CA1247437A - Method of processing silver halide color photographic materials - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method of processing a silver halide color photo graphic material is disclosed. The material is treated with a bleach-fixing solution or a fixing solution, and then, without washing with water, treated with a stabilizing solution incorporating a water-soluble chelate compound of at least one metal selected from the group consisting of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn, Zn and Zr and the group consisting of Mg, Al and Sr.

Description

'7 METHOD OF PROCESSING SILVER MALIDR
COLOR PHOTOGRAPMIC MATERIALS

BACKGROUND OF THE INVENTION
1. Field of the Invention S The present invention relates -to a method oE processing a silver halide color pho-tographic material (her~under referred to as a pho-tographic rnaterial), and more particula~ly, to a stabilizing process that involves no step of washiny with water ~ubsequent to a desilvering Rtep.

2. Description of the Prior Art Photofinishers capable of automatic and continuous development of photographic materials are in current use.
However, in order to prevent water pollution while at the same time saving valuable water resources, it is desired to reduce or eliminate the use of water in the washing step that follows the treatmént with a fixing solution or a bleach-fixing solution. Therefore, several methods have been proposed for stabilizing the fixed or bleach-fixed photographic material without washing it with water.
Japanese Patent Applications (OPI) Nos. 8542/82, 132146/82, 14834/82 and 18631/83 (the symbol OPI as used herein means an unexamined published Japanese patent application) show the use of stabilizing solutions containing isothiazoline derivatives, benzisothiazoline derivatives, polyaminocarboxylic acid soluble iron complex salts or organophosphonic acids.
However, these techniques are not highly effective in preventing the deterioration of an image, especially an incr~ased yellow stain in the uncolored area, due to the fixing or bleach-fixing component that is carried over into the stab.ilizing solution by the photoyraphic mate.rial in an amount that increases as l:he image storage time is extended. In particular, if an organic acid iron (III) complex salt used as a bleaching ayent i9 left in -the stabili2ing solutlon, the dye image may be sufficiently protacted from discoloration but is subject to appreciable yellow staining. This is particularly true if a relatively small amount of make-up stabilizer is used. Furthermore, the increase in the fixing component and the soluble silver complex salt in the stabilizing solution has been found to decrease the light stability of a cyan dye (i.e. the re~
sistance to light discoloration).

SUMMARY OF THE INVENTION
Therefore, one object of the present invention is to provide a method of processing a photographic material in which the amount of a make-up stabilizer for the stabiliz-ing solution used in the stabilizing step is significantly reduced.
Another object of the present invention is to provide a method of processing a photographic material with a stabi-lizing solution of improved time-dependent stability, wherein a thiosulfate or its soluble silver complex salt that is carried over into the stabilizing solution from the preceding bath experiences less decomposition into silver sulfide.
r~hese and other objects of the present invention will become apparent by reading the following descrip-tion.

1;~ 7 ~ ccord.ing -to the method of the present inventi.on, a photographic material that has been treated with a bleach-fixing solu-tion or a fixiny solution is immediately (without washing with water) treated wi-th a s-tabilizing solu-tion incorporating a water-soluble chelate compound of at least one metal selecte~ either rom the group consisting oE Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, 'Lli, Sn, Zn and Zr, or from the group consistin~J o Mg, Al and Sr.
DE'rAILED DESCRIPTION_OF THE INVENTION
The water-soluble chelate compound as incorporated in the stabill~ing solution of the present invention is such that the.ion of one of the metals listed above reacts with a chelating agent to form a water-soluble complex salt.
Preferred chelating compounds are selected from among those which have the following formulas tI) to (VIII~.

m m 3m (I) (M: hydroyen, alkali metal or ammonium; m: an integer of 3 - 6);
n+2 n 3n~ (II) (n: an integer of 2 - 20);

A - Rl - Z - R2 ~ COOH (III) - N - D - N \ (IV) whcrein D is a substituted or unsubstituted alkylene yroup, c~ycloalkylene group, phenylene group, -R70R7-,-R70R70R7~ or -R7ZR7-(wherein Z is >N-R7-A6 or >N-A6; R7 is a substituted or unsubstituted alkylene yroup; and A6 is hydrogen, -OH, -COOM, or -P03M2, M being a hydrogen atom, an alkali metal atom or ammonium); Rl -to R6 are each the same as R7; and Al to A5 are each the same as A6;

~8N(cH2po3~2)2 (V) wherei.n R8 is a lower alkyl group, aryl group, aralkyl group, nitroqen-containing 6-membered cyclic group (which may be substituted by -OH, OR or -COOM~; M is a hydrogen atom, alkali metal atom or ammonium;

I llO lll Rg-~ C )n ~ P03M2 (VI) ~1 B2 B3 wherein Rg to Rll are each a hydrogen atom, -OH, or a lower alkyl group (either unsubstituted or substituted by -0~, -COOM or -P03M2~; Bl to B3 are each a hydrogen atom, -OH, -COOM, -P03M2 or -NJ2 (J is a hydrogen atom, a lower alkyl, C2H40H or -P03M2); M is a hydrogen atom, alkali metal or ammonium; m and n are each O or l;

OM

R12-~0 ~ ~ o 13 (VII) whcreLn R12 and R13 are each A hydrogen atom, an alkali metal, ammonium, an alkyl group haviny 1 to 12 carbon akoms, an alkenyl group or a cyclic alkyl group;

O
R14 - P - O - P - Q3 ~VIII) Ql Q2 wherein R14 is an alkyL group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carhon atoms, a monoalkylamino L0 group having 1 to 12 carbon atoms, a dialkylamino yroup having 2 to 12 carbon atoms, an amino yroup, an aryloxy group having 1 to 24 carbon atoms, an arylamino group having 6 -to 24 carbon atoms, or an amyloxy group; Ql ko ~3 each represents -OH, an alkoxy group having 1 to 24 carbon atoms, an aralkyloxy group, aryloxy group, -OM3 lM is a cation), amino group, morpholino group, eyelic amino group, alkylamino group, dialkylamino group, arylamino group or alkyloxy group.
Chelate compounds other than those represented by the formulas (I) to (VIII) may also ~e used, and they include 1-2-dihydroxybenzene-3,5-di6ulfonic acid and glycine.
However, these compounds are not as effective as the compounds of formulas (I) to (VIII).
Specific examples of the compounds of -the formulas (I) to (VIIT) are listed below.

(1) Na4P4O12 ( ) N 3 3 9 r~ r~

(3) ~14P27 (D,) H5P30lo 5 3 Na6P4013 NaOOCCM2\ /` CH2CH
( 6 ) ) NCH ClI N
HOOCCH2 / C112COON~

HOOCCH 2 \ / CH 2 COOH
( 7 ) ~ NCH 2CH 21l CH 2CH 2N

(~) HN < (9) H-N ~
\ CH2COOH 2 4 ~ CH2COOH / CH2COOH
(10) CH3N ~ (11) HOC2H4N ~

(12) N ~CH2COOH

3'~

(13) ~
( CH2COOlH

CH2COO'H

EIOOCCH2 \ fE13 / CE~I COOH
(:L~ 11 CH2CH N
HOOCCE12 / \ CH2COOH

(1~) (HC2H4) 2NCH2CH

HOOCCH2 \ / C~12CH
(16) ~ NC2H40C2H40c2H4 HOOCCH;2 / CH2COOH

HOOCCH2 \ / CH2COOH
(17) > NC2H40C2H4N ~
HOOCCH2 / \ CH2COOH

HOOCCH2CH2 \ / CH2CH2COOH
(18) ~ IIC2H4N ~
~.[OOCCH2CH2 / \ CH2CH2COOH

~ CH2CH

(19) ~/ \ C~12COOH
~\ ~ CH2COOI
CH 2 COO~I

MOOCCH2 \ / CH2C'OOH
(20) ) NC2H~N ~
HOOCCH2/\ (~H2CH

f'OOCCH2Cl-12COO ~3 (21) ~ NC2H~N ~ ¦ 3 ~11NCE13 ~OOCCH2 /\ CH2cooHJ

NaOOCCH2 \ / CH2COONa (22) ) NC2H4NC2H4N ~
WaOOCCH2 / CH2CooNa CH2COONa 2 3 ) l 3H2 ( 2 ~ ) IPO3H2 (25)P13H2 126)P13H2 HO - C - H HO - C - COOH
HOOC - C - H H - C - COOH

13'~

(27) P13H2 ~28) CH~COOH
}IC ~ COOH CH - COOH
HC - COOEI CH - COOEI

~2g) CH2COONa (30) CH2 - COOH

C113 ~ C - COONa CH - COOH
P03N~2 CEI2 ~ P3H2 ~31) CH2COOH (32) CH2COOH

HOOccH2C - COOH CH3 - IC ~ P3H2 (33) CH2COOH (34) CH2COOH

~35) CH2COOH ~36) CH2COOH

H3C - C - COOH ¦ ~ P3H2 ~37) CH2COOH (38) CH2 - COOH

HOOCC2H4 - C - COOH CH ~

( 3 9 ) CH2 COOH ( 4 0 ) CHi! COOH
CHCH2 COOH l H2 CHP03}~2 C2H5 - lC - P3H2 P.3~12 P3H2 (41) CH2 - COOH (42) CH2COOH
CH - C2H5 Cl HCH3 HOOC -- C - COOH CH - COOH

(43) CH2COOH (44) ~CH2P03H2 CE~COOH N ~CH~P03H2 C4Hg - C - COOH CH2P03H2 ~45) CH2COOH (46) N ~
N ~CH2P3H2 ~ \ CH2P03H2 l~ 'Y

4 7 ) / CE12P03H2 ( 4 ~ ) / CH2P03H2 N ~ N ~
/ \CH2P03E~2 ~ ~ ~ / \CH2P03H2 ~\ ~CH2COOH ~

(~9) C3H7 N ~

H203PCH2 \ / CH2P03H2 ~ N CH2CH CH2N ~

(51) t52) CH3 CH2P03H2 H203p - I - P3H2 (53) CE12PO3H2 (54~ CIH20H
H203p - Cl-PO3H2 H203p - C - P3H2 OH OH

'7~3~

~55)OH (56) CIH2PO3H2 H2O3P - 1 ~ P3H2 CH - COOH

(57)CH2 - COOH t5~) H
p - I ~ P3H2 ~IOC~C - C - P03H2 N

(59)OH
H203p - Cl - P3H2 /N\

(60) O
HOCH2CH (OH~ -CH2O-P- (ONa) 2 (61) O
HOCH2CH2O-P (OH) 2 '74~

~62) O
HOCH2CIl-O-P- (ONa) (63) O
HOCH 2C-CH 2 -0-P~ H ) 2 (6~ . O
HO-CH2-CH-CH2-O-P- (OH) 2 OH

(6S) HOCH2 \ il ~ CH - O - P - ONa HocH2 / ONa (66) O
HOOC-CH-CH2-O-P- (OH) 2 (67) O
H2C = C - O - P -- (OK) 2 COOX

~6~) O
El3C - CH - O - P (OH) 2 COOH

(69) O
~2N-C~2c~2-O-p- (OEI) 2 (70) O
~ 11 o N-CEl2cH2-O-P- (~) 2 (71) O
H2N-COO-P- (~) 2 (72) O
H3C--COO-P- (OH) 2 (73) O
Il O
NaO - P - OCH2 ll ONa ¦ CH20P - ONa ~/HH\l ONa Wb~
OH OH

1~'7q,~
(7'1 ) O O
Il ~ 11 (HO) 2-P-CH2CH2-N~ ~N-CH2CH2-P- (O~I) 2 (75) O CH3 O
H2cH2NHc-cHoHl-c-c~l2o-p (OH) 2 (76) 1l CH O-P-O-CH CH~CH

OK OH

(77) O
Il OH

~78) O O
Il 11 C6H5O-PI-O-P (OII) 2 OH

(79) O O
Il 11 C6H5CH2-0-PI-o- I OCE~2C6 5 ONa ONa ~80) O O
Il 11 C6~150~ 0- IP-O C6~5 OH OH

( 81) 0 CH O
Il I 3 11 HO - P - C - P - OH
OEI Oll OH
.

(8~) I C1~2C~3 0 HO P - C P - OH
OH OH OH

(83) O O
Il 11 HO ~ P - CH -- P - OH
. 1 OH OH OH

(~4) 0 0 Il 11 (85~ 0 0 Il 11 OH OH

-- 1~ --o o (C6H5COO)2-P-O-p-(ococ6~l5)2 (87) O O
[(CH3)2N]2-P-O~p[N(cH3)2]2 Chelating agents of the formula (VI) are more efEect-lve than tho~e of the other formulas, and of the compounds o~ formula (VI), Compound No. 81 gives the be~t results.
Chelating agents of formula (I) to (VIII) may be used either alone or in combination with themselves or with a compound of one formula may be combined with a compound of another formula.
The water-soluble chelate compound of at least one metal selected from the group consisting of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn, Zn and Zr may be used in an amount of 1 x 10 to 1 x 10 1 mol per liter of the stabilizing solution. The preferred amount ranges from 4 x 10 to 2 x 10 mol per liter of the stabilizing solution. A particularly preferred range is from 8 x 10 to 1 x 10 mol per liter of the stabilizing solution.
The water-soluble chelate compound of at least one metal selcct~d E.rom thc group consistiny of Mg, Al and Sr rnay be u~ed .in an amount generally rancJing Erom 1 x 10 to 3.5 x 10 mol, preferably from 5 x 10- to 3 x 10- mol, more preferably from 1 x 10 to 2 x 10 mol, per liter of the stabilizing bath. If les~ than 1 x 10 mol of the chelate compound is used per li.ter of the stabilizing bath, the intended ob~ects of the present inven-tion cannot be attained. If more than 3.5 x 10 mol o the chela-te compound is used per li-ter of the s-tabilizing bath, tiny crystal grains may form on the surEace of an emulsion l.ayer dryiny, or the image may undergo yellow staining.
Pre:Eerred metallic ions that should be selected from the first group of metals are Ba, Ca, Sn, Zn and Zr ions.

A preferred metallic ion that should be selected from the second group of metals is a Mg ion. Two or more metals may of course be used in the present invention.
Compounds which are the same as the chelate compounds that are to be deliberately incorporated in the stabil.izing solution may naturally occur in the water used to make the stabilizing solution, but their content is so small that such naturally occurring compounds are not all effective in attaining the objects of the present invention.
The wa-ter-soluble chelate compound according to the present invention may be incorporated in the stabilizing solution by one of the following two methods: a metal salt or metallic lon and a chelating agent are separately added to the stabilizing solution; or said compound may be added in the form of a metal chelating compound. The lat-ter method 1 ~f~

i~; preEerr~d.
The amount of the chelating agent as against the metal is not critical in -the present invention so long as the metallic ion does not form a precipitate (e.g. hydroxide) in the stabili~ing solution. ThP chelating agent is preferably used in a more-than-~equirnolar amount.
When a cyan coupler of the ~ollowing Eormula (C I) or ~C-II) is incorporated in the silver halide photographic material o the present inventlon, an additional advantage results in tha-t the cyan dye produced by coLor development has an improved resistance to :Liyht.

OH
~ NHX (C-I) R CONH

.

OH
~ NHCORl (C-II) XNH ~

wherein X is -COR2, -COId \ ~ S2R2' ll \ , -SO2N /

-SO2NHCOId\ , -CONHCOR2 or -CONHSO2R2 (wherein R2 is an alkyl group, alkenyl group, cycloalkyl group, aryl group or a hetero ring; R3 is a hydrogen atom, an alkyl group, alkenyl ~roup, cycloallcyl group, aryl group or a he-tero ring, provided that ~2 and R3 may combine to form a 5- or 6-membered riny);
Rl is a ballast group; Z is a hyclrogen atom or a group -that is capable of leaving upon coupling with the oxidized product of an aromatic primary aminecolor developing agent.
The group R2 in X oE formula (C-I) or ~C-II) is an alkyl group (preferably an alkyl group having 1 to 20 c~rbon atoms, such as methyl, ethyl, t-butyl or dodecyl), an alkenyl group (pre~erably an alkenyl group having 2 to 20 carbon atoms, such as acyl or oleyl), a cycloalkyl group (preferably a

5- to 7-membered ring such as cyclohexyl), an aryl group (e.g. phenyl, tolyl or naphthyl), or a hetero cyclic group (preferably a 5- or 6-membered hetero ring having 1 to 4 nltrogen, oxygen or sulfur atoms, such as a furyl group, thienyl group or benzothiazolyl group). The symbol R3 is either a hydrogen atom or the same as R2, provided that R2 and R3 may combine to form a nitrogen-containing 5- ox

6-membered hetero ring. The groups R2 and R3 may be unsub-stituted or substituted. Illustrative substituents are an alkyl group having 1 to 10 carbon atoms (e~g. e-thyl, i-propyl, i-butyl, t-butyl or t-octyl), an aryl group (e.g. phenyl or naphthyl), a halogen atom (e.g. F, CQ or Br), a cyano group, nitro group, sulfonamido group (e.g. methanesulfonamide, butanesulfonamide or p-toluenesulfonamide), a sulfamoyl yroup (e.g methylsulfamoyl or phenylsulfamoyl), a sulfonyl group (e.g. methanesulfonyl or p-toluenesulfonyl), a fluorosulfonyl group, a carbamoyl group (e.g. dimethylcarbamoyl or phenylcarbamoyl), an oxycarbonyl group (e.g. ethoxycarbonyl

7~

or ph~nox~carbonyl), an acyl yroup (e.g. acetyl or benzoyl), a heterocyclic group (e.g. pyridyl or pyrazolyl group) an alkoxy group, an aryloxy group or an acyloxy group.
The group Rl in -the formulas (C-I) and (C-II) represents a ballast group that imparts anti-dif~using property to the cyan coupler of formula (C-I) or (C-II), as well as the cyan dye formed from such coupler. Pre~erred ballast groups are an alkyl group having 4 to 30 carbon atoms, an aryl group and a heterocyclic group. More speci~ically, a straight-chaln or branched alkyl group (e.g. t-butyl, n-octyl, t-oatyl or n-dodecyl), an alkenyl group, a cycloalkyl group and a 5- or 6-membered heterocyclic group.
The symbol Z in the formulas (C-I) and (C-II) represents a hydrogen atom or a group that is capable of leaving upon coupling with the oxidized product of an aromatic primary amine color developing agent. Examples of such leaving group include a halogen atom (e.g. Cl, Br or F atom), as well as an aryloxy group, carbamoyloxy group, a carbamoyl-methoxy group, acyloxy group, sulfonamido group or succinimido group having an oxygen or nitrogen atom directly bonded to a coupling site. More specific examples are shown in U~S.
Patent No. 3,741,563, Japanese Patent Application (OPI) No.
37425/72, Japanese Patent Publication No. 36894/73, Japanese Patent Applications (OPI) Nos. 10135/75, 117422/75, 130441/75, 10~841/76, 120334/75, 18315/77, 105226/7~, 14736/79, 48237/7~, 32071/80, 65957/80, 1938/81, 12643/81 and 27147/81.
Particularly preferred cyan couplers are those having the following formulas (XIV), (XV) and (XVI).

0~1 NHCON~IR~ ~XIV) RlCONH

0~

l ll (XV) RlCONH f~
z OH
HcoRl ~ (XVI) In the formula (XIV), R~ represents a substituted or unsubstituted aryl group (prefera~ly a ph~nyl group).
The aryl group may be substituted by at least one member selected from among -SO2R6, halogen atom (e.g. Cl, Br or F), CF -NO , -CN, -COR6, -COOR6; SO2 6~ e ~ R7 R7 ~COR6 \SO2~6 P \ OR ~ wherein R is an alkyl group (pre~erably an alkyl having 1 to 20 carbon atoms, such as methyl, ethyl, tertbutyl or dodecyl~, an alkenyl group (prefPrably an alkenyl group having 2 to 20 carbon atoms, such as acyl or oleyl), a cycloalkyl group (preferably a 5-to 7-membered ring such as cyclohexyl group~, or an aryl group (e.g. phenyl, tolyl or naphthyl), and R7 is a hydrogen atom or the same as R6.

Pre.err~d phenolic cyan coupl~r~ of the formula ~XIV) are such that R~ is an unsubstituted phenyl group or a phenyl group substituted by cyano, nitro, -SO2R6 (R6 being an alkyl group), halogen atom or trifluoromethyl, In the formulas (XV) and ¦XVI), R5 represents an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, tert-hutyl or dodecyl), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, such as acyl or oleyl), a cycloalkyl group (pre~erably a 5- to 7-membered ring such as cyclohexyl), an aryl group (e.g. phenyl, tolyl or naphthyl), or a heterocyclic group ~prefe.rably a 5- or 6-membered hetero ring having 1 to 4 nltrogen, oxygen or sulfur atoms, such as furyl, thienyl or benzothiazolyl group).
The groups R6 and R7 in formula (XIV) and R5 in formulas (XV) and (XVI) may be substituted by any of the groups that are listed as substituents which can be introduced into R2 or R3 in formulas (C-I) and (C II). A particularly preferred substituent is a halogen atom (e.g. Cl or F atom).
The symbols Z and Rl in the formulas (XIV), (XV) and (XVI) have the same meanings as defined for the formulas (C-I) and (C-II). A preferred example of the ballast group as Rl is represented by formula (XVII):

~ J - R7~-Q (XVII) ( R3 ) k wherein J is an oxygen atom, sulfur atom or a sulfonyl group;

k 1~ ~n lnteCJer Oe o to 4; Q 1~ 0 or l; when k is 2 or more, ~8 may be the same or different; R7 is a straight-chain ox branch~d alkylene group having l to 20 carbon atoms, or an alkylene group substituted by an aryl group or the like;
R~ is a monovalent group such as a hydrogen atom, a halogen atom (preferably Cl or Br), an alkyl group (preferably a straight-chain or branched alkyl group having l to 20 carbon atoms, such as methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl or phenetyl), an aryl group (e.g phenyl), a heterocyclic group (preferably a nitrogen-containing heterocyclic group), an alkoxy group (preferably a straight-chain or branched alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, t-butyloxy, octyloxy, dec~loxy or dodecyloxy), an aryloxy group (e.g. phenoxy), a hydroxy-acyloxy group (preferably an alkylcarbonyloxy group or anarylcarbonyloxy group such as acetoxybenzoyloxy), a carboxy-alkyloxycarbonyl group (preferably a straight-chain or branched alkyloxycarbonyl group having l to 20 carbon atoms), an aryloxycarbonyl group (preferably phenoxycarbonyl), an alkylthio group (preferably having 1 to 20 carbon atoms), an acyl group (preferably a straight-chain or branched alkylcarbonyl group having 1 to 20 carbon atoms), an acylamino group (preferably a straight-chain or branched alkylcarboamido having 1 to 20 carbon atoms or a benzenecarboamido), a sulfonamido group (preferably a straight-chain or branched alkylsulfonamido group having 1 to 20 carbon atoms or a benzenesulfonamido group), a carbamoyl group (preferably a straight-chain or branched alkylaminocarbonyl group or lL'7~.3'~

havlny 1 to 20 carhon atoms, or a phenyl aminocarbonyL
grollp), or a sulfamoyl group (preferahly a s-traight-chain or branched alkylaminosulfonyl group having 1 to 20 carbon atoms, or a phenylaminosulfonyl group).
Specific examples of the cyan couplers that can be used in the present invention are li.sted below.

()H
( C - 1 ) asHIl t ,[~,NH~ONH--<~CN

t 0 5 H ~ O OHOONH
O,~Hg ! c - 2 ) (~4H~,t ,~NHUoNH~30N

t a ~ ~1 9 {~-o--OHOON~ ooH !~

I C ~ 3 ) C)H
15 H 3~ NHOOMH~
~O-~HCONH Jq~
O~I5 ( C - 4 ) O~

~lr NHaONH~
HO~O--CHCONH
C ,, H 9 ~ 12E~ 25 OH
( c - 5 ) ~ NHCONHC 15 H 3 Ho~30- IHOONH ~

a4Hg t C12 25 ( c - 6 ) O~I
05H,l t ~NH~ONH~a tOsH11~O--CIlCONH'~ o~
OzH5 t C - 7 ) O.H
a ~j H 11 t ,~3~N~IOON~9O2a,,H9 tO5f~ ~O~ HC~ON~I
I
a2Hs I C - 8 ) OH
~, NHOONH~ON
2 H 25 ~O--CHCON~ NO 2 ~ I .
aH3 ~, NHCOI~H ~ CN

HO~O-OHOONH
C4Hg t a4H9 OCH2OOOa2H5 ( c - 10 ) G~H9 t ~IIHCONH~SO~C2H5 t C 4 H g ~ O- CHCONH . CN
C l2H25 '7~

( C ~ IHCIONH~CIL

n O ~ H ~ S 0 2 NH4~o-aHao~H CN
~=/ I
~H3 C - 12 ) ~NHOONH~7 ~OH3 ) ~OOC)O-~O-OHCON ~
I I ~OOOH3 al2H2S
Oa~2(:loN~laH2oH2oaHs OH ~'3 ( C 13 ) I
a 4H9 t ~NHCONH~
, a 4 ~ 9 ~O - CHCONH~ NO 2 al2H25 NHS2~aH3 ( C - 14 ) a 5 H 11 t ~ NHCONH~
t C 5 H ll ~O--( aH2 ) s CC)NHJ~

S 021 IHO,,H9 0~
C - 15 ) ~,NHCoNH ~37 o-oH 2 CONH~J CF 3/
/=/ /
nC l2H25 NHOO
COC2~]5 C - 1 6 ) O~I C~-l 3 0 5 H " t ~Nf-lOONH~
ta5~ o-a~lcoNH I a~l3 O ,, H 9 C .~

c ~ 17 ) c~ NHOONH~3O(~ 3 t a 5 H 1~ ~0-OHC30NH ~
O ,2 H 25 O OH 2 aooH

OH
( C - 18 ) ,~NHCONH~
~3-o--aHaONH
2~ a2H5 a~

( C - 19 ) OH
C 12 H25 ,~NHCONH
t C 5 H 11 ~O-aHCONH
Cb ~sHll t ( C - 20 ) OH
C 12~25 ,~NHCONH~SO2CH3 t C 5 H 11 ~O-CHCONH

C 5 ~

C - 21 ) ,~NH O ON.H~ S 0~, C2Hs t O 4 ~1 9 ~;3so 2 OHC~ONH
o~30C~H5 C - 22 ) OH
asHl, t ~NHaoNH~3so2a3H7 , a ~ H " ~O-OHOONH~
[~3 a~

( c - 23 ) C4~1~ t O~l aH~ ~NHaONH~SO206HI3 tC4Hg~O-0-CONH~

( C - 24 ) ~3~
~NHOONH-~3SOC" H5 ~0 -CHCONH~J
>=~/ I C' c ,5H3l a2~s ( c - 25 ) OH 11 ~OCH3 ~3,NflCONH~P~

C12H250~30-OHCONH
CzH5 C~

- 3û -C - 26 ) OH
~, N~ICONH4/~C
o,2~l25o~30--CHaON~J~ a ~
02H 5 OCON (CH3 ) 2 ( c - 27 ) OH
G5HIl t ~rNHOONH~C

t05H,I ~ 0--OHaONH ~ (:~

- 2~ ) I
~NHSO2NHO,~Hg 0 41~ 9 S 0 2 NH430--CHOONH~
Cl2H2s OH
( c - 29 ) ~,NHSO2NHCO~7 n a~H25O~3So2NH-~coNH~ G/3 OH
c - 3Q ) ~,~HCoNHCo~3So2CH,~

t a 4 H 9 ~3 S C~la ONH
C~2H2s ,7~

F F

,~NHI~ ONHS x~ ~@
n C,2H.,sO~00~1801`1H F F
C2Hs OH ~Hs ~3 CO NH~ S 0 2 CJF 3 alCH3300 F
o OH
~,NHCON O
( c - 33 ) ~3OCHOONH~
04HgSO2NH Cl2H25 - 34 ) CsHll t ~N~OON=O(cH3)2 t a 5 H 11 ~0--( OH 2 ) 3--OONH~

OH
C - 3 5 ) ~b-NHCN~3CF 3 a4Hg SOzNH~CONH~ S
C~

( C - 36 ) OH
~, NH CO--C~ICH ~ S 0 2 C ~ ~125 t O ,IH 9 NHCI~lH I CH 3 S 0~

( C ~ 37 ) O~l asHll t ~,NHaOaHO~c3Hll t C)2~-1G SO2 -~NHOI:)NH a4H~
I

( C - 38 ) OH
ao~col~Ha 12 HZ5 ~GH ~ NHCONH ~
N--N
N--N

(C-39) OH
C2H5 ~ ~ NHCOaH2o ~ 3 0C~ s NaONH
C2~s C

OH
( C - 40 ) C5H" t ,~fNHCO-C3F7 sHll ~O-CHCONH~
i C ~Hg ( c - 41 ) OH F F
O ~ H ~ t ,[~I`;lHOO~ F
tC,,Hg~O--aHCO~H F F
~=/ I
a4fIg F

c - 4 2 ) OH

H()4~o- CHOONH
>==/ I
ta~H9 ClZH25 ( C - 43 ) OH
~,NHCO (cF2)2 C 12 H25 o~30-C2~s :)H
( C - 44 )C5HI, t ~rNHCO~OCE~zCHE~C~
t C 5H 11 ~O-CHCONH OCF 2 CHFC

OH
1 C - 45 ~O Hg ~NHCO (cF2cF2)~
t ~ 5 H 11 ~0--CHCONH
a5Hll ~

C - '1 6 ) O~
~NHaO (a~
a l2H25 ~30-c~laoN~lJ~J
F

~1 ( C - ~ 7 ) ~ NH(~O~3 O ~ H 9 S 0 2 NH~3-o--OHOONH ' I
~1 ( C - 48 ) OH
,~, N~ICO~

a~
NHSO 2 ~H 3 ( C - 49 ) Cl5Hll t ~,NHCo~3 t a sH ~1 ~O-CHCONH NHS O 2 CH ~
{ 2~H5 OH
C - 50 ~ ~NHSO2 CH3 H3O(CH2) lo(~

3~;' ( C - 51 ) OH
,~NHCO ( ClH2 ) 1~ OH 3 Ho~3so 2 NH~

OH
( C - 52 ) ,~NHOO~

H3a~aH2),2-OH=aHCH~CHCONH' ~3 CH2 COOE~[

C 12 H 2; t~NH
~--O--CHOONH ~b~J
G,,H9SO2NH ~
OH
l2H25 r~NH(:~0~ 3 F
1 C - 54 ) ~ O--GHCONH
C~
S02N~
(C~12)20~2~5 ( C - 55 ) OH
,~NHCo~3 ~30 -OHCONH

\~;2--CH 2 ~

C - 56 ) a~

~ NHOO~
\ CHCONH~ F
a 6Hl3 /

F li' ( C - S7 ) O~
C~ H 11 t ~NHCJO~F
t 6 H ll ~O~C~HaONH ~l~ F F
a~g OH
( C - 58 ) ~JL ~NHa~a (~I3 ) 3 O ~ ~ O--(~HOON~ ~
a~ ~oE12l ~L

OH
( C - 59 ) I / \
~, NHOO~) 012H25~3S (CH2)300NH~
OOH2CO~cH2~H20~H3 OH
( C - 60 ) ~ ,~ H 11 t ~NHCOOH2 (:~H--~I 2 t a4Hll ~O (CH233CoNH~

C - 61 ) OH
~, NHCONH~S o2~3 ~0 ,,H~O--OHaONH~
OH3 {)(:~12 aov~

C - 62 ) OH
a l2H2S ~[~NE~lCONH~ ~F 3 ~32 -N~ONH
aH 2~ ~F
[~3 ( C - 63 ) ~
,~NHO(3NH~
G ,6H 37 aC)NH NO 2 C - 6 4 ) C)H
C 5 H 11 t ~ NHCoNH-~3 S 020H3 t C 5H 11 ~0--CHCONH~

C - 6 5 )~ NHOON~

~ OOHt:JONH~J SO2N~2 O,~Hg SO2NH OOOOH~

1 C - 66 )OH
OH3 ~ NHOONH e3SozOaH3 a lz H 25 O~OCHCONH~ J
aH3 ( C - 67 ) ~NHCONH~ /''t3H3 ta4Hg~OCH2CONH
O~Hg t ( C - 68 ) ,~,NHCoNH~3so2NHc2~s al2H25 '~3 CH2 C~l2 OCH3 ( C- 6~ ~ C5~1t ,~ ICON~

tC~Hll~;~ 2 ) 3CONH
NHCOCH~

The pH of the stabilizing solution used in -thP
present invention is not critical. Preferably, it has a pH in the range of 0.5 to 10.(), more preferably from 3.0 to 9.0, and particularly preferably from 6.0 to 8~0.
The stabilizing solution is desirably buffered by a pH
buffer~ The buffering action is known to be provided by solutions containing mixtures (salts) of weak acids 1~ and stroncJ bases or weak bases and strong acids.
Illustrativ~ acid salts include acetates, borates, metaborates, phosphates, monocarboxylates, dicarboxylates, polycarboxylates, oxycarboxylates, amino acid salts, aminocarboxylates, primary phosphates, secondary phosphates lS and tertiary phosphates.
The stabilizing solution according to the present invention may incorporate any other known additives such as brighteners, surfactants, mold inhibitors, antiseptics, organosulfur compounds, onium salts, and formalin.
Any of these compounds may be used in any combinations to the extent that the desired pH of the stabilizing bath is maintained and that the color photographic image produced can be held stable without causing any unwanted precipitation.
Other compounds that are desirably incorporated in the stabilizing solution according to the present invention -- ~0 --L;~

includ~ p~l mod.if.iers such as acetic acld, sulfuric acid!
hydrochlor.ic acid, sulfanilic aci~, potassium hydroxicle, sodium hydroxide and ammonium hydroxide; mold inhibitors such as sodium benzoate, butyl hydroxybenzoate, antibiotics, S dehydroacetic acid, potassium sorbate, thiabendazole and ortho-phenylphenol; preserva-tives such as 5-chloro-2-methyl-4-isothiazoline-3-one, 2-octyl--4-i.sothiazoline-3-one, 1-2-benzisothiazoline-3-one, and water-soluble b.ismuth cornpounds;
dispersants such as ethylene g:Lycol~ polyethylene ~lycol and polyvinyl pyrrolidone; hardeners such as formalin; and brighteners.
The treatmen-t with the stabilizing solution of the present invention is generally performed at a temperature in the range of 15 and 60C, preferably in -the range of 20 to 45C. Since rapid processing is preferred, the stabilization is generally performed in a period of 20 seconds to 10 minutes, and most prefera~ly, it is performed in a period of 1 to 5 minutes. If a plurality of stabili-zation tanks are used, the retention time of the photographic material being processed in the tanks closer to the fixing or bleach-fixing bath is preferably shorter than that in the tanks closer to the drying step. It is particularly preferred that the retention time in a specific stabilizing tank is 20 to 50~ longer than that in the preceding stabi-lizing tank. In a multistage stabilization process, themalsé-up stabilizer is preferably fed into the final tank so that it overflows into successive tanks in the reverse order. According to the present invention, the photographic material that has passed through -the stAbilizing step need not be washed with water at all. ~lowever, iE
required, rinsing with a small amount of water or the washing of the surface of the photographic ma-terial may be effected only for a very short period of time.
The bleach fixing bath or fixing bath used in the present invention may employ and kind of bleaching agent, but particularly good results are ob-tained with ~n organic acid iron ~III) complex salt. The type of the Eixing soluti.on is also not critical, but particularly good results are obtained with a -thiosulfat~. It is most effective to use a f.ixinq bath or a bleach-ixing bath containing both an organic acid iro~ (III) complex salt and a thiosulfate.
The stabilizing solution of the present invention may be brought into contact with the photographic material by immersing the latter in the stabllizing solution, as i5 usually performed with other.processing solutions.
I~ desiredy a sponge or a synthetic fiber cloth may be used to apply the stabilizing solution onto the surface of the emulsion layer in the photographic material or both sides of a transport leader, or the surace of a transport belt on which the photographic material rests. Alternatively, the stabilizing solution may be sprayed onto any one of these surfaces.
The method of the present invention may be used to process any photographic materials such as color paper, reversal color paper, color positive film, color negative film, color reversal film and color X-ray film.

- ~.2 -~ ~t~3~

IE the stabilizing solution of the presen-t invention contains a soluble silver salt, the former may be subjected to silver recovery. Silver can be recovered with an ion exchange resin, or by metal displacement, electrolysis or S silvex sulflde precipitation may be employed.
The photographic material that is to be processed by the present invention may be of the coupler-in-emulsion type as shown in U.S. Patents ~los. 2,376,67~ and 2,801,171, or of -the coupler-in-developer type as shown in U.S. Patents Nos. 2,25~,718, 2,592,243 and 2,590,g70~ Couplers other than the cyan couplers listed above may also be used, and they are well known to those skilled in the art. 5uitable magenta couplers are those having as the basic structure a 5-pyrazolone ring with an active methylene group.
Suitable yellow couplers are those having as the basic structure benzoyl acetanilide, pivalyl acetanilide or acyl acetanilide with an active methylene chain. Magenta couplers and yellow couplers may or may not have a substituent at the coupling site. Either 2~equivalent or 4-equivalent couplers may be used. Any of the conventional silver halides may be used in the silver halide emulsion, and they include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. These silver halides may be protected by natural colloids such as gelatin or by any of the synthetic colloids. The silver halide emulsion may contain any of the conventional photographic addenda such as stabilizers, sensitizers, hardeners, sensitizing dyes - ~ 3 -1;~'3L'7~

~nd ~urP~ctant~
Any conventional support may he used and typical examples include polyethylene coated paper, triace-tate film, polyethylene terephthalate film and white polyethylene terephthalate film.
~ he method of the present invention uses a black-and-white developer, which may be a "first black-and-white developer" conv~ntionally used in the processing oE color photographic mater~als, or any of the developers that are used in the processing of black-and-white photographic materials. The black-and-whike developer used in the present invention may contain a variety of additives commonly incorporated in black-and-white developers.
Typical additives that may be incorporated in the black-and-white developer include developing agents such as l~phenyl-3-pyrazolidona, Metol and hydroquinone; pre-servatives such as sulfites; accelerators made of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzothiazole;
water softeners such as polyphosphoric acid salts; and agents to prevent excessive surface development such as trace amounts of iodides or mercapto compounds.
rrhe aromatic primary amine color developing agent incorporated in the color developer may be selected from many known compounds that are conventionally used in various color photographic processes. These compounds include aminophenolic and p-phenylenediamine derivatives, which are ~4 general.ly us~d in the form of salts, such as hydrochlorides or sulfa-tes, which are more stable than when these compounds are in the free state. These developing agents are used in concentrations which generally ranye from about 0,1 g S to about 30 g, preferably from about 1 g to about 15 g, per liter of the color developer. Illus-trative aminophenolic developing agents are o-aminophenol, p-aminophenol, 5-amino 2-oxy toluene, 2-amino-3-oxy-toluene and 2-oxy-3-amino-1,4-dime-thylbenzene. Useful primary aromatic amino compounds are N,N-dialkyl-p-phenylenediamines, wherein the alkyl and phenyl yroups may or may not be substituted.
Particularly useful N,N-dialkyl-p-phenylenediamine compounds 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-~-methanesulfonarnidoethyl-3-methyl-4-aminoaniIine sulfate, N-ethyl-N-~-hydroxyethyl-aminoaniline, 4-amino-3-methyl-N,N-diethylanine, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3 methylaniline-p-toluene sulfonate.
The alkaline color developing agent used in the method of the present in~ention may contain any additives other than the primary aromatic amine developing agent, and such optional additives include alkali agents (e.g. sodium hydroxide, sodium carbonate and potassium carbonate), alkali rnetal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners ancl thickeners. The color developer used in th~ present i.nv~nt.ion is genera:lly adjusted to a pH o~ 7.0 or more, and most typically, to a pH in the range of from about lO to about 13. As w:ill be apparent from the foregoing description and from the working examples shown below, the method of the present invention uses a lesser amount o:E the make-up stab.ilizer for the stabilizing solution, and yet the image formed is resistant to yellow staining even after extended storage oE t~le photographic material p.~ocessed.
Fu.rthermore, the stabilizing solutlon used in the pre~ent invention has an excell~nt lony-term stabil:ity because the decompos.ition to silver sulfide of a thiosulfate and its soluble silver complex salt that are carri0d over Erom the preceding bath .is held minimum and the formation of an unwanted precipitate is effectively prevented.
The advantages of the present invention are hereunder described in greater detail by reference to the following examples which are given here for illustrative purposes only and are by no means intended to limit the scope of the present invention.
Example Samples of photographic material were prepared by sequentially applying the layers listed below to a support made of polyethylene coated paper. The support was prepared by the following procedure. Two hundred parts by weight of a polyethylene having an average molecular weight of lOOjOOO and a density of 0.95 was mixed with 20 parts by weiyh-t of a polyethylene having an average molecular weight of 2,0~0 and a density of 0.80. To the mixture, 6.8 wt% o~

- ~6 -titanium oxide o~ anatase type wa~ added. The result1ny mix was extruded onto the surface of quality paper (basis weiyht: 170 g/m2) to form a coat in a thickness of 0.035 mm.
The back side of the paper was provided with a coat 0~040 mm 5 thick that was extruded from only the polyethylene mixture (no TiO2). Before application of the following layers, the obverse face of the support was treated with corona discharge.
First~
This was a blue-sensitive silver halide emulsion layer comprislng a silver chlorobromide emulsion containing 95 mol% silver bromide. The emulsion contained 350 g of gelatin per mol of the silver halide and was sensitized with 2.5 x 10 mol, per mol of the silver halide, o a sensi-tizing dye of the following structure:

H3C ~ ~ CH ~ ~ ~ OCH3 (CH2)3s3H (CH2)3S03 For the sensitization purpose, isopropyl alcohol was used as a solvent. The emulsion also contained 2,5-di-t-butyl hydroquinone as dispersed in dibutyl phthalate, and 2 x 10 mol, per mol of the silver halide, of a yellow coupler, i.e.
~-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidyl)]-a-pivalyl-2-chloro-5-[y-(2,4-di-t-amylphenoxyl)butylamido]-acetanilide. The silver deposit was 350 mg/m2.

- 4~ -~' This was a gel~tin layer cont~ining 300 my/m2 of di-t-octyl-hydroquinone dispersecl in dibutyl phthalate, and 200 mg/m o a UV absorber which was a mixture of 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)b~nzotriazole, 2-(2'-hydroxy-3'-t-bu-tyl-5'-methylphenyl)-5-chlorobenzotriazole and 2 (2'~hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzot~iazo]e.
rrhe gelatin deposit was 2,000 mg/m2.
T ~ e_:
'l'his was a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 85 mol% silver bromide. The emul6ion contained 450 g of gelatin per mol of the silver hallde and was sensitized with 2.5 x 10 mol, per mol of the si.lver halide, of a sensitizing dye of the following structure:

- CH - C = CH

(CH2)3s3H (CH2)3SO3 The emulsion also contained 2,5-di-t-butyl hydroquinone dispersed in a 2:1 mixed solvent of dibutyl phthalate and tricresyl phosphate, and 1.5 x 10 moll per mol of the silver halide, of a magenta coupler, i.e. 1-(2,4,6-trichloro-phenyl)~3-(2--chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone. The silver deposit was 300 mg/m2. This layer contained O.i mol, per mol of the coupler, of an antioxidant, .i.e. 2,2,~-trimethyl-6-lauryloxy-7-t-octylchroman.
Fourth layer:
This was a gelatin layer containing 30 mg/m2 of di~
t-octylhydroquinone dispersed in dibutyl phthalate, and 500 mg/m of a UV absorber which was a 2:1~5:1.5:2 mixture of 2-t2'-hydroxy-3',5'-di-t-but:ylphenyl)benzo-tria~zole, 2-(2'-hydroxy--5'-t-butylphenyl)benzotriazole, 2~(2'-hydroxy-3'-t-butyl~5'-methylphenyl)-5-chlorobenzotriazole, ~nd 2-(2'-hydroxy-3',5'-t-butylpherlyl)-5-chloro ben~otrlazole.
The gelatin deposlt was 2,000 rncJ/m2.
Fi~th la~er-5'his was a red-sensitive silver halide emulqion layer comprising a ~llver chlorobrornide emulsion containiny ~5 mol~ silver bromide. The emulsion contained 500 g o~
yelatin per mol of the silver halide, and was sensit.ized with 2.5 x 10 mol, per mol of the silver halide, of a sensitizing dye of the following structure:

H5C2 - ~ CH - C~ ~ ~ CH ~ ~ ~
C2~5 (CH~)3S03 The emulsion also contained 2,5-di-t-butylhydroquinone as dispersed in dibutyl phthalate, and 3.5 x 10 mol, per mol of the silver halide, of a cyan coupler, i.e. 2,4-dichloro-3-methyl-6-1y-(2,4-diamylphenoxyl)butylamido~phenol.
The silver dleposit was 270 mg/m2.

-- ~19 --Six h ~ r:
This was a ge:l.a-tin layer with a gelakin deposit o~
1,000 mg/m .
The s.ilver halide emulsions used in the photosensitive emulsion layers (lst, 3rd and 5th layers) were prepared by the methods shown in Japanese Patent Publication No. 7772/71.
These emulsions were chemica].ly sensitized with sodium thiosulfate (pentahydrate) and contained 4~hydroxy-6-meth~l-1,3,3a-7-tetrazaindene, b.is(vinylsulfonylrne-thyl)-~ther and saponin as stabiliz~r, hardener and coating aid,respectively.
The color paper sample.s thus prepared were printed and suh~ected to running processing in an automatic proces-, sing machine. The processing schedule and the processing 15 solutions used,were as follows.
Processing schedule:
Steps Temperature Time (1) Color development 33C 3 min and 30 S8C
(2) Bleach-fixing 33C 1 min and 30 sec (3) Stabil.ization 25-30C 3 min (43 Drying 75~80C ca. 2 min Color developer (as tank solution):
C _ onents Amounts Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g - 5.~ -Sodium chloride 0.2 y Potassium carbonate . 30O0 g Hydroxylam.ine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino-N-ethyl~
methanesulfonarnidoethyl)-an:iline sulfate 5.5 g Bxigh-tener (4,4'-diaminosti:Lbene disulfonic acid derivative) 1.0 g Potassium hydrox.ide 2~0 g Water to make 1,000 ml Color de~ replenisher ~:
Components Amounts Benzyl alcohol 2.0 ml Ethylene glycol 2.0 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g ~ydroxylamine sulfate 4.0 g Polyphosphoric acid (TPPS) 3.0 g 3-Methyl-4-amino-N~ethyl-l~
methanesulfonamidoethyl)-aniline sulfate 7.0 g Brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Potassi~n hydroxide 3.0 g Water to make . 1,000 ml Color developer replenisher B:
Components Amounts Benzyl alcohol 20 ml Ethylene glycol 20 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g .3~

IIydroxylamine su:l.fate ~.0 g ~Iyclroxyethoxyiminodlacetic ac.id 4~0 g l-Hydroxy-ethylidene-l,l'-d:iphosphonic acid 1.0 g Magnesium chloride 0.8 g 3-~ethyl-4-amino-N-ethyl-N-(~-methanesulfonamidoethyl) an:iline sulfate 7.0 y Brightener t4,4'-diaminosti:Lbene disulfonic acid derivative) 1.5 g Potas~ium hydroxide 3.0 g Water ~o make 1,000 ml ~leach-fixing bath a9 tank solut.~on):
~ onents ~mounts _ Ethylenediaminete-traacetic acid iron (III) ammonium dihydrate salt 60 g Ethylenediaminetetraacetic acid3 g lS Ammonium thiosulfate (70% sol.)100 ml Ammonium sulfite (40% sol.)27.5 ml Potassium carbonate or glacial acetic acid to give a pH of 7.1 Water to make 1,000 ml Bleach-fixing replenisher A:
Components Amounts Ethylenediaminetetraacetic acid iron (III) ammonium dlhydrate salt 260 g Potassium carbonate 42 g Water to make 1,000 ml pH 6.7 + 0.1 - 5~2 -Ble~ch-~ixing replenisher B:
Components Amounts Ammoni~ thiosulfate (70% sol.)500 ml Ammonium sulfite (40% sol.) 250 ml Ethylenediaminete-traacetic acid17 g Glacial acetic acid 85 ml Water to make 1,000 ml p~ 4.6 ~ 0.1 Stabil~ ti~n A:
_ C'omponent Amount Acetic acid 0.5 g/1,000 ml Stabilizing solution B:

~E~ Amounts 5-Chloro-2-methyl-4-isothiazoline-3-one 0.05 g/1,000 ml lS 2-Octyl-4-isothiazoline-3-one 0.05 g~1,000 ml The automatic processor was filled with the color developer (tank solution), bleach-fixing tank solution, and stabilizing solution A or B. While the color paper samples were processed through this automatic processor, the color developer replenisher A or B, bleach-fixing replenishers A and B, and stabilizing solution A or B
were fed through metering cups. The color developer A
or B was supplied to the color developer tank in an amount of 324 ml per square meter of each color paper; each of the bleach-fixing replenishers A and B was fed into the bleach-fixing tank in an amount of 25 ml per square meter - 5~ -. A.-. ..

oE ~ach color paper; ancl th~ stabilizing solution A or B
was supplied into the stabilizing tank in an ~mount of 150 ml per s~uare meter o~ each color paper. The stabilizlng tank in the automatic processor consisted of -three stages that were operated in a counter-current fashionO
Stabilizing solution A or B was fed into the last (-third) stage tank, and an overflow was caused to enter -the second staye, and an overflow from this second stag~ was caused to flow into the first stage.
The runni.ng test was conducted until the total amount oE the bleach-fixiny rep:Lenishers A and B used was -three times the capacity of the bleach-fixing solution tank.
Experiment 1 After the running operation, eleven samples of the stabili2ing solution each weighing 1,000 ml were taken from each of the three stages of the stabilizing tank.
To each of these samples, the ~ormulations identified as Nos. 1 to 21 in Table 1 and as Nos. 22 to 33 in ~able 2 were added, and each of the mixtures was adjusted to a pH
of 6.0 with KOH and H2SO4. Color papers prepared as above were color-developed and bleach-fixed as in the processing with the automatic processor. Then, the color papers were sequentially immersed in the mixtures of formulation Nos.
1 to 33 and the solutions in the three stages of the stabi-lization tank. Thereafter, the papers were recovered ~romthe stabilizing solutions, dried, and held in a constant temperature bath (60C, 80% r.h.) for 15 days. The density of the yellow stain on the unexposed area of each paper was ;3'~

moasured w.ith an opt.ical densitometer, PDA-65 of Konishiroku Photo Indus-try Co., Ltd. The results are shown in Tables 3 and 4.

_ 5:5 -3'~

Table Formula-t.ion Components and Their ~moun-ts _ (l) l~one (2) 5-chloro-2 methyl-4-isothia201ine-3-one 0.1 g (3) 1,2-benzoisothiazoline-3-one 0.1 g (4) Chelati.ng agent (7) 5 g (S) do, (~) 5 g (6) do. (81) 5 g (7) do. (81) 5 g + CuCQ2 0-5 g

(8) do. + CrCQ3 "
~_

(9) do. + BaCQ 2 a (10) do. + CaCQ2 a (ll) do. + Ce(S04) 3 (12) do. + CoCQ 2 H ( 13j do. + InCQ 3 M ( 14) do. ~ LaCQ 3 1l (15) do. -~ MnCQ2 "
(16) do. + NiCQ2 "
o (17) do. + PbcQ2 (18) do. + TiCQ3 "
(19) do. + SnCQ4 ~
(20) do. ~ Zn504 "
(21) do. + Zr(S04) 2 "
Formulation Nos. l to 21 were used with color developer replenishe:r A and stabilizing solution A.

- ~6 -Table 2 ___ Formulation Components and Their Amounts _ _ (22) None (23) Citric acid (24) Chelating agent (7) 5 g (25) do. (44) 5 g . ~ (26) do. (81) 5 g .~ (27) do.5 y -~ cuCQ2 1.0 g ~ (28) do.5 g -~ CdCQ2 1.0 g (29) do.50 g -~ MgSO4 10.0 g (30) do.50 g ~ A~CQ3 10.0 g _.

o (31) do.5 g + SrS04 1.0 g H (3~) do.5 g -~ AQCQ3 1.0 g (33) do.5 g + MgSO4 1.0 g a~
~ a) L~ ~ _ .

Formulation l~os. 22 to 33 were used with color developer replenisher B and stabilizing solution B.

Table 3 _ ~ ~
Formulation Yellow Stain ( Blue reflection density~
_ ] !. Before Stora~e = After Storage (l) o. 06 o. 45 D (2) do. 0.4~
(3) do. 0.44 (~) ~o. 0.44 . ~d (5) d~. 0.44 ~ (6) do. 0.44 u (7) do. 0.49 (8) do. 0.48 (9) do. 0.18

(10) do. 0.13 3 (11) do. 0.22 ~D (12) do. 0.23 (13) do. 0.24 ~ (14) do. 0.23 h (15) do, 0.24 (16) do. o. 26 o (17) do. 0. 26 D (18) do. o. 26 (19) do. o. 2 0 ~ (20) do. 0.16 _ (21) do. L 0.20 4'~

Table Formulation Yellow Stain ~Blue reflection density) N ~. ~ Before Storage After Sto ge (~2) 0~06 0.41 ~ (23) do. 0.44 Q. (24) do. 0.44 (25) do. 0.44 (26) ~o. 0.~4 (27) do. 0.42 ~ (28) do. 0.43 U (29) do. 0.38 (30) do 0.47 o ~ (31) do. 0.22 (32) do. 0.23 (33) ~o. 0.13 As Table 3 shows, formulations Nos. 2 and 3 having iso-thiazoline derivatives added to the stabilizing solution A, and formulation Nos. 4 to 6 having chelating ayents added to the stabilizing solution A were ineffective in reducing yellow staining. Formulation Nos. 7 and 8 in which metals o-ther than -those claimed in the present invention, as well as a chelating agent were added to the stabilizing solution A
were also undesired since they increased yellow staining.

- ~59 -On kho o~her hand, ~o~.~nulatlon No~. 9 to 21 wherein mecals as claimed ln the present inven-tion, a5 well as a chelat-ing agent were ~dded to the stabiliziny solu-tian A were hi~hly effective in minimizing the occurrence of yellow 5 staining. Of the metals used r Ba, Ca, Sn, Zn and Zr were preferred, and Ba, Ca and Zr were more preferred.
The best results were obtained with Ca.
~ he ormulation~ t~sted had no signiicclnt difference wlth respect ko the ab.ility to prevent the decrease in dye den~ity. Referring now to 'rable 4, ~ormula-tion No. 22 was made oE on].y the stabiliziny solution B~ formulat.ion No. 23 had citric acid added to the solution B, formulations 24 to 26 had chelating agents added to the solution B, formulation Nos. 27 and 28 had incorporated in the solution B respectively a copper salt and a cadmium salt, both of which were outside the group of the metals claimed in the invention, and in formulation Nos. 29 and 30 water-soluble chelate compounds as claimed in the present invention were incorporated in the solution B but in the amounts outside the range specified in the present invention. All of these formulations were little effective in inhibiting the occurrence of yellow staining during storage.
On the other hand, formulation Nos. 31 to 33 wherein the solution B contained Sr, Al and Mg according -to the present invention and a chelating agent in the amounts within the range specif.ied in the present invention were highly effective in preventing the increase in yellow staining during storage. Of these formulations, formulation No. 33 using Mg wa9 the most efective.
As it turned out, using an excess:ive amount of a water-soluble, chelate compound as in ormulation Nos. 29 and 30 gave another undesirable result, i.e. tiny crystal grains formed on the surface of the emulsion layer in the dried photographic material.
Experiment 2:
The same procedure of Experiment 1 was repeated for ~ormulation Nos. 34 to ~2 shown in Table 5 and for~lulation Nos. 43 to 51 listed in Tabl0 6. The xesul-ts are respectively sho~n in Tables 7 and 8. In the testing with formulation Nos. 34 to 42, color developer replenisher A was used in combination with stabilizing solution A. In the testing with formulation l~os. 43 to 51, color developer replenisher B was used in combination with the stabilizing solution B.
As Table 7 shows, formulation Nos. 36 to 41 using water-soluble chelate compounds of metals as claimed in the present invention were effective in inhibiting the increase in yellow staining. Formulation Nos. 38 to 41 were particularly effective, and the best results were obtained with formulation l~os. 39 and 41 using chela-ting agent No. 81. Formulation No. 42 contained only a salt of a metal included in the scope of the present invention, but it was entirely ineffective in preventing yellow staining.
As Table 8 shows, formulation Nos. 45 to 50 using water-soluble chelate compounds of Mg included in the scope of the present invention were more effective than formulation Nos. ~3 and 44 us.ing citr.tc: acid and glya:ine, respectively. Of these effectlve formulations, Nos. 47 to 50 were particularly effective, and the best results were obtained with formulation Nos. 48 to 50 using chelat-ing agent No. 81. Formulation No. 51 contained only a Mgsalt (no chelating agent), but this was unable to prevent the increase in.yellow staining and a precipitate formed in the stabiliæing solution. It was therefore clear that using a metal salt alone.was not effective in achieving the objects oE the present invention.

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'7 Table 7 Formulation Yellow Staln ~Blue reflection den~ity) No. Be~ore Storage After Storage . _ _ I
(3~ ) 0 . 06 0. 32 G (35) do. 0.34 .,l (36) do. 0,23 o ~ (37~ do. 0.25 . ~ ~ ~38) do. O.lR
3 9 ) do. 0,14 ~40) do. 0.19 . (41) ~o. 0.13 . _ ~a) L~ ~ (42) do. 0.44 Table 8 Formulation Yellow Stain (Blue r flection density) _ _ No. _ Before Storaqe After Storaae _ _ (43) 0.06 0,32 o (A4) do. 0.32 (45) do. 0.24 o ~ (A6) do~ 0.22 ~47) do. 0.17 ~48) do, 0.12 t49) do. 0.12 . (50) do 0 14 __ .

. ~ (5l) do. 0.42 '7~;3';' Example 2 .
Color paper samples prepared ag in Example 1 were given step exposure and sub~eated to running processing according to the scheme and with the processing solutions the same as used in Example 1. The stabilizing solution A was used in combination with the formulations A to F
shown in Table 9. The color developer tank was supplied with the color developer replenisher A.
The color paper sarnples thus processed were stored in a constant temperature/humidity hath (60C, 80% r.h.) Eor 15 days and the yellow stain that occurred in the unexposed area of each sample was measured with a densitometer PDA-65 The results are shown in Table 10.
For each of the formulations A to F, a 500-ml sample of the stabilizing solution was taken out of the third stage of the stabilization tank. Each of the samples was left to stand at room temperature for 25 days and checked for the formation of a precipitate at 5-day intervals.
The results are shown in Table 11.

'7 T~bl~ 9 mulation A B C D E F
Components CacQ2 - 0.C1~ 0.08 0.5 6.0 20.0 (g/Q) Ortho-phenylphenol 0.050.05 0.050.0S 0.05 0.05 (g/Q) S-chloro-2-methyl-4-isothiazoline-3-ctne 0.050.()5 0.050.05 0.05 0.05 (g/Q) Chela-ting agent (81) 3.0 3.0 3.03.0 30.0 100.0 (s/Q) p~l 6.06.0 6.0 6.06.0 6.0 ~D~

- 68. -'7 Table 10 Formulat;ion ~ellow Stain ~,~ 1~BePore ~Storage After Storage 8 A 0.06 0.41 o i C do oo 25 H D do. 0.13 . ~ E do. 0.18 _ ~, L __ _ _ 0.31 - 69 ~

TAble 11 Fo.rmuLat~on _ A~pearance of Solut~on No. 5 daYs 10 days 15 days 20 days 25 days . .P ~ _ __ ___ _ _ 9_~ A _ _ . _ _ _ ~ ~_ _ ~

- : Clear and no precipitation + : Very slight precipitation - ~ : Some precipitation ++ : Extensive precipitation - 7~ -As Table 10 shows, formulation A containing an i~o-thiazoline derivative and a chelating agent was not as effective as formulations B to F in minimizing the increase in yellow staining. Formulations B to F contained a water-soluble chelate compound of a metal in the scope of the present invention in combination with the isothiazoline derivative and chelating agent. The data for these formu-lations also show that the water~soluble chelate compound according to the present invention (ln this case, a calcium salt) exhibited its intended effect when it was used in amounts in the range o~ 4 x 10 to 2 x 10 mol.
As Table 11 shows, formulations B to F according to the present invention were also effective in preventing the formation of a precipitate in the stabilizing solution, and hence increasing the long-term stability of that solution, Example 3 Color paper samples prepared as in Example 1 were given step exposure and subjected to running processing according to the scheme and with the processiny solutions the same as used in Example 1. The stabilizing solution B
was used in combination with the formulations 52 to 59 shown in Table 12. The color developer tank was supplied with the replenisher B.
The color paper samples thus processed were stored in a constant temperature/humidity bath ~60C, 80% r.h.~ for 15 days and the yellow stain that occurred in the unexposed area of each sample was measured with an optical densi-tometer.

_ 71 -rrhe results are shown in Table 13.
For each of the formulations 52 to 59, a 500-ml sample of the stabilizing solution was taken out of the third stage of the stabiliæation tank. Each of the samples was left to stand at room temperatwre for 25 days and checked for the formation of a precipitate at 5-day intervals.
rrhe results are shown in rrable .14.

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~ 73 -Table 13 . _ _ YelloW Staln Formulation l~o. Be~ore Storage After Storaae . _ comp~ratlive (52) 0.06 0.47 ___ ~53) 0.06 0.30 ~ (5O ., 0.25 a (55) ll 0.1~
.~ ~ (56) ll 0.12 (57) . 0.18 .~, ~58) ll 0.25 _ (59) . . 0.29 3'7 Table 1~

. FormuLat.ion Appearance ol Solution N ~.5 days_ ~ ~ 20 days 2S dlys u (52)_ _ .~ ~+ -tt _ _ -~53) _ _ ~ ~ __ ~ .
~ o (5~) _ _ _ _ .

O ~ (56) _ _ _ _ ~ ~-,1~-;+

- : Clear and no precipitation + : ~ery slight precipitation + : Some precipitation +~ : Extensive precipitation ~ 4u3'~ , .As T~ble 13 shows, Eormul~tlon Nos. 53 to 59 incoxpora.t-ing both a chelating agent and a magnes:ium salt according to the present invention could minimize the increase in yellow staining much more effeckively than did formulation S No. 52 usiny only a chelating agent.
As Table 14 shows, the formulations according to the present invention were also highly effective in preventing the formation of a silver sulflcle precipitate in the stahilizing solution, hence improving the long-term stability of that solution.
'rables 13 and 14 also show that the water-soluble chelate compound of a metal within the scope of the present invention exhibited its intended effect when it was used in amounts in the range of 1 x 10 to 3.5 x 10 mol per liter, especially in the range of 5 x 10 to 3 x 10 mol per liter. T~e best results were obtainéd when the compound was used in amounts in the range of 1 x 10 3 to 2 x 10 2 mol per liter.
Example 4 Cyan couplers according to the present invention, C-7, C-ll, C-22, C-45 and C-53, as well as three comparative cyan couplers having the structures shown below were added to a mixture consisting of 3 g of a high-boiling point organic solvent ~dibutyl phthalate), 18 g of ethyl acetate, and optionally a suitable amount of dimethylformamide.
Each of the couplers was used in an amount of 6 g.
The resulting mixtures were heated at 60C to make uniform solutions. Each of the solutions was added to 100 ml of a 5~ ac~ueo-l.q gelcltin so.l.ution containincJ lO ml of a 5 '[M
aqueous solution oE ~lkanol ~ (alkylnaphthalene sul:Eonate o~ ~.I. Du Pont), and the resultincJ mixtures were treated with ultrasonic waves to.make dispersions.
~ach of the dispersions was added to a silver chloro-bromide emulsion (10 mol~ silver chloride) in such an amount tha-t it contained the specific cyan coupler in an amount of 10 mol-~ oE the silver~ After adding 12 my o~
1,2~bis(vinylqul~onyl)ekhane (as hardener) per gram oE
the gelatin, the resultincJ coating solution was applled onto a polyethylene coated paper to yive a silver deposi-t o.~ 5 mg/lO0 cm2. Color paper samples thus prepared were exposed through an optical wedge made oE an interference filter (700 mm). The exposed paper samples were given running processing according the scheme and with the processing solutions used in Example l. Four different stabilizing solutions were used: solution C (control) and solution D (of the present invention) used in Example 2, as well as solution E ~control) and solution F (of the present invention) used in Example 3. The discoloration of the cyan dye in each sample was determined by the following procedure: after locating an area hav.ing a red reflection density of about l.0, the sample was exposed to sun-light for 250 hours, and the density of the same area was measured. The results are shown in Tables 15 and 16.
The three comparative couplers had the following structures:

coupier ~ a ) OH

~CONH (CH2) ,~,0~C5Hllt C 5Hl l t Coupler (b) OEI
[~ CONHC12H25 Coupler ( c ) OH
~CONHC12H25 ~7 ~ ~ . ~

'rable 15 . ~ Discoloration o~ cyan dye C C:! ~ _ _, coupler ~ ~ Formulation (C) Formulation [D) _ . _ ,_ ,~ ~ (a) 31 28 u (b) 30 26 _ __ _ -- _ . _ ~
(C~7) ~0 11 (C-~l) 21 13 o~ ~l (C-22) 19 10 ~! ~ ( C - 45) 22 14 (C-53) _ 12 .

- .79 -~ t7 Table 16 ~- _ ~ Stabilizing Discoloration of cyan dye ~olutio~ ~ _ _ Cyan ~ Formulation (E) Eormulation ~F) r p~ (a') 28 26 . ~ ~ (c') _ _ _ . ~5 __ _ _ (C-7) 20 10 (C-ll) 21 11 o a (C-2 ~ ) 19 9 R (C-45) 22 11 (C-53) 20 - 10 -- ~0 --'7~37 As 'rables 15 and 16 show, the stabilizing ~olutions according to the present invention were little effective in preventing light discoloration even when they were used together with the compara~ive cyan couplers. On the other hand, the same stabilizing solutions were able to prevent the incr ase in li~h-t discoloration more effectively than did the control stabiliziny solutions wh~n they were used in combina-tion with cyan couplers C-7, C-ll, C-22, C-45 and C-53. It i~ therefore clear that the stabilizing ~olution~ accorcling to the present invention are particularly effective for use with the cyan couplers specified in the present invention.

Claims (18)

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

1. A method of processing a silver halide color photo-graphic material which includes the step of treating said material with a bleach-fixing solution or a fixing solution, and then, without washing with water, treating said material with a stabilizing solution incorporating a water-soluble chelate compound of at least one metal selected from the group consisting of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn, Zn and Zr and the group consisting of Mg, Al and Sr.

2. A method of processing a silver halide color photo-graphic material according to Claim 1, wherein said silver halide photographic material contains at least one coupler of the following formula [C-I] or [C-II]:
Formula [C-I]

[wherein X is -COR2, , -SO2R2, , , -CONHCOR2 or -CONHSO2R2 (wherein R2 is an alkyl group, alkenyl group, cycloalkyl group, aryl group or a hetero ring; R3 is a hydrogen atom, an alkyl group, alkenyl group, cycloalkyl group, aryl group or a hetero ring;
provided that R2 and R3 may combine to form a 5- or 6-membered ring); R1 is a ballast group; and Z is a hydrogen atom or a group that is capable of leaving upon coupling with the oxidized product of an aromatic primary amine color developing agent.]
Formula [C-II]

(wherein R1, X and Z are as defined above.)

3. A method of processing a silver halide color photographic material according to Claim 1, wherein said water-soluble chelate compound is a reaction product of at least one metal selected from the group consisting of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn, Zn and Zr and the group consisting of Mg, Al, and Sr with a chelating agent represented by the following formula [I], [II], [III], [IV], [V] , [VI], [VII] or [VIII]:
Formula [I]
Mm P? O?
(wherein M is a hydrogen atom, alkali metal or ammonium; and m is an integer of 3 to 6.) Formula [II]
Mn+2PnO3n+1 (wherein n is an integer of 2 to 20.) Formula [III]

[wherein A1 is a hydrogen atom, -OH, COOM, or -PO3M2, M being a hydrogen atom, an alkali metal atom or ammonium; R1 and R2 are each an alkylene group; and Z is or (wherein R7 is the same as R1 and R2; and A6 is the same as A1.)]
Formula [IV]

[wherein D is an alkylene group, cycloalkylene group, phenylene group, -R7OR7-, -R7OR7OR7 or -R7ZR7- (wherein Z
and R7 are as defined above); R3 to R6 are each the same as R1 and R2; and A2 to A5 are each the same as A1.)]
Formula [V]
R8N(CH2PO3M2)2 (wherein R8 is a lower alkyl group, aryl group, aralkyl group, nitrogen-containing 6-membered cyclic group; and M is a hydrogen atom, alkali metal atom or ammonium.) Formula[VI]

[wherein R9 to R11 are each a hydrogen atom, -OH, or a lower alkyl group; B1 to B3 are each a hydrogen atom, -OH, -COOM, -PO3M2 or -NJ2 (wherein J is a hydrogen atom, a lower alkyl, C2H4OH or -PO3M2); M is a hydrogen atom, alkali metal or ammonium; and m and n are each 0 or 1.]
Formula [VII]

(wherein R12 and R13 are each a hydrogen atom, an alkali metal, ammonium, an alkyl group having 1 to 12 carbon atoms, an alkenyl group or a cyclic alkyl group.) Formula [VIII]

[wherein R14 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an amino group, an aryloxy group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, or an amyloxy group; Q1 to Q3 each represents -OH, an alkoxy group having 1 to 24 carbon atoms, an aralkyloxy group, aryloxy group, -OM3 (wherein M is a cation), amino group, morpholino group, cyclic amino group, alkylamino group, dialkylamino group, arylamino group or alkyloxy group.]

4. A method of processing a silver halide color photographic material according to Claim 3, wherein said chelating agent is one represented by said formula [VI].

5. A method of processing a silver halide color photographic material according to Claim 1, wherein said at least one metal is selected from among Ba, Ca, Sn, Zn, Zr and Mg.

6. A method of processing a silver halide color photographic material according to Claim 2, wherein said at least one coupler represented by said formula (C-1) or (C-2) is represented by the following formula [XIV], [XV] or [XVI]:

Formula [XIV]

(wherein R1 is a ballast group; R4 is an aryl group; and Z
is a hydrogen atom or a group that is capable of leaving upon coupling with the oxidized product of an aromatic primary amine color developing agent.) Formula XV

(wherein R1 is as defined above; R5 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having a 5- to 7- membered ring, an aryl group or a heterocyclic group; and Z is as defined above.) Formula [XVI]

(wherein R1, R5 and Z are as defined above.)

7. A method of processing a silver halide color photographic material according to Claim 6, wherein the aryl group represented by R4 in said formula [XIV] is a phenyl group that is substituted by at least one member selected from among -SO2R6, halogen atom, -CF3, -NO2, -CN, -COR6, -COOR6, -SO2OR6, , , -OR6, -OCOR6, , and (wherein R6 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having a 5- to 7- membered ring or a phenyl group; and R7 is a hydrogen atom or the same as R6.)

8. A method of processing a silver halide color photographic material according to Claim 6, wherein the ballast group represented by R1 in said formula [XIV] is one represented by the following formula [XVI] :
Formula[XVII]

(wherein J is an oxygen atom, sulfur atom or a sulfonyl group;
R7 is an alkylene group having 1 to 20 carbon atoms; R8 is a monovalent group; k is an integer of 0 to 4; and ? is an integer of 0 to 1; provided that when k is 2 or more, R8 may be the same or different.)

9. A method of processing a silver halide color photographic material according to Claim 8, wherein the monovalent group represented by R3 in said formula [XVII] is a group selected from among a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a heterocyclic group, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, a hydroxy group, an acyloxy group, a carboxy group, an alkyloxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group, an alkylthio group having 1 to 20 carbon atoms, an acyl group, an acylamino group having 1 to 20 carbon atoms, a sulfonamido group, a carbamoyl group and a sulfamoyl group.

10. A method of processing a silver halide color photographic material according to Claim 1, wherein the pH of said stabilizing solution is in the range of 0.5 to 10.

11. A method of processing a silver halide color photographic material accroding to Claim 10, wherein the pH of said stabilizing solution is in the range of 3 to 9.

12. A method of processing a silver halide color photographic material according to Claim 10, wherein the pH of said stabilizing solution is in the range of 6 to 8.

13. A method of processing a silver halide color photographic material according to Claim 1, wherein said water-soluble chelate compound of at least one metal selected from the group consisting of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn, Zn and Zr is used in an amount of 1 x 10-4 to 1 x 10-1 mol per liter of the stabilizing solution.

14. A method of processing a silver halide color photographic material according to Claim 13, wherein said water-soluble chelate compound is used in an amount of 4 x 10-4 to 2 x 10-2 mol per liter of the stabilizing solution.

15. A method of processing a silver halide color photographic material according to Claim 13, wherein said water-soluble chelate compound is used in an amount of 8 x 10-4 to 1x10-2 mol per liter of the stabilizing solution.

16. A method of processing a silver halide color photographic material according to Claim 1, wherein said water-soluble chelate compound of at least one metal selected from the group consisting of Mg, Al and Sr is used in an amount of 1 x 10-4 to 3.5 x 10-2 mol per liter of the stabilizing solution.

17. A method of processing a silver halide color photographic material according to Claim 16, wherein said water-soluble chelate compound is used in an amount of 5 x 10-4 to 3 x 10-2 mol per liter of the stabilizing solution.

18. A method of processing a silver halide color photographic material according to Claim 16, wherein said water-soluble chelate compound is used in an amount of 1 x 10-3 to 2 x 10-2 mol per liter of the stabilizing solution.