CA1252329A - Method of processing a silver halide color photographic light-sensitive material - Google Patents

Abstract

ABSTRACT
The said material is processed at the final step of the color processing, with a stabilizing solution whose pH value is not lower than 5 and to which 0.001 to 1 mol/? of an ammonium compound is added. The ammon-ium compound should be capable of releasing an ammonium ion in an aqueous solution. This method enables to prevent a light discoloration and a dark discoloration, as well as a blueing and a stain.

Description

~s~

METH~D OF PROCESSI~G A SI~VER ~LID~
COhOR P~OT~GRAP~IC LIG~T-SENSITIVE ~TERIA~

BACKGROUND OF T~E INVENTION
Field of the Invention This invention relates to a method of stabilizing a silver halide color photographic light-sensitive material and particularly to a method of stabilizing a color dye image in which both of a light discoloration and a dark discoloration can be preYented, and a bluing and a stain can also be prevented.
Description of the Prior Art In a silver halide color photographic light-sensitive material, as is generally known, a color-developed image may be obtained through the formation of an azomethine dye and an indoaniline dye in a color developing process.
It is also generally known that a discoloration is taken place in these dyes by irradiating them with ultraviolet rays or visible rays, and such a discoloration is also taken place :~5~

even during the storage thereof in the dark. This discoloration is particularly accelerated under the conditions of high temperature and humidity.
This discoloration in a color-developed image is a serious disadvantage to a color photography, and there has been a strong demand for the improvement of this disadvantage.
Conventionallyr there are a variety of well-known antidiscoloration methods in which a color-developed image produced of a silver halide color photographic light-sensitive material is protected against the discoloration taken place in the light or dark. These well known methods include, for example, a process using a zinc solution disclosed in U~S.
Patent No~ 2,788,274; a process using a calcium salt, a magnesium salt or a cadmium salt disclosed in UOSO Patent No.

2,913,338, the processes each using the solution containing monosaccharide, disaccharide and hexitol, and a process using a solution containing formaldehyde and a polycarboxylic acid disclosed in British Patent Nos. 909,824 and 1~001,446; and the like.
In these methods, however, there are the disadvantages such as that the effects may be obtained a little, that even if a discoloration may be prevented in the dark, a discoloration caused in the light, i~e., a light discoloration, is increased to the contrary, and that even if a stain may be protected from increasing in some case~ the discoloration of dyes are

3 --worsened.
In recent years, among the photofinishers who are processing color photographic light-sensitive materials automatically and continuously, the problems of the protection of environment and the safety of water resources are regarded as important and it is desired to reduce or to eliminate a large quantity of washing water used in a washing process following fixing or bleach-fixing process.
In this connection! there have been proposed some o the technique in which a stabilizing process is directly carried out without any washing process after a fixing or bleach-fixing process. There include, for example, the technique using the derivatives of an isothiazoline-3-on compound such as those disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter called Japanese Patent O.P.I.
Publication3 No. 8542/1982; the technique for containing a water-soluble iron salt such as that disclosed in Japanese Patent O.P.I. Publication No. 14834/1983; the technique using a chelating agent suc as a polycarboxylic acid, an organic sulfonic acid, such as those disclosed in Japanese Patent O.P.I. Publication Nos~ 132146/1982 and 18631/1983; and the like. In these technique, however, there are disadvantages that the preservability oE an image is deteriorated and, in particular, that only a little effect may be obtained on the capability of inhibiting the increase in yellow-stains caused in an area where colors are not yet developed when an image is preserved for a long time.
As for the technique capable of solving the described disadvantages, there is the well-known technique disclosed in Japanese Patent O.P.I. Publication No. 8543/1983, in which a stabilizing solution is acidified. However, when the stabilizing solution was acidified, the other new problems were found, that is, one of them is that the black color in a maximum density area will be changed into a blue color under the sunlight, that is so-called a bluing phenomenon~ which is supposedly caused by an optical whitening agent, and another one is tha~ an unexposed area will be tinted with a yellow color, that is so-called a stain phenomenon, which is supposedly caused by the act that a dye eluted from a light-sensitive material in a continuous process is apt to adsorb to the unexposed area. In addition, it was also found that a fixer component and a water-soluble silver complex salt are increased in a stabilizing solution to lower the stability (the light discoloration property) to the light emitted from a cyan dye.

SUMMARY OF THE INVENTION
It is an object of the invention to provide a method of stabilizing a color dye image, in which the abovementioned disadvantages can be improved and a light discoloration as well - s -as a dark discoloration can also be prevented and further a bluing as well as a stain can be prevented from occurring, and, in particular, any color dye image is not affected at all even in a stabilizing process in which the quantity of washing water is reduced or a washing process is eliminated~
The method of processing a silver halide color photographic light-sensitive material, which relates to this invention, is characterized in that -the silver halide color photographic light-sensitive material is processed at the final step in a color process with a stabilizing solution of the pH
value of not lower than 5.0 to which 0.001 ~ 1.0 mol/~ of an ammonium compound is added.
According to one of the preferable embodiments of the invention, the stabilizing process thereof follows a bleach-fixing or fixing process and a washing process is substantially eliminated therefrom~

DETAILED DESCRIPTION OF THE INVENTION
The following is a detailed description of the invention.
The present inventors found out the fact that the back-dyeing of a sensitizing dyes eluted from a photographic material i5 caused by processing the photographic material with an acid stabilizing solutionl and also found out that the back-dyeing of an optical whitening agent or the sensitizing dyes can be avoided by making the pH value of the stabilizing 3~

solution not lower than 5. However, in a process using a stabilizing solution having the pH value of not lower than the neutrality, there causes the disadvantages that a yellow stain is apt to occur when a sample is preserved after processing and a discoloration is increased in cyan dyes, though the disadvantages of the aforementioned prior art may be eliminated. The inventors devoted themselves to study and research the technique capable of solving the abovementioned two disadvantages at a time, and resultantly~ they discovered that a dyeing oE an optical whitening agent or a sensitizing dye can be avoided by using a mixture prepared by adding a stabilizing solution having the pH value of not lower than 5~0 with an ammonium compound at the final processing step, and the deterioration of an image quality caused in the preservation thereof can completely be prevented.
The ammonium compounds to be added to the stabilizing solution of this invention are such a compound capable of releasing an ammonium ion in an aqueous solution, and to be more concrete, they include, for example, an aqueous solution of ammonia9 an ammonium salt of an inorganic acid such as ammonium bromide, ammonium carbonate, ammonium chloride, ammonium chromate, ammonium dichromate~ ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, acid ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogencarbonate, ammonium hydrogenfluoride, ammonium ~25~

hydrogensulfate, ammonium hydrogensulfiter ammonium iodide, ammonium nitrate~ ammonium pentaborate, ammonium perchlorate, ammonium peroxydisulfide, ammonium persulfate, ammonium molybdophosphate, ammonium tungstophosphate, ammonium silicofluoride, ammonium sulfamide, ammonium sulfate, ammonium sulfite, ammonium tetraborate, ammonium tetrafluoroborate, ammonium thiocyanate, ammonium tungstate, ammonium vanadate, ammonium polyphosphate, ammonium pyrophosphate and the like;
ammonium salts of an organic acid such as ammonium acetate, ammonium adipate, ammonium aurintricarboxylate, ammonium benzoate 9 ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogenmalate, ammonium hydrogenoxalate, ammonium hydrogenphthalate, ammonium hydrogentartrate, ammonium lactate~
ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylatel ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,5-trinitrophenol ammonlum, ammonium iminodiacetate, ammonium hydroxyethyliminodiacetate, ammonium nitrilotriacetate, ammonium ethylenediamine tetraacetate, ammonium hydroxyethylethylenediamine triacetate, ammonium diethylenetriamine pentacelate, ammonium trans--cyclohexanediamine tetraacetate, ammonium diaminopropanol tetraacetate, ammonium nitrilotripropionatel ammonium l~S~

nitrilotrimethylene phosphonate, ammonium ethylenediamine tetramethylene phosphonate, ammonium l-hydroxyethylidene-l,l'--diphosphonate, ammonium 2-phosphobutane-1,2,4-tricarboxylate, ammonium di(2-hydroxyethyl)aminomethane sulfonate, and the like; and an ammonia metal complex such as ammonia copper sulfate, an ammonia calcium complex salt, an ammonia magnesium complex salt, and the like; and ammonium alum, ceric ammonium sulfate, ammonium manganese sulfateO
The ammonium compounds to be used in this invention may be added within the range of 0.001 to 1.0 mol and preferably, 0.00~ to 0.2 mol, per liter of a stabilizing solution.
The pH value of a stabilizing solution ~a stabilizing bath) of this invention is not lower than 5~0, and preerablyr 5 0 to 10Ø The particularly preferable p~ value is within the range of 6.0 to 9Ø When using a continuous processing method in which the process comprises a number of tanks containing stabilizing solution and the processing is made in a counter current method, and the replenishments of the stabilizing solution are made from the last tank, the desired pH value of the stabilizing bath is that of the last tank.
It may be allowed to add the stabilizing solution oE this invention with a variety of compounds including, for example, a pH-buffer, an optical whitening agent, a surfactant, an antifungal agent, a preservative, a chelating agent~ a hardner, various metallic salts and the like. It shall not be limited ~5X~

to use any compound or those in combination, provided that no photographic characteristic is af ected.
A preferable stabilizing process relating to this invention is to follow a bleach-fixing process or a fixing process without substantially carrying out any washing process.
This means that it may be allowed to carry out a short process for silver recovery, a rinsing process and the like between the bleach~fixing or fixing process and the stabilizing processl though it is preferred that no process is carried out between the bleach-fixing or fixing process and the stabilizing process.
Any washing process is not necessary at all after the stabilizing process of -the inventionJ and it is also allowable, if occasion demands, to carry out optionally a rinse~ a surface-washing or the like using a small amount of water for a very short time, however, it is anyway preferred that a drying process may follow directly after the stabiliz.ing proc~ss.
The range of the temperature in the stabilizing process is from 10C to 60C~ and preferably~ from 15C to 40C. The processing time in the stabilizing process is the shorter, the better, from the viewpoint of a rapid processing, and is namely 20sec to lOmin.~ and most preferably, of the order of 30sec to 5min. The temperature and the time required for a drying process may arbitrarily be selected, however it is desired to select a temperature of not lower than 50C.

~25~

Fixing bath or bleach-fixing bath of the invention shall not specifically be limited. The fixers to be used in the invention include, for example, a thiosulfate, a thiocyanate~
an iodide, a bromide, a thioether, thiourea and the like, and the bleaching agents include, for example, potassium ferricyanate, iron chloride, a persulfate, hydrogen peroxide, an organoferric complex salt and the like.
As for the methods of bringing a stabilizing solution of this invention into contact with a light-sensitive material, a preferable method i5 to dip the light-sensitive material into the solution as in the case of using an ordinary type of processing solution, however, it is also allowed to coat the emulsion surace of a light-sensitive material and both surfaces of a transport leader with the stabilizing solution of the invention by means of a piece of sponge synthetic fiber or the like~ or~ to spray out such surfaces with the stabilizing solution by means of a spray-gun.
The processing methods of the invention can be used for processing a color printing paper, a reversal color printing paper, a color positive film, a color neg~tive film, a color reversal film, a color X-ray film, and the like.
When a stabilizing solution contains a soluble silver salt, silver may be recovered from the solution. As for the methods of recovering silver, an ion exchange resin method, a transmetallation method, an elec~rolyzing method, a silver :~5~

sulfide precipitation method and the like may be used.
In this invention, when a cyan coupler having the Formula (I) or (II) below is to be used in a silver halide color photographic light-sensitive material, there is added with such an effect that cyan dyes produced in a color development process may be improved on the stability thereof against light.
Formula (I) OH

RlCONH~

Formula (II) OH
~ ,NHCOR
XNH
wherein, X is a radical having the formula of -~OR~, -CON~ r -S2R2~ -I_N~ , -SO2N~ , -SO2NHCON~ , -CONHCOR2, or -CONHSO2R2; R2 represents an alkyl radical and preferably, those having one to 12 carbon atoms, such as methyl, ethyl, butyl~ dodecyl and the like; an alkenyl raidcal and pref~rably, those having 2 to 20 carbon atoms, such as acyl, oleyl and the like; a cycloalkyl radical and preferably, those having 5 to 7 member ring, such as cyclohexyl, an aryl radical such as ~s~

phenyl, tolyl or naphthyl radical and the like; and a heterocyclic radical and preferably, a 5 to 6 member hetero ring containing 1 to 4 nitrogen, oxygen or sulfur atoms, such as ~uryl~ thienyl or benzothiazole radical and the like; R3 represents hydrogen atom or a radical represented by R2. It is also allowed that R2 and R3 may be bonded together so as to form a 5 to 6 member hetero ring containing nitrogen atom. In addition, any arbitrary substituent can be introduced into R2 or R3, and such substituents include, for example, an alkyl radical having 1 to 10 carbon atoms such as ethyl, i-propyl, i-butyl, t-butyl, t-octyl and the like; an aryl radical such as phenyl and naphthyl, a halogen such as fluorine, chlorine or bromine atom and the like; a cyano radical; a nitro radical; a sulfonamide radical such as methanesulfonamide, butanesulfonamide, p-toluenesul~onamide and the like; a sulfamoyl radical such as methylsulfamoyl, phenylsulfamoyl and the like; a sulfonyl radical such as methanesul~onyl, p-toluenesulfonyl and the like; a fluorosulfonyl radical; a carbamoyl radical such as dimethylcarbamoyl, phenylcarbamoyl and the like; an oxycarbonyl radical such as ethoxycarbonyl, phenoxycarbonyl and the like; an acyl radical such as acetyl, benzoyl and the like; a heterocyclic radical such as pyridyl or pyrazolyl radical and the like; an alkoxy radical; an aryloxy radical; an acyloxy radical; and the like In Formulas (I) and (II), Rl represents a ballast radical ~ 13 -necessary for vesting cyan dyes formed of the abovementioned cyan couplers with a diffusion resistance. The preferable ballast radicals include an alkyl radical having 4 to 30 carbon atoms, an aryl radical or a heterocyclic radical. They are, for example, a straight-chain or branched chain alkyl radical such as t-butyl, n~octyl, t-octyl, n-dodecyl and the like, an alkenyl radical, a cycloalkyl radical 9 a 5 to 6 member heterocyclic radical and the like.
In Formulas (I) and (II), Z represents hydrogen or a radical capable of splitting off in a coupling reaction will an oxidi2ed product of a color developing agent. They include, for example, a halogen such as chlorine, bromine, fluorine atom and the like, and, an aryloxy, carbamoyloxyl carbamoylmethoxy, acyloxy, sulfonamide or succinimide radical in which an oxygen or nitrogen atom couples directly to the coupling position of the radical. The further concrete examples thereof include those disclosed in U.S. Patent NoO 3,741,563, Japanese Patent Examined Publication No. 36894~1973, and Japanese Patent O~P~Io Publication Nos 37425~1972, 10135/1975, 117422/1975, 130441/lg75, 108~41/197~, 120334/1375, 18315/1977, 105226/1978 14736il979, 48237/1979, 32071/1980, 65957/1980, 193B/1981, 12643/1981, and 27147/1981.
In this invention, more preferable cyan couplers have the following Formula (III), ~IV) or (V);

3~

Formula (III) OH

RlCONH

Formula (IV) OH

RlCONH

Formula (V) OH
,~,NHCORl R5CONH ~

In Formula (III), R4 is a substituted or unsubstituted aryl radical and more preferably, phenyl radical. When the aryl radical has a substituent, such substituents include at least one selected from the group of -SO2R6~ a halogen such as fluorine, bromine or chlorine atom and the like, -CF3, -NO2, COR COOR , -SO20R6, -CON\ ' S2~\R 6 _N~R7 , -N 7 , and -p 6 ~COR6 S2R6 \OR7 Wherein, R6 is an alkyl radical and preferably those having 1 to 20 carbon atoms, such as methyl, ethyl, t-butyl, or dodecyl radical and the like; an alkenyl radical and preferably those having 2 to 20 carbon atoms, such as acyl or oleyl radical and the like; a cycloalkyl radical and preEerably a 5 to 7 member ring, such as cyclohexyl radical and the like; and an aryl radical such as phenyl, tolyl or naphthyl radical and the like. R7 is hydrogen or a radical represented by the abovementioned R6.
The compounds suitable for the phenol type cyan couplers having the Formula (III) are such a compound that R~ is a substituted or unsubstituted phenyl radical and the substituent to phenyl radical is a cyano, nitro or -SO2R6 radical in which R6 is an alkyl radical, a halogen ato~, or trifluoromethyl.
In Formula (IV) and (V), R5 represents an alkyl radical and preferably those having 1 to 20 carbon atoms, such as methyl, ethyl, t-butyl or dodecyl radical and the like; an alkenyl radical and preferably those having 2 to 20 carbon atoms, such as acyl o~ ~leyl radical and the like; a cycloalkyl radical and preferably a 5 to 7 member ring, such as cyclohexyl radical and the like; an aryl radical such as phenyl, tolyl or naphthyl radical and ~he like; a heterocyclic radical and preferably those o~ 5 to 6 member ring containing 1 to 4 nitrogen, oxygen or sulfur atoms, such as furyl, thienyl or benzothiazolyl radical and the lik~.
Any arbitrary substituent may further be introduced into R6, R7 of Formula (III) and R5 of Formula (IV) or (V), and to be more concrete, and such substituents are those capable of being introduced into R2 or R3 of Formulas tI) and (II). And, a halogen including, for example, chlorine or fluorine atom and the like is particularly preferred to serve as the substituent.
In Formulas (III1~ (IV) and (V), Z and Rl each have the same meaning as those in Formulas (I) and (II)~ The preferred examples of the ballast radicals represented by Rl have the following Formula (VI~;
Formula ~VI~

~ , ~ 7 (R8)k Wherein, J represents oxygen~ sulfur or a sulfonyl radical; k is an integer oE 0 to 4; and ~ is 0 or 1. When k is a value of not smaller than 2, two or more R8 existing therein may be the same or diEferent from each other; R7 is a straight-chain or branched-chain alkylene radical having 1 to 20 carbon atoms and substituted by an aryl radical; and R8 represents a monovalent radical includingt for example, hydrogen; a halogen such as chlorine, bromine and the like; an alkyl radical and preferably a straight-chain or branched-chain alkyl radical having 1 to 20 carbon atoms, such as methyl, t-butyl, t-pentyl r t-octyl r dodecyl t pentadecyl, benzyl and phenethyl; an aryl radical such as phenyl; a heterocyclic radical and pre:Eerably those containing nitrogen; an alkoxy radical and preferably a straight-chain or branched-chain alkoxy radical having 1 to 20 carbon atoms, such as methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy and dodecyloxy radicals;
an aryloxy radical such as phenoxy radical; a hydroxy radical;
an acyloxy radical and preferably an alkylcarbonyloxy radical and an arylcarbonyloxy radical such as acetoxy and benzoyloxy radicals; a carboxy radical; an alkyloxycarbonyl radical and preferably a straight-chain or branched-chain alkyloxycarbonyl radical having 1 to 20 carbon atom~; an aryloxycarbonyl radical and preferably phenoxycarbonyl radical; an alkylthio radical and preferably those having 1 to 20 carbon atoms; an acyl radical and preferably a straight-chain or branched-chain alkylcarbonyl radical having 1 to 20 carbon atoms; an acylamino radical and preferably a straight-chain or branched-chain alkylcarbamide or benzenecarbamide radical; a sulfonamide radical inclding, preferablyy a straight-chain or branched-chain alkylsulfonamide radical having 1 to 20 carbon atoms and ben~enesulfonamide; a carbamoyl radical including, preferably, a straight chain or branched-chain alkylaminocarbonyl radical having 1 to 20 carbon atoms and phenylaminocarbamoyl radical; and a sulamoyl radical including, preferably, a straight-chain or branched-chain alkylaminosulfonyl radical and phenylamino~ulfonyl radical.
The ~ollowing exemplified compounds are some concrete ~2S~ 3 examples of the cyan couplers to be used in this invention;
tExemplified Compounds]
(1) /C5Hll~ ~ NHCONH ~ CN
tC5H~ o-cHcoNH
C4Hg ~2) C4Hgt ~ NHCONH ~ CN

tC4Hg ~ O-CHCONH ~ ~ OCH3 ~3) OH

O-CHCONH

(~) ~ MHCONH

HO ~ O-fHCONH

C4Hgt 12H25 (5) OH
~NHCNHC15~13 HO ~ O-CHCONH
~=/ I CQ, C4Hgt 12H25 (6) ON ~ C~

tC5Hll~O-fHCONH

(7~

C5Hllt ~~ SO~C~Hg tC5Hll ~ O CHCON

(~) ~ NHCONH ~ CN

C12H25 ~ O CHCONH ~ NO2 I

~5~ 3 ~9) ~ NHCONH ~ CN

C12H250 ~ O-CHCONH
~ C4Hg OCH2COOC2H5 C~Hgt (10) , ~ ~NHCONH ~ S02C2H5 t 4H9 ~ O-CHCONH
C1:2H25 (11) ~ NHCONH ~ CQ

nC4HgSo2NH ~ O-CHCONH ~ CN

~12) NHCONH ~ COOCH3 ~C~3)3CCOO ~ O-CHCONH ~

3'~3 (13) CF

tC4Hg-~O-CHCONH~ 2 C12H~5 o2~3CH3 (14) C5Hllt J~NHCoNH~3So2NHC4H~
tC5Hll~O--(CH2~ 3CON

tl5) ,NHCONH ~ COC2H5 ~O~CH 2 CONH'~J C~ 3 nC12H25NHC

CH

tC5Hll- ~ O-CHCONHJ ~ 3 C4Hg ~ZX~ 3 (17) OH _~t-OCH 3 tC5Hll~O-CHCON

OEI S
~,NHCONH~

~0--CHCONH
~/ I cQ, C2Hd~/ C2H5 (19) C 1 2E~ 2 5,~ ~ S
-tC5Hll~O-CHCON

C5Hllt ~20) Cl2H25J~ NH~S02cH3 tC5Hll ~ O--CHCON

C5Hllt (21) I ,NHCoNH~3So2C2H5 tC4Hg ~ SQ2CHCoNH ~

( 22) C5Hllt , ~ NHCONH ~ S02C3H7 tC5H 11 ~O-CHCONH

(23) ~4 9 ~NHcoNH~so2c6Hl3 t C ~H ~ O-C-CONH

(24) ~ ~NHCONH ~ SOC2H5 ~30 f HCONH~jJ

5~

2~

(25) O

~ NHCONH ~ ~ OCH3 12H250 ~ O-CHCONH

(26) ~ NHCONH ~ Q

C12H250 ~ 0~CHCONH
~2H5 OCON(CH3)2 (27 ~ NHCONH ~ C~

tC5Hll ~ O-CHCONH

(28) OH
~NHS02NHC4H9 C~HgS02NH ~ O f HCONH

(29) OH
~,NHSO 2NHCOCH 3 nCl 2H250~3~o2NH~CoNH

(30) ~ ~ ,NHCONHCO ~ S02CH~

4H 9 ~o -S CHCONH

(31) ~ 3,NHCONHS02 ~ F

nC12H250 ~ 0fHCONH
~H5 (32) C ~_ C~CON
ClÇ~33~l (33) OH
~,NHCON~ O

~OCHCONH~
>=/ I CQ
C4HgS02NH C12H25 (34) OH
C5Hllt ~NHCON=C (CH3~ 2 tC5Hll~O- (CH2) 3-CONH~, ~35) ,~,NHCN~CF3 C4HgSO2NH CONH

(35~
OH
~l,NHCO- I HCH2S02C12H25 tC4HgNHCNE1 3 S

(37) C5Hll~
NHCOfHO~C5H1lt C2H5SO2~NHCONH)~ C~Hg (38) ,~IHCO~CONHC12H25 ~3CH 2NH CONH _< N -N
~N

(39) ~J

~,NHCOCH20~30C1 2E1 25 NCONH
C2~15 (~0) OH
~,NHCO-C3F7 tC5Hli ~ O-CHCONH ~ J
C4Hg (41) F F

C ~H gt ,~NHCO~F
t C 4H 9~0--fHCONE~
C4H~

( 42) ~,NHCo4~F

Ho4~o-CHCoNH~

tC H C12H25

4 9 (43) OH
~ CO ~CF2) 2CHFCQ

Cl 2H 2 50~30-CHCoNH~

(44) HJ~ CF2CHFC'Q
~ OCF 2CHFC Q, tC5~ O-CHCONH

~ .3.~

45) OH
C4Hg ,~ CO ~CF2CF2~ H
tc5Hll~o-cHcoNH
C5Hllt (46) OH
~NHCO t CF ~2 ) 3H

C12H 250~3.o_ (47) C~aH9S02NH ~ O-CElCON~

(48) ~,NHCO~

~O--CHCONEI)q~J 2H 2 5 ~< C~

~5~ 3 ( ~9) tC 5H 11 ~O-CHCONHJ~ 2 3 (50) OH
~,NHSO 2CH 3 H3C (CH2) loCON~J

(51) OH
~,NHCO ~CH2) 14CH3 HO~SO ~NH

t 52) GH
H3C (CH2~ 1~-CH=CHcH2cHcONH~NHCO~3 (53) ~O-CHCONH~J
C4H9S2N C,~

( 54) ~O-CHCONH~
l 02N cL

~H 2 ~ 20C 2H 5 55) ,~ MHCo~3 ~O-CHCONH
NH
\o2-c~2~3 ~56) C~

C6Hl 3 ~ ~ F
C~H13~

(57) tC5~11 ~ 0-C~COII~
C4Hg (58) OH
CQ I~NHCOC (CH3) 3 CR,~ O-CHCONH~J
\y I C~
\C,e, Cl OE~21 (59) ~NHCO~

C12~25~S (CH ) CONHJ~J

( 60) OH
C 4H 11 t ~NHCOCH ;~CH =CH 2 tCd~Hll~O (CH2) 3CONH~

12~X;~

(61) ,[ ~ ,NHCONH ~ S02 ~

tC4H94~0-CHCONH

(62) 1 12H25 ,~ CoNH~3CF3 (63) ~3,NHCONH

(~i4) C 5H 1 lt ,[~ ~SO 2CH 3 tC5Hll ~ O-fHCON
Cl 2H25 (65) ~,NHCoNE~3so2NH 2 ~3OCHCONH~
OCOCl~
C4HgS02NH

~2S;~

(66) OH
CH3 ~NHCoNH~3so2ocH3 1 2H 2 5o~;~ocHcoNHJ~

(67) NHCONH~ ~CH3 tC4Hg~OCH2CON
C4~9t (68) ,~,NHCONH~ 3 S2NHC2HS

C 1 6H 3 30C~ CON
Cl 2H 25 ~

(69) NHCoNH~3NHCOC:H
~C5~ t ~f 3 tC5Hll~O- (CH2) 3CONH~

Silver halide color photographic light sensitive material applicable to the present invention may b~ the one having the coupler in developer type (see U.S.P. Nos. 2,252,718, 2,592,243 and 2,590,970) wherein coupler is contained in the developer in addition to the one having the coupler in emulsion type (see U.S.P. Nos. 2,376,679 and 2,8Dl,171) wherein coupler is contained in the light sensitive material~ In addition to aforesaid cyan coupler, any of those known generally in the field may be used as a coupler.
Magenta coupler having 5-pyrazolone ring having active methylene group in an essential structure or yellow coupler in the structure of benzoylacetoanilide, pivalylacetoanilide or acylacetoanilide having active methylene chain may be used regardless of whether substituent is owned at the coupling position or not. Thus J the coupler in either type of 2-e~uivalent coupler or 4-equivalent coupler may be applied.
Silver halide emulsion to be used can contain any of silver halides such as silver chloride~ silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Further, as a protective colloid for these silver halidesl various types ones obtained from synthesis may be used in addition to the natural one such as gelatin or the like. Silver halide emulsion can contain ordinary additives for photographic use such as stabilizer, sensitizer, hardener, sensitizing dye 7 surfactant and others.

Any of polyethylene coat paper, triacetate ~ilm, polyethylene terephthalate film and white polyethylene terephthalate film may be used as a support.
Black and white developer used for the processing o~ the present invention is the one called the first black and white developer to be used for the processing of normally known color photographic light sensitive material or the one to be used for the processing of the black and white photographic light sensitive material and it can contain additives in many kinds which are usually added to the normal black and white developer.
As a typical additive, l-phenyl-3-pyrazolidone, developing agent such as metol and hydroquinone, preservative such as sulfite, accelerator consisting of alkali such as sodium hydroxider sodium carbonate and potassium carbonate etc~, inor~anic inhibitor such as potassium bromide~
2-methylbenzimidazole, methylbenzthiazole etc~ or organic inhibitor, hard water softener such as a polyphosphate and a surface-over-development-preventive agent consisting of small amount of an iodide and mercapto compound and others are given.
Aromatic primary amine color developing agent to ~e used for color developer which is employed in the processing of the present invention includes known developing agents widely used in various color photographic processings. These developers include aminophenol derivative and p phenylenediamine derivative. These compounds are usually used in the form of salt such as hydrochloride or sulfate because they are more stable in the form of salt than in the free state. Further, these compounds are used under the concentration of about O.lg about 30g per 1~ of color developing liquid, preferably of about lg ~ about 15g per 1~ of color developing liquid.
Aminophenol developing agent includes, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy 3-amino-1,4-dimethyl-benzene and others.
Primary aromatic amino color developing agent which is especially useful is an N,N-dialkyl-p-phenylenediamine compound and alkyl radical and phenyl radical may either be substituted one or be unsubstituted one. Examples of the compound especially useful among them include N,~-diethyl p--phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-~-methanesulFonamideethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-~-hydroxyethylaminoaniline and 4-amino-N--(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and others.
Alkali color developing liquid to be used in processing of the present invention can further contain freely, in addition to aforesaid primary aromatic amine color developing agent, q'3 various ingredients normally added to color developing liquid such as, for examplet alkali agent like sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal s~lfite, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol, water softener and thickener etc. The pH value of this color developing liqu.id is usually 7 or more and most generally is about 10 ~ about 13.
Metallic complex salt of organic acid as a bleaching agent to be used in the bleaching solution used at bleaching step or in the bleach-fix solution has functions to ox.idize the metallic silver produced through the development and convert it to silver halide and concurrently to cause uncolored portion of coupler to color, and in its structurel metal ions of cobalt and copper etc~ are coordinated with aminopolycarboxylic acid or organic acid such as oxalic acid or citric acid. As the most desirable organic acid to be used for the formation of such metallic complex salt of organic acid, polycarboxylic acid or aminopolycarboxylic acid is givenl These polycarboxylic acid or aminopolycarboxylic acid can be alkali metal salt, ammonium salt or water soluble amine salt. Concrete typical examples of them are shown as follows.
(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N~ oxyethyl) N,N',N'-triacetic acid ~4) Propylenediaminetetraacetic acicl -~x~

~5) Nitryltriacetic acid (6~ Cyclohexanediaminetetraacetic acid (or tartaric acid) (7) Iminodiacetic acid (8) Hydroxyethylglycinecitric acid (9) Ethyletherdiaminetetraacetic acid ~10) Glycoletherdiaminetetraacetic acid ~11) Ethylenediaminetetrapropionic acid (12) Phenylenediaminetetraacetic acid (13) Disodium ethylenediaminetetraacetate (14) Tetra-trimethylammonium ethylenediaminetetraacetate (15) Tetrasodium ethylenediaminetetraacetate (lÇ) Pentasodium diethylenetriaminepentaacetate ~17) Sodium ethylenediamine-N~ oxyethyl)-N,N',N'-triacetate ~18~ Sodium propylenediaminetetraacetate (19) Sodium nitrilotriacetate (20) Sodium cyclohexanediaminetetraacetate Bleaching solution to be used may contain metallic complex salt of organic acid like the one stated above as a bleaching -agent and may also contain various additivesO As an additive, it is desirable that alkali-halide or ammonium~halide, for example re-halogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc~ is contained, in particular. Further, pH buffer agent such as korate, oxalate, acetate, carbonate, phosphate, etc. and the one known as an additive to be usually added to bleaching solution such as alkylamine or polyethyleneoxide may properly be addedO
When a bleach-fix solution is used for the bleaching step, the bleach fix solution is to have both bleaching function and fixing function and therefore the solution containing bleaching agent as well as fixing agent which is identical to the one used for ordinally fixing solution, is applied as a bleach-fix solution. As a fixing-solution and a bleach-fix solution to be used, a compound that reacts with silver halide and forms wa~er soluble complex salt, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanate such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea and thioether are given.
Further, the fixing solution and bleach-fix solution may contain singular or plural kinds of pH buffer agent consisting of sulfite such as ammonium sulfiteJ potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite~
ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite~ etc. and cf various kinds of salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide etc.
When bleach fix replenisher is separately replenished to -- ~1 the bleach-fix solution (bath), the composite solution of the present invention may contain thiosulfate, thiocyanate or sulfite etc. but it is desirable that they are replenished separately between fixing agent and bleaching agent.
In order to enhance the degree of activity of the bleach-fix solution in the present invention, air or oxygen can blow in the bleach-fix bath and in the xeservoir tank for bleach-fix replenisher or optimum oxidi2ing agent such as hydrogen peroxide, bromate or persulfate etc. may be added thereto~
In the processing of the present invention, silver recovery may be performed in the known method for processing solution containing soluble silver complex salt such as fixing solution and bleach-fix solution etc. as well as for stabilizer. For example, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method ~described in Japanese Patent Publication Open to Public Inspection No.
73037/1977 and West German Patent No. 2,331,220), an ion exchange method (described in Japanese Patent Publication Open to Public Inspection No. 17114/1976 and German Patent No.
2~548,237) and a metal-substitution method (described in British Patent No. 1,353~805) may effectively employed.

EXAMPLES
While the invention will be described in detail with - ~2 -reference to some embodiments thereof, it is to be understood that the invention is not limited thereto.

A sheet of color printing paper was prepared in the manner that a pretreatment was applied with a corona-discharge onto a paper-made support coated thereon with a polyethylene layer containing an anatase type titanium oxide that is a white pigment, and the following layers were coated thereon in order;
1st layer: A silver chlorobromide photographic emulsion containing 5 mol% of silver chloride was optically sensiti~ed with anhydro-5-methyl-5'-methoxy-3,3'-di(3-sulfopropyl)-selenacyanine hydroxide, and thus optically sensitized emulsion was added with the protective dispersion solution comprising 2,5-di-t-butylhydroquinone and yellow coupler that is ~-l4-(1-benzyl-2-phenyl-3,5-dioxo-1~2,4-triazoli)]-~-pivalyl--2-chloro-5~ (294-di-t-amylphenoxy)butylamide]acetanilide, and the mixture was then coated over the support~ so that the amount of silver coated can be 0.35g per sqO m.
2nd layer: A gelatin solution was added with a protective dispersion solution containing di-t-octylhydroquinone and an ultra-violet ray absorber comprising a mixture of 2-(?'-hydroxy-3',5l-di-t-butylphenyl)benztriazole, 2-(21-hydroxy-5'-t-butylphenyl)benztriazole~
2-(2'-hydroxy-3'-t butyl-5'-methylphenyl)-5-chlorobenztriazole and 2-(2-hydroxy-3',5l-di-t-butylphenyl)-5-chlorobenztriazole, ~ 43 ~

and thus prepared gelatin solution was then coated over the 1st layer, so as to serve as an interlayer.
3rd layer: A silver chlorobromide photographic emulsion containing 15 mol% of silver chloride was optically sensitized, and thus sensitized emulsion was then added with a protective dispersion solution comprising 2,5-di-t-butylhydroquinone, 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman and a magenta coupler that is l-(2,4,6-trichlorophenyl)-3 (2-chloro-5--octadecenylsuccinimide anilino)-5-pyrazolone. Thus prepared solution was co ted over the 2nd layer, so that the amount of silver coated can be 0.4g per sq~ m.
4th layer: The same solution as that used for the 2nd layer was coated to serve as an interlayerO
5th layer: A silver chlorobromide photographic emulsion containing 15 mol~ of silver chloride was optically sensitized with anhydro-2-~3-ethyl-5-(1-ethyl-4(lH)-quinolylidene)-ethylidene-4-oxo-thiazolidine-2-indene]methyl-3-(3-sul~opropylj-benzoxazolium hydroxide, and thus sensitized emulsion was then added with a protectie dispersion solution comprising 2-di-t-butylhydroquinone and a cyan coupler that is 2,4--dichloro-3-methyl-5- r~- ( 2,4-diamylphenoxy)butylamide~pehnol.
Thus prepared solution was coa~ed over the 4th layer, so that the amount of silver coated can be 0.27g per sq. m.
6th layer: A gelatin solution was coated over the 5th layer, so as to serve as a protective layer.

The silver halide photographic emulsions used in each of the abovementioned light-sensitive layers were prepared respectively in the process disclosed in Japanese Patent Examined Publication No. 7772~1971, and they were chemically sensitized by sodium thiosulfate and were then added with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as the stabilizer.
The coating solution for every layer was added with saponin as a coating assistant and bis(vinylsulfonylmethyl)ether as a hardner, respectively.
Thus prepared color pinting paper was exposed stepwise to light by a Sensitometer (Model RS-7, mfd. by Konishiroku Photo Ind. Co., Ltdo~ Japan) and, the color-development, bleach-fixation and washing were carried out so as to obtain seven pieces of samples. These samples were dipped in the solutions having the Recipes (1) through (7) indicated in the following Table-l, respectively, at the temperature of 30C for a minute and were then dried~ so that they were used for the trial samples. The samples were measured on the reflection density in blue, green and red by means of an optical densitometer (Model PDA-65, mfd. by Konishiroku Photo IndO Co.
Ltd., Japan), and were then preserved in a thermo-hygrostat chamber at 70C~ and 75~ RH, for 4n days. Again, these samples were measured on the density thereof so as to obtain the density lowering rate in the areas having approx. 1.5 in the initial density and the yellow-stain density in the unexposed - ~5 -areas by measuring in blue. The results thereof are shown in Table-2.

Table-l .~e-~e ~. ___ ___ ~ __ ___ _ ~ (1) (2) (3) (4) ~5) (6) (7) Che~
l-hydroxy--ethylidene-l,l _ 2 2 2 2 2 2 -diphosphoric acid (q) _ ~ _ Citric acid Sg) 3 _ _ _ _ _ _~_. ~__. __ ,__ _ ___ ~__ * Aqueous solu-tion of ammonia 100 0.1 0.5 5 15 25% (g) _ (mol/~)1.47 O.OOlS 0.007 0.074 0.225 __ ___ ___ __ __ ___

5-chloro-2--methyl-4-_ 0.05 0.05 0.05 0.05 0.05 0.05 -isothiazoline-~__ __ ____. _. _._ __ ~ _ pH value (Adjusted the pH with potas- 7.5 7.5 7.5 7.S 7.5 7.5 7~5 sium hydroxide and sulfuric ~ __ _ _ _ l . Compa rative __ _ _ ExamE les oi the Note Examples Invention note:
* percentage of ammonia in aqueous solution of ammonia ~2~3~3 - 4~ -Table-2 ~ .
\ Result Yellow Rate of Density Lowering S%) Stain Blae Green Red (1~ (Comparative 0.41 12 9 53 ~r~ e~ _ (2) ( n ) 0.35 11 8 48 ~_ .____ (3) ( ~I ) 0.18 13 9 70 (4) (Example of 0.29 11 B 35 ~he l~e~ti~A~ _ _ (5) ( " ) 0~12 11 7 22 ~_ ______ ___ 0 19 10 ~ 15 _ _ _ _ 0.13 11 7 32 From Table-2, it is found that, in contrast with such a case as in Recies ~1) and t2) in which one or two kinds of an organic acid are merely added while no ammonia is added, in the cases of following the Recipes (4) through (7) as in this invention in which a certain amount of aqueous solution of ammonia was added within the range of the amount claimed in this invention to carry out a stabilizing process, a yellow-stain does not increase and a red reflection density is less discolored, that is very effective.

In the recipe (3) of ammonia to be added which is other than that of the invention, it is found that the discoloration rate of red is ex~remely remarkable, that is not preferable, despite its excellently less yellow-stain~

A series of experiments of Recipe Nos~ t8) through (12) shown in Table-3 were tried respectively in the same manner taken in EXAMPLE-1. The results are shown in Table-4.
Table-3 . ___ __ _ ___ ~ ___ (8~ ~9) (10) ~11) (12) (13) (14) ~ ~ ~ __ ___ __ 1 -hyd roxy--~thylidene-l~l 2 2 2 2 2 2 -diphosphoric .~g~e~ tio~ ~ ~ ~ _.
of ammonia _ 4 4 4 4 4 _Z~ ~ ~0.06) (0.06) (0,06) (0.~6) (0.06) (0.06) 5-chloro-2--methyl-4- 0.05 0.05 0.05 0~05 0.05 0.05 0.05 -isothiazoline-~2~L_ _~ __ . __ ~__ benzoic acid 1.5 1.5 1.5 1.5 1.5 1.5 1.5 ~ __ __, __ ~_ ~ _ Antimold (*) 0.3 0.3 0.3 0.3 0.3 0.3 0~3 ~ __ _~ _~ ~ __ __ .
pH value (Adjusted the pH with potas- 7.5 3.5 5O5 602 7.5 9.5 11.5 sium hydroxide and sulfuric --__ ____ ____. __ _ __ Comparative Examples of the Note Examples Invention , ... _ __~
(*) A mixed-emulsified dispersion comprising 15% of butyl paraoxy benzoate, 15% of isobutyl paraoxybenzoate and 20~
of isopropyl paraoxy benzoate was used for the autimold in each case.

~2~3.~3 Table-4 ~ _ _ _ . . ._,. . . .
\ Result Yellow Rate of Density Lowering (%) Recipe No ~ Stain ~lue Green Red ..... , _ =~ ~ ~ .~
(8) (Comparative 0.49 12 9 50 Example) .. ., ~ _ _ __ ( ~ O.l8 11 9 62 (lO)tExample of 0.18 11 8 33 the Invention) _~__~

0.19 11 8 21 ~12~ " ) 0.19 10 8 16 ~_ __ (13)( " ) 0.19 11 8 20 _ ~
0.22 11 9 32 As is obvious from Table-4, in the cases of Recipe Nosg (10) through (13) each having an ammonium salt therein and the desirable values within the allowable range of the invention, the stains and the red reflection density thereof were also desirable~ so that the discoloration caused by keeping the samples for a long time.

A sheet Gf color paper prepared in Example-l was printed picturewise and was then processed in a continuously ~25~
- 4~ -replenisbing process by means oE an automatic processor, ~hereinafter called a running process). The steps of this process and the composition of the processing liquids were as ~ollows;
Basic Processing Steps tl] Color developing 33C 3 min.30 sec.
[2] Bleach-fixing 33C 1 30 [3] Stabilizing 25 - 30C 3 0 [4] Drying 75 - 80C 2 approx.
Composition of the Processing Liquid <Tank color-developing liquid>
Benzylalcohol 15m~
Ethyleneglycol 15m~
Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sul~ate 3.0g Polyphosphoric acid ~TPPS) 2.5g 3-methyl-4-amino-N-ethyl--N-(~-methanesulfonamideethyl)-=aniline sulate 5.5g Optical whitening agent (4,4'-diaminostilbene disulfonate derivative) 1.0g Potassium hydroxide 2.0g Add water to make 1,000 c.c.

<Color-developing replenisher>
Benzyl alcohol 20m~
Ethylene glycol 20m~
Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g 3-methyl~4-amino-N-ethyl- --N~(~-methanesulfonamideethyl)--aniline sulfate 7.09 Optical whitening agent ~4,4/~diaminostilbene disulfonate derivative) 1.5g Potassium hydroxide 3.0g Add watex to make 1,000 c.c.
<Tank bleach-fixing solution>
Iron (II) ammonium ethylenediamine tetraacetate, dihydrate 60g Ethylenediamine tetraacetic acid 3g . Ammonium thiosulfate (70% solution~1001~
Ammonium sulfite ~40~ solution) 27.5mQ
Adjust the pH value with potassium carbonate or glacial acetic acid topH 7.1 Add water to make 1,000 c.c.
<Bleach-fix replenisher A>
Iron (II) ammonium ethylenediamine tetraacetatey dyhydrate 260g Potassium carbonate 42g Add water to make 11000 c.c.

l The pH value of this solutionp~ 6~7 ~ Ool <Bleach-fix replenisher B>
Ammonium thiosulfate (70% solution)500m~
Ammonium sulfite (40% solution)250m~
Ethylenediamine tetraacetate 17g Glacial acetic acid 85m~
Add water to make 1,000 c.c.
The pH value of this solution pH 4.6 + 3O1 A running test was tried in the manner that an automatic developing machine was filled up with the abovementioned tank color-developing solution and tank bleach-fixing solution and the below-mentioned stabilizing solution~ and a sheet of color paper was processed with replenishiny every three minutes the abovementioned color developing replenisher, bleach-fix replenishers A and B and stabilizing replenisher with the use of a quantitative determination cupO Amounts of each solution replenished per sq. meter o color paper were 324m~ to the color developing tank, 25m~ each of bleach-fix replenishers A
and B to the bleach~fixing tank and 150m~ of the below-mentioned stabilizing solution to the stabilizing tank, respectively.
The stabilization processing tanks of the automatic developing machine comprised three stabilizing tanks, No. 1 through 3 in the downstream dir~ction oE a light-sensitive material and adopted a multi-tank counter-current system ln which a replenish~ent was made from the final tank and the over-flow therefrom was introduced into the preceding tank and further the overflow therefrom was then introduced into the second tank before the final tank~
A continuous processing was tried until when the total amount of bleach-fix replenishers A and B used was as much as three times of the capacity of the bleach-fixing tank.
5tabilizing solution l-hydroxyethylidene l,l-diphosphoric acid 2~09 Bismuth chloride (50% aqueous solution containing chloric acid) 0~6g calcium chloride 0.4g 5 chloro-2-methyl-4-isothiazoline--3-one 0.05g 2-octyl-4-isothiazoline-3-one 0~05g Orthophenyl phenol 0.04g Aqueous solution of ammonia (25~) 5.0g Add water to make 1,000 c.c.

Adjust the pH value with sulfuric acid and potassium hydroxide to pH 7.5 After continuously processing, a sheet of color paper prepared in Example-l was made for a sample by expos.ing it stepwise to light. The pH values each of the stabilizing baths No. 1 to 3 were changed respectively as shown in Table-5~ The 3~3 adjustments of the pH values thereof were made with potassium hydroxide and sulfuric acid.
Next, the samples were processed with each stabilizing solution. After then, the stabilizing solutions were thrown away and were replaced by city water to process the other samples. Each of the samples was applied to a torture test for an image preservability in the same manner as taken in Example-l, The results thereof are shown in Table~5. The reflectivity of the stained portions produced in unexposed areas were meansured by 445~m immediately after the samples were processed, and the bluing phenomena produced in the darkened areas (i.e. a Dmax) were visually observed by eye under the sunlightO The results thereof are also shown in Table-5.

Table-5 rle~ ~le T~se pH value ~ _ _ Rec- of Ref- Visual Yellow- Discolor-ipe Stabiliz- lec- Bluing Stain ation Rate No. ing tive of Red Solution of Reflection Stain Density ___ _ ___ _ ~ ~, Compa- almost 14 rative Washing 80 invis- 0.42 45 Exam- ible ple _ _~ ~ . _ _ ~ ___ 15 .- 3.8 72 Strong 0~18 52 __ _~ ____ __ ~
Exam~ almost ple of invis 16 the 5.5 78 ible 0~18 29 tnivOnn-__~ _.~ ~_ invis-17 ,. 7.5 81 balle at 0.18 16 _____ __ ~
8 ,, 8.5 80 ., 0.l9 l8 As is obvious from Table-5, in Recipe NOSL (16) through (18) each using the stabilizing solution of the invention, it is found that the red density discoloration was extremely small without any yellow stain caused by adhering fresh sensitizing dyes to the sample and not only any bluing caused by adhering a whitening agent thereto but also any yellow stain caused by 3~

preserving the sample for a long time~ that is preferable.

The Exemplified cyan couplers ~7), (11), (22), t45) and ~53) and 6g of cyan coupler used in the undermentioned couplers (a), (b) and tc) were mixed with 3g of dibutyl phthalate i.e., a high boiling organic solvent, and 18g of ethyl acetate and if necessary some amount of dimethyl formaldehyde as needed to prepare the mixture solution~ and the mixture was heatedly dissolved at 60C and then was mixed again with lOOm~ of 5%
aqueous gelatin solution containing lOmQ of 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, mfd. by Du Pont) and was then emulsified and dispersed by an ultrasonic dispersing means to prepare a dispersed solution.
Next, the dispersion solution was added to a silver chlorobromide emulsion containing 10 mol% of silver chloride so that the amount of cyan couplers shown in Table-1 could be 10 mol% to the silver, and 1,2 bis(vinyl sulfonyl) ethane was further added to serve as a hardner in the proportion o~ 12mg to lg of gelatin~ and thus prepared mixture was coated over a polyethylene-coated paper-support so that the amount of silver coated could be 5mg~100cm . The color paper sample thus obtained was exposed wedgewise to light with setting an interference filter of 700~m in an ordinary manner, and the p~
values of the running-processed stabili~ing solutions of Example-3 stored in Tank Nos. 1 to 3 were adjusted to pH 3O5 ~ 3 and 7~5 by making use of potassium hydroxide and sul~uric acid and the sample was processd in the process taken in Example-3 and with the processing solution used therein. After measuring the areas of ~he sample where the red reflection density was about 1.0, it was allowed to stand under the sunlight for 250 hours. Then, the described areas were measured again to obtain the discoloration rate of the cyan dyes. The result~ thereof are shown in Table-6.
The following couplers were used for the purpose of comparison;
Coupler ~a) ~ CONH(CH2)4O ~ tC5H

Coupler ~b?
OH

~ CONHC12H25 Coupler (c) OH

[~,C ONI:C 1 2H 2 5 Table-5 _ _ _ ~ ....... ....
Cyan ~
CouplerpH 3.5 ~Comparison) pH 7.5 ~Invention) _ __~

~a) 45 37 _ ~
(b~ 42 36 ~c) ~

(7) 25 11 __ ~_ (11~ 24 10 (22 (45) ~7 1 _ ~
(33~ ~ _ ____ As is obvious from Table-6, the couplers (7), (11), (22), (45) and (53) showed a great reduction in the photodiscoloration when using the recipe for the stabilizing solution of the invention.
Effects of the Invention As is obvious from the abovementioned examples~ this invention may be able to display the effects that a light or dark discoloration as well as a bluing phenomenon can also be .''3 prevented, and in particular, a color dye image finishing is not affected at all even in a stabilizing process in which the amount of washing water is reduced or is eliminated.

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A method for color processing of a silver halide color photographic light-sensitive material wherein said material is processed after a fixing or bleach-fixing step with a stabilizing solution whose pH value is not lower than 5 and to which 0.001 to 1 mol/? of an ammonium compound is added.

2. A method according to claim 1, wherein said color process comprises a developing step, a bleach-fixing step and a stabilizing step.

3. A method according to claim 1, wherein said color process comprises a developing step, a bleaching step, a fixing step and a stabilizing step.

4. A method according to claim 1, wherein said step of processing with said stabilizing solution follows directly a bleach-fixing step or a fixing step.

5. A method according to claim 1, 2 or 3, wherein said method does not substantially comprise a washing step.

6. A method according to claim 1, wherein said pH value is 5 to 10.

7. A method according to claim 1, wherein said ammonium compound is a compound capable of releasing an ammonium ion in an aqueous solution.

8. A method according to claim 7, wherein said ammonium compound is an aqueous solution of ammonia, an ammonium salt of an inorganic acid, an ammonium salt of an organic acid or an ammonia-metal complex.

9. A method according to claim 1, wherein said material comprises cyan coupler represented by the following formula (I) or (II):
Formula (I) Formula (II) wherein, X is a radical having the formula of -COR2, -SO2R2, , -CONHCOR2, or -CONHSO2R2 wherein R2 represents an alkyl radical, an alkenyl, an aryl radical or a heterocyclic radical and R3 represents a hydrogen atom or the same radical as defined by R2; Z
represents a hydrogen atom or a radical capable of splitting off in a coupling reaction with an oxidized product of a color developing agent; and R1 represents a ballast radical.

10. A method according to claim 9 wherein R2 represents an alkyl radical having 1 to 12 carbon atoms, an alkenyl radical having 2 to 20 carbon atoms, a cycloalkyl radical of 5 to 7 member ring, a phenyl radical, a naphthyl radical or a heterocyclic radical of 5 to 6 member ring having a nitrogen atom, an oxygen atom or a sulfur atom.

11. A method according to claim 9, wherein said ballast represented by Z has the following formula:

wherein J represents an oxygen atom, a sulfur atom or a sulfonyl radical; k is an integer of 0 to 4; ? is or or 1; R7 represents a straight-chain or a branched-chain alkylene radical having 1 to 20 carbon atoms; and R8 represents a monovalent radical.