Note: Descriptions are shown in the official language in which they were submitted.
'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.
-- 2 --
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)
- 2 3 / 5 4
- N - D - N \ (IV)
A3-R4 / R6 A5
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)
-- 4
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
HOOCCH2 CH2COOH CH2COOH
/ CH2COOH / 2 4
(~) HN < (9) H-N ~
\ CH2COOH 2 4
~ CH2COOH / CH2COOH
(10) CH3N ~ (11) HOC2H4N ~
CH 2 COOH CH 2 COOH
CH2COOH
(12) N ~CH2COOH
CH2COOH
3'~
CE12COOH
CE1 2COOH
(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
HO - C - CH3 HO - CH
COOH HOOC - CH2
(25)P13H2 126)P13H2
HO - C - H HO - C - COOH
HOOC - C - H H - C - COOH
PO3H H
-- 8
13'~
(27) P13H2 ~28) CH~COOH
}IC ~ COOH CH - COOH
HC - COOEI CH - COOEI
P3H2 P3H2
~2g) CH2COONa (30) CH2 - COOH
IIC - CH3 CH - COOH
C113 ~ C - COONa CH - COOH
P03N~2 CEI2 ~ P3H2
~31) CH2COOH (32) CH2COOH
CIH2 CH - COOH
HOOccH2C - COOH CH3 - IC ~ P3H2
P3H2 P3H2
(33) CH2COOH (34) CH2COOH
CIH2 CH - COOH
HOOCCH2 - C - COOH CH - C - COOH
CH2P03H2 P3H2
~35) CH2COOH ~36) CH2COOH
CH2 CHCH3
H3C - C - COOH ¦ ~ P3H2
3 2 P3H2
~37) CH2COOH (38) CH2 - COOH
TH2 HOOC - C - P03H2
HOOCC2H4 - C - COOH CH ~
P3H2 CH2COOH
( 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
CH2P03H2 P3H2
(43) CH2COOH (44) ~CH2P03H2
CE~COOH N ~CH~P03H2
C4Hg - C - COOH CH2P03H2
P3 2
/ CH2P03H2
~45) CH2COOH (46) N ~
N ~CH2P3H2 ~ \ CH2P03H2
CH2P03H2
-- 10 --
l~ 'Y
4 7 ) / CE12P03H2 ( 4 ~ ) / CH2P03H2
N ~ N ~
/ \CH2P03E~2 ~ ~ ~ / \CH2P03H2
~\ ~CH2COOH ~
C H 2 COOH COOH
/ CH2P03H2
(~9) C3H7 N ~
CH2P03E12
H203PCH2 \ / CH2P03H2
~ N CH2CH CH2N ~
H203PCH2 OH CH2PO3H2
(51) t52) CH3
CH2P03H2 H203p - I - P3H2
CH2P03H2 P3H2
(53) CE12PO3H2 (54~ CIH20H
H203p - Cl-PO3H2 H203p - C - P3H2
OH OH
'7~3~
~55)OH (56) CIH2PO3H2
H2O3P - 1 ~ P3H2 CH - COOH
ICH2 CH2COOH
ICH2
P3H2
(57)CH2 - COOH t5~) H
p - I ~ P3H2
~IOC~C - C - P03H2 N
CH2 CCH3 CH3
CH 2 COOH
(59)OH
H203p - Cl - P3H2
/N\
C2H5 H
(60) O
HOCH2CH (OH~ -CH2O-P- (ONa) 2
(61) O
HOCH2CH2O-P (OH) 2
'74~
~62) O
HOCH2CIl-O-P- (ONa)
CH20H
(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
NH2
(67) O
H2C = C - O - P -- (OK) 2
COOX
-- 13 --
~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
-- 14 --
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
CH3
(76) 1l
CH O-P-O-CH CH~CH
3 1 21 3
OK OH
(77) O
Il
C2H50-1P-OC2H5
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
-- 15 --
~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
CH30 - P - O - P - OCH3
OCH3 OCH3
(85~ 0 0
Il 11
C 6H 5NH - P - O - P - NHC6H5
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
- 17 -
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
- 18 -
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 ~
R2 R2 R2
wherein X is -COR2, -COId \ ~ S2R2' ll \ , -SO2N /
/R2 S R3 R3
-SO2NHCOId\ , -CONHCOR2 or -CONHSO2R2 (wherein R2 is an
R3
alkyl group, alkenyl group, cycloalkyl group, aryl group or
a hetero ring; R3 is a hydrogen atom, an alkyl group, alkenyl
-- 19 --
~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
- 20 -
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).
- 21 -
0~1
NHCON~IR~ ~XIV)
RlCONH
0~
NHCOR5
l ll (XV)
RlCONH f~
z
OH
HcoRl
~ (XVI)
R5CONH
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.
- 22 -
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;
- 23 -
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
- 24 -
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.
- 25 -
()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
- 26 -
( 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
-- 27 --
'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
-- 28 --
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 ~
-- 29 --
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~
GH3
( 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 ~ (:~
0
- 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
C - 31
,~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
0
- 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~
-- 3 2 --
( 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
C2H5
OH
1 C - 45 ~O Hg ~NHCO (cF2cF2)~
t ~ 5 H 11 ~0--CHCONH
a5Hll ~
-- 34 --
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(~
-- 35 --
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~[
01-1
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 ~
-- 36 --
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~
12 H 25
-- 38 --
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
C 16 H 33 0 OHCONH
al2H25
'~3
CH2 C~l2 OCH3
( C- 6~ ~ C5~1t ,~ ICON~
tC~Hll~;~ 2 ) 3CONH
NHCOCH~
39
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
- 41 -
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
- 45 -
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,
- 48 -
.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
- 51 -
.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
- 54
;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.
- 57 -
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
- 58 -
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
- 60 -
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
- 61 -
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.
- 6 2-
3'7
. . ~,,
,n
o o, I I I I I I I O
. . ~
~ n I I I I I i I n
~P o
ô n I I I I i Ln I I ~!,
~r o . 'LO~
n O I I I In ~i
. ' ,~o o I I I ~ Ln I Cl
I~ o o o I I I n I I a
_ ~/o o ~
n ~ n n O
o , I I n
E~ n o I Ln
_ r, Ln
~ o o o
~ ,~ o o In I I I I I
o I ~
, ¦ O ,~ o ~ ~r
~ 1 I
~1 r~
O N
l ~1- h
I O ~O r~
I O ~h I ~ O
uo n ,l u~ ~ u u u v
_ ~ 3 _
'7
~a) ,,,~'
n o o ~ h ~
_~ r1 0 ~i
o o Uol ~
_r-i O
~ O 1:~
_~i 1 1 1 1 Il ~ rt
~0 O ~' . a
,i o t ~ I I I I In H
r~ o o R
r ¦ O ~1
-` Il') ~1
~ O O 1~
_rl O 4~
r l _ O O O
h ~ o o
_ r i O U~
_~ IS)
~ O O
. ~r n I I I I I .
_
r~ î~
~1 ¦ O _ ~ ~ r-l
~ I a
o l
r~
I o O ,~
¦ ~ m P~ .rl rl rl .rl
I 1 O O ~ ~) ~ ~ ~
I O ~J .C rl ~1 ~d (d n~ a)
h ~ U ~ L
-- 64 --
'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
- 65 -
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.
- 67 -
'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.
_ 7? _
~a ~
.~
,~ ~In In
a~c:~ o o o o
In .
~_ r- o o o
n
C~ o o o o o
n
_ n~a O
n n
o o o o o
t~er o o
,~ Lo n
~Ul o o o o
n . . . . .
_ ~ o o ~ ~
. .
_~ In ~n
U~U'~ o ~ o o
U
_ o o o "
,~ n n
.~ N O O Q o
Ln
~,C~ O Or~
Ln Ln
~J ~~J O O O O .
.~
_ O O O
_ Ln U~
E~ ~ I o o o o
U'l
_ o ort) ~
_ _
_ _ _ _
g ~
ri I _ _ _ _ ~
~ I I _ O
~_1 1 d' a~
h ¦ ~ O Co .~:
¢~ I
I ~q O
I ~ ~ ~ I Ot:nUl
I ~ ~ ~ O M 1
I ot~
I O ~ O ',~
I Po~ ,~
1 8 u ~ ~, o ~ $
U ~
~ 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
74
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
- 75 -
~ 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
- 7 6 -
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:
- - 77 -
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.
- 31 -
