Note: Descriptions are shown in the official language in which they were submitted.
~s~
METH~D OF PROCESSI~G A SI~VER ~LID~
COhOR P~OT~GRAP~IC LIG~T-SENSITIVE ~TERIA~
BACKGROUND OF T~E INVENTION
Field of the Invention
This invention relates to a method of stabilizing a silver
halide color photographic light-sensitive material and
particularly to a method of stabilizing a color dye image in
which both of a light discoloration and a dark discoloration
can be preYented, and a bluing and a stain can also be
prevented.
Description of the Prior Art
In a silver halide color photographic light-sensitive
material, as is generally known, a color-developed image may be
obtained through the formation of an azomethine dye and an
indoaniline dye in a color developing process.
It is also generally known that a discoloration is taken
place in these dyes by irradiating them with ultraviolet rays
or visible rays, and such a discoloration is also taken place
:~5~
even during the storage thereof in the dark. This
discoloration is particularly accelerated under the conditions
of high temperature and humidity.
This discoloration in a color-developed image is a serious
disadvantage to a color photography, and there has been a
strong demand for the improvement of this disadvantage.
Conventionallyr there are a variety of well-known
antidiscoloration methods in which a color-developed image
produced of a silver halide color photographic light-sensitive
material is protected against the discoloration taken place in
the light or dark. These well known methods include, for
example, a process using a zinc solution disclosed in U~S.
Patent No~ 2,788,274; a process using a calcium salt, a
magnesium salt or a cadmium salt disclosed in UOSO Patent No.
2,913,338, the processes each using the solution containing
monosaccharide, disaccharide and hexitol, and a process using a
solution containing formaldehyde and a polycarboxylic acid
disclosed in British Patent Nos. 909,824 and 1~001,446; and the
like.
In these methods, however, there are the disadvantages
such as that the effects may be obtained a little, that even if
a discoloration may be prevented in the dark, a discoloration
caused in the light, i~e., a light discoloration, is increased
to the contrary, and that even if a stain may be protected from
increasing in some case~ the discoloration of dyes are
3 --
worsened.
In recent years, among the photofinishers who are
processing color photographic light-sensitive materials
automatically and continuously, the problems of the protection
of environment and the safety of water resources are regarded
as important and it is desired to reduce or to eliminate a
large quantity of washing water used in a washing process
following fixing or bleach-fixing process.
In this connection! there have been proposed some o the
technique in which a stabilizing process is directly carried
out without any washing process after a fixing or bleach-fixing
process. There include, for example, the technique using the
derivatives of an isothiazoline-3-on compound such as those
disclosed in Japanese Patent Publication Open to Public
Inspection (hereinafter called Japanese Patent O.P.I.
Publication3 No. 8542/1982; the technique for containing a
water-soluble iron salt such as that disclosed in Japanese
Patent O.P.I. Publication No. 14834/1983; the technique using a
chelating agent suc as a polycarboxylic acid, an organic
sulfonic acid, such as those disclosed in Japanese Patent
O.P.I. Publication Nos~ 132146/1982 and 18631/1983; and the
like. In these technique, however, there are disadvantages
that the preservability oE an image is deteriorated and, in
particular, that only a little effect may be obtained on the
capability of inhibiting the increase in yellow-stains caused
-- 4 --
in an area where colors are not yet developed when an image is
preserved for a long time.
As for the technique capable of solving the described
disadvantages, there is the well-known technique disclosed in
Japanese Patent O.P.I. Publication No. 8543/1983, in which a
stabilizing solution is acidified. However, when the
stabilizing solution was acidified, the other new problems were
found, that is, one of them is that the black color in a
maximum density area will be changed into a blue color under
the sunlight, that is so-called a bluing phenomenon~ which is
supposedly caused by an optical whitening agent, and another
one is tha~ an unexposed area will be tinted with a yellow
color, that is so-called a stain phenomenon, which is
supposedly caused by the act that a dye eluted from a
light-sensitive material in a continuous process is apt to
adsorb to the unexposed area. In addition, it was also found
that a fixer component and a water-soluble silver complex salt
are increased in a stabilizing solution to lower the stability
(the light discoloration property) to the light emitted from a
cyan dye.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a method of
stabilizing a color dye image, in which the abovementioned
disadvantages can be improved and a light discoloration as well
- s -
as a dark discoloration can also be prevented and further a
bluing as well as a stain can be prevented from occurring, and,
in particular, any color dye image is not affected at all even
in a stabilizing process in which the quantity of washing water
is reduced or a washing process is eliminated~
The method of processing a silver halide color
photographic light-sensitive material, which relates to this
invention, is characterized in that -the silver halide color
photographic light-sensitive material is processed at the final
step in a color process with a stabilizing solution of the pH
value of not lower than 5.0 to which 0.001 ~ 1.0 mol/~ of an
ammonium compound is added.
According to one of the preferable embodiments of the
invention, the stabilizing process thereof follows a
bleach-fixing or fixing process and a washing process is
substantially eliminated therefrom~
DETAILED DESCRIPTION OF THE INVENTION
The following is a detailed description of the invention.
The present inventors found out the fact that the
back-dyeing of a sensitizing dyes eluted from a photographic
material i5 caused by processing the photographic material with
an acid stabilizing solutionl and also found out that the
back-dyeing of an optical whitening agent or the sensitizing
dyes can be avoided by making the pH value of the stabilizing
3~
solution not lower than 5. However, in a process using a
stabilizing solution having the pH value of not lower than the
neutrality, there causes the disadvantages that a yellow stain
is apt to occur when a sample is preserved after processing and
a discoloration is increased in cyan dyes, though the
disadvantages of the aforementioned prior art may be
eliminated. The inventors devoted themselves to study and
research the technique capable of solving the abovementioned
two disadvantages at a time, and resultantly~ they discovered
that a dyeing oE an optical whitening agent or a sensitizing
dye can be avoided by using a mixture prepared by adding a
stabilizing solution having the pH value of not lower than 5~0
with an ammonium compound at the final processing step, and the
deterioration of an image quality caused in the preservation
thereof can completely be prevented.
The ammonium compounds to be added to the stabilizing
solution of this invention are such a compound capable of
releasing an ammonium ion in an aqueous solution, and to be
more concrete, they include, for example, an aqueous solution
of ammonia9 an ammonium salt of an inorganic acid such as
ammonium bromide, ammonium carbonate, ammonium chloride,
ammonium chromate, ammonium dichromate~ ammonium hypophosphite,
ammonium phosphate, ammonium phosphite, ammonium fluoride, acid
ammonium fluoride, ammonium fluoroborate, ammonium arsenate,
ammonium hydrogencarbonate, ammonium hydrogenfluoride, ammonium
~25~
-- 7 --
hydrogensulfate, ammonium hydrogensulfiter ammonium iodide,
ammonium nitrate~ ammonium pentaborate, ammonium perchlorate,
ammonium peroxydisulfide, ammonium persulfate, ammonium
molybdophosphate, ammonium tungstophosphate, ammonium
silicofluoride, ammonium sulfamide, ammonium sulfate, ammonium
sulfite, ammonium tetraborate, ammonium tetrafluoroborate,
ammonium thiocyanate, ammonium tungstate, ammonium vanadate,
ammonium polyphosphate, ammonium pyrophosphate and the like;
ammonium salts of an organic acid such as ammonium acetate,
ammonium adipate, ammonium aurintricarboxylate, ammonium
benzoate 9 ammonium carbamate, ammonium citrate, ammonium
diethyldithiocarbamate, ammonium formate, ammonium
hydrogenmalate, ammonium hydrogenoxalate, ammonium
hydrogenphthalate, ammonium hydrogentartrate, ammonium lactate~
ammonium malate, ammonium maleate, ammonium oxalate, ammonium
phthalate, ammonium picrate, ammonium pyrrolidine
dithiocarbamate, ammonium salicylatel ammonium succinate,
ammonium sulfanilate, ammonium tartrate, ammonium
thioglycolate, 2,4,5-trinitrophenol ammonlum, ammonium
iminodiacetate, ammonium hydroxyethyliminodiacetate, ammonium
nitrilotriacetate, ammonium ethylenediamine tetraacetate,
ammonium hydroxyethylethylenediamine triacetate, ammonium
diethylenetriamine pentacelate, ammonium trans-
-cyclohexanediamine tetraacetate, ammonium diaminopropanol
tetraacetate, ammonium nitrilotripropionatel ammonium
l~S~
-- 8 --
nitrilotrimethylene phosphonate, ammonium ethylenediamine
tetramethylene phosphonate, ammonium l-hydroxyethylidene-l,l'-
-diphosphonate, ammonium 2-phosphobutane-1,2,4-tricarboxylate,
ammonium di(2-hydroxyethyl)aminomethane sulfonate, and the
like; and an ammonia metal complex such as ammonia copper
sulfate, an ammonia calcium complex salt, an ammonia magnesium
complex salt, and the like; and ammonium alum, ceric ammonium
sulfate, ammonium manganese sulfateO
The ammonium compounds to be used in this invention may be
added within the range of 0.001 to 1.0 mol and preferably,
0.00~ to 0.2 mol, per liter of a stabilizing solution.
The pH value of a stabilizing solution ~a stabilizing
bath) of this invention is not lower than 5~0, and preerablyr
5 0 to 10Ø The particularly preferable p~ value is within
the range of 6.0 to 9Ø When using a continuous processing
method in which the process comprises a number of tanks
containing stabilizing solution and the processing is made in a
counter current method, and the replenishments of the
stabilizing solution are made from the last tank, the desired
pH value of the stabilizing bath is that of the last tank.
It may be allowed to add the stabilizing solution oE this
invention with a variety of compounds including, for example, a
pH-buffer, an optical whitening agent, a surfactant, an
antifungal agent, a preservative, a chelating agent~ a hardner,
various metallic salts and the like. It shall not be limited
~5X~
to use any compound or those in combination, provided that no
photographic characteristic is af ected.
A preferable stabilizing process relating to this
invention is to follow a bleach-fixing process or a fixing
process without substantially carrying out any washing process.
This means that it may be allowed to carry out a short process
for silver recovery, a rinsing process and the like between the
bleach~fixing or fixing process and the stabilizing processl
though it is preferred that no process is carried out between
the bleach-fixing or fixing process and the stabilizing
process.
Any washing process is not necessary at all after the
stabilizing process of -the inventionJ and it is also allowable,
if occasion demands, to carry out optionally a rinse~ a
surface-washing or the like using a small amount of water for a
very short time, however, it is anyway preferred that a drying
process may follow directly after the stabiliz.ing proc~ss.
The range of the temperature in the stabilizing process is
from 10C to 60C~ and preferably~ from 15C to 40C. The
processing time in the stabilizing process is the shorter, the
better, from the viewpoint of a rapid processing, and is namely
20sec to lOmin.~ and most preferably, of the order of 30sec to
5min. The temperature and the time required for a drying
process may arbitrarily be selected, however it is desired to
select a temperature of not lower than 50C.
~25~
-- 10
Fixing bath or bleach-fixing bath of the invention shall
not specifically be limited. The fixers to be used in the
invention include, for example, a thiosulfate, a thiocyanate~
an iodide, a bromide, a thioether, thiourea and the like, and
the bleaching agents include, for example, potassium
ferricyanate, iron chloride, a persulfate, hydrogen peroxide,
an organoferric complex salt and the like.
As for the methods of bringing a stabilizing solution of
this invention into contact with a light-sensitive material, a
preferable method i5 to dip the light-sensitive material into
the solution as in the case of using an ordinary type of
processing solution, however, it is also allowed to coat the
emulsion surace of a light-sensitive material and both
surfaces of a transport leader with the stabilizing solution of
the invention by means of a piece of sponge synthetic fiber or
the like~ or~ to spray out such surfaces with the stabilizing
solution by means of a spray-gun.
The processing methods of the invention can be used for
processing a color printing paper, a reversal color printing
paper, a color positive film, a color neg~tive film, a color
reversal film, a color X-ray film, and the like.
When a stabilizing solution contains a soluble silver
salt, silver may be recovered from the solution. As for the
methods of recovering silver, an ion exchange resin method, a
transmetallation method, an elec~rolyzing method, a silver
:~5~
sulfide precipitation method and the like may be used.
In this invention, when a cyan coupler having the Formula
(I) or (II) below is to be used in a silver halide color
photographic light-sensitive material, there is added with such
an effect that cyan dyes produced in a color development
process may be improved on the stability thereof against light.
Formula (I)
OH
RlCONH~
Formula (II)
OH
~ ,NHCOR
XNH
wherein, X is a radical having the formula of -~OR~, -CON~ r
-S2R2~ -I_N~ , -SO2N~ , -SO2NHCON~ , -CONHCOR2, or
-CONHSO2R2; R2 represents an alkyl radical and preferably,
those having one to 12 carbon atoms, such as methyl, ethyl,
butyl~ dodecyl and the like; an alkenyl raidcal and pref~rably,
those having 2 to 20 carbon atoms, such as acyl, oleyl and the
like; a cycloalkyl radical and preferably, those having 5 to 7
member ring, such as cyclohexyl, an aryl radical such as
~s~
phenyl, tolyl or naphthyl radical and the like; and a
heterocyclic radical and preferably, a 5 to 6 member hetero
ring containing 1 to 4 nitrogen, oxygen or sulfur atoms, such
as ~uryl~ thienyl or benzothiazole radical and the like; R3
represents hydrogen atom or a radical represented by R2. It is
also allowed that R2 and R3 may be bonded together so as to
form a 5 to 6 member hetero ring containing nitrogen atom. In
addition, any arbitrary substituent can be introduced into R2
or R3, and such substituents include, for example, an alkyl
radical having 1 to 10 carbon atoms such as ethyl, i-propyl,
i-butyl, t-butyl, t-octyl and the like; an aryl radical such as
phenyl and naphthyl, a halogen such as fluorine, chlorine or
bromine atom and the like; a cyano radical; a nitro radical; a
sulfonamide radical such as methanesulfonamide,
butanesulfonamide, p-toluenesul~onamide and the like; a
sulfamoyl radical such as methylsulfamoyl, phenylsulfamoyl and
the like; a sulfonyl radical such as methanesul~onyl,
p-toluenesulfonyl and the like; a fluorosulfonyl radical; a
carbamoyl radical such as dimethylcarbamoyl, phenylcarbamoyl
and the like; an oxycarbonyl radical such as ethoxycarbonyl,
phenoxycarbonyl and the like; an acyl radical such as acetyl,
benzoyl and the like; a heterocyclic radical such as pyridyl or
pyrazolyl radical and the like; an alkoxy radical; an aryloxy
radical; an acyloxy radical; and the like
In Formulas (I) and (II), Rl represents a ballast radical
~ 13 -
necessary for vesting cyan dyes formed of the abovementioned
cyan couplers with a diffusion resistance. The preferable
ballast radicals include an alkyl radical having 4 to 30 carbon
atoms, an aryl radical or a heterocyclic radical. They are,
for example, a straight-chain or branched chain alkyl radical
such as t-butyl, n~octyl, t-octyl, n-dodecyl and the like, an
alkenyl radical, a cycloalkyl radical 9 a 5 to 6 member
heterocyclic radical and the like.
In Formulas (I) and (II), Z represents hydrogen or a
radical capable of splitting off in a coupling reaction will an
oxidi2ed product of a color developing agent. They include,
for example, a halogen such as chlorine, bromine, fluorine atom
and the like, and, an aryloxy, carbamoyloxyl carbamoylmethoxy,
acyloxy, sulfonamide or succinimide radical in which an oxygen
or nitrogen atom couples directly to the coupling position of
the radical. The further concrete examples thereof include
those disclosed in U.S. Patent NoO 3,741,563, Japanese Patent
Examined Publication No. 36894~1973, and Japanese Patent O~P~Io
Publication Nos 37425~1972, 10135/1975, 117422/1975,
130441/lg75, 108~41/197~, 120334/1375, 18315/1977, 105226/1978
14736il979, 48237/1979, 32071/1980, 65957/1980, 193B/1981,
12643/1981, and 27147/1981.
In this invention, more preferable cyan couplers have the
following Formula (III), ~IV) or (V);
3~
- 14 -
Formula (III)
OH
NHCONHR4
RlCONH
Formula (IV)
OH
NHCOR5
RlCONH
Formula (V)
OH
,~,NHCORl
R5CONH ~
In Formula (III), R4 is a substituted or unsubstituted
aryl radical and more preferably, phenyl radical. When the
aryl radical has a substituent, such substituents include at
least one selected from the group of -SO2R6~ a halogen such as
fluorine, bromine or chlorine atom and the like, -CF3, -NO2,
COR COOR , -SO20R6, -CON\ ' S2~\R 6
_N~R7 , -N 7 , and -p 6
~COR6 S2R6 \OR7
Wherein, R6 is an alkyl radical and preferably those
- 15 -
having 1 to 20 carbon atoms, such as methyl, ethyl, t-butyl, or
dodecyl radical and the like; an alkenyl radical and preferably
those having 2 to 20 carbon atoms, such as acyl or oleyl
radical and the like; a cycloalkyl radical and preEerably a 5
to 7 member ring, such as cyclohexyl radical and the like; and
an aryl radical such as phenyl, tolyl or naphthyl radical and
the like. R7 is hydrogen or a radical represented by the
abovementioned R6.
The compounds suitable for the phenol type cyan couplers
having the Formula (III) are such a compound that R~ is a
substituted or unsubstituted phenyl radical and the substituent
to phenyl radical is a cyano, nitro or -SO2R6 radical in which
R6 is an alkyl radical, a halogen ato~, or trifluoromethyl.
In Formula (IV) and (V), R5 represents an alkyl radical
and preferably those having 1 to 20 carbon atoms, such as
methyl, ethyl, t-butyl or dodecyl radical and the like; an
alkenyl radical and preferably those having 2 to 20 carbon
atoms, such as acyl o~ ~leyl radical and the like; a cycloalkyl
radical and preferably a 5 to 7 member ring, such as cyclohexyl
radical and the like; an aryl radical such as phenyl, tolyl or
naphthyl radical and ~he like; a heterocyclic radical and
preferably those o~ 5 to 6 member ring containing 1 to 4
nitrogen, oxygen or sulfur atoms, such as furyl, thienyl or
benzothiazolyl radical and the lik~.
Any arbitrary substituent may further be introduced into
- 16 -
R6, R7 of Formula (III) and R5 of Formula (IV) or (V), and to
be more concrete, and such substituents are those capable of
being introduced into R2 or R3 of Formulas tI) and (II). And,
a halogen including, for example, chlorine or fluorine atom and
the like is particularly preferred to serve as the substituent.
In Formulas (III1~ (IV) and (V), Z and Rl each have the
same meaning as those in Formulas (I) and (II)~ The preferred
examples of the ballast radicals represented by Rl have the
following Formula (VI~;
Formula ~VI~
~ , ~ 7
(R8)k
Wherein, J represents oxygen~ sulfur or a sulfonyl
radical; k is an integer oE 0 to 4; and ~ is 0 or 1. When k is
a value of not smaller than 2, two or more R8 existing therein
may be the same or diEferent from each other; R7 is a
straight-chain or branched-chain alkylene radical having 1 to
20 carbon atoms and substituted by an aryl radical; and R8
represents a monovalent radical includingt for example,
hydrogen; a halogen such as chlorine, bromine and the like; an
alkyl radical and preferably a straight-chain or branched-chain
alkyl radical having 1 to 20 carbon atoms, such as methyl,
t-butyl, t-pentyl r t-octyl r dodecyl t pentadecyl, benzyl and
phenethyl; an aryl radical such as phenyl; a heterocyclic
- 17 -
radical and pre:Eerably those containing nitrogen; an alkoxy
radical and preferably a straight-chain or branched-chain
alkoxy radical having 1 to 20 carbon atoms, such as methoxy,
ethoxy, t-butyloxy, octyloxy, decyloxy and dodecyloxy radicals;
an aryloxy radical such as phenoxy radical; a hydroxy radical;
an acyloxy radical and preferably an alkylcarbonyloxy radical
and an arylcarbonyloxy radical such as acetoxy and benzoyloxy
radicals; a carboxy radical; an alkyloxycarbonyl radical and
preferably a straight-chain or branched-chain alkyloxycarbonyl
radical having 1 to 20 carbon atom~; an aryloxycarbonyl radical
and preferably phenoxycarbonyl radical; an alkylthio radical
and preferably those having 1 to 20 carbon atoms; an acyl
radical and preferably a straight-chain or branched-chain
alkylcarbonyl radical having 1 to 20 carbon atoms; an acylamino
radical and preferably a straight-chain or branched-chain
alkylcarbamide or benzenecarbamide radical; a sulfonamide
radical inclding, preferablyy a straight-chain or
branched-chain alkylsulfonamide radical having 1 to 20 carbon
atoms and ben~enesulfonamide; a carbamoyl radical including,
preferably, a straight chain or branched-chain
alkylaminocarbonyl radical having 1 to 20 carbon atoms and
phenylaminocarbamoyl radical; and a sulamoyl radical
including, preferably, a straight-chain or branched-chain
alkylaminosulfonyl radical and phenylamino~ulfonyl radical.
The ~ollowing exemplified compounds are some concrete
~2S~ 3
- 18 -
examples of the cyan couplers to be used in this invention;
tExemplified Compounds]
(1)
/C5Hll~ ~ NHCONH ~ CN
tC5H~ o-cHcoNH
C4Hg
~2)
C4Hgt ~ NHCONH ~ CN
tC4Hg ~ O-CHCONH ~ ~ OCH3
~3)
OH
O-CHCONH
C2H5
(~)
~ MHCONH
HO ~ O-fHCONH
C4Hgt 12H25
- 19 -
(5)
OH
~NHCNHC15~13
HO ~ O-CHCONH
~=/ I CQ,
C4Hgt 12H25
(6)
ON ~ C~
tC5Hll~O-fHCONH
C2H5
(7~
C5Hllt ~~ SO~C~Hg
tC5Hll ~ O CHCON
C2H5
(~)
~ NHCONH ~ CN
C12H25 ~ O CHCONH ~ NO2
I
CH3
~5~ 3
- 20 -
~9)
~ NHCONH ~ CN
C12H250 ~ O-CHCONH
~ C4Hg OCH2COOC2H5
C~Hgt
(10)
, ~ ~NHCONH ~ S02C2H5
t 4H9 ~ O-CHCONH
C1:2H25
(11)
~ NHCONH ~ CQ
nC4HgSo2NH ~ O-CHCONH ~ CN
CH3
~12)
NHCONH ~ COOCH3
~C~3)3CCOO ~ O-CHCONH ~
C12H25 2CNHCH2CH2CH3
3'~3
(13) CF
tC4Hg-~O-CHCONH~ 2
C12H~5 o2~3CH3
(14)
C5Hllt J~NHCoNH~3So2NHC4H~
tC5Hll~O--(CH2~ 3CON
tl5)
,NHCONH ~ COC2H5
~O~CH 2 CONH'~J C~ 3
nC12H25NHC
CH
tC5Hll- ~ O-CHCONHJ ~ 3
C4Hg
~ZX~ 3
-- 22 --
(17)
OH _~t-OCH 3
tC5Hll~O-CHCON
OCH2COOH
OEI S
~,NHCONH~
~0--CHCONH
~/ I cQ,
C2Hd~/ C2H5
(19)
C 1 2E~ 2 5,~ ~ S
-tC5Hll~O-CHCON
C5Hllt
~20)
Cl2H25J~ NH~S02cH3
tC5Hll ~ O--CHCON
C5Hllt
23
(21)
I ,NHCoNH~3So2C2H5
tC4Hg ~ SQ2CHCoNH ~
( 22)
C5Hllt , ~ NHCONH ~ S02C3H7
tC5H 11 ~O-CHCONH
(23)
~4 9 ~NHcoNH~so2c6Hl3
t C ~H ~ O-C-CONH
CH3
(24)
~ ~NHCONH ~ SOC2H5
~30 f HCONH~jJ
C H C2H5
15 31
5~
2~
(25) O
~ NHCONH ~ ~ OCH3
12H250 ~ O-CHCONH
C2H5
(26)
~ NHCONH ~ Q
C12H250 ~ 0~CHCONH
~2H5 OCON(CH3)2
(27
~ NHCONH ~ C~
tC5Hll ~ O-CHCONH
(28)
OH
~NHS02NHC4H9
C~HgS02NH ~ O f HCONH
C12H25
(29)
OH
~,NHSO 2NHCOCH 3
nCl 2H250~3~o2NH~CoNH
(30)
~ ~ ,NHCONHCO ~ S02CH~
4H 9 ~o -S CHCONH
C12H25
(31)
~ 3,NHCONHS02 ~ F
nC12H250 ~ 0fHCONH
~H5
(32)
C ~_
C~CON
ClÇ~33~l
-- 26 --
(33)
OH
~,NHCON~ O
~OCHCONH~
>=/ I CQ
C4HgS02NH C12H25
(34)
OH
C5Hllt ~NHCON=C (CH3~ 2
tC5Hll~O- (CH2) 3-CONH~,
~35)
,~,NHCN~CF3
C4HgSO2NH CONH
(35~
OH
~l,NHCO- I HCH2S02C12H25
tC4HgNHCNE1 3
S
-- 27 -
(37) C5Hll~
NHCOfHO~C5H1lt
C2H5SO2~NHCONH)~ C~Hg
(38)
,~IHCO~CONHC12H25
~3CH 2NH CONH _< N -N
~N
(39) ~J
~,NHCOCH20~30C1 2E1 25
NCONH
C2~15
(~0)
OH
~,NHCO-C3F7
tC5Hli ~ O-CHCONH ~ J
C4Hg
-- 28 --
(41)
F F
C ~H gt ,~NHCO~F
t C 4H 9~0--fHCONE~
C4H~
( 42)
~,NHCo4~F
Ho4~o-CHCoNH~
tC H C12H25
4 9
(43)
OH
~ CO ~CF2) 2CHFCQ
Cl 2H 2 50~30-CHCoNH~
C2H5
(44)
HJ~ CF2CHFC'Q
~ OCF 2CHFC Q,
tC5~ O-CHCONH
C2H5
~ .3.~
-- 29 --
45)
OH
C4Hg ,~ CO ~CF2CF2~ H
tc5Hll~o-cHcoNH
C5Hllt
(46)
OH
~NHCO t CF ~2 ) 3H
C12H 250~3.o_
(47)
C~aH9S02NH ~ O-CElCON~
(48)
~,NHCO~
~O--CHCONEI)q~J 2H 2 5
~< C~
NHS02CH3
~5~ 3
-- 30 --
( ~9)
tC 5H 11 ~O-CHCONHJ~ 2 3
2H5
(50)
OH
~,NHSO 2CH 3
H3C (CH2) loCON~J
(51)
OH
~,NHCO ~CH2) 14CH3
HO~SO ~NH
t 52)
GH
H3C (CH2~ 1~-CH=CHcH2cHcONH~NHCO~3
CH 2COOH
-- 31 --
(53)
~O-CHCONH~J
C4H9S2N C,~
( 54)
0
~O-CHCONH~
l 02N cL
~H 2 ~ 20C 2H 5
55)
,~ MHCo~3
~O-CHCONH
NH
\o2-c~2~3
~56) C~
C6Hl 3 ~ ~ F
C~H13~
-- 32
(57)
tC5~11 ~ 0-C~COII~
C4Hg
(58)
OH
CQ I~NHCOC (CH3) 3
CR,~ O-CHCONH~J
\y I C~
\C,e, Cl OE~21
(59)
0
~NHCO~
C12~25~S (CH ) CONHJ~J
2 3 OCH 2CONHOE1 2CH 2OCH 3
( 60)
OH
C 4H 11 t ~NHCOCH ;~CH =CH 2
tCd~Hll~O (CH2) 3CONH~
12~X;~
- 33 --
(61)
,[ ~ ,NHCONH ~ S02 ~
tC4H94~0-CHCONH
CH3 OCH2COOH
(62)
1 12H25 ,~ CoNH~3CF3
(63)
~3,NHCONH
C16H37CNH
(~i4)
C 5H 1 lt ,[~ ~SO 2CH 3
tC5Hll ~ O-fHCON
Cl 2H25
(65)
~,NHCoNE~3so2NH 2
~3OCHCONH~
OCOCl~
C4HgS02NH
~2S;~
-- 34 --
(66)
OH
CH3 ~NHCoNH~3so2ocH3
1 2H 2 5o~;~ocHcoNHJ~
CH3
(67)
NHCONH~ ~CH3
tC4Hg~OCH2CON
C4~9t
(68)
,~,NHCONH~ 3 S2NHC2HS
C 1 6H 3 30C~ CON
Cl 2H 25 ~
OCH 2CH20CH3
(69)
NHCoNH~3NHCOC:H
~C5~ t ~f 3
tC5Hll~O- (CH2) 3CONH~
- 35 -
Silver halide color photographic light sensitive material
applicable to the present invention may b~ the one having the
coupler in developer type (see U.S.P. Nos. 2,252,718, 2,592,243
and 2,590,970) wherein coupler is contained in the developer in
addition to the one having the coupler in emulsion type (see
U.S.P. Nos. 2,376,679 and 2,8Dl,171) wherein coupler is
contained in the light sensitive material~ In addition to
aforesaid cyan coupler, any of those known generally in the
field may be used as a coupler.
Magenta coupler having 5-pyrazolone ring having active
methylene group in an essential structure or yellow coupler in
the structure of benzoylacetoanilide, pivalylacetoanilide or
acylacetoanilide having active methylene chain may be used
regardless of whether substituent is owned at the coupling
position or not. Thus J the coupler in either type of
2-e~uivalent coupler or 4-equivalent coupler may be applied.
Silver halide emulsion to be used can contain any of silver
halides such as silver chloride~ silver bromide, silver iodide,
silver chlorobromide, silver chloroiodide, silver iodobromide
and silver chloroiodobromide. Further, as a protective colloid
for these silver halidesl various types ones obtained from
synthesis may be used in addition to the natural one such as
gelatin or the like. Silver halide emulsion can contain
ordinary additives for photographic use such as stabilizer,
sensitizer, hardener, sensitizing dye 7 surfactant and others.
36 -
Any of polyethylene coat paper, triacetate ~ilm,
polyethylene terephthalate film and white polyethylene
terephthalate film may be used as a support.
Black and white developer used for the processing o~ the
present invention is the one called the first black and white
developer to be used for the processing of normally known color
photographic light sensitive material or the one to be used for
the processing of the black and white photographic light
sensitive material and it can contain additives in many kinds
which are usually added to the normal black and white
developer.
As a typical additive, l-phenyl-3-pyrazolidone, developing
agent such as metol and hydroquinone, preservative such as
sulfite, accelerator consisting of alkali such as sodium
hydroxider sodium carbonate and potassium carbonate etc~,
inor~anic inhibitor such as potassium bromide~
2-methylbenzimidazole, methylbenzthiazole etc~ or organic
inhibitor, hard water softener such as a polyphosphate and a
surface-over-development-preventive agent consisting of small
amount of an iodide and mercapto compound and others are given.
Aromatic primary amine color developing agent to ~e used for
color developer which is employed in the processing of the
present invention includes known developing agents widely used
in various color photographic processings. These developers
include aminophenol derivative and p phenylenediamine
- 37 -
derivative. These compounds are usually used in the form of
salt such as hydrochloride or sulfate because they are more
stable in the form of salt than in the free state. Further,
these compounds are used under the concentration of about O.lg
about 30g per 1~ of color developing liquid, preferably of
about lg ~ about 15g per 1~ of color developing liquid.
Aminophenol developing agent includes, for example,
o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene,
2-amino-3-oxy-toluene, 2-oxy 3-amino-1,4-dimethyl-benzene and
others.
Primary aromatic amino color developing agent which is
especially useful is an N,N-dialkyl-p-phenylenediamine compound
and alkyl radical and phenyl radical may either be substituted
one or be unsubstituted one. Examples of the compound
especially useful among them include N,~-diethyl p-
-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine
hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)-toluene,
N-ethyl-N-~-methanesulFonamideethyl-3-methyl-4-aminoaniline
sulfate, N-ethyl-N-~-hydroxyethylaminoaniline and 4-amino-N-
-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate
and others.
Alkali color developing liquid to be used in processing of
the present invention can further contain freely, in addition
to aforesaid primary aromatic amine color developing agent,
q'3
- 38 -
various ingredients normally added to color developing liquid
such as, for examplet alkali agent like sodium hydroxide,
sodium carbonate and potassium carbonate, alkali metal s~lfite,
alkali metal bisulfite, alkali metal thiocyanate, alkali metal
halide, benzyl alcohol, water softener and thickener etc. The
pH value of this color developing liqu.id is usually 7 or more
and most generally is about 10 ~ about 13.
Metallic complex salt of organic acid as a bleaching agent
to be used in the bleaching solution used at bleaching step or
in the bleach-fix solution has functions to ox.idize the
metallic silver produced through the development and convert it
to silver halide and concurrently to cause uncolored portion of
coupler to color, and in its structurel metal ions of cobalt
and copper etc~ are coordinated with aminopolycarboxylic acid
or organic acid such as oxalic acid or citric acid. As the
most desirable organic acid to be used for the formation of
such metallic complex salt of organic acid, polycarboxylic acid
or aminopolycarboxylic acid is givenl These polycarboxylic
acid or aminopolycarboxylic acid can be alkali metal salt,
ammonium salt or water soluble amine salt. Concrete typical
examples of them are shown as follows.
(1) Ethylenediaminetetraacetic acid
(2) Diethylenetriaminepentaacetic acid
(3) Ethylenediamine-N~ oxyethyl) N,N',N'-triacetic acid
~4) Propylenediaminetetraacetic acicl
-~x~
- 39
~5) Nitryltriacetic acid
(6~ Cyclohexanediaminetetraacetic acid (or tartaric acid)
(7) Iminodiacetic acid
(8) Hydroxyethylglycinecitric acid
(9) Ethyletherdiaminetetraacetic acid
~10) Glycoletherdiaminetetraacetic acid
~11) Ethylenediaminetetrapropionic acid
(12) Phenylenediaminetetraacetic acid
(13) Disodium ethylenediaminetetraacetate
(14) Tetra-trimethylammonium ethylenediaminetetraacetate
(15) Tetrasodium ethylenediaminetetraacetate
(lÇ) Pentasodium diethylenetriaminepentaacetate
~17) Sodium ethylenediamine-N~ oxyethyl)-N,N',N'-triacetate
~18~ Sodium propylenediaminetetraacetate
(19) Sodium nitrilotriacetate
(20) Sodium cyclohexanediaminetetraacetate
Bleaching solution to be used may contain metallic complex
salt of organic acid like the one stated above as a bleaching
-agent and may also contain various additivesO As an additive,
it is desirable that alkali-halide or ammonium~halide, for
example re-halogenating agent such as potassium bromide, sodium
bromide, sodium chloride, ammonium bromide, etc~ is contained,
in particular. Further, pH buffer agent such as korate,
oxalate, acetate, carbonate, phosphate, etc. and the one known
- 40 -
as an additive to be usually added to bleaching solution such
as alkylamine or polyethyleneoxide may properly be addedO
When a bleach-fix solution is used for the bleaching step,
the bleach fix solution is to have both bleaching function and
fixing function and therefore the solution containing bleaching
agent as well as fixing agent which is identical to the one
used for ordinally fixing solution, is applied as a bleach-fix
solution. As a fixing-solution and a bleach-fix solution to be
used, a compound that reacts with silver halide and forms wa~er
soluble complex salt, for example, thiosulfate such as
potassium thiosulfate, sodium thiosulfate and ammonium
thiosulfate, thiocyanate such as potassium thiocyanate, sodium
thiocyanate, and ammonium thiocyanate, thiourea and thioether
are given.
Further, the fixing solution and bleach-fix solution may
contain singular or plural kinds of pH buffer agent consisting
of sulfite such as ammonium sulfiteJ potassium sulfite,
ammonium bisulfite, potassium bisulfite, sodium bisulfite~
ammonium metabisulfite, potassium metabisulfite and sodium
metabisulfite~ etc. and cf various kinds of salts such as boric
acid, borax, sodium hydroxide, potassium hydroxide, sodium
carbonate, potassium carbonate, sodium bicarbonate, potassium
bicarbonate, acetic acid, sodium acetate and ammonium hydroxide
etc.
When bleach fix replenisher is separately replenished to
-- ~1
the bleach-fix solution (bath), the composite solution of the
present invention may contain thiosulfate, thiocyanate or
sulfite etc. but it is desirable that they are replenished
separately between fixing agent and bleaching agent.
In order to enhance the degree of activity of the
bleach-fix solution in the present invention, air or oxygen can
blow in the bleach-fix bath and in the xeservoir tank for
bleach-fix replenisher or optimum oxidi2ing agent such as
hydrogen peroxide, bromate or persulfate etc. may be added
thereto~
In the processing of the present invention, silver
recovery may be performed in the known method for processing
solution containing soluble silver complex salt such as fixing
solution and bleach-fix solution etc. as well as for
stabilizer. For example, an electrolysis method (described in
French Patent No. 2,299,667), a precipitation method ~described
in Japanese Patent Publication Open to Public Inspection No.
73037/1977 and West German Patent No. 2,331,220), an ion
exchange method (described in Japanese Patent Publication Open
to Public Inspection No. 17114/1976 and German Patent No.
2~548,237) and a metal-substitution method (described in
British Patent No. 1,353~805) may effectively employed.
EXAMPLES
While the invention will be described in detail with
- ~2 -
reference to some embodiments thereof, it is to be understood
that the invention is not limited thereto.
EXAMPLE-1
A sheet of color printing paper was prepared in the manner
that a pretreatment was applied with a corona-discharge onto a
paper-made support coated thereon with a polyethylene layer
containing an anatase type titanium oxide that is a white
pigment, and the following layers were coated thereon in order;
1st layer: A silver chlorobromide photographic emulsion
containing 5 mol% of silver chloride was optically sensiti~ed
with anhydro-5-methyl-5'-methoxy-3,3'-di(3-sulfopropyl)-
selenacyanine hydroxide, and thus optically sensitized emulsion
was added with the protective dispersion solution comprising
2,5-di-t-butylhydroquinone and yellow coupler that is
~-l4-(1-benzyl-2-phenyl-3,5-dioxo-1~2,4-triazoli)]-~-pivalyl-
-2-chloro-5~ (294-di-t-amylphenoxy)butylamide]acetanilide,
and the mixture was then coated over the support~ so that the
amount of silver coated can be 0.35g per sqO m.
2nd layer: A gelatin solution was added with a protective
dispersion solution containing di-t-octylhydroquinone and an
ultra-violet ray absorber comprising a mixture of
2-(?'-hydroxy-3',5l-di-t-butylphenyl)benztriazole,
2-(21-hydroxy-5'-t-butylphenyl)benztriazole~
2-(2'-hydroxy-3'-t butyl-5'-methylphenyl)-5-chlorobenztriazole
and 2-(2-hydroxy-3',5l-di-t-butylphenyl)-5-chlorobenztriazole,
~ 43 ~
and thus prepared gelatin solution was then coated over the 1st
layer, so as to serve as an interlayer.
3rd layer: A silver chlorobromide photographic emulsion
containing 15 mol% of silver chloride was optically sensitized,
and thus sensitized emulsion was then added with a protective
dispersion solution comprising 2,5-di-t-butylhydroquinone,
2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman and a magenta
coupler that is l-(2,4,6-trichlorophenyl)-3 (2-chloro-5-
-octadecenylsuccinimide anilino)-5-pyrazolone. Thus prepared
solution was co ted over the 2nd layer, so that the amount of
silver coated can be 0.4g per sq~ m.
4th layer: The same solution as that used for the 2nd
layer was coated to serve as an interlayerO
5th layer: A silver chlorobromide photographic emulsion
containing 15 mol~ of silver chloride was optically sensitized
with anhydro-2-~3-ethyl-5-(1-ethyl-4(lH)-quinolylidene)-
ethylidene-4-oxo-thiazolidine-2-indene]methyl-3-(3-sul~opropylj-
benzoxazolium hydroxide, and thus sensitized emulsion was then
added with a protectie dispersion solution comprising
2-di-t-butylhydroquinone and a cyan coupler that is 2,4-
-dichloro-3-methyl-5- r~- ( 2,4-diamylphenoxy)butylamide~pehnol.
Thus prepared solution was coa~ed over the 4th layer, so that
the amount of silver coated can be 0.27g per sq. m.
6th layer: A gelatin solution was coated over the 5th
layer, so as to serve as a protective layer.
- 44 -
The silver halide photographic emulsions used in each of
the abovementioned light-sensitive layers were prepared
respectively in the process disclosed in Japanese Patent
Examined Publication No. 7772~1971, and they were chemically
sensitized by sodium thiosulfate and were then added with
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as the stabilizer.
The coating solution for every layer was added with saponin as
a coating assistant and bis(vinylsulfonylmethyl)ether as a
hardner, respectively.
Thus prepared color pinting paper was exposed stepwise to
light by a Sensitometer (Model RS-7, mfd. by Konishiroku Photo
Ind. Co., Ltdo~ Japan) and, the color-development,
bleach-fixation and washing were carried out so as to obtain
seven pieces of samples. These samples were dipped in the
solutions having the Recipes (1) through (7) indicated in the
following Table-l, respectively, at the temperature of 30C for
a minute and were then dried~ so that they were used for the
trial samples. The samples were measured on the reflection
density in blue, green and red by means of an optical
densitometer (Model PDA-65, mfd. by Konishiroku Photo IndO Co.
Ltd., Japan), and were then preserved in a thermo-hygrostat
chamber at 70C~ and 75~ RH, for 4n days. Again, these samples
were measured on the density thereof so as to obtain the
density lowering rate in the areas having approx. 1.5 in the
initial density and the yellow-stain density in the unexposed
- ~5 -
areas by measuring in blue. The results thereof are shown in
Table-2.
Table-l
.~e-~e ~. ___ ___ ~ __ ___ _
~ (1) (2) (3) (4) ~5) (6) (7)
Che~
l-hydroxy-
-ethylidene-l,l _ 2 2 2 2 2 2
-diphosphoric
acid (q) _ ~ _
Citric acid Sg)
3 _ _ _ _ _
_~_. ~__. __ ,__ _ ___ ~__
* Aqueous solu-
tion of ammonia 100 0.1 0.5 5 15
25% (g) _
(mol/~)1.47 O.OOlS 0.007 0.074 0.225
__ ___ ___ __ __ ___
5-chloro-2-
-methyl-4-_ 0.05 0.05 0.05 0.05 0.05 0.05
-isothiazoline-
~__ __ ____. _. _._ __ ~ _
pH value
(Adjusted the
pH with potas- 7.5 7.5 7.5 7.S 7.5 7.5 7~5
sium hydroxide
and sulfuric
~ __ _ _ _ l
. Compa rative __ _ _ ExamE les oi the
Note Examples Invention
note:
* percentage of ammonia in aqueous solution of ammonia
~2~3~3
- 4~ -
Table-2
~ .
\ Result Yellow Rate of Density Lowering S%)
Stain Blae Green Red
(1~ (Comparative 0.41 12 9 53
~r~ e~ _
(2) ( n ) 0.35 11 8 48
~_ .____
(3) ( ~I ) 0.18 13 9 70
(4) (Example of 0.29 11 B 35
~he l~e~ti~A~ _ _
(5) ( " ) 0~12 11 7 22
~_
______ ___ 0 19 10 ~ 15
_ _ _ _ 0.13 11 7 32
From Table-2, it is found that, in contrast with such a
case as in Recies ~1) and t2) in which one or two kinds of an
organic acid are merely added while no ammonia is added, in the
cases of following the Recipes (4) through (7) as in this
invention in which a certain amount of aqueous solution of
ammonia was added within the range of the amount claimed in
this invention to carry out a stabilizing process, a
yellow-stain does not increase and a red reflection density is
less discolored, that is very effective.
In the recipe (3) of ammonia to be added which is other
than that of the invention, it is found that the discoloration
rate of red is ex~remely remarkable, that is not preferable,
despite its excellently less yellow-stain~
EXAMPLE-2
A series of experiments of Recipe Nos~ t8) through (12)
shown in Table-3 were tried respectively in the same manner
taken in EXAMPLE-1. The results are shown in Table-4.
Table-3
. ___ __ _ ___ ~ ___
(8~ ~9) (10) ~11) (12) (13) (14)
~ ~ ~ __ ___ __
1 -hyd roxy-
-~thylidene-l~l 2 2 2 2 2 2
-diphosphoric
.~g~e~ tio~ ~ ~ ~ _.
of ammonia _ 4 4 4 4 4
_Z~ ~ ~0.06) (0.06) (0,06) (0.~6) (0.06) (0.06)
5-chloro-2-
-methyl-4- 0.05 0.05 0.05 0~05 0.05 0.05 0.05
-isothiazoline-
~2~L_ _~ __ . __ ~__
benzoic acid 1.5 1.5 1.5 1.5 1.5 1.5 1.5
~ __ __, __ ~_ ~ _
Antimold (*) 0.3 0.3 0.3 0.3 0.3 0.3 0~3
~ __ _~ _~ ~ __ __ .
pH value
(Adjusted the
pH with potas- 7.5 3.5 5O5 602 7.5 9.5 11.5
sium hydroxide
and sulfuric
--__ ____ ____. __ _ __
Comparative Examples of the
Note Examples Invention
, ... _ __~
(*) A mixed-emulsified dispersion comprising 15% of butyl
paraoxy benzoate, 15% of isobutyl paraoxybenzoate and 20~
of isopropyl paraoxy benzoate was used for the autimold in
each case.
~2~3.~3
- 48 -
Table-4
~ _ _ _ . . ._,. . . .
\ Result Yellow Rate of Density Lowering (%)
Recipe No ~ Stain ~lue Green Red
..... , _ =~ ~ ~ .~
(8) (Comparative 0.49 12 9 50
Example)
.. ., ~ _ _ __
( ~ O.l8 11 9 62
(lO)tExample of 0.18 11 8 33
the Invention)
_~__~
0.19 11 8 21
~12~ " ) 0.19 10 8 16
~_ __
(13)( " ) 0.19 11 8 20
_ ~
0.22 11 9 32
As is obvious from Table-4, in the cases of Recipe Nosg
(10) through (13) each having an ammonium salt therein and the
desirable values within the allowable range of the invention,
the stains and the red reflection density thereof were also
desirable~ so that the discoloration caused by keeping the
samples for a long time.
EXAMPLE-3
A sheet Gf color paper prepared in Example-l was printed
picturewise and was then processed in a continuously
~25~
- 4~ -
replenisbing process by means oE an automatic processor,
~hereinafter called a running process). The steps of this
process and the composition of the processing liquids were as
~ollows;
Basic Processing Steps
tl] Color developing 33C 3 min.30 sec.
[2] Bleach-fixing 33C 1 30
[3] Stabilizing 25 - 30C 3 0
[4] Drying 75 - 80C 2 approx.
Composition of the Processing Liquid
<Tank color-developing liquid>
Benzylalcohol 15m~
Ethyleneglycol 15m~
Potassium sulfite 2.0g
Potassium bromide 0.7g
Sodium chloride 0.2g
Potassium carbonate 30.0g
Hydroxylamine sul~ate 3.0g
Polyphosphoric acid ~TPPS) 2.5g
3-methyl-4-amino-N-ethyl-
-N-(~-methanesulfonamideethyl)-
=aniline sulate 5.5g
Optical whitening agent
(4,4'-diaminostilbene
disulfonate derivative) 1.0g
Potassium hydroxide 2.0g
Add water to make 1,000 c.c.
- 50 -
<Color-developing replenisher>
Benzyl alcohol 20m~
Ethylene glycol 20m~
Potassium sulfite 3.0g
Potassium carbonate 30.0g
Hydroxylamine sulfate 4.0g
Polyphosphoric acid (TPPS) 3.0g
3-methyl~4-amino-N-ethyl- -
-N~(~-methanesulfonamideethyl)-
-aniline sulfate 7.09
Optical whitening agent
~4,4/~diaminostilbene
disulfonate derivative) 1.5g
Potassium hydroxide 3.0g
Add watex to make 1,000 c.c.
<Tank bleach-fixing solution>
Iron (II) ammonium ethylenediamine
tetraacetate, dihydrate 60g
Ethylenediamine tetraacetic acid 3g
. Ammonium thiosulfate (70% solution~1001~
Ammonium sulfite ~40~ solution) 27.5mQ
Adjust the pH value with potassium
carbonate or glacial acetic acid topH 7.1
Add water to make 1,000 c.c.
<Bleach-fix replenisher A>
Iron (II) ammonium ethylenediamine
tetraacetatey dyhydrate 260g
Potassium carbonate 42g
Add water to make 11000 c.c.
51 -
l The pH value of this solutionp~ 6~7 ~ Ool
<Bleach-fix replenisher B>
Ammonium thiosulfate (70% solution)500m~
Ammonium sulfite (40% solution)250m~
Ethylenediamine tetraacetate 17g
Glacial acetic acid 85m~
Add water to make 1,000 c.c.
The pH value of this solution pH 4.6 + 3O1
A running test was tried in the manner that an automatic
developing machine was filled up with the abovementioned tank
color-developing solution and tank bleach-fixing solution and
the below-mentioned stabilizing solution~ and a sheet of color
paper was processed with replenishiny every three minutes the
abovementioned color developing replenisher, bleach-fix
replenishers A and B and stabilizing replenisher with the use
of a quantitative determination cupO Amounts of each solution
replenished per sq. meter o color paper were 324m~ to the
color developing tank, 25m~ each of bleach-fix replenishers A
and B to the bleach~fixing tank and 150m~ of the
below-mentioned stabilizing solution to the stabilizing tank,
respectively.
The stabilization processing tanks of the automatic
developing machine comprised three stabilizing tanks, No. 1
through 3 in the downstream dir~ction oE a light-sensitive
- 52 -
material and adopted a multi-tank counter-current system ln
which a replenish~ent was made from the final tank and the
over-flow therefrom was introduced into the preceding tank and
further the overflow therefrom was then introduced into the
second tank before the final tank~
A continuous processing was tried until when the total
amount of bleach-fix replenishers A and B used was as much as
three times of the capacity of the bleach-fixing tank.
5tabilizing solution
l-hydroxyethylidene l,l-diphosphoric acid 2~09
Bismuth chloride (50% aqueous solution
containing chloric acid) 0~6g
calcium chloride 0.4g
5 chloro-2-methyl-4-isothiazoline-
-3-one 0.05g
2-octyl-4-isothiazoline-3-one 0~05g
Orthophenyl phenol 0.04g
Aqueous solution of ammonia (25~) 5.0g
Add water to make 1,000 c.c.
Adjust the pH value with sulfuric
acid and potassium hydroxide to pH 7.5
After continuously processing, a sheet of color paper
prepared in Example-l was made for a sample by expos.ing it
stepwise to light. The pH values each of the stabilizing baths
No. 1 to 3 were changed respectively as shown in Table-5~ The
3~3
- 53 -
adjustments of the pH values thereof were made with potassium
hydroxide and sulfuric acid.
Next, the samples were processed with each stabilizing
solution. After then, the stabilizing solutions were thrown
away and were replaced by city water to process the other
samples. Each of the samples was applied to a torture test for
an image preservability in the same manner as taken in
Example-l, The results thereof are shown in Table~5. The
reflectivity of the stained portions produced in unexposed
areas were meansured by 445~m immediately after the samples
were processed, and the bluing phenomena produced in the
darkened areas (i.e. a Dmax) were visually observed by eye
under the sunlightO The results thereof are also shown in
Table-5.
- 54 -
Table-5
rle~ ~le T~se
pH value ~ _ _
Rec- of Ref- Visual Yellow- Discolor-
ipe Stabiliz- lec- Bluing Stain ation Rate
No. ing tive of Red
Solution of Reflection
Stain Density
___ _ ___ _ ~ ~,
Compa- almost
14 rative Washing 80 invis- 0.42 45
Exam- ible
ple
_ _~ ~ . _ _ ~ ___
15 .- 3.8 72 Strong 0~18 52
__ _~ ____ __ ~
Exam~ almost
ple of invis
16 the 5.5 78 ible 0~18 29
tnivOnn-
__~ _.~ ~_
invis-
17 ,. 7.5 81 balle at 0.18 16
_____ __ ~
8 ,, 8.5 80 ., 0.l9 l8
As is obvious from Table-5, in Recipe NOSL (16) through
(18) each using the stabilizing solution of the invention, it
is found that the red density discoloration was extremely small
without any yellow stain caused by adhering fresh sensitizing
dyes to the sample and not only any bluing caused by adhering a
whitening agent thereto but also any yellow stain caused by
3~
- 55 -
preserving the sample for a long time~ that is preferable.
EXAMPLE-4
The Exemplified cyan couplers ~7), (11), (22), t45) and
~53) and 6g of cyan coupler used in the undermentioned couplers
(a), (b) and tc) were mixed with 3g of dibutyl phthalate i.e.,
a high boiling organic solvent, and 18g of ethyl acetate and if
necessary some amount of dimethyl formaldehyde as needed to
prepare the mixture solution~ and the mixture was heatedly
dissolved at 60C and then was mixed again with lOOm~ of 5%
aqueous gelatin solution containing lOmQ of 5% aqueous solution
of Alkanol B (alkylnaphthalene sulfonate, mfd. by Du Pont) and
was then emulsified and dispersed by an ultrasonic dispersing
means to prepare a dispersed solution.
Next, the dispersion solution was added to a silver
chlorobromide emulsion containing 10 mol% of silver chloride so
that the amount of cyan couplers shown in Table-1 could be
10 mol% to the silver, and 1,2 bis(vinyl sulfonyl) ethane was
further added to serve as a hardner in the proportion o~ 12mg
to lg of gelatin~ and thus prepared mixture was coated over a
polyethylene-coated paper-support so that the amount of silver
coated could be 5mg~100cm . The color paper sample thus
obtained was exposed wedgewise to light with setting an
interference filter of 700~m in an ordinary manner, and the p~
values of the running-processed stabili~ing solutions of
Example-3 stored in Tank Nos. 1 to 3 were adjusted to pH 3O5
~ 3
- 56 -
and 7~5 by making use of potassium hydroxide and sul~uric acid
and the sample was processd in the process taken in Example-3
and with the processing solution used therein. After measuring
the areas of ~he sample where the red reflection density was
about 1.0, it was allowed to stand under the sunlight for 250
hours. Then, the described areas were measured again to obtain
the discoloration rate of the cyan dyes. The result~ thereof
are shown in Table-6.
The following couplers were used for the purpose of
comparison;
Coupler ~a)
~ CONH(CH2)4O ~ tC5H
Coupler ~b?
OH
~ CONHC12H25
Coupler (c)
OH
[~,C ONI:C 1 2H 2 5
Table-5
_ _ _ ~ ....... ....
Cyan ~
CouplerpH 3.5 ~Comparison) pH 7.5 ~Invention)
_ __~
~a) 45 37
_ ~
(b~ 42 36
~c) ~
(7) 25 11
__ ~_
(11~ 24 10
(22
(45) ~7 1
_ ~
(33~ ~ _ ____
As is obvious from Table-6, the couplers (7), (11), (22),
(45) and (53) showed a great reduction in the
photodiscoloration when using the recipe for the stabilizing
solution of the invention.
Effects of the Invention
As is obvious from the abovementioned examples~ this
invention may be able to display the effects that a light or
dark discoloration as well as a bluing phenomenon can also be
.''3
- 58 -
prevented, and in particular, a color dye image finishing is
not affected at all even in a stabilizing process in which the
amount of washing water is reduced or is eliminated.
