Note: Descriptions are shown in the official language in which they were submitted.
r f ~L24L4703
FP--1 3 6 7
This invèntion relates to a method for processing oE a
light-sensitive silver halide color photographic
material, more particularly to a method for processing of
a light-sensitive silver halide color photographic
material which is capable of forming a cyan dye image
excellent in storage stability during storage over a long
term, even when the step of washing with water may be
omitted.
Generally speaking, color photoraphic images can be
formed after imagewise exposure of a ligh-t-sensitive
silver halide color photographic material, by color
developing the image with a color developer containing an
aromatic primary amine developing agent such as
p-phenylenediamine, and subsequently applying processlngs
of bleaching, fixing, washing with water and stabilizing
on the developed image. In the above processing
procedures, in order to expedite the processings, bleach
fixing processing is generally practiced, which performes
. bleaching and fixing processings at the same` time.
The color photographic images obtained according -to such
.~ .
' - 12~dS703
processing steps is stored for a long term as recording,
and during the storage term, undesirable phenomena such
as color fading or discoloration will frequently be
caused by the influences from humidity in the air,
temperature and light.
The stabilizing processing in the above processing steps
is a processing required particularly for e~hancement of
the stability during storage over a long term oE the
aforesaid color photographic images. These methods Çor
stabilizing process are disclosed in, for example, U.S.
Patents 2,647,057; 2,788,274; 2,913,338; 3,667,952;
3,676,136; 2l515,121; 2,518,686; 3,1~0,177; 3,291,606;
and 3,093,479; Japanese Patent Publication Nos.
8779/1962, 5735/1973 and 32369/1973; Japanese Unexamined
Patent Publication No. 107736/1974; and German Pat.
DT-1770074, DT-1919045 and DT-2218387.
However, according to any method of these disclosures,
while a slight effect can be recognized on stabilization
of the color photographic image, the effect obtained
cannot be satisfactory at all. Since stabilizing
processing of the prior art has been practiced with a
bath constituted of a single tank which is suitable for
processing within a short period of time, it has not been
possible to attempt to reduce the pollution load or
reduce the amount of water.
Further, stabilizing processing wherein the step of
washing with water is omitted is also known as disclosed
in U.S. Paent 3,335,004. However, this method is a
silver stabilizing processing with a thiocyanate and a
3Q large amount of sulEite is contained in the stabilizing
bath. Therefore, the image dye formed is liable to be
converted to a leuco form to have great influences on
deterioration of the color photographic images.
-- 3 -- .
Further, as the method in which the water washing step is
omitted or the amount of washing water is extremely
reduced, there have been proposed the multi-stage
countercurrent stabilizing processing technique as
disclosed in Japanese Unexamined Patent Publication No.
8543/1982 and a processing technique with the use of a
stabilizing solution containing a bismuth complex as
disclosed in Japanese Unexamined Patent Publication No.
134636/1983.
In either of these cases, while it is a technique to
reduce the amount of stabilizing solution supplemented in
continuous processing, the fixing agent and the soluble
silver complex salt in the stabilizing solution will be
increased by the fixing solution carried over with the
photographic material to be processed if the amount of
the stabilizing solution supplemented is reduced
extremely, whereby stability of the cyan dye to light
tlight fading characteristic) was found to be lowered.
This phenomenon may be prevented by increasing the number
of stabilizing tanks, by employment of a multi-stage
countercurrent system, by use of increased amount of
stabilizing solution supplemented and by provision of a
- large volume of washing water between the fixing solution
and the stabilizing solution. However, these measures
are not advantgeous from the standpoint of compaction of
the processing instrument and protection of water
resources. Accordingly, it would be desirable to have a
stabilizing processing technique which is more compact
and small in the amount of stabilizing solution
supplemented.
The present invention provides a method
for stabilizing processing of a light-sensitive
~24~70~
-- 4 -- .
silver halide color photographic material capable of
forming a stable color photographic image during a long
term storage even when the step of water washing
processing may be omitted.
The invention also provides a method ~or
processing of a light-sensitive silver halide
color photographic material which can reduce the amount
of stabilizing solution supplemen-ted or reduce the number
of the stabilizing baths, thereby enabling reduction in
polltion load and cost as well as compacting oE the
processing instrument.
The method for processing o~ a light-sensitive silver
halide color photographic material according to this
invention is a continuous processing method comprising a
stabilizing processing step involving substantially no
water washing step after the fixing processing, wherein
said light-sensitive silver halide color photographic
material contains at least one of cyan couplers
represented by the formula (I) or (II) shown below, and
the amount of the stabilizing solution supplemented is
0.1 to 30 times the amount carried over from a precedent
bath per unit area of said light-sensitive material to be
processed:
Formula (I)
OH
¦ NHX
RlCONH
Z
~ . .
~2~47~3
- 5 -
Formula (II)
OH
N~CORl
~/1
NHX
Z
wherein X represents -COR2, -CON( 2, -S02R2, -C-N~
-S02N~ 2, -So2NHCON~ 2, -CONHCOR2 or -CONHS02R2 ~R2
is an alkyl group, an alkenyl group, a cycloalkyl
group, an aryl group or a hetero ring; R3 is a
hydrogen atom, an alkyl group, an alkenyl group, a
cycloalkyl group, an aryl group or a hetero ring; or
R2 and R3 may be bonded together to form a 5- or
6-membered ring), Rl represents a ballast group and Z
represents a hydrogen atom or an eliminable group
through coupling with the oxidized product of an
aromatic primary amine color developing agent.
.
In the stabilizing processing wherein water washing
processing is substantially omitted, whereby the
processing is made continuous from fixing processing or
bleach-fixing processing directly to stabilizing
processing, a large amount of the components in the
fixing solution and the bleach-fixing solution which is
the precedent bath must inevitably be carried over into
the stabilizing solution with the light-sensitive
material to be processed. When stabilizing processing is
performed without substantially carrying out water
washing processing in the continuous processing by means
of an automatic developing machine, the light fading of
"`'1
71)3
-- 6 --
cyan dye was ~ound to be worsened and it was not possible
to reduce the number of tan~s for stabilizing solution or
the amount of the stabilizing solution to be supplemented
to a great extent.
The present inventors, as a result of extensive studies,
have found that worsening of the light fading of a cyan
dye was due to a soluble silver complex salt or a
decomposed product of a soluble silver complex salt
remaining in the light-sensitive material, and also found
that the effect by such a soluble silver complex salt or
its decomposed product is more strengthened by the
presence of an organic ferric salt such as iron (III)
ethylenediaminetetraacetate complex salt in the
stabilizing solution.
The present inventors, as the result of further progress
of the studies, have found that very excellent character-
istics of storage stability of a cyan dye to light can be
exhibited when stabilizing processing is applied by use
of the light-sensitive silver halide color photographic
material containing the cyan coupler of this invention.
Also, according to this invention, in the light-sensitive
silver halide color photographic material containing the
cyan coupler of this invention, a surprising discovery
has been made that the dye obtained by continuous
processing with the stabilizing processing by using the
supplemental amount of this invention is improved in
light fading stability of the cyan dye, as compared with
the dye obtained by the water washing processing or the
stabilizing processing with greater supplemental amount
of the prior art. The fact that stability of dye is
higher as the residual reagent is less is entirely
unexpected from the knowledge commonly accepted in the
prior art.
~244~03
-- 7 --
In this invention, "to perform stabilizing processing
without substantially passing through the step of water
washing processing" means that it does not exclude
processing such as rinsing processing, auxiliary washing
with water and known washing water accelerating bath of a
very short period of time by means of a single bath or a
plural bath counter-current system to an extent such that
the concentration of the fixing solution or bleach-fixing
solution in the forefront tank in said stabilizing
processing is not diluted to 1/30 or less.
In this invention, fixing processing is carried out in a
processing bath containing a solubilizing complexing
agent which solubilizes a silver halide as a silver
halide complex salt, and not only fixing solutions, but
also bleach-fixing solutions, one bath developing-fixing
solutions and one bath developing-bleach-fixing solutions
are included.
To describe in more detail, in carrying out generally
continuous photographic processing, the fixing bath and
the bleach-fixing bath contain soluble silver ions, in
addition to fixing agent such as thiosulfates or
sulfites. And, in this invention, presence of such
- soluble silver ions or decomposed products of silver
salts will act advantageousely.
This invention has been a~complished on the basis of such
facts as described above, ant it is more desirable to
constitute the stabilizing processing step of a multiple
number o~ tanks in order to further develop the effect of
this invention. The most desirable amount of the
stabilizing solution supplemented is of course determined
dependin~ on the number of tanks for the stabilizing
solution.
12fl~ 3
-- 8 --
Although the cyan coupler of this invention exhibits more
preferably storage stability of dye, when the soluble
silver salt or its decomposed product in the fixing
solution or bleach-fixing solution is mixed in the
stabilizing solution in a certain amount, presence of
such a component in too much an amount is restricted by
another problem of generation of ~ellow stain.
Accordingly, it is not possible to lower extremely the
supplemented amount without limitation, and even within
the range of supplemental amount of this invention, it is
preferred to increase the number of processing tanks when
the amount of the stabilizing solution supplemented is
within the range from 0.1 to 20 times, desirably from 0.5
to 10 times.
To describe in more detail, the effect can be exhibited
with the use of a supplemental amount of stabilizing
solution in an amount within the range from 0.1 to 30
times the volume carried over from the precedent bath per
unit area of the light-sensitive material. Desirably,
however, processing is conducted with 3 to 30 times in
the case of one stabilizing processing tank, with 0.3 to
20 times in the case of two stabilizing processing tanks,
0.1 to 10 times in the case of three stabilizing
processing tanks and 0.1 to 5 times in the case of four
stabilizing processing tanks. However, five or more
tanks are not preferably in view of stability of the dye,
and processing is required to be done with at most 7
tanks. At a level of 0.1 times of the supplemental
stabilizing solution of this invention, concentration
through evaporation of the solution will cause a problem
to result in generation of precipitates. On the other
hand, in e~cess of 30 times, the light fading of the dye
by the coupler of this invention is increased, and it is
not of course desirable from the standpoint of economy
and prevention of environmental contamination.
~4~703
9 _
The stabilizing solution ln this invention has a pH which
is not particularly limited, but preferakly a pH of 0.1
to 10, more preferably of 3 to 9 and particularly
preferably of 6 to 9. The stabilizing solution of this
invention may desirably contain a pH buffering agent
added therein in order to have a buffering action. Said
buffering action is known to be played generally by a
mixed solution (salt) of a weak acid and a strong base
relative thereto or by a mixed solution (salt) of a weak
base and a strong acid relative thereto. Typical
examples of such acid salts may include acetate, borate,
metaborate, phosphate, mono-carboxylate, di-carboxylate,
poly-carboxylate, amino acid salt, aminocarboxylate,
primary phosphate, secondary phosphate, tertiary
phosphate and the like. Further, various kinds of
chelating agents may also similarly be added. Examples
of such agents are aminopolycarboxylates, aminopolyphos-
phonate, phosphonocarboxylate, alkylidenediphosphonate,
polyphosphate, pyrolate, metaphosphate, gluconate, etc.
In addition, as conventional additives generally known in
the art, there are, for example, fluorescent whiteners,
surfactants, antifungal agents, preservatives, organic
sulfur compounds, onium salts, film hardeners and others.
As the antifungal agents, there may be employed, for
example, isothiazoline type, benzyimidazole type,
benzisothiazoline type, thiabendazole type, phenol type,
organic halo-substituted compounds, mercapto type
compounds, benzoic acid and derivatives thereof, and at a
neutral pH, isothiazoline type or benzisothiazoline type
antifungal agents may preferably be used, while under
acidic conditions, thiabendazole type, phenol type,
benzoic acid, etc. may preferably be used. The amount of
these additives into the stabilizing bath added may be
varied as desired necessary for maintaining the pH of the
12~7~)3
-- 10 --
stabilizing bath and within the range, provided that
there is no bad influence on stability during storage of
the color photographic image and generation of
precipitates, and any compound may be used in any desired
combination. However, according to the processing method
of this invention, which is capable of efficient silver
recovery and non-pollution processing, the concentration
is desired to be as dilute as possible, if sufficient
buffering ability is provided, from the stand point of
pollution load and cost.
The processing temperature during stabilizing processing
may be 15 to 60 C, preferably 20 to 45 C. The
processing time may preferably be as short as possible
from the standpoint of rapid processing, but generally 20
seconds to 10 minutes, most preferably 1 to 5 minutes,
the processing time being preferably shorter in the
earlier stage tanks and longer in the later stage tanks.
Before or after the stabilizing processing of this
invention, no water washing processing is required at
all, but rinsing with a small amount of water within a
very short period of time or surface cleaning with a
sponge may be conducted freely if desired.
The processing method of this invention may be employed
also for processing of color paper, reversal color paper,
color posi film, color nega film, color reversal film,
color X-ray film, etc.
Now, the cyan couplers represented by the formula (I) and
tII) to be used in this invention are to be described in
detail.
In the formulae (I) and (II), X is a group represented by
:L2~4~)3
2 ~R ' 2R2' 3 N( , -S02N~ , -S02NHCON~ 2,
-CONHcOR2 or -CONHS02R2
Here, R2 represents an alkyl group (preferably an alkyl
group having 1 to 20 carbon atoms, such as methyl, ethyl,
butyl, dodecyl), an alkenyl group (preferably an alkenyl
group having 2 to 20 carbon atoms, such as acyl, oleyl),
a cycloalkyl group (preferably a 5- to 7-membered ring,
such as cyclohexyl), an aryl group (e.g. phenyl, tolyl,
naphthyl), a heterocyclic group ~preferably a 5- to
6-membered hetero ring containing 1 to 4 nitrogen a-tom,
oxygen atom or sulfur atom, such as furyl group, thienyl
group, benzothiazolyl group). R3 represents a hydrogen
atom or a group represented by R2. R2 and R3 may be
bonded together to form a 5- to 6-membered hetexo ring
containing a nitrogen atom. Any desired substituent may
be introduced into R2 and R3. For example, there may be
included alkyl groups having 1 to 10 carbon atoms (e.g.
ethyl, i-propyl, i-butyl, t-butyl, t-octyl), aryl groups
(e.g. phenyl, naphthyl), halogen atoms (e.g. fluorine,
chlorine, bxomine atoms), cyano, nitro, sulfonamide
groups (e.g. methanesulfonamide, butanesulfonamide,
p-toluenesulfonamide), sulfamoyl groups (e.g.
methylsulfamoyl, phenylsulfamoyl), sulfonyl groups (e.g.
methanesulfonyl, p-toluenesulfonyl), fluorosulfonyl,
carbamoyl groups (e.g. dimethylcarbamoyl, phenyl-
carbamoyl), oxycarbonyl groups (e.g. ethoxycarbonyl,
phenoxycarbonyl), acyl groups (e.g. acetyl, benzoyl),
heterocyclilc groups (e.g. pyridiyl group, pyrazolyl
group), alkoxy groups, aryloxy groups, acyloxy groups,
and so on.
In the formulae (I) and (II), Rl represents a ballast
group necessary for imparting a diffusion resistance to
the cyan coupler represented by the formulae (I) and (II)
~2D~4703
- 12 -
and the cyan dye formed from said cyan coupler.
Preferably, it is an alkyl group having 4 to 30 carbon
atoms, an aryl group or a heterocyclic group. For
example, there may be included straight or branched alkyl
groups (e.g. t-butyl, n-octyl, t-octyl, n-dodecyl),
alkenyl groups, cycloalkyl groups and 5- to 6-membered
heterocyclic groups.
In the formulae tI) and (II), Z is a hydrogen atom or an
eliminable group during coupling reaction with the
oxidized product of the color developing agent. For
example, there may be included halogen atoms te.g.
chlorine, bromine and fluorine atoms); aryloxy groups,
carbamoyloxy groups, carbamoylmethoxy groups, acyloxy
group, sulfonamide groups and succinimide groups, of
which oxygen atom or nitrogen atom is bonded directly to
the coupling position; etc. Further, specific examples
may include those disclosed in U.S. Patent No. 3,741,563,
Japanese Unexamined Patent Publication No.37425/1972,
Japanese Patent Publication No.36894/1973, Japanese
Unexamined Patent Publication Nos.10135/1975,
117422/1975, 130441/1975, 108841/1976, 120334/1975,
18315/1977, 105226/1978, 14736/1979, 48237/197g.
32071/1980, 65957/lg80, 1938/1981, 12643/1981 and
27147/1981.
In this invention, the cyan couplers represented by the
following formulae (III), (IV) and tV) are further
preferred.
- 13 _ ~ 2 ~ ~7 0 3
Formula (III)
OH
NHCONHR4
RlCONH
Formula (IV)
OH
~ NHCOR5
,~
RlCONH z
Formula (V)
OH
,~,NHCOP~l
R5CONH
In the formula (III), R~ is a substituted or
unsubstituted aryl group (particularly preferably a
phenyl group). As the substituents when said aryl group
has a substituent, there may be included -SO2R2, halogen
atoms (a.g. fluorine, bromine, chlorine atoms), -CF3,
6' COOR6, -S020R6, -CON~ 6 SO ~R6
0 -OR6, -OCOR6, -N~ , -N~ , and -P~ , from which at
COR2 ~2R6 OR7
least one substituent may be selected.
~4~03
- 14 -
Here, R6 represents an alkyl group (preferably an alkyl
group having 1 to 20 carbon atoms, such as methyl, ethyl,
t-butyl, dodecyl), an alkenyl group (preferably an
alkenyl group having 2 to 20 carbon atoms, such as an
allyl group, heptadecenyl group), a cycloalkyl group
(preferably a 5- to 7-membered ring, such as cyclohexyl
group), an aryl group (phenyl group, tolyl group,
naphthyl group) and R7 is a hydrogen atom or a group
represented by the aforesaid R6
Suitable compounds of the phenol type cyan couplers
represented by the formula (III) are compounds wherein R4
is a subsituted or unsubstituted phenyl group, and the
substituent on the phenyl group is cyano, nitro, -SO2R6
(R6 is an alkyl group), a halogen atom or
trifluoromethyl.
In the formulae (IV) and (V), R5 may preferably be an
alkyl group (preferably an alkyl group having 1 to 20
carbon atoms, such as methyl, ethyl, t-butyl, dodecyl),
an alkenyl group (preferably an alkenyl group having 2 to
20 carbon atoms such as an allyl group, heptadecenyl
group), a cycloalkyl group (preferably a 5- to 7 membered
ring, such as cyclohexyl), an aryl group (phenyl group,
tolyl group, naphthyl group), a heterocyclic ring
(preferably a 5- to 6-membered hetero ring containing 1
to 4 nitrogen atom, oxygen atom or sulfur atom, such as
furyl group, thienyl goup, benzothiazolyl group).
Into R6, R7 in the formula (I~I) or R5 in the formulae
(IV) and (V), any desired substituent may be further
introduced, such as the substituents which can be
introduced into R2 or R3 in the formulae (I) and SII).
And, as the substituent, halogen atoms (e.g. chlorine and
fluorine atoms) are particularly preferred.
~L2~4703
- 15 -
In the formulae (III) r ( IV) and (V), Z and Rl have the
same meanings as in the Formulae (I) and (II),
respectively. Pe~erable examples represented by Rl are
groups represented by the following formula (VI):
Formula ~VI)
J - R
(~8)k
In the above formula, ~ represents an oxygen atom, a
sulfur atom or a sulfonyl group, k represents an integer
of 0 to 4, Q represents 0 or 1, and when k is 2 or more,
the two or more R8ls may be either identical or
different, R7 represents an alkylene group substituted
with a straight or branched alkyl having 1 to 20 carbon
atoms or an aryl group, R8 represents a monovalent groups
such as a hydrogen atom, a halogen atom (preferably
chlorine, bromine), an alkyl group [preferably a straight
or branched alkyl group having 1 to 20 carbon atoms (e.g.
methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl,
benzyl, phenetyl)], an aryl group ~e.g. phenyl), a
heterocyclic group (preferably a nitrogen containing
heterocyclic group), an alkoxy group tpreferably a
straight or branched alkoxy group having 1 to 20 carbon
atoms (e.g. methoxy, ethoxy, t-butyloxy, octyloxy,
decyloxy, dodecyloxy), an aryl oxyl (e.g. phenoxy),
hydroxy, an acyloxy group {preferably an alkylcarbonyl-
oxy group, an arylcarbonyloxy group (e.g. acetoxy,
benzoyloxy}, carboxy, an alkyloxycarbonyl group
(preferably a straight or branched alkyloxycarbonyl group
having 1 to 20 carbon atoms), an aryloxycarbonyl group
(preferably phenoxycarbonyl), an alkylthio group
~24L~a~03
- 16 -
tpreferably having 1 to 20 carbon atoms), an acyl group
(preferably a straight or branched alkyl carbonyl group
having 1 to 20 carbon atoms), an acylamino group
tpreferably a straight or branched alkylcarboamide,
having 1 to 20 carbon atoms, benzenecarboamide), a
sulfonamide group (preferably a straight or branched
alkylsulfonamide group having 1 to 20 carbon atoms, a
benzenesulfoamide group), a carbamoyl group (preferably a
straight or branched alkylaminocarbonyl group having 1 to
20 carbon atoms, a phenylaminocarbonyl group), a
sulfamoyl group (preferably a straight or branched
alkylaminosufonyl group having 1 to 20 carbon atoms, a
phenylaminosulfonyl group), and so on.
Specific examples of the cyan couplers to be used in this
invention are enumerated below:
~Exemplary compounds]
!l)
OH
C 5 Hl 1 t ~ HCONH~--CN
tC5Hll~--~ IChCONH
C~ H9
~2~7[13
- 17 -
(2)
OH
C4Hllt ~ NHCONH ~ -CN
tC4Hg ~ -O-CHCONH
o~OCH 3
C2H5
(3)
OH
C15H31n ~ NHCONH
-CHCONH C~
CzH5
(4)
OH
~ NHCONH
HO ~ -O-CHCONH
~ I
C4Hgt ClzH2s
OH
~ NHCONHClsH
HO ~ -O-CHCONH
~ I C~ I
C4Hgt C12Hzs
- 18 _ ~2~4703
(O
OH
C5Hllt ~ NHCONH ~ C~
tC5Hll ~ O-CHCONH C~
I
C2H5
(7)
OH
C5Hllt ~ NHCONH ~ -S02C4Hg
tC5Hl1- ~ O-CHCONH
C2H5
(8)
OH
~ NHCONH ~ CN
Cl2H250 ~ -O-CHCO~H N02
CH3
(9) OH
I NHCONH ~ CN
HO ~ O-CHCONH
C4Hgt C4Hg OCH2COOC2H5
- 19 - ~2-~L7~3
( 1 o )
OH
C4Hgt ~ NHCONH ~ S02C2Hs
tC4Hg ~ O-CHCONH CN
C12H25 C~
( 1.1 )
OH
~ NHCONH ~ C~
nC4HgSO2NH ~ O-CHCONH CN
CH3
(12) ~ NHCONH
(CH3)3CCOO ~ O-CHCONH ~ /
ClZHzs ¦ COOCH3
OCH2CONHCH2CH20CH3
~1-3) CF3
OH
C4Hgt ~ NHCONH ~
tC4Hg- ~ -O-CHCONH NO2
Cl2H25 NHS02~CH3
~2~7~);1
- 20 -
( 1 ~ )
OH
C5Hllt ~ NHCONH ~ -
tC5Hll ~ O-(CH2)3CONH
SOzNHC4Hg
(15~
OH
NHCONH
~ O-CH2CONH C
nC12HzsN~ICo
COCzH5
(16) CH3
OH
C5Hllt ~ NHCONH
tC5Hll ~ O-CHCONH CH3
C4H9
(17)
OH
C5Hllt ~ NHCONH ~ -OCH3
tc5Hll~CHCONH~
I OCHzCOOH
C12Hz5
- 21 - ~2~703
( 18) OH
~S
~NHCO~.tl~
(~0--CHCONH~
- C
C 2H4 0 CzH 5
( 19 )
Cl 12H25 ,~NHCONH~
tC 5Hll~--O--CHCONH
C~
C5Hll t
(20)
OH
C 1 2H25 ~ NHCONH~--S 02 CH3
tC5Hll~CHCON
C~
C 5Hll t
( 2 1 )
OH
,~3~NHcoNH~so2 C2H5
t C 1I Hg ~S O 2 CHC ONH
0~--OC2H5
- 22 - ~2~4~03
(22)
OH
C5Hllt ~ NHCONH ~ -S02C3H7
tC5Hll ~ O-CHCONH ~
~3 `
(23)
C~Hgt OH
/ CH3 ~ NHCONH ~ ~02C6H13
tC~Hg ~ -O-C-CONH
CH3
(24) OH
NHCOMH ~ SOC2H5
~ 0-CHCO~H
/ C2H5 C~
Cl5H31
(25) 0
~ NHCONH ~ -P~
C12H250 ~ o-CHCONH
C2H5
- ~3 - :~L2~1L47:03
( 26 ) OH C~ ;
~ NHCONH~C
C 1 2 H 2 5 0~~0--CHC ONH Jq~ C
C2H5 OCON ( CH3 ) 2
(27)
OH
C 5 H 1 1 t d~NHC ONH~C
t C sHl l--~o--CHCOhH~bJ C~
(28)
(3H
NHS O 2NHC~ H g
C 4 H g S 0 2 NH~O--CHC ON~ J~.
C12H25 C~
(29)
OH
o~NHS O 2NHCOCH3
nC l2H250~So 2NH~ CONH~
- 24 - ~2447~3
(30)
OH
~ NHCONHCO ~ -SO2CH
tCI~Hg ~ SCHCONH
ClzH25
(31) F F
OH \ /
~ NHCONHSO2 ~ F
nC12H2sO ~ OCHCONH F F
C2H5
~32) OH C2H5
,NHCON~S02CF3
CONH
~ F
C16H330C
o
~33)
OH
~ OCHCONH
C~HgSO2NH C12H25 C~
~4703
(34)
OH
C5Hllt ~ NHCON=CtCH3~2
tC5Hll ~ -O-(CH2)3-CONH ~
c ,e
(3S)
OH
~ ,NHCN ~ CF3
C~HgSOzNH ~, ~ CONH ~ S
~J CR
(36)
OH
NHco-cHcH2so2cl2H25
tC4HgNHCNH CH3
11C~
(37)
OH C5Hllt
; ~ NHCOCHO ~ C5Hllt
C2H5SO2 ~ NHCONH ~ C~Hg
C~
~2447~3
-- 26 --
(38) OH
d~,, NHCO~--CONHC 1 2H2 5
~CH2NHCONH~ N--N
S~ 11
~N--N
(39)
OH
C 2H5 ,~NECOCH2 O~OC 1 2E2 5
NC ONH
C~
C2H5
~40 ~
OH
C5Hl 1 t ,~, NHCO--C3F7
tC5Hl 1~--O--CHCONH
C 4 Hg
F F
OH \ /
C 4 H g t ~ H~O~F
t C 4Hg O--CHCONH F F
C4 Hg
- 27 - ~2~9L'703
(42)
OH
~,NHCO~F
HO~--O--CHCONH ~bJ~
tC4Hg C12H25
(43)
OH
~,NHCO ( CF2 ) 2 CHFC~
C 1 2 H 2 5 ~--O--CHCONH~
C2H5
(44)
OH
C 5H11 t ,~NHCO~--OCF2CHFC~
t C 5Hll~CHCONH OCF2CHFC~
C 2H5
(45) OH
C ~ H 9 ,~i!lHC O ( CF 2 CF 2 ) H
tC5Hl 1~0--CHCONH
C5Hll t
~2~703
-- 28 --
(46)
OH
~ NHCO(CF2 )3 H
C 1 2H 25 o~3--O--CHCONH~J
F
(~7)
OH
C 12H25 ~NHCO~
C 4H g S 0 2 NH~O--CHCONH~
(48)
OX
NHC O~
~0--CHC ONH~ C 1 2 H 2 5 -
NHSO2CH3
(49)
OH
C 5 H 1 1 t ,~ NHC O~
tC5Hl 1~0--CHCONH NHS02C~3
I
C2H5
- 29 - ~l2~4703
(50)
OH
NHso2cH3
~ I
H3C(CH2)10 CONH
(51)
OH
,~ NHCO (cH2 ) 14 CH3
HO--~S O 2NH
52 )
OH
,b~NHC ~D
H3C(CH2)l2--CH=CHCH2CHCONH
CH 2 COOH
(53)
OH
C 1 2 H2 5 J~ NHC 0
O--CHC ONH
~ C~
C4 Hg SO 2NH
- 30 - 1Z~4703
(~4)
OH
C12H25 ~ NHCOC3F7
~ O-CHCONH
S 0 2NH
(cH2~2oc2H5
OH
(55~ ~ ~ NHCO
~ O-CHCONH
NH
SO2-CH2
(56) C~
OH
~b' NHCO
C6H13~ ~ ~
CHCONH F
C6H13~
(57) OH F F
C5Hllt ~ NHCO ~ F
tC5Hll ~ -O-CHCONH F F
C~ I
C4Hg
- 31 ~ 7
~58)
OH
C~ ~ NHCOC(~H3)3
C~ ~ O-CHCONH
~ I C~
c.e CloH
(59)
OH
NHCO
` C12H250~S(CH2 j3CoNH~
OCHzCONHCH2CH20CH3
(60)
OH
C4EIllt ~ NHCOCHzCH=CH2
tC~Hll ~ O(CH2)3CONH
(61)
OH
~ NHCONH ~ S02
tC4Hg ~ -O-CHCONH ~
CH3 OCH2COOH
~24~703
-- 32 --
( 6 2 )
OH
C 1 2H 2 5 ~ NHCONH~CF 3
S 0 2--N~CONH ~
~' ~
(63)
OH
~NHC ONH~
~ N02
C 1 6H 3 7 CONH
(64) OH
C 5H1 1 t ~NHCONH~S 02CH3
tC5Hl 1~--O--CHCONH
Cl 2H25
(65) OH
,~NHCOl!TH~S O2 NH 2
¢~ OCHCONH
,~=' o c (:) CH 3
C ~ Hg S 0 2NH
_ 33 _ ~4703
(66)
OH
CH3 ~ NHCONH ~ -SOzOCH3
Cl2H250 ~ OCHCONH
CH3
(67)
~ NHCONH ~ CON~
tC~Hg ~ OCH2CONH
C~Hgt
(68) ~ NHCONH ~ SO2NHCzH5
C16H330CHCONH
Cl2H25
OCH2CH20CH3
(69)
OH
C5Hllt ~ NHCONH
tC5Hll~o--(CH2 ) 3CONH
NXCOCH3
~L4~3
- 34 -
The light-sensitive silver halide color photographic
material applicable for this invention may include, in
adition to the internal developing system wherein
chromogenic agent is contained within the light-sensitive
material (see U.S. Patents 2,376,679 and 2,801,171),
external developing system wherein chromogenic agent is
contained in the developer (see U.S. Patents 2,252,718,
2,592,243 and 2,590,970). As the chromogenic agent, any
one generally known in the art other than the cyan
couplers as mentioned above may be available.
As the magenta chromogenic agents, there may be employed
those having a skeltal structure of 5-pyrazolone ring
with an active methylene group. As the yellow
chromogenic agents, it is possible to use a compound
having a structure of benzoylacetanilide, pivalylacet-
anilide or acylacetanilide with an active methylene
chain, which may have or have no substituent at the
coupling position. Thus, as the chromogenic agents,
either the so-called diequivalent type and
tetraequivalent type coupler may be applicable. The
silver halide emulsion available may be any of silver
halides such as silver chloride, silver iodide, silver
chlorobromide, silver chloroiodide, silver iodobromide,
silver chloroiodobromide and the like. As the protective
colloid for these silver halides, there may be employed
natural products such as gelatin and also various kinds
of synthetic products. The silver halide emulsion may
contain conventional additives for photography such as
stabilizers, sensitizers, film hardeners, sensitizing
dyes, surfactants, etc.
The support is not particularly limited and may be, for
e~ample, polyethylene coated paper, triacetate film,
polyethylene terephthalate film, white polyethylene
terephthalate film or the like.
12~a~7~3
- 35 -
The black-and-white develope to be used for processing of
this invention may be one which is called as black-and-
white first developer to be used in processing of light-
sensitive color photographic materials generally known in
the art or those to be used in light-sensitive black-and-
white photographic materials, and it is possible to
incorporate various additives to be added generally in
black-and white developers.
Typical additives may include developing agents such as
1-phenyl-3-pyrazolidone and hydroquinone; preservatives
such as sulfites; promokers comprising an alkali such as
sodium hydroxide, sodium carbonate, potassium carbonate
and the like; inorganic or organic inhibitors such as
potassium bromide, 2-methylbenzimidazole, methylbenz-
thiazole, etc.; hard water softeners such as polyphospho-
ric acid; surface overdeveloping preventives comprising
minute amount of an iodide or a mercapto compound; and so
on.
The aromatic primar~ amine color developing agent used in
the color developer to be used in processing of this
invention may include various known compounds widely used
in various color photographic processes. These
developers include aminophenol type and p-phenylene-
diamine type derivatives. These compounds are used
generally in the form of salts, such as hydrochlorides or
sulfates, for the purpose of stability rather than in the
free forms. Also, these compounds are used at a
concentration generally of about 0.1 g to about 30 g per
one liter of color developer, more preferably of about 1
g to about 15 g per one liter of color developer.
Aminophenol type developers may include, for example,
o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene,
2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene
~2~4703
- 36 -
and the like.
Particularly useful primary aromatic amino type color
developers are N,N-dialkyl-p-phenylenediamine compounds,
of which alkyl group and phenyl group may be either
substituted or unsubstituted. Examples of particularly
useful compounds among them are N,N-diethyl-p-phenylene-
diamine hydrochloride, N,N-dimethyl-p-phenyldnediamine
hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene,
N-ethyl-N-~-methanesulfonamidoethyl-3-methyl-4-amino-
aniline sulfate, N-ethyl-N-~-hydroxyethylaminoaniline,
4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-~2-
methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate
and the like.
The alkaline color developer to be used in the processing
of this invention may also contain as desired, in
addition to the aforesaid primary aromatic amine type
color developing agent, various components conventionally
added in color developers, for example, alkali agents
such as sodium hydroxide, sodium carbonate and potassium
carbonate, alkali metal sulfites, alkali metal
bisulfites, alkali metal thiocyanates, alkali metal
halides, benzyl alcohol, water softeners and thickeners.
The color developer may have a pH value generally of 7 or
more, most generally about 10 to about 13.
The metal complex salt of an organic acid as the
bleaching agent to be used in bleaching solution or
bleach-ixing solution in the bleaching step has the
action of color forming the non-color formed portion of
the chromogenic agent simultaneously with oxidation of
metallic silver formed by development into silver halide,
and its structure comprises a metal ion such as of iron,
cobalt, copper, etc. coordinated with an organic acid
such as aminopolycarboxylic acid, oxalic acid, citric
acid, etc.
47~3
- 37 -
The most preferred organic acid for ~ormation of such a
metal complex salt of organic acid may include polycarbo-
xyic acids or aminopolycarboxylic acids. These polycar-
boxylic acids or aminopolycarboxylic acids ~ay be alkali
metal salts, ammonium salts or water-soluble amine salts.
Typical examples of these compounds are set forth below.
[1] Ethylenediaminetetraacetic acid
[2] Diethylenetriaminepentaacetic acid
[3] Ethylenediamine-N-(~-oxyethyl)-N,N',N'-triacetic acid
[4] Propylenediaminetetraacetic acid
~5] Nitrilotriacetic acid
~6] Cyclohexanediaminetetraacetic acid
[7] Iminodiacetic acid
[8] Dihydroxyethylglycinecitric acid (or tartic acid)
[9] Ethyl ether diaminetetraacetic acid
[10] Glycol ether diaminetetraacetic acid
~11] Ethylenediaminetetrapropionic acid
[1~] Phenylenediaminetetraacetic acid
[13] Disodium ethylenediaminetetraacetate
[14] Tetra(trimethylammonium) ethylenediaminetetraacetate
[15] Tetrasodium ethylenediaminetetraacetate
[16] Pentasodium diethylenetriaminepentaacetate
[17] Sodium ethylenediamine-N-(~-oxyethyl)-N,N',N'-
triacetate
[18] Sodium propylenediaminetetraacetate
[19] Sodium nitrilotriacetate
~20] Sodium cyclohexanediaminetetraacetate
The bleaching solution, while containing the metal
complex salt of an orgnic acid as described above as the
bleaching agent, may contain various additives. As the
additive, it is desirable to incorporate a rehalogenating
agent r including alkali halides or ammonium halides such
as potassium bromide, sodium bromide, sodium chloride,
ammonium bromide and the like. It is also possible to
1~470~
- 38 -
add suitably the additives generally ~nown in the art to
be added into bleaching solutions, for example, pH
buffers such as borates, oxalates, acetates r carbonates,
phosphates, etc., alkyl amines, polyethylene oxides and
others.
When the bleaching step is conducted with the use of a
bleach-fixing solution, the bleach-fixing solution has
fixing ability in addition to bleaching ability and a
solution with a composition containing the same fixing
agent as used in a fixing solution in addition to a
bleaching agent may be applicable. The fixing solution
of bleach-fixing solution to be used may contain, other
than the bleaching agent as mentioned above, a compound
capable of forming a water-soluble complex salt through
the reaction with a silver halide, as exepmlified by
thiosulfates such as potassium thiosulfate, sodium
thiosulfate, ammonium thiosulfate; thiocyanates such as
sodium thiocyanate, ammonium thiocyanate; or thiourea,
thioether, and others.
Further, the fixing solution and the bleach-fixing
solution may also contain one or two or more pH buffering
agents, selected from various kinds of salts such as
sulfites, including ammonium sulfite, potassium sulfite,
ammonium bisulfite, potassium bisulfite, potassium
metabisulfite, sodium metabisulfite and the like, boric
acid, borax, sodium hydroxide, potassium hydroxide,
sodium carbonate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate, acetic acid, sodium
acetate, ammonium hydroxide, etc.
When a bleach-fixing supplemental liquid agent is
supplemented separately into the bleach-fixing solution
(bath), the constituent liquid agent of the present
invention may contain a thiosulfate, a thiocyanate or a
~2~4703
- 39 -
sulfite, but they are preferably supplemented separately
from each other.
In this invention, for enhancement of the activity of the
bleach-fixing solution, it is possible to blow air or
oxygen into the bleach-fixing bath or into the storage
tank for supplemental bleach-fixing solution, or
alternatively a suitable oxidi~ing agent such as hydrogen
peroxide, a hydrobromide, a persul~ate, etc. may also be
added.
In the processing of this invention, silver may be
recovered from the stabilizing solution, as a matter of
course, and also from other processing solutions
containing soluble silver complexes such as fixing
solution r bleach-fixing solution, etc. For example,
there may be effectively utilized the electrolytic method
(disclosed in French Pat. 2,299,667), the precipitation
method (disclosed in Japanese Unexamined Patent
Publication No.73037/1977, German Pat. 2,331,220), the
ion-exchange method (disclosed in Japanese Unexamined
Patent Publication No.17114/1976, German Pat. 2,548,237),
and the metal replacement method (see U.X. Pat.
1,353,805).
The present invention is described in detail by referring
to the following Examples, by which the present invention
is not limited.
Example 1
Six grams (6 g) of the Exemplary cyan coupler (7) of this
invention as shown in the exemplary compounds and the
Control coupler as shown below, 3 g of a high boiling
organic solvent dibutyl phthalate and 18 g of ethyl
acetate, optionally together with a necessary amount of
~2~4703
- 40 -
dimethylformamide were mixed and dissolved by heating at
60 C to prepare a solution. The resultant solution was
mixed with 100 ml of an aqueous 5 % gelatin solution
containing 10 ml of an aqueous 5 % solution of Alkanol B
(alkylnaphthalene sulfonate, produced by Du Pont de
Nemours & Company), followed by emulsification by means
of an ultrasonic dispersing machine to prepare a
dispersion.
As the next step, the dispersion was added to a silver
chlorobromide emulsion ~containing 10 mole ~ of silver
chloride) so that the cyan coupler as indicated in Table
1 may be 10 mole ~ based on silver, and further 12 mg of
1,2-bis(vinylsulfonyl)ethane was added as the film harder
per 1 g of gelatin. The resultant mixture was coated on
a polyethylene coated paper support to a coated silver
quantity of 5 mg/100 cm2. The thus prepared color paper
sample was subjected to wedge exposure in a conventional
manner, followed by application of the development
processings as described below.
Control couplers
Control coupler (1)
~ COl~H(CH2)~0~tC5HIl
Control coupler ~2)
OH
CO~HClzHzs
C~
~Z44703
- 41 -
Control coupler (3)
OH
CO~THCl2H25
I
Further, by use of the couplers of the present invention
(Exemplary compounds) as indicated in Table 1, samples
were prepared, processed with the processing liquor for
completion of running processing and provided for use in
storage test of image.
The running solutions to be used in the tests were
prepared by the following running processings.
Sakura color paper (in shape of roll) (produced by
Konishiroky Photo Industry Co~) after picture printing
was subjected to continuous supplemental processing
(hereinafter called as running processing) by means of an
automatic developing machine. The processing solutions
during the processing steps are shown below.
Standard processing steps (processing temperature and
processing time):
[1] Color developing 38 C 3 min. 30 sec.
[2~ Bleach-fixing 38 C l min. 30 sec.
[3] Stabilizing processing 25 to 30 C 3 min.
~4] Drying 75 to 80 C about 2 min.
Compositions of processing solutions
[Color developing tank solution]
Benzyl alcohol 15 ml
Ethylene glycol 15 ml
~Z4~7~)3
- 42 -
Potassium sulfite 2.0 g
Potassium bromide 0 7 g
Sodium chloride 0.2 g
Potassium carbonate 30.0 g
5 Hydroxylamine sulfate 3.0 g
Polyphosphoric acid (TPPS) 2.5 g
3-Methyl-4-amino-N-ethyl-N-(~-
methanesulfonamidoethyl)aniline sulfate 5.5 g
Fluorescent whitener (4,4'-diaminostil-
10 benzsulfonic acid derivative) . 1.0 g
Potassium hydroxide 2.0 g
Make up to one liter with addition of water.
Supplemental solution for color developing
Benzyl alcohol 20 ml
15 Ethylene glycol 20 ml
Potassium sulfite 3.0 g
Potassium carbonate 30.0 g
Hydroxylamine sulfate 4.0 g
Polyphosphotic acid (TPPS) 3.0 g
20 3-Methyl-4-amino-N-ethyl-N-t~-
methanesulfonamidoethyl)aniline sulfate 7.0 g
Fluorescent whitener (4,4'-diaminostil-
benzsulfonic acid derivative) 1.5 g
Potassium hydroxide 3.0 g
Made up to one liter with addition of water~
Bleach-fixing~tank solution
Ferric ammonium ethylenediaminetetraacetate dihydrate
60 g
Ethylenediaminetetraacetic acid 3 g
Amm~nium thiosulfate (70 % solution) 100 ml
Ammonium sulfite (40 % solution) 27.5 ml
Adjusted to pH 7.1 with potassium carbonate or glacial
~L24~'703
- 43 -
acetic acid and the total volume made up to one liter
with addition o~ water.
Supplemental solution for bleach-fixing
Ferric ammonium ethylenediaminetetraacetate dihydrate
130 g
5 Potassium carbonate 20 g
Ammonium thiosulfate (70 ~ solution)250 ml
Ammonium sulfite ~40 ~ solution)125 ml
Ethylenediaminetetraacetic acid 8 g
Glacial acetic acid 42 ml
The total volume made up to one liter, and the pH of this
solution adjusted to 6.4.
The automatic developing machine was filled with the
color developing tank solution and the bleach-fixing tank
solution as described above and the stabilizing solution
shown below. While processing the color paper, the
supplemental solutions for color deveoping and
bleach-fixing were supplemented through quantitative cups
per every 3 minutes to perform running test. The amounts
supplemented were 150 ml to the color developing tank and
50 ml to the bleaching tank, respectively, per 1 m2 of
the color paper. The amounts of stabilizing solution
supplemented are as indicated in Table 1.
Stabilizing processing was conducted by modifying the
stabilizing processing tank in the automatic developing
machine into one tank and three tanks so that continuous
processing may be performed. The respective stabilizing
tanks in the automatic developing machine, except for the
single tank, were arranged as first tank to third tank in
the direction o~ the flow of a light-sensitive material,
and there was employed the multi-tank countercurrent
system wherein supplement solution was charged in each
case into the last tank while permitting the overflow
- _ 44 _ ~2~4703
from the last tank to be flown into the tank in the
precedent stage, and further permitting the overflow from
said stage to be flown into the tank in the stage
precedent to said stage.
The stabilizing processing time was 2 minutes
irrespective of the number of the tanks, and continuous
processing was performed until the total amount of the
bleach-fixing supplemental solution became the same as
the volume of the bleach-fixing solution tank.
The bleach-fixing solution carried over into the
stabilizing solution per 1 m2 of color paper was 50 ml.
The stabilizing solution and supplemental solution had
the following composition:
60 % Aqueous solution of l-hydroxyethylidene-l,l-
15 diphosphoric acid 8.0 g
Calcium chloride 3.5 g
2-Octyl-4-isothiazoline-3-Gne 0.2 g
5-Chloro-2-methyl-4-isothiazoline-3-one 0.2 g
Adjusted to pH 6.90 with ROH.
The amount of the stabilizing solution supplemented was
varied as 8 1/m2, 1 1/m2, 250 ml/m2, 100 ml/m2, 50 ml/m2,
and 5 ml/m2, and the self-made papers in which the
couplers were varied after completion of the running test
were processed. After processing, the red light density
(cyan dye density) was measured and thereafter the sample
was left to stand for 300 hours under irradiation of
xenon lamp (80,000 lux) at a distance of 50 cm therefrom.
Then, the red light density was measured and the
percentage of fading of cyan dye was measured. The
results are shown in Table 1.
~Z447~3
-- 45 --
o,_
4~
U~ ~ rC
oo ~ ~ ~r ~ ~ 1` CO ~ ~r ~1
C ~ ~ o ~ ~ ~ ~ ~ ~ ~ ~1 ~1 ~ ~ ~1
a)~ dO
~)
o
a)--
.Y ~ ~ ,~ ~ ~
h O O ~ O
5-/ ~ ~: ~1 ~
~:=:: ~::: ~:::
C ~
~r; ~ C~ ~ ~ ~
O ~ I` U~ ~ ~ I` ~1 ~ ~D ~ ~1
~ u~ ~ d' ~ ~ ~1
____ ____ ____
~1 C ~ ~ ~ ~
_ ~ _ ~ _ :S
)-I O h O )~ O
a) ~ ~ ~ a
~ C) ~ ~O~ P~
a) o ~ o o
_ ~ ~ ~ ~ C~
~1 ~ L~ S~
_ ~ ~ ~ ~1 ~ ~1
l O O ~ O ~ O ~
,_1 C~
~ c a~ ~ ~ ~ a
_l O X O X O X
~ ~ l 0 1~1 C-) E3
E-
I
O ~
l S~
O ~:
~1 Ql U~
~ O ~
O ~1 ~ o o
~ aJ Ei o ~ a) 3 o u7
::1 ~-- o ,~ ~ o ~
~0 ~ ao ~ ~.C
~ C~-X-
.~ J~
N U~
,1 ~
,1 u~ .Y B
.~,
Q
': ~ U~
I
u~ ~ ~ ~n
~O ~ ol
E~ Z
12~4703
-- 46 --
o
c ~ ~r ~ ~ ~ ~ a~ a~ o ~ ~r ~ o ~D ~ ~r a~ ~1 a~
C ~ ~ o ~ ~1
a) ~ ~0
~_
to o o o o
_~ ~ ,~ ~ ~ ... .. ,
O~ o~ o o~ ~
C ~ C ~ ~ ~ C
a~ : = ~ ~ ~ : : ~ : : = ~ a
C ~ C ~ C
r; OC O~ O OC ~:
H C ) H O ~ H H
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ _ ~ _ _
O ~ I~ In ~ O 1` u~ ~ C`~ ~ ~ d' I`
~ u~ ru~ r ~ ~ ~
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_ r~ _ r~ _ r~
~1 ~ ~ ~ ~1 ~ ~1 C
_~ _ ~ _ ~ _ :~
O ~ O ~ O ~ O
~ E~ ,
o ~ o ~ o ~ o
C~ ~ ~ ~ o
o o o o = o
~1 ~ U ~ O ~ O
_ R. s~
l ~ ~ ~ ~ ~ ~ ~ ~ ~
o o ~ O _l o ~ O
c aJ c ~ c ~
o X o x o x o x
E~ C~ ~ C~ ~ ~ ~ C~ 1i3
o o~ o
o ~n o ~1 ~ u~
~_ ~ O ~ a~ 3
o ~ co .,~ ~
~ E~ ~o ~S,l
uX3
.,~ J~
~ u~ a~
.,~ ~ O ~_
_~ ~o ~ ~ ~ ~ ~
~.Y ~
~ ~ ~ J U~
~ ~ I ~
ol ~ u~ ol ~
E~ Z ~ ~ ~ ~ ~1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~1 ~7 ~ ~ ~ ~1
~2~47~3
-- 47 --
O
0 ~ â~
4~ 1 ~ h
C ~1 ~ ~o 1` ~ ~ ~ ~ ~I ~1 ~r co a~ o ~o
~ a) c o r~ ~ ~ 1
V
~_
ta o o o
~1 ~1 ~1 ~1 ~
~1 O ~ O ~ O ~)
C ~ C S~ C
::: ~ = _ ~ : :
O C O ~ O C
~,) H C,) H C~ H
_ ~ ~ ^ ~ _ _ _ _ _ _
~1 ~ ~r 1` ~1 ~ ~ ~r ,~
C~l
_ _ _ _ _ _ _ _,
_ ~ _
C~l C ~ C
_ ~ _ :S _
O 5~ 0 S~ O
o~ a~ ~ a~
O ~ O ~ O
~1~ C~ ~ ~ ~ ~
O = : : O : _ ,~ O - - :
~ ~ ~ ~ O ~ C~ ~ -
l ~1.~ 5 ~ (~5
_l O O ~ O ~1 O ~
C.)h Q. ~I Q. 1-1 Q.
O ~ ~ ~ E~
r-l C O C ~ S~
~ O X O X O X
E~ C,) lY ~_) W C~
~ ~.-1 o o U~
C ~ ~ ~ U~
C~
N Ul O
._1
.,~ ~,~
~1) 0
cn~ . .
~ O' ~ CO cn o ~ O
-
~L2~703
- 48 -
As can also be seen from Table 1, according to any of the
stabilizing processings without recourse to the present
invention (Test Nos. 1 to 6, 11, 16, 21, 26 to 31, 3~,
41, 46), the percentage of fading of cyan dye is large.
On the other hand, in the case of Control couplers,
according to the processing with small amount of the
stabilizing solution supplemented as compared with No. 1
conditions approximate to the so-called water washing
processing with greater amount of the stabilizing
solution supplemented, the percentage of fading of cyan
dye increases with reduction of the amount suplemented.
On the other hand, when the cyan couplers of this
invention are employed, the percentage of fading of cyan
dye was smaller for the cases with smaller amount of
stabilizing solution supplemented, i.e. Nos. 7 to 10,
Nos. 12 to 15, Nos. 17 to 20, Nos. 22 to 25, Nos. 32 to
35, Nos. 37 to 40, Nos. 42 to 45 and Nos. 47 to 50, than
for the cases of Nos. 2 to 5 and Nos. 27 to 30 with
greater amounts supplemented relative to the amount
carried over by a light-sensitive material.
Substantially the same results were obtained when the
stabilizing processing was conducted by use of six
stabilizing tanks arranged as first tank to sixth tank in
the same manner as in the case where the three tank
system was employed.
As described above, according to the stabilizing
processing with smaller amount of stabilizing solution
supplemented by use of the coupler of this invention, it
can be appreciated that the light fading percentage of
cyan dye, which was increased in the case of using the
coupler of the prior art, it can be seen that it will
contrariwise be made smaller.
~Z447~)3
- 49 -
Example 2
Samples were prepared according to the same method as in
Example l, and processing tests were conducted therefor.
However, bleach-fixing processing was divided into
bleaching processing and fixing processing. As the
bleaching solution and the fixing solution, Sakura Color
tr~ole~J~
negative processing agents (CNK-4, ~a~ee~ ~
Konishiroku Photo Industry Co.) CN-2R and CN-3R were
employed and the use solution and the supplemental
solution were prepared according to the respective
processing manuals and provided for use in processing.
The color developing solution and the stabilzing solution
employed were the same as in Example 1. The processing
steps and the amounts supplemented were as follows.
Processing step Temperature Time Amount supplemented
[l] Color deve- 38C 3 min. 150 ml/m2
loping 30 sec.
[2] Bleaching 38 C 1 min. 75 ml/m2
[3] Fixing 38 C 1 min. 75 ml/m2
[4] Stabilizing 38 C 2 min. Similarly as in
~ Example l, running
test was conducted
at various stages of
8 lit, 250 ml, 1~0
ml, 50 ml and 5 ml.
After the running processing, the samples were processed
similarly processed as in Example 1 and immediately
subjected to measurement of the red light densities and
stored under xenon lamp to determine the light fading
percentages. As the result, similar results as in
Example l were obtained to verify the fact that the
coupler of this invention is also suitable for
stabilizing processing with smaller amount of supplement
even in the case of fixing processing. As a consequence,
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the step of washing with water could be omitted and color
photograph with stable dye image was obtained.
As apparently seen from the foregoing Examples, according
to the present invention stable color photographic images
could be formed which are stable during a long term
storage even when the step of washing with water may be
omitted, and at the same time the amount of the
stabilzing solution supplemented can be lowered or the
number of stabilizing processing baths can be reduced.
With such effects, pollution load and cost can be lowered
with additional advankage of accomplishing compaction of
the processing instrument.
