that is, to supply 
water corresponding to the evaporated amount of water of the bleaching 
solution. This is particularly preferred in the bleaching solution 
containing a color developer and a bleaching agent having a high electric 
potential. 
There is no particular restriction on the practical method of supplying 
such water, but the evaporation correction method of using a monitering 
bath separately from the bleaching bath, determining the evaporation 
amount of water in the monitering bath, calculating the evaporation amount 
of water in the bleach bath from the evaporation amount of water thus 
determined, and supplying water to the bleaching bathing in proportion to 
the evaporation amount in the bleaching bath described in JP-A-1-254959 
and JP-A-1-254960 and the evaporation correction method using a liquid 
level sensor or an overflow sensor described in Japanese Patent 
Application Nos. 2-46743, 2-47777, 2-47778, 2-47779, and 2-117972 are 
preferred. 
In the present invention, the color photographic material after processed 
by the bleaching solution is processed by a processing solution having a 
fixing ability. The processing solution having a fixing ability is 
practically a fixing solution or a blixing solution. When processing step 
having a bleaching ability is carried out using a blixing solution, the 
step may also include a fixing ability as step (5) described before. In 
steps (2) and (4), wherein a color photographic material is processed with 
a blixing solution after bleaching with a bleaching solution, the 
bleaching agent in the bleaching solution may differ from the bleaching 
agent in the blixing solution. Also, in the case of employing a washing 
step between the bleaching step and the blixing step as step (3) described 
above, the compound for use in this invention may be incorporated in the 
washing solution. 
The processing solution having a fixing ability contains a fixing agent. 
Examples of the fixing agents include thiosulfates such as sodium 
thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium 
thiosulfate, etc.; thiocyanates (rhodanates) such as sodium thiocyanate, 
ammonium thiocyanate, potassium thiocyanate, etc.; thiourea; thioethers, 
etc. In these compounds, ammonium thiosulfate is preferably used. The 
amount of the fixing agent is preferably from 0.3 to 3 mols, and more 
preferably from 0.5 to 2 mols per liter of the processing solution having 
the fixing ability. 
Also, from the view point of fixing acceleration, it is preferred to use 
ammonium thiocyanate (ammonium rhodanate), thiourea, or a thioether (e.g., 
3,6-dithia-1,8-octanediol) together with the thiosulfate. Of these, a 
combination of the thiosulfate and the thiocyanate is most preferred. The 
combination of ammonium thiosulfate and ammonium thiocyanate is 
particularly preferred. The amount of the compound which is used together 
with the thiosulfate is preferably from 0.01 to 1 mol, and more preferably 
from 0.1 to 0.5 mol per liter of the processing solution having a fixing 
ability but, as the case may be, by using the compound in an amount of 
from 1 to 3 mols, the fixing accelerating effect can be greatly increased. 
The processing solution having a fixing ability can contain a sulfite 
(e.g., sodium sulfite, potassium sulfite, and ammonium sulfite), 
hydroxylamines, hydrazines, hydrogensulfite addition products of aldehyde 
compounds (e.g. acetaldehyde sodium hydrogensulfite, and particular 
preferably the compounds described in JP-A-3-158848 and EP 432499), or the 
sulfinic acid compounds described in JP-A-1-231051 as a preservative. 
Furthermore, the processing solution can contain various optical 
brightening agents, defoaming agents, surface active agents, 
polyvinylpyrrolidone, and organic solvents such as methanol, etc. 
Furthermore, it is preferred that the processing solution having a fixing 
ability contains a chelating agent such as various aminopolycarboxylic 
acids, organic phosphonic acids, etc., for stabilizing the processing 
solution. Examples of preferred chelating agents include 
1-hydroxyethylidene-1,1-diphosphonic acid, 
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 
nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, 
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 
1,2-propylenediaminetetraacetic acid, etc. Of these compounds, 
1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic 
acid are particularly preferred. 
The amount of the chelating agent is preferably from 0.01 to 0.3 mol, and 
more preferably from 0.1 to 0.2 mol per liter of the processing solution. 
The pH of the fix solution is preferably from 5 to 9, and more preferably 
from 7 to 8. Also, the pH of the blixing solution is preferably from 4.0 
to 7.0, and more preferably from 5.0 to 6.5. Furthermore, the pH of the 
blixing solution after processing with a bleaching solution or a first 
blixing solution is preferably from 6 to 8.5, and more preferably from 6.5 
to 8.0. 
For controlling the processing solution having a fixing ability to the pH 
range, a compound having pKa of from 6.0 to 9.0 is preferably used as a 
buffer. Imidazoles such as imidazole, 2-methylimidazole, etc., are 
preferred as the buffer. The amount of such a buffer preferably from 0.1 
to 10 mols, and more preferably from 0.2 to 3 mols per liter of the 
processing solution. 
The blixing solution can further contain the above compounds which can be 
used for the bleaching solution. 
In the present invention, the blixing solution (starting solution) at the 
initiation of processing is prepared by dissolving the above-described 
compounds for blixing solution in water or by mixing a bleaching solution 
and a fixing solution. 
The replenishing amount for the fixing solution or the blixing solution in 
the case of employing a replenishing system is preferably from 100 to 3000 
ml, and more preferably from 300 to 1800 ml per square meter of the color 
photographic material. The replenisher for the blixing solution may be 
replenished as a replenisher for blixing solution or may be replenished by 
using the overflow solutions of the bleaching solution and the fixing 
solution as described in JP-A-61-143755 and EP 0427204A1 corresponding to 
Japanese Patent Application No. 2-216389. 
Also, in bleaching process described above, it is preferred that the 
blixing process is carried out while supplying water corresponding to 
evaporated water and replenishing the replenisher for the blixing 
solution. 
Furthermore, in the present invention, the total processing time of the 
processing step having a fixing ability is preferably from 0.5 to 4 
minutes, more preferably from 0.5 to 2 minutes, and most preferably from 
0.5 to 1 minute. 
In the present invention, the sum of the total processing times of the 
desilvering steps composed of a combination of bleaching, blixing, and 
fixing is preferably from 45 seconds to 4 minutes, and more preferably 
from 1 minute to 2 minutes. Also, the processing temperature is preferably 
from 25.degree. C. to 50.degree. C., and more preferably from 35.degree. 
C. to 45.degree. C. 
From the processing solution having a fixing ability in this invention, 
silver can be recovered and then the regenerated solution after silver 
recovery can be reused. The effective silver recovering methods are an 
electrolysis method (described in French Patent 2,299,667), a 
precipitation method (described in JP-A-52-73037 and German Patent 
2,331,220), an ion exchange method (described in JP-A-51-17114 and German 
Patent 2,548,237), and a metal substitution method (described in British 
Patent 1,353,805). These silver recovering methods are preferably carried 
out for the tank solutions in an in-line system since the rapid processing 
aptitude can be further improved. 
After the processing step having a fixing ability, a washing step is 
usually carried out. However, a simple processing method wherein after 
processing with the processing solution having a fixing ability, 
stabilization process using the stabilizing solution containing the 
compound for use in this invention is carried out without applying 
substantial washing can be used. 
Washing water used in the washing step can contain the surface active agent 
which can be contained in the stabilizing solution described above, an 
anti-bacterial agent, an antifungal agent, a germicide, a chelating agent, 
and the above preservative which can be contained in the processing 
solution having a fixing ability. 
The washing step and the stabilization step are preferably carried out by a 
multistage counter-current system and in this system, the stage number is 
preferably from 2 or 4. The replenishing amount for the washing step or 
the stabilization step is preferably from 1 to 50 times, more preferably 
from 2 to 30 times, and most preferably from 2 to 15 times the carried 
amount of a processing solution from the pre-bath per unit area of the 
color photographic material being processed. 
As water used for the washing step, city water can be used, but water 
deionized with ion exchange resins, etc., to reduce the concentrations of 
Ca ions and Mg ions to 5 mg/liter or less and water sterilized by a 
halogen, a ultraviolet sterilizing lamp, etc., are preferably used. 
Also, as water for supplying evaporated water of each processing solution, 
city water may be used, but water deionized and water sterilized, which 
can be preferably used for the washing step, are preferably used. 
Also, by a method of introducing the overflow solution from the washing 
step or the stabilization step into the bath having a fixing ability, 
which is the prebath thereof, the amount of the waste solution can be 
preferably reduced. 
In the processing steps, it is preferred to supply a suitable amount of 
water, a correction water, or a processing replenisher to not only the 
bleaching solution, the blixing solution, and the fixing solution but also 
to other processing solutions (e.g., the color developer, washing water, 
and stabilizing solution) for correcting the concentration by evaporation. 
In the present invention, when the total time from bleaching process to 
drying step is generally from 1 minute to 3 minutes, and preferably from 1 
minute and 20 seconds to 2 minutes, the effect of the present invention of 
particularly effectively obtained. 
In the present invention, the drying temperature is preferably from 
50.degree. C. to 65.degree. C., and more preferably from 50.degree. C. to 
60.degree. C., and the drying time is preferably from 30 seconds to 2 
minutes, and more preferably from 40 seconds to 80 seconds. 
The color photographic material processed by the processing of the present 
invention can have at least one of a blue-sensitive silver halide emulsion 
layer, a green-sensitive silver halide emulsion layer, and a red-sensitive 
silver halide emulsion layer on a support and there is no particular 
restriction on the layer number and the layer disposition order of the 
silver halide emulsion layers and light-insensitive layers. 
A typical example thereof is a silver halide color photographic material 
having on a support at least a light-sensitive layer composed of plural 
silver halide emulsion layers each having a substantially same color 
sensitivity but having a different light sensitivity, the light-sensitive 
layer is a unit light-sensitive layer having a color sensitivity to blue 
light, green light or red light, and in a multilayer silver halide color 
photographic material, the unit light-sensitive layers are disposed on a 
support in the order of a red-sensitive layer, a green-sensitive layer, 
and a blue-sensitive layer from the support side. However, according to 
the purpose, other disposition order of the color-sensitive layers may be 
employed and also a layer structure that light-sensitive layers having a 
same color sensitivity have a light-sensitive layer having a different 
color sensitivity between the layers may be employed. 
Furthermore, light-insensitive layers such as the uppermost layer, the 
lowermost layer, interlayers, etc., may be formed in addition to the 
silver halide light-sensitive emulsion layers. 
The interlayers may contain the couplers, etc., described in JP-A-61-43748, 
JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 and also 
may contain color mixing inhibitors, ultraviolet absorbers, stain 
inhibitors (anti-stain agents), etc. 
As plural silver halide emulsion layers constituting each unit 
light-sensitive layer, the two-layer structure of a high-speed emulsion 
layer and a low-speed emulsion layer as described in West German Patent 
1,121,470 and British Patent 923,045 can be preferably used. Usually, it 
is preferred that these light-sensitive layers are disposed such that the 
light-sensitivity becomes successively lower towards the support and in 
this case, a light-insensitive layer may be formed between the 
light-sensitive emulsion layers. Also, a low-speed emulsion layer may be 
placed farther from the support and a high-speed emulsion layer may be 
placed near the support as described in JP-A-57-112751, JP-A-62-200350, 
JP-A-62-206541, and JP-A-62-206543. 
In practical examples, the silver halide emulsion layers can be placed on a 
support from the farthest side of the support in the order of a low-speed 
blue-sensitive emulsion layer (BL)/a high-speed blue-sensitive emulsion 
layer (BH)/a high-speed green-sensitive emulsion layer (GH)/a low-speed 
green-sensitive emulsion layer (GL)/a high-speed red-sensitive emulsion 
layer (RH)/a low-speed red-sensitive emulsion layer (RL), in the order of 
BH/BL/GL/GH/RH/RL, or in the order of BH/BL/GH/GL/RL/RH. 
Also, they can be also placed from the farthest side of a support, in the 
order of a blue-sensitive emulsion layer/GH/RH/GL/RL as described in 
JP-B-55-34932. Furthermore, they can be also placed from the farthest side 
of a support, in the order of a blue-sensitive emulsion layer/GL/ RL/GH/RH 
as described in JP-A-56-25738 and JP-A-62-63936. Moreover, a three-layer 
structure composed of the highest light-sensitive emulsion layer as the 
upper layer, a light-sensitive emulsion layer having a lower 
light-sensitivity than the upper layer as in inter layer, and a silver 
halide emulsion layer having a far lower light sensitivity than the inter 
layer as the lower layer as described in JP-B-49-15495 can be used. Even 
in the case composed of three layers each having a different light 
sensitivity, the layers may be disposed in the order of the medium-speed 
light-sensitive emulsion layer/the high-speed light-sensitive emulsion 
layer/the low-speed light-sensitive emulsion layer from the side apart 
from a support in a same color-sensitive layer as described in 
JP-A-59-202464. 
As described above, various layer structures and layer dispositions can be 
selected according to the purpose of the color photographic 
light-sensitive material. 
The dry layer thickness of the whole constituting layers of the color 
photographic material excluding the support, the subbing layer on the 
support and the back layer is preferably from 12.0 .mu.m to 20.0 .mu.m, 
and more preferably from 12.0 .mu.m to 18.0 .mu.m from the view points of 
preventing the formation of bleaching fog and preventing the occurrence of 
stains with the passage of time. 
The layer thickness of a color photographic material is measured as 
follows. That is, the color photographic material being measured is stored 
for 7 days under the conditions of 25.degree. C., 50% RH after the 
preparation thereof, the whole thickness of the color photographic 
material is first measured, and then, after removing the coated layers on 
the support, the thickness thereof is measured again, and the difference 
of the thicknesses is defined as the layer thickness of the whole coated 
layers of the color photographic material excluding the support. The 
thickness can be measured using, for example, a film measuring device by a 
contact type piezoelectric conversion element (K-403B Stand., trade name, 
manufactured by Anritsu Electric Co., Ltd.). In addition, the coated 
layers on the support can be removed using an aqueous sodium hypochlorite 
solution. Also, by photographing the cross section of the color 
photographic material using a scanning type electron microscope 
(magnification is preferably 3,000 or more), the thickness of the whole 
layers on the support can be determined. 
In the present invention, the swelling ratio the color photographic 
material is preferably from 50 to 200%, and more preferably from 70 to 
150%. The swelling ratio is defined by the following formula: 
EQU Swelling ratio=(A-B)/B.times.100(%) 
A: Equilibrium swollen layer thickness in water at 25.degree. C. 
B: Whole dry layer thickness at 25.degree. C., 55% RH. 
If the swelling ratio falls outside the preferred ranges, residue from a 
color developing agent increases and photographic performance, image 
qualities, such as desilvering property, etc., and film properties, such 
as the film strength, are adversely affected. 
The swelling speed of a color photographic material in the present 
invention, represented by T.sub.1/2 is preferably 15 seconds or less, and 
more preferably 9 seconds or less, wherein T.sub.1/2 is defined as the 
time for the swelling to decrease to one half of a saturated swollen layer 
thickness. This saturated swollen layer thickness is defined as 90% of the 
maximum swollen layer thickness attained when the color photographic 
material is processed in a color developer at 38.degree. C. for 3 minutes 
and 15 seconds. 
The silver halide contained in the photographic emulsion layers of the 
color photographic material being processed by the process of the present 
invention may be silver bromide, silver iodochlorobromide, silver 
chlorobromide, silver bromide or silver chloride. The preferred silver 
halide is silver iodobromide, silver iodochloride, or silver 
iodochlorobromide containing about 0.1 to 30 mol % of silver iodide. 
Silver iodobromide containing from 2 to 25 mol % of silver iodide is 
particularly preferred. 
The silver halide grains in the photographic silver halide emulsions may 
have a regular crystal form, such as cubic, octahedral, tetradecahedral, 
etc.; an irregular crystal form, such as spherical, tabular, etc.; or a 
crystal defect such as twin planes, etc.; or a composite form of them. 
The grain sizes of the silver halide grains may be fine as about 0.2 micron 
or less or as large as up to about 10 microns in projected area diameters. 
Also, the silver halide emulsion may be polydispersed emulsion or 
monodispersed. 
The silver halide photographic emulsions for use in this invention can be 
prepared by using the methods described, e.g., in Research Disclosure 
(RD), No. 17643 (December), pages 22-23, "I. Emulsion Preparation and 
Types", ibid., No. 18716 (November, 1979 ), page 648, P. Glafkides, Chimie 
et Physique Photographique, published by Paul Montel, 1967, G. F. Duffin, 
Photoqraphic Emulsion Chemistry, published by Focal Press, 1966, and V. L. 
Zelikman et al, Making and Coating Photoqraphic Emulsion, published by 
Focal Press, 1964. 
The monodisperse silver halide emulsion described in U.S. Pat. Nos. 
3,574,628 and 3,655,394 and British Patent 1,413,748 is preferably used. 
Furthermore, tabular silver halide grains having an aspect ratio of at 
least about 5 can be used in this invention. The tabular silver halide 
grains can be prepared as described in Gutoff, Photographic Science and 
Engineering, Vol. 14, 248-257(1970, U.S. Pat. Nos. 4,434,226, 4,414,310, 
4,430,048, and 4,439,520, and British Patent 2,112,157. 
The crystal structure of the silver halide grains may have a uniform 
halogen composition throughout the whole grain, may have a different 
halogen composition between the inside and the surface portion thereof, or 
may have a multilayer structure. Also, a silver halide having a different 
halogen composition may be junctioned to the silver halide grains by an 
epitaxial junction. Also the silver halide grains may be junctioned to a 
compound other than silver halide, such as silver rhodanate, lead oxide, 
etc. 
Also, a mixture of silver halide grains having various crystal forms can be 
used in the present invention. 
Silver halide emulsions are usually subjected to physical ripening, 
chemical ripening, and a spectral sensitization before use. Additives used 
in these steps are described in Research Disclosure (RD), No. 17643 
(December,1978), ibid., No. 18716 (November, 1979), and ibid., No. 307105 
(November, 1989) and the corresponding portions are summarized in the 
following table. 
Also, photographic additives which can be used in the present invention are 
described in the three publications (RD) and the related portions are 
shown in the same table. 
______________________________________ 
Kind of Additive 
RD 17643 RD 18716 RD 307105 
______________________________________ 
1. Chemical Sensitizer 
p. 23 p. 648, right 
p. 866 
column (RC) 
2. Sensitivity Increas- 
-- p. 648, right 
-- 
ing Agent column (RC) 
3. Spectral Sensitizer, 
pp. 23-24 p. 648, RC 
pp. 866-868 
Super sensitizer to p. 649, RC 
4. Brightening Agent 
p. 24 p. 647, RC 
p. 868 
5. Anti-foggant, pp. 24-25 p. 649, RC 
pp. 868-870 
Stabilizer 
6. Light Absorber, 
pp. 25-26 p. 649, RC to 
p. 873 
Filter Dye, UV p. 650, left 
Absorber column (LC) 
7. Anti-staining Agent 
p. 25, RC p. 650, LC 
p. 872 
to RC 
8. Dye Image p. 25 p. 650, LC 
p. 872 
Stabilizer 
9. Hardener p. 26 p. 651, LC 
pp. 874-875 
10. Binder p. 26 p. 651, LC 
pp. 873-874 
11. Plasticizer, p. 27 p. 650, RC 
p. 876 
Lubricant 
12. Coating Aid, pp. 26-27 p. 650, RC 
pp. 875-876 
Surfactant 
13. Anti-static Agent 
p. 27 p. 650, RC 
pp. 876-877 
14. Matting Agent -- -- pp. 878-879 
______________________________________ 
Various color couplers can be used in the color photographic materials. 
Practical examples of typical couplers are described in patents cited in 
Research Disclosure, No. 17643, VII-C to G and ibid., No. 07105, VII-C to 
G. 
Examples of preferred yellow coupler are described in U.S. Pat. Nos. 
3,933,501, 4,022,620, 4,326,024 4,401,752, 4,248,961, 3,973,968, 
4,314,023, and 4,511,649, JP-B-58-10739, British Patent 1,425,020 and 
1,476,760, and European Patent 249,473A. 
Preferred magenta couplers are 2-equivalent and 4-equivalent 5-pyrazolne 
series and pyrazoloazole series compounds. The more preferred magenta 
couplers are described in U.S. Pat. Nos. 4,310,619, 4,351,897, 3,061,432, 
3,725,064, 4,500,630, 4,540,654, and 4,556,630, European Patent 73,636, 
Research Disclosure, No. 24220 (June 1984), ibid., No. 24230 (June, 1984), 
JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-5730, JP-A-55-118034, 
and JP-A-60-185951, and WO(PCT) 8/04795. 
In the present invention, the effect of this invention becomes more 
remarkable when at least one kind of a 4-equivalent magenta coupler is 
used. 
Preferred 4-equivalent magenta couplers are the 4-equivalent 5-pyriazolone 
series magenta couplers represented by formula (M) and the 4-equivalent 
pyrazoloazole series magenta couplers represented by formula (m). 
##STR25## 
In formula (M), R.sub.24 represents an alkyl group, an aryl group, an acyl 
group, or a carbamoyl group. Ar represents a substituted or unsubstituted 
phenyl group. Either R.sub.24 or Ar may be a divalent or higher valent 
group forming a polymer, such as a dimer or a polymer coupler, which links 
the coupling mother nucleus to the main chain of a polymer. 
In formula (m), R.sub.25 represents a hydrogen atom or a substituent and Z 
represents a non-matellic atomic group necessary for forming a 5-membered 
azole ring containing 2 to 4 nitrogen atoms. This azole ring may have a 
substituent or a condensed ring. In addition, either R.sub.25 or the group 
substituting the azole ring may become a divalent or higher valent group 
to form a polymer such as a dimer or a polymer coupler, or form a polymer 
coupler by bonding a high molecular chain with a coupling mother nucleus. 
In formula (M), the alkyl group represented by R.sub.24 represents a 
straight or branched alkyl group having from 1 to 42 carbon atoms, an 
aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or 
a cycloalkenyl group; the aryl group represented by R.sub.24 represents an 
aryl group having from 6 to 46 carbon atoms; the acyl group represented by 
R.sub.24 is an aliphatic acyl group having from 2 to 32 carbon atoms or an 
aromatic acyl group having from 7 to 46 carbon atoms;. and the carbamoyl 
group represented by R.sub.24 is an aliphatic carbamoyl group having from 
2 to 32 carbon atoms or an aromatic carbamoyl group having from 7 to 46 
carbon atoms. 
These groups each may have a substituent and the substituent is an organic 
substituent or a halogen atom bonding with a carbon atom, an oxygen atom, 
a nitrogen atom or a sulfur atom. Examples of the substituent are an alkyl 
group, an aryl group, a heterocyclic group, a cyano group, a hydroxy 
group, a nitro group, a carboxy group, an amino group, an acyl group, an 
aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an 
alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy 
group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino 
group, an acylamino group, an alkylamino group, an anilino group, a ureido 
group, a sulfamoylamino group, an alkoxycarbonylaimo group, a sulfonamido 
group, an aryloxycarbonylamino group, an imido group, an alkylthio group, 
an arylthio group, a heterocyclic thio group, a sulfamoyl group, a 
sulfonyl group, a sulfinyl group, an azo group, a phosphonyl group, an 
azolyl group, a fluorine atom, a chlorine atom, and a bromine atom. 
R.sub.24 represents, in more detail, an alkyl group (e.g., methyl, ethyl, 
butyl, propyl, octadecyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, 
methoxyethyl, ethoxyethyl, t-butoxyethyl, phenoxyethyl, 
methanesulfonylethyl, and 2-(2,4-di-tert-amylphenoxy)ethyl), an aryl group 
(e.g., phenyl, 2-chlorophenyl, 2-methoxyphenyl, 
2-chloro-5-tetradecanamidophenyl, 
2-chloro-5-(3-octadecenyl-1-succinimido)phenyl, 
2-chloro-5-octadecylsulfonamidophenyl, and 
2-chloro-5-[2-(4-hydroxy-3-tretbutylphenoxy)tetradecanamidophenyl]), an 
acyl group (e.g., acetyl, pivaloyl, tetradecanoyl, 
2-(2-,4-di-tertpentylphenoxy)acetyl, 
2-(2,4-di-tert-pentylphenoxy)butanoyl, benzoyl, and 
3-(2,4-di-tret-amylphenoxyacetamido)benzoyl), or a carbamoyl group (e.g., 
N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-hexadecylcarbamoyl, 
N-methyl-N-phenylcarbamoyl, and 
N-[3-{2,4-di-tert-pentylphenoxy)butylamido}]phenylcarbamoyl). 
R.sub.24 is preferably an aryl group or an acyl group. 
In formula (M), Ar represents a substituted or unsubstituted phenyl group. 
The preferred substitute for the phenyl group include a halogen atom, an 
alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or 
an acylamino group. In more detail, Ar is, for example, phenyl, 
2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-dimethyl-6-methoxyphenyl, 
2,6-dichloro-4-methoxyphenyl, 2,6-dichloro-4-ethoxycarbonylphenyl, 
2,6-dichloro-4-cyanophenyl, or 
4-[2-(2,4-ditert-amylphenoxy)butylamido]phenyl. 
Ar is preferably a substituted phenyl group, more preferably a phenyl group 
substituted with at least one halogen atom (in particular, chlorine), and 
most preferably 2,4,6-trichlorophenyl or 2,5-dichlorophenyl. 
Of the pyrazoloazole series magenta couplers represented by formula (m), 
the preferred couplers include 1H-imidazo[1,2-b]pyrazole 
1H-pyrazolo[1,5-b][1,2,4]-triazole, 1H-pyrazolo[5,1-c][1,2,4]triazole, and 
1H-pyrazolol[1,5-d]tetrazole skeletons and they are represented by 
formulae (m-1), (m-2), (m-3) and (m-4). 
##STR26## 
Then, R.sub.25, R.sub.51, R.sub.52, and R.sub.53 in formula (m) and the 
above formulae (m-1), (m-2), (m-3) and (m-4) are explained. 
R.sub.25 and R.sub.51 each represents a hydrogen atom or a substituent and 
Examples of the substituent, include a halogen atom, an alkyl group, an 
aryl group, a heterocyclic group, a cyano group, a hydroxy group, a sulfo 
group, a nitro group, a carboxy group, an amino group, an alkoxy group, an 
aryloxy group, an acylamino group, an alkylamino group, an anilino group, 
a ureido group, a sulfamoylamino group, an alkylthio group, an aryl thio 
group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl 
group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a 
heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy 
group, a silyloxy group, an aryloxycarbonylamino group, an imido group, a 
heterocyclic thio group, a sulfinyl group, a phosphonyl group, an 
aryloxycarbonyl group, an acyl group, and an azolyl group. 
These groups may be substituted by the same group of substituents for 
R.sub.24. Also, R.sub.25 and R.sub.51 each may be a divalent group or 
higher valent group to form a polymer such as a dimer or a polymer 
coupler, or for a polymer coupler by bonding a high molecular chain with a 
coupling mother nucleus. 
In more detail, R.sub.25 and R.sub.51 each represents a hydrogen atom, a 
halogen atom (e.g., chlorine and bromine), or an alkyl group (which may be 
a straight chain, branched, or cyclic). The alkyl group includes an 
aralkyl group, an alkinyl group, and a cycloalkyl group. 
R.sub.25 and R.sub.51 each represents preferably an alkyl group having from 
1 to 32 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, t-butyl, 
tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propyl, 
2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 
3-(2,4-di-t-amylphenoxy)propyl), an alkenyl group (e.g., allyl), an aryl 
group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, and 
4-tetradecanamidophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 
2-pyrimidinyl, and 2-benzothiazolyl), a cyano group, a hydroxy group, a 
sulfo group, a nitro group, a carboxy group, an amino group, an alkoxy 
group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, and 
2-methanesulfonylethoxy), an aryloxy group (e.g., phenoxy, 
2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 
3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamouylphenoxy), an 
acylamino group (e.g., acetamido, benzamide, tetradecanamide, 
2-(2,4-di-t-amylpheoxy)butanamide, 
4-(3-t-butyl-4-hydroxyphenoxy)butanamide, and 
2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decanamide), an alkylamino group 
(e.g., methylamino, butylamino, dodecylamino, diethylamino, and 
methylbutylamino), an anilino group (e.g., phenylamino, 2-chloroanilino, 
2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, 
N-acetylanilino, and 
2-chloro-5-{.alpha.-(3-t-butyl-4-hydroxyphenoxy)dodecanamido}anilino), a 
ureido group (e.g., phenylureido, methylureido, and N,N-dibutylureido), a 
sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino and 
N-methyl-N-decylsulfamoylamino), an alkylthio group (e.g., methylthio, 
octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 
3-(4-t-butylphenoxy)propylthio), an arylthio group (e.g., phenylthio, 
2-butoxy-5-t-octylphenylthio 3-pentadecylphenylthio, 2-carboxyphenylthio, 
and 4-tetradecanamidophenylthio), an alkoxycarbonylamino group (e.g., 
methoxycarbonylamino and tetradecyloxycarbonylamino), a sulfonamide group 
(e.g., methanebenzenesulfonamide, hexadecanesulfonamide, 
benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 
2-methoxy-5-butylbenzenesulfoneamide), a carbamoyl group (e.g., 
N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, 
N-methyl-N-dodecylcarbamoyl, and 
N-{3-(2,4-t-amylphenoxy)propyl}carbamoyl), a sulfamoyl group (e.g., 
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, 
N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl), a sulfonyl group 
(e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, and 
toluenesulfonyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, 
butyloxycarbonyl, dodecyloxycarbonyl, and octadecyloxycarbonyl), a 
heterocyclic oxy group (e.g., 1-phenyltetrazol-5-oxy and 
2-tetrahydropyranyloxy), an azo group (e.g., phenylazo, 
4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 
2-hydroxy-4-propanoylphenylazo), an acyloxy group (e.g., acetoxy), a 
carbamoyloxy group (e.g., N-methylcarbamoyloxy and N-phenylcarbamoyloxy), 
a silyloxy group (e.g., trimethylsilyloxy and dibutylmethylsilyloxy), an 
aryloxycarbonylamino group (e.g., phenoxycarbonylamino), an amido group 
(e.g., N-succinimido, N-phthalimido, and 3-octadencenylsuccinimido), a 
heterocyclic thio (e.g., 2-benxothiazolylthio, 
2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio), a sulfinyl group 
(e.g., dodecansulfonyl, 3-pentadecylphenylsulfinyl, and 
3-phenoxypropylsulfinyl), a phosphonyl group (e.g., phenoxysulfonyl, 
octyloxysulfonyl, and phenylsulfonyl), an aryloxycarbonyl group (e.g., 
phenoxycarbonyl), an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, 
and 4-dodecyloxybenzoyl), or an azolyl group (e.g., imidazolyl, pyrazolyl, 
3-chloro-pyrazol-1-yl, and triazolyl). 
R.sub.25 and R.sub.51 are preferably an alkyl group, an aryl group, an 
alkoxy group, an aryloxy group, an alkylthio group, an ureido group, a 
urethane group, or an acylamino group. 
R.sub.52 has the same meaning as R.sub.51 and is preferably a hydrogen 
atom, an alkyl group, an aryl group, a heterocyclic group, an 
alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl 
group, an acyl group, or a cyano group. 
Also, R.sub.53 has the same meaning as R.sub.51 and is preferably a 
hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an 
alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an 
alkoxycarbonyl group, a carbamoyl group, or an acyl group, and more 
preferably an alkyl group, an aryl group, a heterocyclic group, an 
alkylthio group, or an arylthio group. 
The effect of this invention becomes particularly remarkable when the 
4-equivalent pyrazolone series magenta couplers represented by formula (M) 
are used. 
Specific non-exclusive examples of the preferred 4-equivalent magenta 
couplers are illustrated below. 
##STR27## 
In the present invention, the coating amount of the 4-equivalent magenta 
coupler is preferably from 0.4.times.10.sup.-3 to 3.5.times.10.sup.-3 mol 
per square mater of the color photographic material. Additionally, the 
4-equivalent magenta coupler may be used together with a 2-equivalent 
magenta. 
A cyan coupler can be used in the color photographic material, such as 
phenolic couplers and naphtholic couplers and those cyan couplers 
described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 
2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 
4,334,011, and 4,327,173, West German Patent Publication (OLS) 3,329,729, 
European Patents 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622, 
4,333,999, 4,753,871, 4,451,559, 4,427,767, 4,690,889, 4,254,212, 
4,296,199, JP-A-3-196037 and JP-A-61-42658. 
Particularly, pyrrolotriazole, pyrroloimidazole, imidazopyrazole, 
imidazole, pyrazolotriazole, a cyclic active methine coupler (e.g., those 
described in JP-A-2-302078, JP-A-2-322051, JP-A-3-226325, JP-A-3-236894, 
JP-A-64-32250, and JP-A-2-141745) are preferred. 
A colored coupler for correcting unnecessary absorption of colored dye can 
be used in the present invention. Preferred colored couplers are described 
in Research Disclosure, No. 17643, VII-G, U.S. Pat. Nos. 4,163,670, 
4,004,929, and 4,138,258, JP-B-57-39413, British Patent 1,146,368, and 
Japanese Patent Application No. 2-50137. Also preferred are couplers for 
correcting unnecessary absorption of a colored dye by a fluorescent dye 
released therefrom at coupling as described in U.S. Pat. No. 4,774,181. 
Couplers having a dye precursor capable of forming a dye by reacting with 
a color developing agent as a releasing group described in U.S. Pat. No. 
4,777,120 is preferably used in this invention. 
In the present invention, a coupler giving a colored dye having a proper 
diffusibility can be also used in this invention. Preferred couplers are 
described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European 
Patent 96,570 and West German Patent Publication (OLS) 3,234,533. 
Also, in the present invention, polymerized dye-forming couplers can be 
used. Typical examples of the polymerized coupler are described in U.S. 
Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, and 4,576,910, and 
British Patent 2,102,173. 
Furthermore, preferred couplers release a photographically useful residue 
upon coupling. Preferably, the couplers imagewise releasing a nucleating 
agent or a developing accelerator are described in British Patents 
2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840. 
Other couplers in the color photographic materials processed by this 
invention are competing couplers described in U.S. Pat. No. 4,130,427, 
couplers releasing a dye which is color-restored described in European 
Patent 173,302A, bleaching accelerator-releasing couplers described in 
Research Disclosure, No. 11449, ibid., No. 24241, and JP-A-61-201247, 
ligand-releasing couplers described U.S. Pat. No. 4,553,477, couplers 
releasing a leuco dye described in JP-A-63-75747, and couplers releasing a 
fluorescent dye described in U.S. Pat. No. 4,774,181. 
The couplers for use in this invention can be introduced into color 
photographic light-sensitive materials by various dispersion methods. 
An oil drop-in-water dispersion method of a high-boiling point organic 
solvent are described in U.S. Pat. No. 2,322,027, etc. Practical examples 
of a high-boiling point organic solvent (boiling point of 175.degree. C. 
or more at normal pressure) used for the oil drop-in-water dispersion 
method include phthalic acid esters [e.g., dibutyl phthalate, dicyclohexyl 
phthalate, di-2-ethylhexyl phthalate, decylphthalate, 
bis(2,4-di-amylphenyl)phthalate, bis(2,4-di-t-amylhenyl)isophthalate, and 
bis(1,1-diethylpropyl)phthalate], phosphoric acid esters and phosphonic 
acid eaters (e.g., triphenyl phosphate, tricresyl phosphate, 
2-ethyl-hexyldiphenyl phosphate, trichlorohexyl phosphate, 
tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, 
trichloropropyl phosphate, and di-2-ethylhexylphenyl phosphonate), benzoic 
acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, and 
2-ethylhexyl-p-hydroxy benzoate), amides (e.g., N,N-diethyldodecanamido, 
N,N-benzoate), diethyllaurylamide, and N-tetradecylpyrrolidone), alcohols 
and phenols (e.g., isostearyl alcohol and 2,4-di-tert-amylphenol), 
aliphatic carboxylic acid esters [e.g., bis(2-ethylhexyl)sebacate, dioctyl 
azelate, glycerol tributyrate, isostearyl lactate, and trioctyl citrate], 
aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-tertoctylaniline ), and 
hydrocarbons (e.g., paraffin, dodecylbenzene, and diisopropylnaphthalene 
). 
Also, an organic solvent (boiling point of about 30.degree. C. or more, and 
preferably from about 50.degree. C. to 160.degree. C.) can be used as an 
auxiliary solvent in dispersion methods. Typical examples are ethyl 
acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, 
cyclohexanone, 2-ethoxyethyl acetate, and dimethyl-formamide. 
A latex dispersion method can also be used. Practical examples of the steps 
and effects of the latex dispersion method as well as the latexes for 
impregnation are described in U.S. Pat. No. 4,199,363, West German Patent 
Publications (OLS) 2,541,274 and 2,541,230. 
Also, the couplers can be dispersed by emulsification in an aqueous 
hydrophilic colloid solution impregnated with a loadable latex polymer and 
couplers, in the presence or absence of the described high-boiling organic 
solvent (as described in U.S. Pat. No. 4,203,716), or after dissolving the 
couplers in a polymer which is insoluble in water but soluble in an 
organic solvent. Preferred such polymers are the homopolymers or 
copolymers described in WO(PCT) 88/00723, pages 12 to 30. Acrylamide 
series polymers are particularly preferred to stabilize dye images. 
Supports suitable used for the color photo-graphic materials of the present 
invention are described in Research Disclosure, No. 17643, page 28 and 
ibid., No. 18716, from page 647, right column to page 648, left column. 
The present invention can be applied to various kinds of color photographic 
materials. Preferably, the invention can be used for processing general or 
cine color negative photographic films and reversal photographic films for 
slides or television. 
WORKING EXAMPLES 
The invention is described in more detail by the following non-exclusive 
examples: 
EXAMPLE 1 
1. Layers 
A multilayer color photographic material (Sample 101) was used as a 
support. Sample 101 had the following layer compositions arranged on a 
cellulose triacetate film support having a subbing layer. 
The coated amounts are given in units of g/m.sup.2. The silver halide 
emulsion and colloid silver, coated amounts are given in units of 
g/m.sup.2 based on the silver content thereof. Coated amounts for couplers 
additives, and gelatin are given in units of g/m.sup.2. Coated amounts for 
sensitizing dyes are given in units of mols per mol of silver halide 
contained in the same layer. 
______________________________________ 
Layer 1 (Antihalation Layer) 
Black Colloid Silver 0.20 as Ag 
Gelatin 2.20 
UV-1 0.11 
UV-2 0.22 
Cpd-1 4.0 .times. 10.sup.-2 
Cpd-2 1.9 .times. 10.sup.-2 
Solv-1 0.30 
Solv-2 1.2 .times. 10.sup.-2 
Layer 2 (Interlayer) 
Fine Grain Silver Iodobromide 
0.15 as Ag 
(AgI: 1.0 mol %, sphere-corresponding 
diameter: 0.07 .mu.m) 
Gelatin 1.00 
ExC-4 6.0 .times. 10.sup.-2 
Cpd-3 2.0 .times. 10.sup.-2 
Layer 3 (1st Red-Sensitive Emulsion Layer) 
Silver Iodobromide Emulsion 
0.42 as Ag 
(AgI: 5.0 mol %, surface high AgI type, 
sphere-corresponding diameter: 0.9 .mu.m, 
variation coeff. of sphere-corresponding 
diameters: 21%, tabular grains, aspect 
ratio (diameter/thickness): 7.5) 
Silver-Iodobromide Emulsion 
0.40 as Ag 
(AgI: 4.0 mol %, inside high AgI type, 
sphere-corresponding diameter: 0.4 .mu.m, 
variation coeff. of sphere-corresponding 
diameters: 18%, tetradecahedral grains) 
Gelatin 1.90 
ExS-1 4.5 .times. 10.sup.-4 
ExS-2 1.5 .times. 10.sup.-4 
ExS-3 4.0 .times. 10.sup.-5 
ExC-1 0.65 
ExC-3 1.0 .times. 10.sup.-2 
ExC-4 2.3 .times. 10.sup.-2 
Solv-1 0.32 
Layer 4 (2nd Red-Sensitive Emulsion Layer) 
Silver Iodobromide Emulsion 
0.85 
(AgI: 8.5 mol %, inside high AgI type, 
sphere-corresponding diameter: 1.0 .mu.m, 
variation coeff. of sphere-corresponding 
diameters: 25%, tabular grains, 
aspect ratio: 3.0) 
Gelatin 0.91 
ExS-1 3.0 .times. 10.sup.-4 
ExS-2 1.0 .times. 10.sup.-4 
ExS-3 3.0 .times. 10.sup.-5 
ExC-1 0.13 
ExC-2 6.2 .times. 10.sup.-2 
ExC-4 4.0 .times. 10.sup.-2 
Solv-1 0.10 
Layer 5 (3rd Red-Sensitive Emulsion) 
Silver Iodobromide Emulsion 
1.50 
(AgI: 11.3 mol %, inside high AgI type, 
sphere-corresponding diameter: 1.4 .mu.m, 
variation coeff. of sphere-corre- 
sponding diameters, tabular grains, 
aspect ratio: 6.0) 
Gelatin 1.20 
ExS-1 2.0 .times. 10.sup.-4 
ExS-2 6.0 .times. 10.sup.-5 
ExS-3 2.0 .times. 10.sup.-5 
ExC-2 8.5 .times. 10.sup.-2 
ExC-5 7.3 .times. 10.sup.-2 
ExC-6 1.0 .times. 10.sup.-2 
Solv-1 0.12 
Solv-2 0.12 
Layer 6 (Interlayer) 
Gelatin 1.00 
Cpd-4 8.0 .times. 10.sup.-2 
Solv-1 8.0 .times. 10.sup.-2 
Layer 7 (1st Green-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 5.0 
0.28 
mol %, surface high AgI type, sphere- 
corresponding diameter: 0.9 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 21%, tabular grains, 
aspect ratio: 7.0) 
Silver iodobromide Emulsion (AgI: 4.0 
0.16 
mol %, inside high AgI type, sphere- 
corresponding diameter: 0.4 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameter: 18%, tetradecahedral grains) 
Gelatin 1.20 
ExS-4 5.0 .times. 10.sup.-4 
ExS-5 2.0 .times. 10.sup.-4 
ExS-6 1.0 .times. 10.sup.-4 
ExM-1 0.50 
ExM-2 0.10 
ExM-5 3.5 .times. 10.sup.-2 
Solv-1 0.20 
Solv-3 3.0 .times. 10.sup.-2 
Layer 8 (2nd Green-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 8.5 
0.57 
mol %, Inside high AgI type, sphere- 
corresponding diameter: 1.0 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 25%, tabular grains, aspect 
ratio: 3.0) 
Gelatin 0.45 
ExS-4 3.5 .times. 10.sup.-4 
ExS-5 1.4 .times. 10.sup.-4 
ExS-6 7.0 .times. 10.sup.-5 
ExM-1 0.12 
ExM-2 7.1 .times. 10.sup.-3 
ExM-3 3.5 .times. 10.sup.-2 
Solv-1 0.15 
Solv-3 2.0 .times. 10.sup.-2 
Layer 9 (Interlayer) 
Gelatin 0.50 
Solv-1 2.0 .times. 10.sup.-2 
Layer 10 (3rd Green-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 11.3 
1.30 
mol %, Inside high AgI type, sphere- 
corresponding diameter: 1.4 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 28%, tabular grains, aspect 
ratio: 6.0) 
Gelatin 1.20 
ExS-4 2.0 .times. 10.sup.-4 
ExS-5 8.0 .times. 10.sup.-5 
ExS-6 8.0 .times. 10.sup.-5 
ExM-4 4.5 .times. 10.sup.-2 
ExM-6 1.0 .times. 10.sup.-2 
ExC-2 4.5 .times. 10.sup.-3 
Cpd-5 1.0 .times. 10.sup.-2 
Solv-1 0.25 
Layer 11 (Yellow Filter Layer) 
Gelatin 0.50 
Cpd-6 5.2 .times. 10.sup.-2 
Solv-1 0.12 
Layer 12 (Interlayer) 
Gelatin 0.45 
Cpd-3 0.10 
Layer 13 (1st Blue-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 2 
0.20 
mol %, uniform AgI type, sphere- 
corresponding diameter: 0.55 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 25%, tabular grains, aspect 
ratio: 7.0) 
Gelatin 1.00 
ExS-7 3.0 .times. 10.sup.-4 
ExY-1 0.60 
ExY-2 2.3 .times. 10.sup.-2 
Solv-1 0.15 
Layer 14 (2nd Blue-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 19.0 
0.19 
mol %, inside high type, sphere- 
corresponding diameter: 1.0 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 16%, octahedral grains) 
Gelatin 0.35 
ExS-7 2.0 .times. 10.sup.-4 
ExY-1 0.22 
Solv-1 7.0 .times. 10.sup.-2 
Layer 15 (Interlayer) 
Fine Grain Silver iodobromide (AgI: 
0.20 
2 mol %, uniform AgI type, sphere- 
corresponding diameter: 0.13 .mu.m) 
Gelatin 0.36 
Layer 16 (3rd Blue-Sensitive Emulsion Layer) 
Silver iodobromide Emulsion (AgI: 14.0 
1.55 
mol %, inside high type, sphere- 
corresponding diameter: 1.7 .mu.m, varia- 
tion coeff. of sphere-corresponding 
diameters: 28%, tabular grains, aspect 
ratio: 5.0) 
Gelatin 1.00 
ExS-8 1.5 .times. 10.sup.-4 
ExY-1 0.21 
Solv-1 7.0 .times. 10.sup.-2 
Layer 17 (1st Protective Layer) 
Gelatin 1.80 
UV-1 0.13 
UV-2 0.21 
Solv-1 1.0 .times. 10.sup.-2 
Solv-2 1.0 .times. 10.sup.-2 
Layer 18 (2nd Protective Layer) 
Fine Grain Silver Chloride (sphere- 
0.36 
corresponding diameter: 0.07 .mu.m) 
Gelatin 0.70 
B-1 (diameter 1.5 .mu.m) 2.0 .times. 10.sup.-2 
B-2 (diameter 1.5 .mu.m) 0.15 
B-3 3.0 .times. 10.sup.-2 
W-1 2.0 .times. 10.sup.-2 
H-1 0.35 
Cpd-7 1.00 
______________________________________ 
The working example contained: 1,2-benzisothiazolin-3-one in an average 
amount of about 200 ppm based on gelatin; n-butyl-p-hydroxy benzoate in an 
average amount of about 1,000 ppm based on gelatin; and 2-phenoxy ethanol 
in an average amount of about 10,000 ppm based on gelatin. Furthermore, 
the working example contained these compounds: B-4, B-5, W-2, W-3, F-1, 
F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, and F-13, an 
iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and 
a rhodium salt. 
2. Chemical Structures 
The chemical structures used in this working example are shown below: 
##STR28## 
3. Preparation of Sample 
The dry layer thickness of Sample 101, excluding the support, was 22 .mu.m 
and the swelling speed, T1/2, was 9 seconds. 
To prepare Sample 101, it was slit into a width of 35 mm and a length of 2 
meters. This prepared sample was exposed to white light of 50 lux for 0.01 
second and processed using an automatic processor under the following 
conditions. The stabilizing solution only was successively replaced and 
other processings were carried out under the sample conditions. The 
processed sample was then evaluated for stains and image storage 
stability. 
4. Processing Steps 
The processing steps and the compositions of the processing solutions are 
shown below. 
______________________________________ 
Processing Steps 
Re- 
Processing 
plenishment 
Tank 
Processing 
Temp. Amount Volume 
Step Time (.degree.C.) 
(ml) (liter) 
______________________________________ 
Color 3 min. and 
38.0 600 17 
Development 
5 sec. 
Bleaching 
50 sec. 38.0 140 5 
Blixing 50 sec. 38.0 -- 5 
Fixing 50 sec. 38.0 420 5 
Washing 30 sec. 38.0 980 3 
Stab. (1) 
20 sec. 38.0 -- 3 
Stab. (2) 
20 sec. 38.0 560 3 
Drying 1 min. 60 -- -- 
______________________________________ 
In the above table, "Stab" is stabilization and the replenishment amount is 
the amount per square meter of the sample color photographic material. 
The stabilization was carried out by a countercurrent replenishment system 
of from (2) to (1) and the entire overflow solution from the washing step 
was all introduced into the fixing bath. 
The blixing bath was replenished as follows. A cut was formed at the upper 
portion of the bleaching bath and at the upper portion of the fixing bath 
of the automatic processor. All overflow solutions (caused by addition of 
replenishers to the bleaching bath and fixing bath) were introduced into 
the blixing bath. In addition, the amount of color developer carried over 
into the bleaching step, the amount of bleaching solution carried over 
into the blixing step, the amount of blixing solution carried over into 
the fixing step, and the amount of fixing solution carried over into the 
washing step were 65 ml, 50 ml, 50 ml and 50 ml, respectively per square 
meter of the color photographic material. Also, the crossover time was 6 
seconds each which was included in the processing time of the pre-step. 
Also, the composition of the each replenisher was same as the tank 
solution. 
5. Processing Solutions 
The composition of each processing solution is shown below. 
______________________________________ 
Color Developer 
Diethylenetriaminepentaacetic Acid 
2.0 g 
1-Hydroxyethylidene-1,1-diphosphonic 
3.3 g 
Acid 
Sodium Sulfite 3.9 g 
Potassium Carbonate 37.5 g 
Potassium Bromide 1.4 g 
Potassium Iodide 1.3 mg 
Hydroxylamine Sulfate 2.4 g 
2-Methyl-4-[N-ethyl-N-(.beta.-hydroxy- 
4.5 g 
ethyl]aminolaniline Sulfate 
Water to make 1.0 liter 
pH 10.05 
Bleaching Solution 
1,3-Diaminopropanetetraacetic Acid 
130 g 
Ferric Ammonium Monohydrate 
Ammonium Bromide 80 g 
Ammonium Nitrate 15 g 
Hydroxyacetic Acid 50 g 
Acetic Acid 40 g 
Water to make 1.0 liter 
pH (adjusted by aqueous ammonia) 
4.2 
______________________________________ 
Blixing Solution 
A mixture of the above bleaching solution and the above fixing solution at 
a volume ratio of 15/85. (pH 7.0). 
______________________________________ 
Fixing Solution 
______________________________________ 
Ammonium Sulfite 19 g 
Aqueous Ammonium thiosulfate 
280 ml 
Solution (700 g/liter) 
Imidazole 15 g 
Ethylenediaminetetraacetic Acid 
15 g 
Water to make 1.0 liter 
pH (adjusted by aqueous ammonia or 
7.4 
acetic acid) 
______________________________________ 
Water Water 
Tap water was passed through a mixed bed column packed with an H type 
strong acidic cation exchange resin (Amberlite IR-120B, trade name, made 
by Rohm & Haas Co., Ltd.) and an OH type strong basic anion exchange resin 
(Amberlite IRA-400, trade name, made by Rohm & Haas Co., Ltd.). This 
reduced the concentrations of calcium ions and magnesium ions to 3 
mg/liter or less. Then 20 mg/liter of sodium dichloroisocyanurate and 150 
mg/liter of sodium sulfate was added to the water. The pH of the washing 
solution was in the range from 6.5 to 7.5. 
______________________________________ 
Stabilizing solution 
______________________________________ 
Sodium p-Toluenesulfinate 
0.1 g 
Polyoxyethylene-p-monononyl Phenyl 
0.2 
Ether (mean polymerization degree 10) 
Ethylenediaminetetraacetic Acid 
0.05 
Disodium Salt 
Image Stabilizer (shown in Table A) 
0.01 mol 
Water to make 1.0 liter 
pH 7.2 
______________________________________ 
6. Evaluation of Image Storage Stability 
The magenta density of each processed sample was measured using a 
photographic densitometer FSD 103 (trade name, manufactured by Fuji Photo 
Film Co., Ltd.). 
The magenta density of each processed sample was 1.5. The sample was 
allowed to stand for 2 months at 5.degree. C. and 55% RH. The magenta 
density was then measured again. Thus, the image storage stability was 
determined by the reduced magenta density over the passage of time. (M 
fading) 
7. Evaluation of Processing Stain 
Each of the processed samples was visually observed and evaluated for 
staining. The ratings used to evaluate are as follows. 
______________________________________ 
Rank 1: No stain was observed 
2: Slight stain was observed (1/10 or less of 
the sample surface was stained to a slightly 
clouded extent). 
3: Cloud was observed (more than 1/10 of the 
sample surface). 
4: Sticking of substance was observed (less 
than 1/10 of the sample surface). 
5: Sticking of substance was observed (more 
than 1/10 of the sample surface). 
______________________________________ 
8. Measurement of Formaldehyde Vapor Pressure 
Vapor pressure of formaldehyde was then measure as follows: 
100 ml of each stabilizing solution was placed in a separate vessel (open 
area 80 cm.sup.2). The vessel was placed in a 5 liters closed glass 
container and allowed to stand for 7 days at 20.degree. C. The vapor 
pressure of formaldehyde in the glass container was measured by a 
formaldehyde L-type direct reading gas detecting tube made by Gas Teck 
Co., Ltd. 
9. Comparative Examples 
The chemical structures of Comparative (1) to (10) shown in Table (A) are 
shown below. 
Comparative Compound (1) 
##STR29## 
Compound described in U.S. Pat. No. 4,859,574 
Comparative Compound (2) 
##STR30## 
Compound described in European Patent Publication (unexamined) 395,442 
Comparative Compound (3) 
##STR31## 
Compound described in JP-A-2-153348 
Comparative Compound (4) 
##STR32## 
Compound described in JP-A-63-244036 
Comparative Compound (5) 
##STR33## 
Compound described in JP-A-61-42660, JP-A-61-75354, JP-A-62-255948, 
JP-A-1-295258 and JP-A-2-54261 
Comparative Compound (6) 
##STR34## 
Compound described in JP-A-61-42660, JP-A-61-75354, JP-A-62-255948, 
JP-A-1-295258 and JP-A-2-54261 
Comparative Compound (7) 
##STR35## 
Compound described in JP-A-1-230043 
Comparative Compound (8) 
##STR36## 
Compound described in JP-A-1-230043 
Comparative Compound (9) 
##STR37## 
Compound described in JP-A-2-153350 
Comparative Compound (10) 
##STR38## 
Compound described in JP-A-2-153350 
Comparative Compound (11) 
##STR39## 
Compound described in U.S. Pat. No. 3,247,201 
Comparative Compound (12) 
##STR40## 
Compound described in U.S. Pat. No. 4,917,992 
10. Results and Comparisons 
The image stabilizers used and each evaluation result are shown in Table A. 
TABLE A 
______________________________________ 
Sample No. 
Image Stabilizer 
M Fading Stain Rank 
______________________________________ 
1 none 0.30 1 
2 Formalin 0.00 1 
3 Comp. Compound (1) 
0.19 5 
4 Comp. Compound (2) 
0.24 3 
5 Comp. Compound (3) 
0.25 3 
6 Comp. Compound (4) 
0.27 3 
7 Comp. Compound (5) 
0.22 4 
8 Comp. Compound (6) 
0.21 4 
9 Comp. Compound (7) 
0.23 4 
10 Comp. Compound (8) 
0.24 4 
11 Comp. Compound (9) 
0.25 4 
12 Comp. Compound (10) 
0.23 4 
13 Comp. Compound (11) 
0.21 4 
14 Comp. Compound (12) 
0.22 5 
15 Compound I-1 0.05 2 
16 Compound I-5 0.06 1 
17 Compound I-15 0.05 2 
18 Compound I-20 0.03 1 
19 Compound I-24 0.03 1 
20 Compound I-25 0.03 1 
21 Compound II-3 0.06 1 
22 Compound II-7 0.07 1 
23 Compound II-8 0.06 1 
24 Compound II-17 0.00 1 
25 Compound II-18 0.00 1 
26 Compound II-19 0.02 1 
27 Compound II-20 0.02 1 
28 Compound II-22 0.03 1 
29 Compound II-27 0.02 1 
30 Compound II-30 0.00 1 
31 Compound II-34 0.00 1 
32 Compound II-35 0.02 1 
33 Compound II-39 0.02 1 
34 Compound II-40 0.03 1 
35 Compound III-10 
0.07 1 
36 Compound III-16 
0.05 2 
37 Compound III-17 
0.06 1 
38 Compound III-20 
0.06 1 
______________________________________ 
Sample Nos. 1 to 14: Comparative Examples 
Sample Nos. 15 to 38: Examples of the Invention. 
The data in Table A clearly show that the compounds of this invention 
result in color images with excellent image storage stability with 
virtually no stains. 
Measurement of formaldehyde vapor pressure showed formaldehyde of 5 ppm or 
more in Comparative Sample Nos. 1 to 5 and Sample Nos. 7 to 14. 
Comparative Sample No. 6 and the compounds of this invention, Sample Nos. 
15 to 38, produced 2 ppm of formaldehyde or less. Although comparative 
Sample No. 6 produced lower amounts of formaldehyde, Table A clearly show 
that its image storage stability and resistance to staining were inferior. 
The above results conclusively show these desired properties exhibited by 
the compounds of this invention: (1) image storage stability is excellent; 
(2) staining is lessened; and (3) formaldehyde vapor pressure is reduced 
to acceptable safe levels. Conventional formalin substitutes do not 
produce these same results. 
EXAMPLE 2 
The same procedures in Example 1 were followed except that equimolar 
amounts of magenta coupler M-1 or M-17 were substituted for magenta 
coupler ExM-1. Accordingly, Samples 201 and 202 were prepared, and almost 
the same results were obtained when the same teste were applied. 
Sample 203 was prepared by following the same procedures of Example 1 
except that an equimolar amount of magenta coupler M-1 replaced magenta 
coupler ExM-4. Sample 204 was prepared by following the same procedures of 
Example 1 except that an equimotar amount of magenta coupler ExM-4 and 
magenta coupler M-1 at a mol ratio of 1:1 replaced magenta coupler ExM-4. 
Almost the same results in Example 1 were obtained when the same tests 
were applied to Samples 203 and 204. Thus, the compound of this invention 
has laudable properties with various magenta couplers. 
EXAMPLE 3 
The same evaluations of Example 2 were followed except that the amount of 
each image stabilizers was decreased from 0.01 mol to 0.002 mol per liter 
of the stabilizing solution. Also, the pH of the stabilizing solution was 
changed to 7.8. Almost the same results as in Example 1 were obtained. 
This confirmed that the compounds for use in this invention had excellent 
effects even in small amounts. 
EXAMPLE 4 
Sample 101 was processed using the following processing steps and 
processing solution by an automatic processor according to the processing 
method in Example 1 until the accumulated amount of replenisher for each 
stabilizing solution was three times the tank volume. The image storage 
stability was tested in the same method as in Example 1, and almost the 
same results were obtained. That is, it was confirmed that the compounds 
for use in this invention had excellent effects. 
1. Processing Steps 
The processing steps employed were as follows: 
______________________________________ 
Processing Steps 
Re- 
Processing 
plenishment 
Tank 
Processing 
Temp. Amount* Volume 
Step Time (.degree.C.) 
(ml) (liter) 
______________________________________ 
Color 3 min. and 
38 33 20 
Development 
15 sec. 
Bleaching 
6 min. and 
38 25 40 
30 sec. 
Washing 2 min. and 
24 1200 20 
10 sec. 
Fixing 4 min. and 
38 25 30 
20 sec. 
Washing (1) 
65 sec. 24 -- 10 
Washing (2) 
60 sec. 24 1200 10 
Stabiliza- 
65 sec. 38 25 10 
tion 
Drying 4 min. and 
55 -- -- 
20 sec. 
______________________________________ 
(*): Replenishing amount was per 35 mm in width and 1 meter in length. 
Washing step was by a countercurrent system from (2) to (1). 
2. Processing Solutions 
The composition of each processing solution is shown below. 
______________________________________ 
Tank Repleni- 
Solution sher 
______________________________________ 
Color Developer 
Diethylenetriaminepenta- 
1.0 g 1.1 g 
acetic Acid 
1-Hydroxyethylidene-1,1- 
3.0 g 3.2 g 
diphosphonic Acid 
Sodium Sulfite 4.0 g 4.4 g 
Potassium Carbonate 
30.0 g 37.0 g 
Potassium Bromide 1.4 g 0.7 g 
Potassium Iodide 1.5 mg -- 
Hydroxylamine Sulfate 
2.4 g 2.8 g 
4-[N-ethyl-N-(.beta.-hydroxy- 
4.5 g 5.5 g 
ethyl)amino]-2-methyl- 
aniline Sulfate 
Water to make 1 liter 1 liter 
pH 10.05 10.10 
Bleaching Solution 
Ethylenediaminetetra- 
100.0 g 120.0 
g 
acetic Acid Ferric 
Sodium Trihydrate 
Ethylenediaminetetra- 
10.0 g 10.0 g 
acetic Acid Disodium Salt 
Ammonium Bromide 140.0 g 160.0 
g 
Ammonium Nitrate 30.0 g 35.0 g 
Aqueous Ammonia (27 wt %) 
6.5 ml 4.0 ml 
Water to make 1 liter 1 liter 
pH 6.0 5.7 
Fixing Solution 
Ethylenediaminetetra- 
0.5 g 0.7 g 
acetic Acid Disodium Salt 
Sodium Sulfite 7.0 g 8.0 g 
Sodium Hydrogensulfite 
5.0 g 5.5 g 
Aqueous Ammonium Thiosulfate 
170 ml 200.0 
ml 
Solution (700 g/liter) 
Water to make 1 liter 1 liter 
pH 6.7 6.6 
Stabilizing solution 
Image Stabilizer (shown in 
0.01 mol 0.011 
mol 
Table A above) 
Polyoxyethylene-p-monononyl 
0.3 g 0.33 g 
Phenyl Ether (mean polymeri- 
zation degree: 10) 
Ethylenediaminetetraacetic 
0.05 0.055 
Acid Disodium Salt 
Water to make 1 liter 1 liter 
pH 8.2 8.0 
______________________________________ 
EXAMPLE 5 
Sample 101 in Example 1 was processed according to Example 4 using no image 
stabilizer--Sample No. 1--and using bleaching solutions each containing 
0.03 mol/liter of each of the image stabilizers shown in Table A. Stain 
and image storage stability evaluations of the sample after processing 
produced, and almost the same results as in Example 1 were obtained. That 
is, it was confirmed that the compounds for use in this invention had 
excellent effects. 
EXAMPLE 6 
1. Layers 
A multilayer color photographic material (for Sample 501) was used as a 
support. Sample 501 had the following layer compositions arranged on a 
cellulose triacetate film support of 127 .mu.m in thickness having a 
subbing layer. The numbers below show the coated amount per square meter. 
In addition, the function of each compound is not limited to the use 
thereof as given below. 
______________________________________ 
Layer 1 (Antihalation Layer) 
Black Colloid Silver 0.25 
Gelatin 1.9 g 
U.V. Absorber U-1 0.04 g 
U.V. Absorber U-2 0.1 g 
U.V. Absorber U-3 0.1 g 
U.V. Absorber U-4 0.1 g 
U.V. Absorber U-6 0.1 g 
High-Boiling Organic Solvent Oil-1 
0.1 g 
Layer 2 (Interlayer) 
Gelatin 0.40 g 
Compound Cpd-D 10 mg 
High-Boiling Organic Solvent Oil-3 
0.1 g 
Dye-D-4 0.4 mg 
Layer 3 (Interlayer) 
Surface- and Inside-Fogged Fine 
0.05 g as Ag 
Grain Silver Iodobromide Emulsion 
(mean grain size: 0.06 .mu.m, varia- 
tion coeff.: 18%, AgI: 1 mol %) 
Gelatin 0.4 g 
Layer 4 
(Low-Speed Red-Sensitive Emulsion Layer) 
Emulsion A 0.2 g as Ag 
Emulsion B 0.3 g as Ag 
Gelatin 0.8 g 
Coupler C-1 0.15 g 
Coupler C-2 0.05 g 
Coupler C-9 0.05 g 
Compound Cpd-D 10 mg 
High-Boiling Organic Solvent Oil-2 
0.1 g 
Layer 5 (Medium-Speed Red-Sensitive 
Emulsion Layer) 
Emulsion B 0.2 g as Ag 
Emulsion C 0.3 g as Ag 
Gelatin 0.8 g 
Coupler C-1 0.2 g 
Coupler C-2 0.05 g 
Coupler C-3 0.2 g 
High-Boiling Organic Solvent Oil-2 
0.1 g 
Layer 6 
(High-Speed Red-Sensitive Emulsion Layer) 
Emulsion D 0.4 g as Ag 
Gelatin 1.1 g 
Coupler C-1 0.3 g 
Coupler C-3 0.7 g 
Additive P-1 0.1 g 
Layer 7 (interlayer) 
Gelatin 0.6 g 
Additive M-1 0.3 g 
Color Mixing Inhibitor Cpd-K 
2.6 mg 
U.V. Absorber U-1 0.1 g 
U.V. Absorber U-6 0.1 g 
Dye D-1 0.02 g 
Layer 8 (Interlayer) 
Surface- and Inside-Fogged Silver 
0.02 g as Ag 
Iodobromide Emulsion (mean grain 
size: 0.06 .mu.m, variation coeff.: 16%, 
AgI: 0.3 mol %) 
Gelatin 1.0 g 
Additive P-1 0.2 g 
Color Mixing Inhibitor Cpd-J 
0.1 g 
Color Mixing Inhibitor Cpd-A 
0.1 g 
Layer 9 
(Low-Speed Green-Sensitive Emulsion Layer) 
Emulsion E 0.3 g as Ag 
Emulsion F 0.1 g as Ag 
Emulsion G 0.1 g as Ag 
Gelatin 0.5 g 
Coupler C-7 0.05 g 
Coupler C-8 0.20 g 
Compound Cpd-B 0.03 g 
Compound Cpd-D 10 mg 
Compound Cpd-E 0.02 g 
Compound Cpd-F 0.02 g 
Compound Cpd-G 0.02 g 
Compound Cpd-H 0.02 g 
High-boiling Organic Solvent Oil-1 
0.1 g 
High-boiling Organic Solvent Oil-2 
0.1 g 
Layer 10 (Medium-Speed Green-Sensitive 
Emulsion Layer) 
Emulsion G 0.3 g as Ag 
Emulsion H 0.1 g as Ag 
Gelatin 0.6 g 
Coupler C-7 0.2 g 
Coupler C-8 0.1 g 
Compound Cpd-B 0.03 g 
Compound Cpd-E 0.02 g 
Compound Cpd-F 0.02 g 
Compound Cpd-G 0.05 g 
Compound Cpd-H 0.05 g 
High-boiling organic Solvent Oil-2 
0.01 g 
Layer 11 
(High-Speed Green-Sensitive Emulsion Layer) 
Emulsion I 0.5 g as Ag 
Gelatin 1.0 g 
Coupler C-4 0.3 g 
Coupler C-8 0.1 g 
Compound Cpd-B 0.08 g 
Compound Cpd-E 0.02 g 
Compound Cpd-F 0.02 g 
Compound Cpd-G 0.02 g 
Compound Cpd-H 0.02 g 
High-boiling Organic Solvent Oil-1 
0.02 g 
High-boiling Organic Solvent Oil-2 
0.02 g 
Layer 12 (Interlayer) 
Gelatin 0.6 g 
Dye D-1 0.1 g 
Dye D-2 0.05 g 
Dye D-3 0.07 g 
Layer 13 (Yellow Filter Layer) 
Yellow Colloidal Silver 0.1 g as Ag 
Gelatin 1.1 g 
Color Mixing Inhibitor Cpd-A 
0.01 g 
High-boiling Organic Solvent Oil-1 
0.01 g 
Layer 14 (Interlayer) 
Gelatin 0.6 g 
Layer 15 
(Low-Speed Blue-Sensitive Emulsion Layer) 
Emulsion J 0.4 g as Ag 
Emulsion K 0.1 g as Ag 
Emulsion L 0.1 g as Ag 
Gelatin 0.8 g 
Coupler C-5 0.6 g 
Layer 16 (Medium-Speed Blue-Sensitive 
Emulsion Layer) 
Emulsion L 0.1 g as Ag 
Emulsion M 0.4 g as Ag 
Gelatin 0.9 g 
Coupler C-5 0.3 g 
Coupler C-6 0.3 g 
Layer 17 
(High-Speed Blue-Sensitive Emulsion Layer) 
Emulsion N 0.4 g as Ag 
Gelatin 1.2 g 
Coupler C-6 0.7 g 
Layer 18 (1st Protective Layer) 
Gelatin 0.7 g 
U.V. Absorber U-1 0.04 g 
U.V. Absorber U-2 0.01 g 
U.V. Absorber U-3 0.03 g 
U.V. Absorber U-4 0.03 g 
U.V. Absorber U-5 0.05 g 
U.V. Absorber U-6 0.05 g 
High-boiling Organic Solvent Oil-1 
0.02 g 
Formalin Scavengers: 
Cpd-C 0.2 g 
Cpd-I 0.4 g 
Dye D-3 0.05 g 
Layer 19 (2nd Protective Layer) 
Colloidal Silver 0.1 mg as Ag 
Fine Grain Silver Iodobromide 
0.1 mg as Ag 
Emulsion (mean grain size: 0.06 .mu.m, 
AgI: 1 mol %) 
Gelatin 0.4 g 
Layer 20 (3rd Protective Layer) 
Gelatin 0.4 g 
Polymethyl Methacrylate (mean 
0.1 g 
grain size: 1.5 .mu.m) 
Copolymer of Methyl-Methacrylate 
0.1 g 
and Acrylic Acid (4:6) (mean 
grain size: 1.5 .mu.m) 
Silicone Oil 0.03 g 
Surface Active Agent W-1 3.0 mg 
Surface Active Agent W-2 0.03 mg 
______________________________________ 
Each silver halide emulsion layer also contained additives F-1 to F-8, 
gelatin hardener H-1, surface active agents W-3 and W-4 for coating and 
emulsification, and antiseptics and antimolds, such as phenol, 
1,2-benzisothiazolin-3-one, 2-pheoxy ethanol, p-hydroxybenzoic acid butyl 
eater and phenethyl alcohol. 
2. Silver Iodobromide Emulsions 
The properties of the silver iodobromide emulsions used in this example are 
shown below: 
______________________________________ 
Mean 
Grain Variation 
AgI 
Size Coeff. Content 
Emulsion (m) (%) (%) 
______________________________________ 
A Monodisperse Tetradeca- 
0.25 16 3.7 
hedral grains 
B Monodisperse Cubic Internal 
0.30 10 3.3 
Latent Image Type Grains 
C Monodisperse Tetradeca- 
0.30 18 5.0 
hedral Grains 
D Polydisperse Twin Grains 
0.60 25 2.0 
E Monodisperse Cubic Grains 
0.17 17 4.0 
F Monodisperse Cubic Grains 
0.20 16 4.0 
G Monodisperse Cubic Internal 
0.25 11 3.5 
Latent Image Type Grains 
H Monodisperse Cubic Internal 
0.30 9 3.5 
Latent Image Grains 
I Polydisperse Tabular Grains 
0.80 28 1.5 
(Mean Aspect Ratio: 4.0) 
J Monodisperse Tetradeca- 
0.30 18 4.0 
hedral Grains 
K Monodisperse Tetradeca- 
0.37 17 4.0 
hedral Grains 
L Monodisperse Cubic Internal 
0.46 14 3.5 
Latent Image Type Grains 
M Monodisperse Cubic Grains 
0.55 13 4.0 
N Polydisperse Tabular Grains 
1.00 33 1.3 
(Mean Aspect Ratio: 7.0) 
______________________________________ 
______________________________________ 
Spectral Sensitization of Emulsion A to N 
Added Amount 
Sensitizing 
per mol of AgX 
Timing For Adding 
Emulsion 
Dye Added (g) Sensitizing Dye 
______________________________________ 
A S-1 0.025 (a) 
S-2 0.25 (a) 
B S-1 0.01 (b) 
S-2 0.25 (b) 
C S-1 0.02 (a) 
S-2 0.25 (a) 
C S-1 0.01 (a) 
S-2 0.10 (a) 
S-7 0.01 (a) 
E S-3 0.5 (a) 
S-4 0.1 (a) 
F S-3 0.3 (a) 
S-4 0.1 (a) 
G S-3 0.25 (b) 
S-4 0.08 (b) 
H S-3 0.2 (c) 
S-4 0.06 (c) 
I S-3 0.3 (d) 
S-4 0.07 (d) 
S-8 0.1 (d) 
J S-6 0.2 (c) 
S-5 0.05 (c) 
K S-6 0.2 (c) 
S-5 0.05 (c) 
L S-6 0.22 (b) 
S-5 0.06 (b) 
M S-6 0.15 (a) 
S-5 0.04 (a) 
N S-6 0.22 (b) 
S-5 0.06 (b) 
______________________________________ 
(a): Immediately after chemical sensitization. 
(b): Immediately after finishing grain formation. 
(c): During formation of grains. 
(d): Immediately before the initiation of chemical sensitization 
3. Chemical Structures 
The chemical structures of compounds used in the color photographic 
material of this example are shown below: 
##STR41## 
4. Processing Steps 
Sample 501 was subjected to an imagewise exposure and then processed using 
a cine type automatic processor. First, 0.5 square meter of the sample was 
processed with Bleaching Solution 1 and then with each stabilizing 
solution. Next, the sample was similarly processed using Bleaching 
Solution 2. Details of the processing steps are provided below: 
______________________________________ 
Processing Steps 
Replenish- 
Process- Process- ment Tank 
ing Time ing Temp. Amount* Volume 
Step (minute) (.degree.C.) 
(liter) (liter) 
______________________________________ 
Black & White 
6 38 1.5 12 
Development 
1st Washing 
1 38 7.5 4 
Reversal 1 38 1.1 4 
Color 4 38 2.0 12 
Development 
Conditioning 
2 38 1.1 4 
Bleaching 4 38 1.3 12 
Fixing 3 38 1.3 12 
2nd Washing (1) 
1 38 -- 4 
2nd Washing (2) 
1 38 7.5 4 
Stabilization 
1 38 1.1 4 
Drying 2 50 -- -- 
______________________________________ 
(*): The replenishing amount was per square meter of the color 
photopraphic material. 
In the above processing steps, the overflow solution from 2nd washing (2) 
was introduced into the bath of 2nd washing (1). 
5. Processing Solutions 
The composition of each processing solution was as follows. 
______________________________________ 
Starting Repleni- 
Black & White Developer 
Solution sher 
______________________________________ 
Nitrilo-N,N,N-trimethylene- 
2.0 g 2.0 g 
phosphonic Acid.Pentasodium Salt 
Diethylenetriaminepentaacetic 
3.0 g 3.0 g 
Acid.Pentasodium Salt 
Potassium Sulfite 30 g 30 g 
Hydroquinone Potassium mono- 
20 g 20 g 
sulfonate 
Potassium Carbonate 33 g 33 g 
1-Phenyl-4-methyl-4-hydroxy- 
2.0 g 2.0 g 
methyl-3-pyrazolidone 
Potassium Bromide 2.5 g 0.9 g 
Potassium Thiocyanate 
1.2 g 1.2 g 
Potassium Iodide 2.0 mg 2.0 mg 
Water to make 1 liter 1 liter 
pH (25.degree. C.) 9.60 9.70 
______________________________________ 
The pH was adjusted with hydrochloric acid or potassium hydroxide. 
______________________________________ 
Reversal Solution Starting solution = Replenisher 
______________________________________ 
Nitrilo-N,N,N-trimethylenephosphonic 
2.0 g 
Acid.Pentasodium Salt 
Stannous Chloride.Dihydrate 
1.0 g 
p-Aminophenol 0.1 g 
Sodium Hydroxide 8.0 g 
Glacial Acetic Acid 15 ml 
Ammonium Sulfite 20 g 
Water to make 1 liter 
pH (25.degree. C.) 6.60 
______________________________________ 
The pH was adjusted with acetic acid or an aqueous ammonia. 
______________________________________ 
Starting Repleni- 
Color Developer Solution sher 
______________________________________ 
Nitrilo-N,N,N-trimethylene- 
2.0 g 2.0 g 
phosphonic Acid Pentasodium Salt 
Diethylenetriaminepentaacetic 
2.0 g 2.0 g 
Acid.Pentesodium Salt 
Sodium Sulfite 7.0 g 7.0 g 
Potassium Tertiary Phosphate- 
36 g 36 g 
Dodecahydrate 
Potassium Bromide 1.0 g -- 
Potassium Iodide 90 mg -- 
Sodium Hydroxide 3.0 g 3.0 g 
Citrazinic Acid 1.5 g 1.5 g 
N-Ethyl-(.beta.-methanesulfonamido- 
10.5 g 10.5 g 
ethyl)-3-methyl-4-aminoaniline 
Sulfate 
3,6-Dithiaoctane-1,8-diol 
3.5 g 3.5 g 
Water to make 1 liter 1 liter 
pH (25.degree. C.) 11.90 12.05 
______________________________________ 
The pH was adjusted with hydrochloric acid or potassium hydroxide. 
______________________________________ 
Conditioning Solution Starting solution = Replenisher 
______________________________________ 
Ethylenediaminetetraacetic Acid 
8.0 g 
Disodium Salt.Dihydrate 
Sodium Sulfite 12 g 
2-Mercapto-1,3,4-triazole 
0.5 g 
pH (25.degree. C.) 6.00 
______________________________________ 
The pH was adjusted with hydrochloric acid or sodium hydroxide. 
______________________________________ 
Bleaching Solution 1 Starting solution = Replenisher 
______________________________________ 
Ethylenediaminetetraacetic Acid 
3 g 
Ethylenediaminetetraacetic Acid 
150 g 
Ferric Ammonium.Dihydrate 
2-Mercapto-1,3,4-triazole 
0.5 g 
Ammonium Bromide 120 g 
Ammonium Nitrate 25 g 
Water to make 1 liter 
pH (25.degree. C.) 4.20 
______________________________________ 
The pH was adjusted with acetic acid or aqueous ammonia. 
______________________________________ 
Bleaching Solution 2 Starting solution = Replenisher 
______________________________________ 
1,3-Diaminopropanetetraacetic Acid 
3 g 
1,3-Diaminopropanetetraacetic Acid 
120 g 
Ferric Ammonium.Dihydrate 
Glycolic Acid 40 g 
Acetic Acid 30 g 
Ammonium Bromide 120 g 
Ammonium Nitrate 25 g 
Water to make 1 liter 
pH (25.degree. C.) 4.20 
______________________________________ 
The pH was adjusted with acetic acid or an aqueous ammonia. 
______________________________________ 
Fixing Solution Starting solution = Replenisher 
______________________________________ 
Ethylenediaminetetraacetic Acid 
1.7 g 
Disodium.Dihydrate 
Sodium Benzaldehyde-o-sulfonate 
20 g 
Sodium Hydrogensulfite 15 g 
Aqueous Ammonium Thiosulfate 
250 ml 
Solution (700 g/liter) 
Water to make 1 liter 
pH (25.degree. C.) 6.00 
______________________________________ 
The pH was adjusted with acetic acid or an aqueous ammonia. 
Stabilizing solution 
Each stabilizing solution shown in Example 1 was used (the starting 
solution=the replenisher). 
The gray colored portion of each sample having a magenta density of 0.5 was 
used to evaluate the image storage stability. The results were almost same 
as in Example 1, that is, improved results were obtained by using the 
stabilizer containing the compound of this invention. 
Also, image storage stability was similarly evaluated for stabilizing 
solutions containing the image stabilizer of this invention and also for 
conditioning solutions containing 0.03 mol/liter of each of the image 
stabilizers shown in Table B below. The results obtained are shown in 
Table B. 
TABLE B 
______________________________________ 
Image Storage Stability* 
Bleach Bleach 
No. Image Stabilizer 
Solution 1 
Solution 2 
______________________________________ 
1 None 0.20 0.20 
2 Formalin 0 0 
3 Compound I-1 0.05 0.05 
4 Compound I-5 0.05 0.06 
5 Compound II-3 0.06 0.06 
6 Compound II-4 0.05 0.05 
7 Compound II-17 
0.01 0.00 
8 Compound II-18 
0.01 0.00 
9 Compound II-19 
0.02 0.01 
10 Compound II-20 
0.01 0.02 
11 Compound II-30 
0.01 0.00 
12 Compound II-39 
0.01 0.02 
13 Compound II-40 
0.01 0.02 
14 Compound III-10 
0.06 0.05 
______________________________________ 
(*) M Fading. 
Sample Nos. 1 and 2: Comparative Examples. 
Sample Nos. 3 to 14: Examples of the invention. 
As is shown in Table B, when the compounds of this invention are used for 
the conditioning baths, they show a substantive fading prevention effect 
on magenta dyes. 
In particular, better results are obtained with use of 
1,3-diamiopropanetetraacetic acid ferric complex salt as a bleaching 
agent. 
Additionally, no stains were observed on surfaces of each sample shown in 
Table B. 
That is, it was confirmed that the compounds for use in this invention had 
excellent effects. 
EXAMPLE 7 
Sample 201 of Example 2, described in JP-A-2-90151, and Light-sensitive 
Materials 1 and 9 of in Example 1 and 3, respectively, described in 
JP-A-2-93641, were processed using Nos. 15 to 38 in Example 1 of the 
present invention. The vapor pressure of formaldehyde was decreased, the 
dye images formed were excellent in fastness property, and no stains were 
formed. That is, it was confirmed that the compounds for use in this 
invention had excellent effects. 
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.