BACXGRO D OF THE INVE~TION
(1) - IBLD OF TH33 INVENTION
Thi3 invention relates to a method for processing o~
imagewise exposed color photographic light-Qensitive elements
containing ~ilver halide thereinafter, referred to a~ "color
photographic elemen~s") and more particula~ly, to an improved
pho~ographic process whlch enables sufficient de~silvering in
a shortened time and produce~ good guality color
rep~oduct~ons.
`
(2) DESC~IPTION OF T~ PRIOR ART
.
Ba~i~ processes for processing color pho~ographic
elements generally include a color development step and de-
lS silvering step, ~n the color development, image~ise exposedsilver halide is reduced by a color developing agent to ~orm
metallic sllver and the oxidized color dev.eloping agen~ reacts
with a coupler (or dye forming agen~) to form a color image.
In the subsequent de-silvering step, the metallic silver
20; formed in the color .development i5 oxidized by an oxidizing
agent (generally called ~a bleaching agentn) and ~he oxidized
silver i~ then dissolved by a silver iron complexing agent
generally called a fixing agent. This de~ilvering step
essent~ally leave~ a dye image on the color photographic
25 ~ elements.
The de-~ilvering step i3 done wi~h either a bleaching
bath containing a bleaching agent followed by a fixing bath
~ ~ i
- 2 - . ~ ,1
,
~,,
,~
containing a fixing agen~ or a single bleach-fixing bath (or
blixing bath) containing both bleaching and fixing agents.
In addition to these basic steps, the actual
procedures of color development processes include various
additional steps such as hardening step, stopping step
stabilizing s~ep and washing step, so as to obtain a dye image
having a better pho~ographic and physical quality and a longer
stability of the dye image.
Ferricyanides, dichromates, ferri chloride,
aminopolycarboxylic acid ferric ion complex salts and
persulfates are generally known as the bleaching agent.
Howeverj ferricyanides and dichromates are liable to
cause environmental pollution and the use thereof requires
special equipment for the treatment of such chemicals. Ferric
chloride has various problems in practical use. For example,
it forms ferric hydroxide and produces stains in a subsequent
washing step. ~Persu'lfates have disadvantages in that they are
very weak in bleaching power and therefore require an
`~ extremely long time for bleachin~. In this connection, there
~0 has been proposed a method for improving the bleaching power
of persulfates by using them together with a ' bleach
accelerator. ~owever, this method is not practical because
the use and storage of persulfates are controlled by Fire
-Prevention Law and consequently require special facilities.
Aminopolycarboxylic acid f'erric ion complex salts (or
ferric salts of an aminopolycarboxyli¢ acid), particularly
ethylenediaminetetraacetic acid ferric ion complex salt (or
ferric salts of ethylenediaminetetraaacetic acid) are the
bleaching agents most widely used at present because, unlike
persulfates, they have few problems regarding environmental
pollution and storage. However, the bleaching power of the
aminopolycarboxylic acid erric ion complex salts i5 not
always sufficient. The complex salts may attain the desired
de-silvering when they are used to bleach or bleach-fix a low-
speed silver halide color photographic element mainly
containing silver chlorobromide emulsion, while the complex
salts cannot achieve sufficient de-silvering or they need a
long time for bleaching when they are used to process a high-
speed color photographic element mainly containing silver
bromoiodide or silver bromochloroiodide emulsion and having
been spectrally-sensi~ized, especially a color reversal
photographic material or a color negative photographic
material for photographing containing an emulsion of high
~. .
silver content.
For example, the bleaching time of the photographic
color negative ligh~sensitive material in the bleach bath of
the aminopolycarboxylic acid ferric ion complex salt is at
least four minutes and it is necessary to take troublesome
precautions such as pH control or aeration in order to
maintain the bleaching power at the desired level. Even if
such precautions are taken, it is not rare that de-silvering
is not carried out sufficiently~
For the purpose of completa de-silvering, it is
further necessary to treat the element in a fixing bath for at
~ ~ 8~
least three minutes following the bleaching bath.
Accordingly, there is a strong need to shorten the time for
de-silvering.
For accelerating the de-silvering, there i5 known a
S bleach-fixing solution, as disclosed in German Patent 866,
605, which contains both aminopolycarboxylic acid ferric ion
complex salt and thiosulfate. However, the bleachins power of
this solution is very weak because the blixing solution
contains aminopolycarboxylic acid ferric ion complex salt
which itself is weak in oxidizing power (or bleaching power)
and thiosulfate which has a reducing power. It is, therefore,
very difficult for this blixing solution to attain the de-
silvering of a photographic color light-sensitive material of
high speed and high silver con~ent and consequently this
lS blixing solution cannot be employed for practical useO Many
attempts have been made to ovexcome these disadvantages of tbe
blixing solution. Examples of such attempts include the
addition of iodides or bromides thereto as disclosed in
British Patent 926, 569 or Japanese Patent Publication
No.11,854/1978 (U.S.P. 4,040,837) and the incorporation of
high concentration of aminopolycarboxylic acid ferric ion
complex sal~ thereto using triethanolamine as disclosed in
Japanese Patent Public Disclosure No.g5,834/1973. However,
none of these methods has sufficient effect for practical use.
In addition to its poor de-silvering ability, the
blixing solution has another serious drawback in that it
reduces the cyan dye formed by color development to the leuco
_ 5 _
. . . . - . . ,
dye and consequently interferes with color reproduction. It
is known that this drawback ~an be reduced by elevating the pH
value of the blixing solution as disclosed in U.S.P.
3,773,510. This method is, however, almost useless from a
S practical point of view because the elevation of the pH value
resul~s in weakening of the bleaching power of the solution.
U.S.P. 3,189,452 discloses a method wherein, after blixing,
the leuco dye is oxidized to the cyan dye by a ferricyanide
bleaching solution. But ~he use of the ferricyanide brings
about the problPm of environmental pollution and the bleaching
after the blixing has almost no effect on the decrease in the
remaining silver content.
As an alternative method for increasing the bleaching
power of the aminopolycarboxylic acid ferric ion complex salt,
there has been proposed a method wherein various bleaching
accelerators are added to the bleaching bath, the blixing bath
or ~he preceding bath.
Examples of such accelerators include various mercapto
compounds as disclosed in U.S.P. 3,893,858, British Pa~.
138,842 and Japanese Patent Public Disclosure No.141,623/1978;
compounds having disulfide linkage as disclosed in Japanese
Patent Public Disclosure No. 95,630/1978 (U.S.P. 4,169,733);
thiazolidine deriva~ives as disclosed in Japanese Patent
Publication No.9,854/1978; isothiourea derivatives as
disclosed in Japanese Patent Public Disclosure No.94,927/1978
~U.S.P. 4,144,068); thiourea derivatives as disclosed in
Japanese Patent Publication Nos. 8506/1970 (U~S.P. 3,617,283)
-- 6 --
.
~8~
and 26,586/1974 ~U.S.P. 3,809,563); thioamide compounds as
disclosed in Japanese Patent Public Disclosure No.42,349/1974
(GB 1,394,357); and, dithiocarbamic acid sal~s as disclosed in
Japanese Patent Public Disclosure No.26,506/1980.
s
Although some of these accelerators do in fact have a
bleach accelerating effect, the effect is, however, not
sufficient to meet the ~eed for shortening of the processing
time.
SUMMARY OF T E INVENTION
A first object of this invention is to provide a
method for the processing of a color photographic element,
especially one of high-speed and high silver content, which
enables sufficient de-silvering of the element in a shortened
time and produces good quality color reproductions.
. A second object of this invention is to provide a
method for th processing of a color photographic element,
` which gives rise to few or no problems of environmental
pollution or storage o chemicals to be used therein so that
the method can easily be put to practical use.
The inventors of this invention found that the objects
of this invention can be attained ~y ~ubjecting an imagewise
exposed color photographic element to a color development,
processing the developed element in a bleaching bath
containing an aminopolycarboxylic acid ferric ion complex
salt, followed by a blixing bath containing an
,
~.
8~6~3
aminopolycarboxylic acid ferric ion complex salt and a fixing
agent. In other words, ~he inven~ors found that by using the
bleaching bath containing the aminopolycarboxylic a~id ferric
ion complex salt, which is weak in the ~leaching power,
followed by the bLixing bath containing the
aminopolycarboxylic acid ferric ion complex salt and the
fixing agent i~ is possible to ensure de-silvering of the
photographic element in a shorter time than in prior art
processes wherein bleaching and fixing baths are used, and to
minimize the likelihood of the formation of the leuco form of
cyan dye, which has been one of the problems in the use of the
blixing bath. These are unexpected advantages since said
blixing bath is weak in bleaching power and would ordinarily
be considered incapable of easily processing a color
lS photographic element particularly one of high sensitivity and
high silver content.
As mention~d above, the bleaching power of the
aminopolycarboxylic acid ferric ion complex salt is not always
sufficient and becomes weaker in the blixing bath in which the
complex salt and the fixing agent coexist. Therefore, de-
silvering of a color ~hotographic element of high-speed and
high silver content has always been done by keeping the coLor
photographic element in a bleaching bath for a long time, and
thereaftPr subjecting it to a separate fixiny bath. In this
method, a water washing s~ep is usually required between the
bleaching and the ~ixing steps in order to avoid the
incorporation of the bleaching solution into the fixing bath
~x~
to thereby interfere wi~h the formation of ~he leuco form of
cyan dye, or elevation of the pH value of the fixing bath is
required to avoid the formation of leuço form o~ cyan dye, as
disclosed in Japanese Patent Public Disclosure No.70533/1982.
U.S.P. 3,189,452 discloses de-silvering in a blixing
solution and it also describes that a bleach bath containing a
ferricyanide having a strong bleaching power is required after
the blixing so that the leuco form of the cyan dye is
converted to the colored form of the cyan dye.
From the common knowledge set out above it is not
possible to imagine or anticipate the advantages of the
process of this invention which comprises processing the
photographic element in the bleaching bath for a shortened
time, followed by the blixing bath, in view of de-silvering
ability and Xormation of leuco form.
Fur~her the inventors found that the color
photographic element containing the cyan dye-forming coupler
o~ the formula (I) or (II) produces good quality color
reproductions when it is processed by the process of this
invention wherein the time for de-silvering is shortened as
much as possible:
,
.
X~
o~
R.3 ~,Nl:~
cor~ I
Z
t ~ )
N HC o R, 4
IJ
~ .
~2
;
:
- 10 -
,
- ', ' ' ~ : '' ' ;' ' :, - . , '
. .
:. ,., :
,
wherein Rl, R2 and R4 represent substituted or unsubstituted
aliphatic, aryl or heterocyclic group, R3 and R6 represent
hydrogen atom, halogen atom, subs~ituted or unsubstituted
aliphatic, aryl or acylamino group, or non-metallic atom group
which forms a nitrogen-containing five or six membered riny,
R5 represents substituted or unsubstituted alkyl group
(preferably having at least two carbon atoms), Zl and Z2
represent hydrogen atom or a group which can be released at
the time of the coupling reaction with a color developing
agent, and n represents 0 or 1.
When the cyan couplers of the above formulas are used,
good quality color reproductions can be attained without
softening of the gradation of the cyan image even when the
bleaching is carried out for a shortened time.
DETAILED DESCRIPTION OF THE INVENTION
The aminopolycarboxylic acid ferric ion complex salts
used as a bleaching agent both in the bleaching bath and in
the blixing bath are a complex of ferric ion and an
aminopolycarboxylic acid or salt thereof. The
aminopolycarboxylic acid ferric ion complex salts used in the
flixing bath may be the same as or different from those used
in the bleaching bath.
Typical examples of the aminopolycarboxylic acid and
salt thereof include:
,
~ X 6~
A-l ethylenediaminetetraaceti~ acid
A 2 disodium ethylenediaminetetraacetate
A-3 diammonium ethylenediaminetetraacetate
A-4 tetra (trimethylammonium) ethylenediaminetetra-
acetate
A-5 tetrapotassium ethylenediaminetetraacetate
A-6 tetrasodium ethylenediaminetetraacetate
A-7 trisodium ethylenediaminetetraacetate
A-8 diethylenetriaminepentaacetic acid
A-9 pentasodium diethylenetriaminepentaacetate
A-10 ethylenediamine-N (~-oxyethyl)-N,N',N'-triacetic
acid
A-ll trisodium ethylenediamine-N-(~-oxyethyl)-
N 9 N'oN'~ triacetate
A-12 triammonium ethylendiamine-N~ oxyethyl)-
N,N',N'-triacetate
~-13 propylenediaminetetraacetic acid
A-14 disodium propylenediaminetetraacetate
A-15 nitrilotriacetic acid
A-16 trisodium nitrilotriacetate
A-17 cyclohexanediaminetetraacetic acid
A-18 disodium cyclohexanediaminetetraacetate
A-l9 iminodiacetic acid
A-20 dihydroxyethylglycine
A-21 ethyletherdiaminetetraacetic acid
A-22 glycole~herdiaminetetra~cetic acid
A-23 ethylenediaminetetrapropionic acid
.
- 12 -
.:
'
'
It is ~o be understood that these compounds are
described only for the purpose of illustration and therefore
other aminopolycarboxylic acids can also be used in this
invention.
SAmong these illustrated compounds, A-l, A-2, A-3, A-8,
A-17, A-l~ and A-19 are particularly preferred.
The aminopolycarboxylic acid ferric ion complex salts
may be used in the form of complex salt or they may be formed
iQ a solution by mixing a ferric salt such as ferric sulfate,
10ferric chloride, ferric nitrate, ferric ammonium sulfate etc.
with the aminopolycarboxylic acid. The complex salt may be
used alone or in combination with one or more of other complex
salts. Nhen the complex salt is formed in a solution, one or
more aminopolycarboxylic acids and one or more ferric salts
lSmay be used. In all cases, aminopolycarboxylic acid may be
used in excess of the amount necessary to form the ferric lon
complex salt.
The bleaching solution or the blixing solution
containing the ferric ion complex salt may contain other
20metallic ion complex salts than iron, such as cobalt, copper,
etc.
The bleaching solutions used in this invention may
contain, in addition to the bleaching agents and the compounds
mentioned above, re-halogenating agents such as bromides, for
25example, potassium bromide, sodium bromide, ammonium bromide,
or chlorides, for example, potassium chloride, sodium
chloride, ammonium chloride. Any of the addenda used in
~ ~ ~2~
conventional bleaching solutions may be added to the bleaching
solutions used in this invention including inorganic acids,
organic acids and ~alts thereof having the capacity for
buffering a pH, for example, nitrates such as sodium nitrate,
S ammonium nitrate, boric acid, bora~, sodium metaborate, acetic
acid, sodium acetate, sodium carbonate, potassium carbonate,
phosphorous acid, phosphoric acid, sodium phosphate, citric
acid, sodium citrate, tartaric acid and the like.
The amount of the bleaching agents con~ained in one
liter of the bleaching solution used in this invention is 0.1
to 1 mole, preferably 0.2 to 0.5 mole. The pH of the
bleaching bath is adjusted to 4.0 to 8.0, preferably 5.0 to
The amount of the bleaching agents contained in one
lS liter of the blixing solution used in this invention is 0.05
to 0.5 mole, preferably 0.1 to 0.3 mole.
The inventors further found that the effect of the
addition of at least one bleach accelerator selected from the
compounds having mercapto group or disulfide linkage,
isothiourea derivatives and thiazolidine derivatives to the
bleaching bath used in this invention is superior to the
e~fect of the addition of the same accelerator to the
bleaching bath used in the prior art bleaching and fixing
steps. In addition, they also found that the bleach
accelerating effect is achieved and maintained for much longer
than is the effect obtained in the prior art de-silvering
process comprising the bleaching bath and the fixing bath.
- 14 -
~x~
The fixing agents which may be used in the blixing
bath used in this invention include thiosulfates such as
sodium thiosulfate, ammonium thiosulfate, sodium ammonium
thiosulfate and potassium thiosulfate, thiocyanates such as
5sodium thiocyanate, ammonium thiocyanate and potassium
thiocyanate, thiourea, thioether, ekc. The amount of the
fixing agents contained in one liter of the blixing solution
is 0.3 to 3 moles, preferably 0.5 to 2 moles.
In addition to the bleaching agents and the fixlng
10agents described above, any of the addenda may be added to the
blixing solution used in this invention, if required.
For example, one or more pH adjusting agents may be
added such as sulfites, e.g. sodium sulfite, ammonium sulfite,
etc., boric acid, borax, sodium hydroxide, potassium
15hydroxide, sodium carbonate, potassium carbonate, sodium
hydrogen carbonate, acetic acid, and sodium acetate. Various
antifoaming agents, surface-active agents, alkali metal
halides such as potassium iodide, potassium bromide, ammonium
` bromide, etc., ammonium halides, hydroxylamine, hydrazine or
20addition products of aldehyde with bisulfite may also be
contained in the blixing solution used in this invention.
The pH of blixing solution used in this invention is
adjusted to 5 to 8, preerably 6 to 7.5.
Preferably, the time for bleaching in` this invention
25is 20 seconds to 4 minutes. The time is more preferably 20
seconds to 2 minu~es, where a color photographic element
containing the cyan dye-forming couplers of the formula (I) or
- 15 ~
6Z8
(II) is processed and the bleach accelerating agent of the
formulas (III) to ~IX) described a~ter is used, while it is
preferably 1 to 4 minu~es where the accelerating agent is not
used. The bleaching time is preferably 40 seconds to 2
minutes where a color photographic ~lement not con~aining the
cyan dye-forming couplers of the formula (I) or (II) is
processed and the bleach accelerating agent of the formulas
(III) to (IX) is used, while it is preferably l.S ~o 4 minu~es
where the accelerating agent is not used.
The time for blixing is preferably 1 to 5 minutes,
more preferably 1.5 to 3.5 minutes. Less than 20 seconds of
bleaching time results in poor de-silvering even i~ the
blixing time is extended, while less than one minute of
blixing time also results in poor de-silvering even if the
bleaching time is extended.
In this invention, a water washing step may be
provided between the bleaching and the blixing steps. The
advantages of this inven~ion are not impaired even when a
water wash step in which very small amount of water is
~0 supplied is used.
Preferably, a replenisher is introduced into the
blixing bath in this invention. The replenisher contains
essential components such as the bleaching agent or the fixing
agent. A replenisher containing the fixing agent is
advantageously used.
When the processing is in progress, the overflow
solution, which flows out of the bleaching bath when the
- 16 -
8',,~ 8
bleaching replenisher is added thereto, may be introduced into
the blixing bath. This is very economical because the level
of the bleaching agen~ in the blixing bath is maintained by
the introduc~ion of the overflow solution from the preceding
bleaching bath. From the stand point of the prevention of
environmental pollution, it is desirable to decrease the
amount of the waste liquid of the photographic process, which
hàs high biochemical oxygen demand (BOD) and high chemical
oxygen demand tCOD). The decrease in the amoun~ of the waste
liquid by the use of the overflow solution makes the
photographic process more economical.
In the process wherein the replenisher is introduced
into the blixing bath, the overflow solution from the
bleaching bath, which is discharged in ~he prior art process,
is introduced into the blixing bath. As a result, the
overflow solution functions as a solvent which dilutes the
replenisher component to the desired level. Accordingly, the
replenisher may be supplied to the blixing bath in the form of
a` concentrated liquid, which results in a decrease in the
amount of was e liquid~
As described earlier, the incorporation of the
bleaching solution into the fixing bath brings a~out the
formation of the leuco form of cyan dye and significantly
damages photographic properties and therefore, it is usual to
2S provide a watex washing step between the bleaching ~tep and
the ixing s~ep so that the incorporation is prevented.
NEQCOLOR CHEMISTRY FOR C-41 NEGATIVES, First Wash (published
- 17 -
~ 28
by L.B. RUSSELL C~EM~CALS, U.S.A.~ describes that
insufficient water washing brings about the problems just
mentioned above and therefore a water wash is very important.
Japanese Patent Public Disclosure No.70533/1982
describes that it is necessary to raise the pH of the
bleaching bath when the water washing step is omitted so that
the formation of the leuco form of cyan dye and the
degradation of ~he bleaching solution are prevented. Thus,
the incorporation of the bleaching solution into the fixing
solution has been considered very disadvantageous. It is
therefore apparent that this invention in which the overflow
solution from the bleaching batb is mixed with the fixing
agent to form the blixing solu~ion is quite different from or
contrary to the prior art concept.
In this invention, the amount of the bleaching bath
overflow solution introduced to the blixing bath and the
amount of the bleaching agent - containing solution supplied
to the blixing bath are adjusted so that the concentrations of
the bleaching agent and the fixing agent in the blixing bath
are maintained within the range described earlier. The
amounts depend on the concentration of the bleaching a~ent in
the overflow solution to be introduced and the concentration
of the fixing agent to be supplied and they are preferably 150
m~ to 900 m~ per one square meter of the photographic element
to be processed.
In this invention, the replenisher supplied to the
blixing bath may contain any of the addenda wbich can be added
- 18 -
.. . .
' ' . ' ' ,' ' '
: . ' .~ ' '~
~'~ 8Z ~'~ 8
to the fixing bath, for example, conventional fixing agents
such as ammonium thiosul~ate, sodium thiosulfate, etc.,
sulfites, bisulfites, buf~ers and chelating agents. The
concentration of each of these components in the replenisher
may be adjusted so as to form a blixing solution of the
desired concentration when the replenisher is mixed with the
overflow solution from the bleaching bath and it may be higher
than the concentration in the replenisher to be supplied to
the conventional fixing bath. As a result, it is possible to
decrease the amount of waste liquid and consequently to lower
the cost for the treatment of the waste liquid.
The concentration of the fixing agent contained in the
replenisher supplied to the blixing bath is preferably 0.5 to
4 mole~, more preferably 1 to 3 mole/~.
The pH of the replenisher is preferably 6 to 10, more
preferably 7 to 9. The replenisher may contain the
aminopolycarboxylic acid ferric ion complex salts, ammonium
halides or alkali metal halides such as ammonium bromide,
sodium bromide, sodium iodide and the like.
In this invention, the overflow solution from the
bleaching bath may be introduced into the blixing bath
directly, for example, by connecting the overflow tube on the
bleaching bath to the blixing bath, or indirectly, for
example, by storing the overflow solution in a container,
mixing it with a fixing agent-containing solution and then
introducing the mixed solution into the blixing bath or
introducing the stored overflow solution and the fixing agent
into the blixing bath separately.
--19--
. . :
~ ~ `
6~
The cyan dye-forming couplers of the formula (I) or
~II) used in this invention will now be explained in detail.
In the formulas, Rl, R2 and R4 represent aliphatic
groups having 1 to 32 carbon atoms such as methyl, butyl/
tridecyl, cyclohexyl and allyl; aryl group such as phenyl and
naphthyl; or heterocyclic group such as 2-pyridyl, 2-
imidazolyl, 2~furyl and 6-quinolyl; and the aliphatic, the
aryl and the heterocyclic groups may be substituted by one or
more groups selected from alkyl, aryl, heterocyclic, alkoxy
such as methoxy and 2-methoxyethoxy, aryloxy such as 2,4~di-
tert-amylphenoxy, 2-chlorophenoxy and 4~cyanophenoxy,
alkenyloxy such as 2-propenyloxy, acyl such as acetyl and
benzoyl, ester such as butoxycarbonyl, phenoxycarbonyl,
acetoxy, benzoyloxy, butoxysulfonyl and toluensulfonyl, amido
such as acetylamino, ethylcarbamoyl, dimethylcarbamoyl,
methanesulfonamido and bu~ylsulfamoyl, sulfamido such as
dipropylsulfamoylamino, imido such as succinimido and
hydantoinyl, ureido such as phenylureido and dimethylureido,
aliphatic or aromatic sulfonyl such a~ methanesulfonyl and
phenylsulfonyl, aliphatic or aromatic thio such as ethylthio
and phenylthio, hydroxy, cyano, carboxy, nitro, sulfo, halogen
atoms and the like.
In the formula (I), R3 represents hydrogen atom,
halogen atom, aliphatic group, aryl group, acylamino group or
a group of non-metallic atoms which form a nitrogen-containing
five or six membered ring together with R2. These groups may
- 20 -
be substitu~ed by one or more substituting groups as defined
previously with respect to Rl.
In the formula (I), n represents 0 or 1.
In the formula (II), R5 represents substituted or
S unsubstituted alkyl having at leas~ two carbon atoms such as
ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl,
cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenylthio-
methyl, butaneamidomethyl and methoxymethyl.
In the formula (I), R6 represen~s hydrogen atom,
halogen atom, aliphatic group, aryl group, or acylamino group.
In the formulas (I) and (II), Zl and Z2 each represent
hydrogen atom or a coupling off group, for example, halogen
atom such as fluorine, chlorine and bromine atoms, alkoxy such
as ethoxy, dodecylocy, methoxyethylcarbamolymethoxy,
carboxypropyloxy and methylsulfonylethoxy, aryloxy such as 4-
chlorophenoxy, 4-methoxyphenoxy and 4-carboxyphenoxy, acyloxy
~uch as acetoxy, tetradecanoyloxy and benzoyloxy, sulfonyloxy
such as methanesulfonyloxy and toluenesulfonyloxy, amido such
as dichloroacetylamino, heptafluorobutyrylamino, methane-
sulfonylamino and toluenesulfonylamino, alkoxycarbonyloxy suchas ethoxycarbonyloxy and benzyloxycarbonyloxy,
aryloxycarbonyloxy such as phenoxycarhonyloxy, aliphatic or
aromatic thio such as ethylthio, .phenylthio and
tetrazolylthio, imido such as succinimido and hydantoinyl, and
aromatic azo such as phenylazo. These coupling off groups may
contain a photographically useful group.
In the formula (I), Rl is pre~erably aryl or
- 21 -
`', : .
;
,
,
~ ~ ~2 ~2 ~
heterocyclic group, and more preferably aryl group substituted
by halogen atom, alkyl, alkoxy, aryloxy, acylamino, acyl,
carbamoyl, sulfonamida, sulfamoyl, sulfonyl, sulfamido
oxycarbonyl or cyano group~
In the formula (I), if R2 and R3 do not form a ring
toge~her, R2 is preferably sub~tituted or unsubsti~uted alkyl
or aryl, and more preferably alkyl substituted by substituted
aryloxy, and R3 is preferably hydrogen atom~
In the formula (II), R4 is preferably substituted or
unsubstituted alkyl or aryl, and more preferably alkyl
substituted by substituted aryloxy.
In the formula (II), R5 is preferably alkyl having 2
to lS carbon atoms or methyl having a substituting group which
has at least one carbon atom, which substituting group is
preferably arylthio, alkylthio, acylamino, aryloxy or
alkyloxy.
In the formula (II), R5 is preferably alkyl having 2
to 15 carbon atoms and more preferably alkyl having 2 to 4
càrbon atoms.
In the formula (II), R6 is preferably hydrogen atom or
halogen atom and more preferably chlorine atom or fluorine
atom.
In the formulas (I) and (II), Zl and Z~ are each
hydrogen atom, halogen atom, alkoxy, aryloxy, acyloxy or
sulfonamido group.
In the formula (II), Z2 is preferably halogen and more
preferably chlorine or fluorine atom.
- 2~ -
~ ~2~jqæs
In the formula (I~, if n is zero, Z2 is preferably
halogen and more preferably chlorine or fluorine atom.
The cyan dye-~orming couplers of the formula (I) or
(II) are usually incorporated in silver halide emulsion
layers, particularly a red sensitive emulsion layerO The
amount of the coupler incorporated is 2 x 10-3 to 5 x 1o-l
mole/mole Ag, and preferably 1 x 1o-2 to 5 x 10-1 mole/mole
Ag.
The cyan dye-forming couplers of the formulas (I) and
(II) may easily be prepared according to the methodst as
described in U.S.P. Nos. 3,772,002; 4,334,001; g,327,173; and
4,427,767.
Typical illustrative examples of the cyan dye-forming
couplers of the formulas (I) and (II) include the following tG
which this invention is not restric ed:
-23 -
~ .
.
;,' .'
æ~
( C--~ ) o~
k~ C OC 3
1 2H~i ,~
(t)C ~ ~OC~CON~I
(t3C 5 H 1 1
C~--2 ) OH
~ M~C O--~)
C,~9~302NH~:)C~CON~I
C~
(~
tC-3 ) ~Cl2~Z5
COlY~I C~
\~=J C~
tC3H7 )~302NH
--24 --
,
2~
C~
OEI
1 2H2 a ~ N~IC ~!~ k ~ H g
~OCHCON~
C--
0~
C6 ~, 5 1~ ~)
c--6 9
C~
Cl2H2s ,~ ~,
ce .
. , .
--25 --
~'~8~6'~8
C--7 )
,~, C~OC~s
NC~OCtICON~l
( C~
,~ OC~,
~OCHCONH
F
C~
C~
~i~C3H7
5)2 N4~0C~CON~I
W C~
- 26 -
~a~8~2~D~3
( C~ / O ) :E F
OH \_~
,~3,N HCO~
~3C5Hg l~OC~CONH
\=< ~b .
.
( C~
O ~ .
~t~5H~ l~Ob~lCON~ I N~302 C~
\=~ , C~
( C--~ a )
N ~C 0
~C~7~oC~cO~H I NH~30;~C2~40 C~
~_ ~ Cl
-- 27 --
: ' ~ ' ' i
.
~2
C~ 3 )
0~1
I 1 2~2 5 ,J~ NH~ 2 C 2 H5
NC~OC HC O N~
~ ce
( C--/ 4 )
N ~IC 1~3
(t)C ~ ~9 C
~7~ 1 ~ N~lS02 C~3
C ,H~aO~OC KCONH
CC
( ~--J ~ )
NHCO~
(t)C~Hg ~ ~ ~ NH~3O2C~3
HQ~/ \~OC HCO NH
.
.
- 2~ -
.
~ c~
OH
(~)C 8 H 1 7 ~ HC 0~
C~C ONH ¦ NH ~ 0 2 ( ~ 3
~ C~
- OC~Hg
C~ 7 )
0
2~2 5 ~1~ NHCO~-~y~ C
~)_~OCHCON~l I
(t)~ 3
( C~
C~LIg
(t)CsH~ O C~I CC) NH o
~t,lC ~ H~
-r ~
~C~I3
_ ;~9 _
:- . .
. .
.
C_J ~ )
N~
1 2H5 ~) ce NH~302~(;ff,
(tlC~Hll~ OC~CON~
tt)C5Hl 1
( C--2 o ) ()H
,~N.YCO~
(~)CsHI I~OC~:lCOI`li~/~ NH~02Cz~OCH~
~t)C5
( C--2 J ~
5~ N~C~ Ct)CS ~11
o NH~o2~23~D~(b~4
--30 --
( C--2 ~ 3
CH3 OH
~3, NUC (: ~
H I N~30~Cl~33
( C~
C~
. 3
~NHCO~)
1) N~ - NH;302 ~CI 2~2 s
~1 2~ 5
N~"NIICOC~CN
CZ
31 -
,
"
.
:. ' ` ' ' ` :
æ~
2 ~ )
F
C ~ H ~_
H
~ ,
( C--2 ~ )
CH~" _~ IC,~{
~ N~COC: t3C5H~
'
2 7 )
2~5
o~N~,NHCOCHO~NH~30,C4H~,
'
--32 --
, .. .. ,; ~-.
826~ ~3
C--~ 8 )
OH
~1!1~CON~CN
(t)Cs~ VC~CON~
(t)C5
--2
C O N 11
~t)C~H, ~OCHCONH
(t)C 8 H,~
( C--3 ~ )
0~1 -
,~ N
~t)C8~l 7~0C~ICONH
(~C 8 IIl,
,
--33 --
,
.
,.
z~
t ~--3 ~ 3
3H7
~t)C 5Hll~O C}IC O N H
~t)C5
( C~3 2
O H _~
'~Oa~~
(i)CS~ll~O(~ 0N~l 3
(t)CSH~, a
( C --3 3 )
( )2N(C2~;) 2
8~17 kl)
(t)C8~1~0CHC~
ce
--34 --
2~3
C~
C4 ~ ~3/ NHC OM~CN
(t)C5~l l~OC~ICONH
~t)C 5
C--3 ~ )
~i
I ~ 7 ,~, N~CONH~;~7
(t)C8Hl~OC~( ON-H
)(8Hl~
IC~4 )~ CN
(t)C5~ l~OC~C~ONH o
(t)C,H~
OC~ 3
:
--35 --
.
' '
~z~
3 7 )
0
~, N~C O NH ~r~
~t~C~ O
(t)C8Hl 7 ~1
'`~
~t,~C 8 ~1 7
( ~--3 ~ )
1)~
$3
(t~C~Hl ,~OC~CON~l
(t)c 8 ~ t 7
--36 --
t C~3
,~3, N HC () N
(t?C ~ ~O~:ICON~l
,=~ .
(~)C5H~ 1
( C~ 4' 0 ) C~3
0~1 ~
~3, NHC Oy \~:
~0 C HC O~H
(t~C
)
f. U
e
cc ~3~NHCOCHl~Cs~
c2~s (lt~C5
~, ` :
.
.
--37 --
..
.: ,
)
C~ ~3, H i ~(t)C5
C~s (t)C5 ~1 1
ce
( C--4~3 )
C~
,NHCOCHO~_(t)C6
C,~Ig~ ~)C~
ce ,
~, N~IC OC uo~')C 5 ~1 1
~t)C4~9 ~J (t)Cs
` --3~ --
.
,. ..
.
s ~
O H I 4
C H 3 ~3~ N~ Oc H~t)c s
C~
6 )
o~ ~ C2Hs
~ ICOCH~ 7
C,, 5~31 ~J (t~C 5 H
C~ .
7 )
ct~3~N~lCoc}lo-~tk 1`
(t~ 5 ~1 1
-- 39 --
`
3x6~Z~3
( C~
ce ~3~N HC ( ) CHO~ )C 5
C3F7cO~c~z
C~
C~
C2~5
HC~ S)CsH~ s
C~3 OCH2 ~ (t)C 5
,
tC--so)
a ~3~N~COC~(t)Cs~
C 2 H5 (~C 5 ~;
~2 C~2
-- 40--
,
~L~ 82 ~ ~
The bleaching accelerators will now be explained in
detail.
The bleaching accelerators which may be incorporated
in the bleaching ba~h used in this invention are any of
compounds which have bleach accelerating effect and are
selected from compounds having mercapto group or disulfide
linkage, thiazolidine derivatives or isothiourea derivatives.
The accelerators are preferably selected from the compounds of
the formulas (III) to (IX).
` 10
C l~L
Rl ~
/N--( CH2 )n~~
R2
wherein Rl and R2 may be the same or dife~ent and
represent h.ydrogen atom, substituted or unsubstituted lower
alkyl preferably baving l to S carbon atoms, particularly
methyl, ethyl and propyl; or acyl preferably having l to 3
carbon atoms, such as acetyl and propionyl, and n is l, 2 or
3.
Rl and R2 may form a ring togetherO
Rl and R2 are preferably substituted or unsubstituted
lower alkyl.
Examples of the substituting groups which R1 and R2
contain include hydroxyl, carboxyl, sulfo and amino groups.
- 41-
1~8Z~2~i3
~3
l ~ N - ~ C ~2 9 ~ - 8
~ 2
wherein R3 and ~4 are the same as described previously
regarding Rl and R2 of the formula (I), and n is 1, 2 or 3.
R3 and R4 may form a ring together.
R3 and R4 are preferably substituted or unsubstituted
lower alkyl group~
Examples of the substituting groups which R3 and R4
contain include hydroxyl, carboxyl, sul~o and amino group~
~:
- 42-
,
~ . ' , ' , ~ ' , ,
32~28
.~ y
N -- N
Il 11
C C
/ \ /\
~s
~)
N ~ N
1~ 11
C
/ ~ /\
Rs N ~I
I
H
N = N
N N
~/ R
~H
.
--4 3--
.
~, . , , ~
.
,
?/L~82~fæ,8
wherein R5 represents hydrogen atom, halogen atom such
as chlorine or bromine, amino, substituted or unsubstituted
lower alkyl preferably having 1 to 5 carbon atoms,
particularly methyl, ethyl and propyl, and alkyl-containing
amino such as me~hylamino, ethylamino, dimethylamino and
diethylamino groups.
Examples of the substituting groups which Rs contain5
include hydroxyl, carboxyl, sulfo and amino groups.
/
7 N
R 8
wberein R6 and R7 may be the same or different and
each represents hydr.ogen àtom, substituted or unsubstituted
alkyl, preferably lower alkyl such as methyl, ethyl and
propyl, subs~ituted or unsubsti~uted phenyl or substituted or
~0 unsubstituted heterocyclic, more specifically heterocyclic
having one or more hetero atoms such as nitrogen, oxygen and
sulfur atoms, for example pyridinP ring, thiophene ring,
thiazolidine ring, benzoxazole ring, benzotriazole ring,
thiazole ring and imidazole ring.
R8 represents hydrogen atom or substituted or
unsubstituted lower alkyl preferably having 1 to 3 carbon
atoms, such as methyl and ethyl.
- 44
., ~ .
~ ~ 8~
Examples of the substituents which ~6, R7 or R8 may
contain include hydroxyl, carboxyl, sulfo, amino and lower
alkyl groups, Rg represents hydrogen atom or a carboxyl group.
S ( ~)
N~1 o
C ~ C ~
N ~1 1 R ~ 2
L0 wherein Rlo~ Rll and ~12 may be the same or different
and each represents hydrogen atom or lower alkyl preferably
having 1 to 3 carbon atoms, such as methyl and ethyl.
Rlo and Rll or R12 may form a ring together.
X represents amino, sulfonic or carboxyl group which
may contain one or more substituents, for example, lower alkyl
such as methyl and acetoxyalkyl such as acetoxymethyl.
Rlo, Rll and R12 are most preferably hydrogen atom,
methyl or ethyl group, and X is most preferably amino or
dialkylamino group.
Typical illustrative examples of the compounds
represented by the formulas (III) to (IX) include the
following:
-45-
. . .
. :'. ' ' ' , ~
:. ~ .. . .
~,. .... . .
,
( m )
\N~ 2 ) 2--SH
/
I3C \
( C~2 3 2 -~3H
~3 C
~ .
( m ) ~ (3)
~N -( C~2 ) 2--8
Hs ~ 2
m ) (4)
H3C
~N--C H ;~
~ ,~
~3 ~
~ m )-~s)
: \/N~ 2 ~ 2~3
. ~3~0~ ::
HOOC~2 C
~N--(C H2 ) 2--
~3C
-- 46 --
,
:
.
.
'. '
.
8~
~ m 3 - (7)
r~3 \
~N--~ CH2 ) ;~ ~H
HOC ~2 C H2
( m ) ~8)
C~3 ~2C~ C~2
,~N--( C~2 ) 2
~ ~{3 ~3 ( ) 2 C~ 2
(9)
O,~N~tC~2 )2
~3C
~N--( CH2 ) 2--~
\ ~3C ~2
( IY )--(2)
H5C2~
~N--( C~ ) 2--~3
Hsc2 J2
47
- . ,. .. . :: . ~ .
.
.: ...
: .
, .:
~8~
3)
/ ~3
~ N--C H 2--
( N ) ~ (4)
, / ~ ~ ~ .
~ C H 2 3 2 ~ t
\~I3COC~ ~2
t
~i~2 C ~
~N--~ C~ 2 ) 2--~3t
( ~ 3 (~)
OH
~3c~ 2
--C~2--~2
\ ~l3cc~lcH:2 12
OH
.
--48--
,
( N ) ~7)
C~3 ~02C~2~2 `~ \
lY--CH2-C~2-s1
C~3 /2
t ~ ~ (8)
( C~ C ~2- ~t
t ~ )--(g)
( Ca--CH2--C~2--37
(10
O N--C .~,--C ~ 2
:--49--
::
: ' ' . ~ .
.
'' ~` ,
. .
. .
,
z~
( ~ ) ~1)
N -- N
Il 11
C
H
) `(23
N -- N
1: C
/\ ~\
H 3 C: 8
( Y)--t3)
N ~ N
` 11 11
H ;~
.
)--~4~
N -- N
11 11
C :
/ \3/ \~
. -- so--
.
' ~ .
'
.
N ~ N
Il 11
~. C
/ \ /\
I
(2)
. . N ~ N
11 ~1
C
/ \/\
NH2 N ~{
3~
N - N
Il . Il
C, C
/ \ / \
. C H 3 N .
( t~ ) Sl)
N -- I C~13
N N ~ C~2 ) 2 ~\
~/ CH3
8~
2~
~T a ~
N ~ H 2 3 2 1~ 2 o ~1~
.
~ ~ ) ~tl~
~ 2 C
3 C~2
1I n ,~
r~2 ~--N
( ~)--(2)
EIz C ~N/ \~
H
3)
H 2 C ~ N C IL,
H
,
` 52-
:, , ' ': . . '
.: .
.
- ~ ,, ' '
;. '
z~
4)
~2 C \C ~
El2 C ~ N C~ 3
5)
S
~2 C ~ CE~;~
C -~ -- C
2 --N H H \l~C~2
H
6)
C--~\
C~2
~)OC--C--N/
i
~ .
( ~ )--(1)
~3C ~ ~ 1J--~3
~tCH2)2 ~-C~
H3 C ~ NH--CH 3 a ~ Cl
- 5 3-
: . '' , ~ '
.
: .' . ~ .
~3C \ 1~--C2~5
N--( C~2 ~ 2~ C
H3 C N~C 2 ~5 ~ 2 Hc~
( K)--~3)
H3 ~ \ ~ N--~ C~2 ) 2 CH3
N~ ~ CH,. )--8--C
H3C \ NH~( C~2 ) 2~E~3
C ~ 4)
~3 ~ 3
N ~C~I2~2--~--C
C \
5)
C~3~ C~232\ ,~N~
/N -CC~)2--9--C\ O a ~1~ -
CH3 ~32 t C~2 ) 2 P~2. .
--54--
. .
.
:
- : . . ' . ,: ., - . .
t ~ )--lo)
C~3 ~3 2 (~2C) 2 \ ~
~2~2~ C\ q~ 2HCt
~13 C ~H;~
7)
3Cl-tH2C)2 \ ~N~l
/N ~C~2)2
H3C NH;~ 2~~
O
~OOC--t C~ 2--~3 C ~
\ MH2
lg~
N~l
H~OC--C~12--9--C ~
\ N~2
--s5--
,
. . .
. ~ ,., . ~ ~. , .
:
6~1
) ~(10)
NH
HC~3~--~C~2~a~ ~\
NH2
~ ~--t
H3 C \ ~ ~ C~l~
/N--~ C~I2~ 2--~--C ~ I ~ ~ 2 ~1
All the compounds of the formulas. (III) to (IX) may be
prepared by well known methods. For example, the method for
preparation of the compounds of the formula (III) is desc~ibed
` in U.S.P. 4,285,98, G. Schwar~enbach et al., ~elv. Chim.
Acta., 38, 1147 (19555), and R.O. Clinton et al., 3.Am. Chem.
SOC., 70, 950 ~1948); that of the formula (IV) is described in
Japanese Patent Public Disclosure No. 95630/1978; that of the
formulas (V) and (VI) i5 described in Japanese Patent Public
Disclosure No. 52534/1979; that of the formula (VII) is
described in Japanese Patent Public Disclosure Mos.
68568/1976, 70763/1976 and 50169/1978; that of the formula
(VIII) is described in ~apanese Patent Publication No~
- 56
- , - ~
- :
. .
. .
.
,
.
~82~Z8
9854/1978 and Japanese Patent Public Disclosure No.
214855/1984 (U.S.P. 4,508,817); and that o~ the formula (IX)
is described in Japanese ~atent Public Disclosure No.
94927/1978.
The amount of the compounds having mercapto group or
disulfide linkage, thiazoline derivatives or isothiourea
derivatives contained in the bleaching solution used in this
invention depends on the kind of photographic elements to be
processed, temperature at which the elements are processed,
time requïred for the desired processing and other conditions
but it is suitably 1 x 10-5 to lo-l mole/æ, and preferably 1 x
10-4 to 5 x lQ~2 mole/~l .
These compounds are usually dis~olved in a solvent
such as water, alkali, organic acids, organic solvents and the
like be~ore they are added to the bleaching solution.
Alternatively~ they may be added directly, that is, in the
form of powder, to the bleaching solution, which does not have
any influence on tbe bleach accelerating effect.
` ` Any of the silver halides such as silver bromide,
silver bromoiodide, silver bromochloroiodide, silver
chlorobromide, silver chloride can be used in the photographic
emulsion layers of the color photographic elements used in
this invention, especially, color photographic elements using
the silver halide emulsions which contain silver iodide in the
amount of preferaby up to lS mole %, particularly 2 to 12 mole
.
- 57 -
x~z~
The emulsions used in the photographic elements
processed by this invention can be prepared by well known
methods as described in P. Glafkides, Chimie et Physique
Photographique (Paul Montel, 19671, G.F. Duffin, Photographic
S Emulsion Chemistry (Th~ Focal Press, 1966), V.L. Zelikman et
al, or Making and Coa~ing Photographic Emulsio~ (The Focal
Press, 1964).
Cadmiu~ salts, zinc salts, lead salts, thallium salts,
iridium sal~s or complex salts thereof, rhodium salts or
complex salts thereof, iron salts or complex salts thereof, or
the like may be allowed to coexist during the forma~ion or
physical ripening of silver halide qrains.
Usually, the silver halide emulsions are chemically
sensitized, although they can be used without chemical
sensitization~ that is, in the. form of the so-called primitive
emulsion. The chemical sensitiza~ion can be. effected by the
methods as described in the book written by. Glafkides or
Zelikman et al, or H. Frieser Die Grundlagen der
~ Photographischen Prozesse mit Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968). Namely, sulfur sensitization
using a sulfur-containing compound which can react with silver
ion or active gelatin, reduction sensitization using a
reducing compound, noble metal sensitization using noble
metals such as gold can be used alone or in a combination of
2S two or more of them.~ Examples of the sulfur sensitizers
include thiosulfates, thioureas, thiazoles, rhodanines and the
like. Examples of the reduction sensitizers include stannous
.
- S8 -
.' , . : ' '
' ' ' ' ' , ~:
~ 2 ~
saltst amines, hydrazine derivatives, formamidinesulfinic acid
silana compounds and the like~ Examples of noble metal
sensitizers include complex salts of noble metals of Group
VIII of the periodic table, such as gold, platinum, iridium
and palladium.
The photographic emulsions may be spectrally
sensitized with methine dyes or the like. E~amples o~ useful
dyes for thi~ purpose include cyanine dyes, merocyanine dyes,
complex cyanine dyes, complex merocyanine dyes, holopolar
cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol
dyes. Especially useful dyes are cyanine dyes, merocyanine
dyes, and complex merocyanine dyes.
In addition to ~he light-sensitive silver halide
emulsion layers described above, emulsion layers of
substantially non light-sensitive silver halide fine grains
may be provided so as to improve graininess or sharpness or to
achieve other objects; Such substantially non light-sensitive
emulsion layer~ can be provided over a light-sensitive silver
`~ halide emulsion layer or between the light-sensitive silver
halide emulsion lay~r and a colloidal silver layer (yellow
filter layer or halation prevent;ng Iayer~.
The photographic elements used in this invention may
contain polyalkyleneoxides or, ether, ester or amine
derivatives thereof, ~hioether compounds, thiomorpholines,
quaternary ammonium salts, urethane derivatives, urea
derivatives, imidazole derivativest 3-pyrazolidone derivatives
- 59 -
GZ~3
or the like to increase sensitivity, or contrast, or to
accelerate development.
As a binder for photographic emulsion layers or other
layers, gelatin is advantageously used, although other
hydrophilic colloids can also be used.
The photographic elements used in this invention may
contain various compounds as antifoggants or stabilizers7
Examples of these antifoggants or stabilizers include azoles
such as benzothlazolium salts, nitroindazoles, triazoles,
ben~otriazoles and benzimidazoles (particulary nitro or
halogen substituted); he~erocycli~ mercapto compounds such as
mercaptothiazoles, mercaptobenzothiazoles, mercapto-
benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles
(particularly l-phenyl-5-mercaptotetrazole) and
mercaptopyrimidines; the heterocyclic mercapto compounds
having a hydrophilic group such as carboxyl and sulfone
groups; thioketo compounds such as oxazolinethione; azaindenes
such ~as tetraazaindenes (particularly 4-hydroxy substituted
` (1,3,3a,7) tetraazaindenes); benzenethiosulfonic acids;
benzenesulfinic acids; and the like.
The photographic elements used in this invention may
contain inorganic or organic hardeners in the photographic
emulsion layers and/or other layers. Examples of these
~ hardeners include chromium compounds such as chromium alum and
chromium acetate, aldehydes such as formaldehyde, glyoxal and
glutaraldehyde, N-methylol compounds such as dimethylol urea
and methyloldimethyl-hydantoin, dioxane derivatives such as
60 ~
~#X62~3
2,3-dihydroxydioxane, active vinyl compounds such as 1,3,5-
triacryloyl-hexahydro-S-triazine and 1,3-vinylsulfonyl-2-
propanol, active halogen compounds such as 2,4-dichloro-6-
hydroxy-s-triazine, mucohalogenic acids such as mucochloric
acid and mucophenoxychloric acid. These hardners may be used
alone or in a combination.
The photographic emulsion layers or other layers of
the photographic element used in this invention may contain
various surface active agents as coating auxiliary agents,
anti-static agents, or agents for improving sliding property,
emulsifiability, dispersibility, anti-adhesion and
photographic properties, for example for the purposes of
development acceleration, high contrast and sensitization.
The photographic emulsion layers of the photographic
lS elements used in this invention may contain, in addition to
the cyan couplers described above, color-forming couplers
which can form color by oxidative coupling with a primary
aromatic amine developing agent such as phenylenediamine
: derivative~ and aminophenol derivatives to form a colored dye
~0 in a color development step. Examples of these couplers
include known cyan couplers such as phenolic couplers and
naphtholic couplers, magenta couplers such as -S-pyrazolone
couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone
couplers and open-chain acylacetonitril couplers, and yellow
couplers uch as acylacetamide couplers (e.g.
benzoylacetanilide~ and pivaloylacetoanilides). The cyan dye-
forming couplers of the formula (I) or (II) can be used in a
- 61 -
z~
combination with known phenolic or naphtholic cyan couplers
and they can also be used in the polymerized form. Of these
couplers, non-diffusible couplers having a hydrophobic group
called ballast group are desirable. The couplers may be of
5either 4-equivalent type or 2-equivalent type to silver ion.
Colored couplers having color-correcting effec~ or couplers
capable of releasing a development inhibitor up~n development
(the so-called DIR couplers) may also be used. In addition to
DIR couplers, colorless DIR coupling compounds which form a
10colorlesq coupling reaction product and release a development
inhibitor or DIR redox compounds may also be incorporated.
The photographic elements used in this invention may
contain a developing agent, typical examples of which are
described in Research Disclosure, VolO 176, p.29 (1978),
15"Developing agents"~
The photographic elements used in this invention may
contain dyes in the photographic emulsion layers or other
layers as a filter dye or for the purposes of the prevention
` of irradiation or other objects. Examples of the dyes are
20described in Rese~rch Disclosure, Vol. 17~, pages 25 to 26,
(1978), "Absorbin~ and filter dyes".
The photographic elements used in this invention may
also contain antistatic agents, plasticizers, matting agents,
lubricating agents, ultra violet light absorbers, fluorescent
25whitening agents, air fog preventing agents and the like, as
described in Resèarch Disclosure, Vol. 176 (1978), pages 22 to
27.
-~2 -
~ ~ 8Z ~Z ~
The silver halide emulsion layers and/or other layers
are coa~ed on a support. The coating methods as described in
Research Disclosure, Vol. 176, pages 27 to 28, (1978) "Coating
Procedures" may be used.
S The process of this invention can advantageously be
applied to the processing of multilayer negative color light-
sensi~ive materials which contain incorporated color-forming
couplers or color light-sensitive ma~erials for reversal color
processing and fur~her, color X-ray light-sensitive materials,
monolayer special color light-sensitive materials or color
light-sensitive materials which contain incorporated black-
and-white developing agents such as 3 pyrazolidones as
described in U.S.P. Nos. 2,751,297 and 3,902,905, Japanese
Patent Public Disclosure Nos. 64339/1~81, 85748/1981 and
85749/1981 and incorporated precursors of color developing
agents as described in U.S.P. Nos. 2,478,400, 3,342,597,
3,342,599, 3,719,492 and 4,214,047 and Japanese Patent Public
Disclosure No. 135~28/1978. The process of this invention can
be effected even if these couplers are incorporated in the
developing solution.
The process of this invention may advantageously be
applied to color photographic elements which contain a large
amount of silver, for example, at least 3 g/m2, preferably 3
to 15 g/m2 of silver.
Primary aromatic amine color developing agents
contained in the color developing solution used in this
invention include those widely used in various color
- 63 -
~8~
photographic processes. These developing agents include
aminophenol and p-phenylenediamine derivatives. These
compounds are usually used in the form of salts, ~or example,
hydrochlorides or sulfates which are more s~able than the free
form thereof. These compounds are usually used in a
concentration of about 0.1 g to about 30 9, preferably about
1 9 to about 15 9 per one liter of the color developing
solution.
Examples of aminophenol developing agents include o-
aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-
oxy-toluene and 2-oxy-3-amino-1,4-dimethyl-benzene.
Especially useful primary aromatic amine color
developing agents are N-dialkyl-p-phenylenediamine compounds,
alkyl and phenyl groups of which may or may not be
substituted. Useful examples of these compounds include N,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-~-methanesulfonamidoethyl-3-
methyl-4-aminoaniline sulfate, N-ethyl-N-~-
hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline,
and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
toluenesulfonate.
`In addition to the primary aromatic amine color
developing agents described above, the alkaline color
developing solution may optionally contain various components
usually added to conventional color developing solutions, for
-64 -
~8~2~
example, alkalis such as sodium hydroxide, sodium carbonate
and potassium carbonate, alkali metal sulfites, alkali metal
bisulfites, alkali metal thiocyana~es, alkali metal halides,
benzylalcohol, water so~eners and thickening agents. The pH
S of the color developing solution is usually at least 7, most
typically about 9 to about 13.
The process of this invention may be applied ~o color
reversal processing. Black-and-whi~e developing solutions
used in the color reversal processing include those called
black-and-whi~e firs~ developing solutions used in reversal
processing of color photographic elements and those used in
processing of black-and-white light-sensitive materials. The
black-and-white developing solutions used in this invention
may contain various well known additives which are usually
added to conventional black-and-white developing solutions.
Examples of typical additiYes include developing
agents such as l~phenyl-3-pyrazoiidone, Me~ol (Registered
trademark) and hydroquinone, preservatives such as sulfites,
` alkali accelerators such as sodium hydroxide, sodium carbonate
and potassium carbonate, inorganic or organic inhibitors such
as 2-methylbenzimidazole and methylbenzthiazole, water
softners such as polyphosphates, and development inhibitors
such as a small amount of iodides or mercapto compounds.
The process of this invention comprises the color
development, the bleaching and the blixing steps described
earlier. After the blixing, water washing and stabilization
steps are usually provided. However, a simpler process in
- 65 -
z~
which after the blixing, the stabiliæation is carried out
without substan~ial water washing can also be used in the
process of this invention.
Washing water used in the water washing step may
contain known additives, if necessary. Examples of the
additives include chelating agents ~uch as inorganic
phosphoric acid, aminopolycarboxylic acid and organic
phosphoric acid, germicides for the inhibition of propagation
o~ bacteria or Algae, hardening agents such as magnesium salts
and aluminum salts, and surface active agents for the
pr~vention of unevenness. The compounds as described in LoE~
West, "Water Quality Criteria "Pho~O Sci. and Eng., vol. g
No.6, page 34~ -359 (1965) can also be incorporated. ~wo or
more washing baths can be used, if required and multi-stage
countercurrent water wash (for example, 2 to 9 stages~ can
also be used to save washing water.
A solution in which a color image is stabilized is
used as a stabilizer in the stabilizing step. Examples of the
` stabilizer include a buffer solution having a pH of 3 to 6 and
an aldehyde-containing solution, e.g. formalin. The
stabilizer may contain, if necessary, fluorescent wnitening
agents, chelating agents, germicides, hardening agents and
surface active agents.
Two or more stabilizing baths can be u~ed, if
necessary and multi-stage countercurrent water wash (e.g. 2 to
9 stages) can also be used to save the s~abilizing solu~ion
and further, water wash can be eliminated.
- 66 -
,
.
:
~2~i2~
Example l
Multilayer color negative films were made on different
pieces of a triacetylcellulose film support. The composition
of each of the layers was as follows
1st layer: Antihalation layer
Gelatin layer which contains black colloidal
silver.
2nd layer: Interlayer
Gelatin layer which contains an emulsified
dispersion of 2,5-di-t octylhydroquinone.
3rd layer: Low speed red-sensitive emulsion layer
Silver bromoiodide emulsion .. .....the amount o
(silver iodide: 5 mole %1 silver coated
l.6 g/m2
lS Sensitizing dye I .... per l mole of
silver
6 x 10-5 mole
5ensitizing dye II O~ per l mole of
silver
l~5 x 10-5 mole
Coupler .... per l mole of
~as described in Table l) silver
0.04 mole
Coupler EX-l .... per ~ mole of
silver
0.003 mole
-67 -
~ .
2~3
Coupler EX-2 .... per 1 mole of
silver
0.0006 mole
4th layer: High speed red-sensitive emulsion layer
Silver bromoiodide .... the amount of
(silver iodide: 10 mole %) silver coated
1~4 g/m2
Sensitizing dye I ... O per 1 mole of
silver
3 x io-5 mole
Sensitizing dye II .. ~. per 1 mole of
silver
1.2 ~ 10-5 mole
Coupler .... per 1 mole of
(as described in Table 1) silver
0.02 mole
Coupler EX~ per 1 mole of
silver
; 0.0016 mole
5th layer: In~rlayer
The same as tha~ of the 2nd layer
6th layer: how speed green-sensitive emulsion layer
Monodlsperse silver .... the amount of
` bromoiodide emulsion silver coated
(silver iodide: 4 mole %) 1.2 g/m2
. 68
. , ,
.
. ' ; , ~
,
- . ' , ;
Z~3
Se~sitizing dye III .... per 1 mole of
silver
3 x 10-5 mole
Sensitizing dye IV O~ per 1 mole of
silver
1 x 10-5 mole
Coupler EX-3 .... per 1 mole of
silver
` 0.05 mole
Coupler EX-4 .... per 1 mole of
silver
0.0015 mole
Coupl~r EX-2 .... per 1 mole of
silver
0.0015 mole.
7th layer: High speed green~sensitlve emulsion layer
Silver bromoiodide emulsion .. ......the amount of
~silver iodide: 10 mole %) silver coated
` 1.3 g~m3
Sensitizing dye III .... per 1 mole of
silver
. 2.5 x 10 5 mole
Sensitizing dye IV .... per 1 mole of
silver
~ 0.~ x 10-5 mole
- 69 -
V~6Z~
Coupler EX-5 .... per 1 mole of
s i lver
O . 017 mole
Coupler EX-4 .... per 1 mole of
silver
0.003 mole
Coupler EX-6 .... per 1 mole of
silver
0.003 mole
8th layer: Yellow f ilter layer
Gelatin layer comprising yellow colloidal ~silv3e
and an emulsified dispersion of 2,5-di-t-
octylhydroquinone in an aqueous gelatin solution.
9th layer: Low speed blue-sensitive emulsion layer
silver bromoiodide emul-qion ......... the amount of
~silver iodide: 6 mole %) silver Goated
' ' O . 0'1 g/m2
Coupler EX-7 .... per 1 mole of
~ silver
0.25 mole
Coupler EX-2 ... O per 1 mole of
silve~
0.015 mole
l~th layer: High speed blu~-sensitive emulsion layer
Silver bromoiodide emulsion ................ ...the amount of
(silver iodide: 6 mole %) silver coated
0~6 g/m2
--70
.
Coupler EX-7 ...................... per 1 mole of
silver
0.06 mole
11th layer: First protective layer
Silver bromoiodide ................ the amount of
(silver iodide 1 mole %, silver coated
average grain size 0.07 )1 ) 0,5 g
Gelatin layer containing an emulsified dispersion
of an ul~raviolet light absorbing agent W -1
12th layer: Second
Gelatin layer containing trimethyl methacrylate
particles of about 1.5 microns in diameter.
Gelatin hardening agent H-l and/or surface active
agent were added to each of the layers in
addition to the compositions ~e~cribed above.
.
< The compounds used to prepare the compositions >
Sensitizing dye I:
anhydro-5rsl-dichloro-3~3l-di-(r-sulfopropyl)-9-
~0 ethylthiacarbocyanine-hydroxide, pyridinium salt
Sensitizing dye II:
anhydro-9-ethyl-3~3~-di-(r-sulfopropyl)-4~5~4l~5l-
dibenzothiacarbocyanine-hydroxide, triethylamine
salt
Sensitizlng dye III:
anhydro-9-ethyl-5,5'-dich}oro-3,3'~ddi-(y-sulfopropyl)
oxacarbocyanine, sodium salt
-71 -
'
i28
Sensitizing dye IV:
anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di
(r-sulfopropyl)ethoxy~ethyl~ imidazolo-
carbocyaninehydroxide, sodium salt
:
: . :: . ~ :; ~ : :
:: ~
: . . . :
.: . - : : ,
` ~
~8X~
JJ O O D
1E O ~;
~ 3 z O
~ a c~ ~ E ~
1 Z ~ D --,
~5
t) "
0 ~, O
~ ~ S ~
Z`Z~Z
S~
Z " O
O ~ C~
V C~ O -
0~- 0
~ ' i _
--73 --
. ~
~8;2tj~
~.
C~
C~ ~
N O
C~__C ~
N N . N
C~ C~ C~ ~ O
o O c~ ~. S , I~
X _ ~Z / ~ Z~ \
~0 ~ ' U~
O'
X ~ U ~ ~
C~
z~
Z~
~ ~3 . V~
' ~ U~
n
~ C~ .
X 3:
~ _ P3
.
--74 --
,
~8~
The color negative films thus prepared were exposed to
tungsten light at 25 cms (the color temperaturei of which had
been adjusted to 4800~ through a fil~er~ thirough a wedge,
5 followed by color development at 38C as follows:
Process 1 (Comparative process)
Color development 3 min. 15 sec.
Bleaching As described in Table 1
Fixing As described in Table 1
Washing 3 min. 15 sec.
Stabilizing 1 min. 5 sec.
Process 2 tComparative process)
Color development 3 min. 15 sec.
Blixing As described in Table 1
Washing 3 min. 15 sec.
Stabilizing 1 mln. 5 sec.
Process 3 ~Process of this invention)
Color development 3 min. 15 sec.
20` Bleaching As described in Table 1
Blixing As described in Table 1
Washing 3 min. 15 secO
Stabilizing 1 min. 5 sec.
The composition of each of the processing solutions
25 used in the steps described above was as ~ollows:
Color developing solution
Trisodium nitrilotriacetate 1.9 g
- 75 -
.~ .
æ~
Sodium sulfite 4 g
Potassium carbonate 30.0 9
Potassium bromide 1.4 g
Potassium iodide 1.3 mg
Hydroxylamine sulEate 2.4 g
4-tN-ethyl-N-~-hydroxyethylamino)- 4,5 9
2-methylaniline sulfate
Water to 1.0 ~
pH 10.0
Bleaching solution
Ethylenediaminetetraacetic acid, 100.0 g
ferric ammonium salt
Ethylenediaminetetraace~ic acid, 8.0 g
disodium salt
Ammonium bromide 150.0 g
Ammonia water 128%) 7.0 m~
Water to l.OL
pH 6,0
Fixing solution
Sodium tetrapolyphosphate 2.0 g
Sodium sulfate 4.0 g
A~ueous ammonium thiosulfate solution 175.0 m~
~70%)
Sodium bisulfite 4.6 g
Water to 1.0~ pH 6~6
- 76 -
Blixing solution
Ethylenediaminetetraacetic acid, ferric 100~0 9
Ammonium salt
Ethylenediaminetetraacetic acid, 4.0 9
disodium salt
Aqueous ammonium thiosulfate solution (70%) 175.0 m~
Sodium sulfite 4-5 g
Ammonia water 15 m
Water to 1.0~
pH 6~8
Stabilizing solution
Formalin (40%) 8.0 mQ
(Polyoxyethylene para- 5.0 m~
monononylphenyl ether, 0.3 g/~
Water to 1.0~
The minimum density, gradation and relative
sensitivity of each of the film samples thus processed were
measured. An amount of residual silver in the area of maximum
color density was measured by X-ray fluorescence analysis.
Separately, the same film sample~ were processed by
another process, FUJI COLOR PROCESS CN-16 of FUJI PHOTO FILM
CO,, ~TD. (color development, 3 min. 15 sec.; bleaching, 6
min. 30 sec.; washiny, 2 min. 10 sec.; fixing, 4 min. 20
sec.; washing, 3 min. 15 sec.; stabilizing, l min. 5 sec.,
followed by drying. Processing temperature was 3~C),
followed by the measurement of the minimum density, gradation
ale~lo~o tr~Je ~n~flC
- 77 -
~ ~ ~Z 6~ ~
and relative sensitivity of the processed samples. The
results were compared with those obtained by the processes 1
to 3 described earlier.
The comparative results are shown in Table 1 by the
differences between the specific values obtained by the
processes 1 to 3 and those obtained by the control ~CN-16
process). ~inimum density values were omitted because they
were not signiflcan~ly dif~eren Table 1 shows that the
greater the absolute numerical values of gradation and
relative sensitivi~y become, that is, the greater the
differences from the results of ~he control process, the worse
the photographic properties get~
The relative sensitivity and yradation were determined
as follows:
lS Relative sensitivity:
The difference between the minimum density and the
density at an exposure value which corresponds on the
characteristic curve, to a density of 0.2 above the
` minimum density of the control sample.
Gradation:
The diference between the density at the exposure
value as defined above and the density at an exposure
value greater by 1.5 of logarithm than the exposure
value as defined above.
Comparative compounds A, B and C as shown in Table 1
are cyan dye-forming couplers of the following formulas.
-78 -
.Z8
Comparative compound.,~,
( ~ 5 ~
~,CONH~CH2)30~Cs~l l(t)
Comparative compouna g
0~
~,CO~
C~2 C ~2 ~ C~lC O 0~
C 1 2 H ~ 5 (n)
Comparative compound C
~,NHCOCHO~C,HIl(t)
--79 --
~ ~ ~Z 6~ ~
Table 1 clearly shows that the process of this
invention enables de-silvering to a sufficient level for
practical use in such a time, during which neither the
.bleaching - fixing process (Comparative sample Nos. 1 to 3)
nor the single blixing process (Comparative sample Nos. 4 to
6) enables de silvering sufficiently. As seen from the
differences in the relative sensitivity and gradation between
the control and the examples, the process of this invention
gives good quality photographic reproductions without the
formation of leuco form of cyan dye. Even in this invention,
when the time for de-silvering is ~hortened to 4 minutes
(bleaching 1 min. 30 sec.; blixing 2 min~ 30 sec.), the
gradation and relative sensitivity of Red-sensitive layer are
reduced on rare occasion as seen from the sample Nos. 13 a~d
14. However, it can generally be said that the process of
this invention can be used in combination wi~h the cya~ dye-
forming rouplers of the formulas I and II to ensure both de-
silvering and exc~llent photographic reproductions.
--~0 --
, ' ' ' '
1 ~6~ .
~ ~ _ ~
~ g ~ ~ ~
~J~8 ~'0
:1 Q ~ n
_ : _
~ Z ~
~ W N I-- O U; 0 ~ OVl ~ (.1 N I' O ~
, , ,,, . . , _ ~ _
~ ~ D ~ 8 ~ . ~ ~
a D~ a :- b ~ 8 ~ ~ la ~ ~
n. n. ~, ~ D. rr ~U~, ~ ~ ~ ~
~ ~ ' ~ ~
C.01 N N 0~ tO :1 O
_ ~ ~
~$ ~$ ~ ~ ~ ,~, 8
8 Dl ~ ~ 8 511 ~ ~ C Q ~
. 1: ~ ~ ~ ~ ~
O- ~ rr ~ ~ r~ ~ rr~ nl ~ .,
tO ~ ~ ~ ~ ~ ~ ~
~, _ . _ _
tD - m 1~ a ~ I ~ ~ ~i ~ a~
. _ O I_
O ~ ~ ~ 1,~a a~
D ~ 8 ~ ~ 1 ~ l
__ _ _ _ ;i~
. 8 ~ n ~ Y 8 ~,~ ~
~ ~ _
. N ~ ~ I--~ ~ S
N N N ~ N N W N ~ Cl ~
i~O i~ W~ ~ W ~ O~ n
._ ,, . _
I+ O l+ O I I I + + ~ ~ + + W
OO ~ O i' i~ C~
a O l+ Y O ~ ~ lo . c . ~ . C~ 1~
__ N I-- _ . _ . O
II 1 1~ 0 1~ ~ ~ O o + :~
O o 0 O o O O O O o ~0
Ul o~ ~ y . U~
- - ~ - . - , - . . -. .
l~ + . J l~ ~ o o o ~ ~
l ~ ~ w --~
~ o l- o ~ c~ ~
~ ~ - ~
a ~ a 1~ O ~ ~ ¦+ O ¦ ~ ~
~ Id ' I' . ~
_ _ , _ _ .
. "...~, ,.-. ;. ' ."
`
2 ~
. ~
~ ~
~ !~'3
. ~
~n ~ w ~ ~ O
e~l O a~ o~ I ~
~1~ c ~ ~ ~ 8. '~ ~ 8
.~ ~ ~ .
. , -',-W ~ ~ .
_ _ __ ,~ ~
.,-~ g ~ n~
~ .- l
w w ~ ~ i W W ~ ~ W W
~ o U~ ~ W
__ . _ _ . _
Y 0 D ~1 ~ O O tO
. . _ __ C~
~ OCl
__ ~
9 0 o
~ ~ ~ O 1~ ~ ~
. . _ . ~ l
_ _._ .. . __ :~
~ G q Ia :il ~
- .__ . . _ ~, .
.;
:
. ' `
62~
Example 2
The color negative film sample No.l as described in
Table 1 (cyan dye-forming couplers used are Comparative
compounds A and B) was cut into a 35 mm-wide film which in
turn was .exposed through a wedge in a similar manner to that
of Example 1, ~ollowed by the processing according to the
Process CN-16 using an automatic developing processor to
prepare a control sample. Separately, the color negative film
sample No.l was sub~ected to the Process 1 or 2 as described
in Table 2 using the automatic developing processor.
- 83 - .
. , . . : .
.
----
a
C u~
O In ~ C un~Ln
c ~ o ~
r~ E~ C ~ ~ C
~::
l ~
u~ ~ c~ u
aJ ~ o - l o o o
C~ ~ ~ G~ O ~D
o ~ s~
E~
-
~ u
tn . . ~q m
c`~
~ ~ ~ ~ o ~
E~ ~ ~ c
E' ~-~
o - -
-~ ~
l ~
u~ ~ c~
~ 11~ 0 5 - I O O
O Q~ ~
E~ _ __ _ __
æ
~ ~ cn r1
J- . ~ N
~n ~ ,, ~ ~ rl
~ /
o ~ 1 x s
O ~
. c~ m ~
It should be noted that the comparison was made under
the condition that ~he time for bleaching in Process 1 that
is, 5 minutes is equal ~o the total time for ~leaching and
blixing in Process 2 as shown in Table 2.
The color negative films (35 mm - wide, 100 m - long
per day) were used for outdoor photography, and were then
subjected ~o the processings o~ Processes 1 and 2.
Separately, the same color negative films were subjected to
wedge-exposure once a day, followed by the processings of
Processesl and 2. Theseprocedureswerecarriedoutforten
successive days.
Compositions of the solutio~s and the replenishers
used in Processes 1 and 2 are as follows:
Color developing solution
Initial
solution Replenisher
Sodium nitrilotriacetate . 1.0 g 1.1 g
Sodium sulfite 4.0 g 4-4 g
Potassium carbonate 30.0 g 32.0 g
Potassium bromide 1.4 g 0.7 g
~ydroxylamine sulfate 2.4 g 2.6 g
4-(N-ethyl-N-~-hydroxyethylamino
-2-methylaniline sulfate 4.5 g 5.0 g
Wa~er to 1.0 Q 1.0 ~
pH 10.0 pH 10~2
- 85 -
Bleaching solution
Initlalsolution Replenisher
Ammonium bromide 160 g 176 g
Ethylenediaminetetraacetic acid,
sodium ferric salt 130 g 143 g
Ethylenediaminetetraacetic acid,
disodium salt 10 g 11.5 g
Ammonia water (28%) 7 m? 4 m~
Wàter to 1 1 1 ~
pH 6.0 pH 5.7
.
Blixing solution
Initial
solution Reple~isher
Ethylenediaminetetraacetic acid,
sodium ferric salt 70 g 70 g
Ethylenediaminetetraacetic acid,
disodium salt 4.0 g 4.0 g
Aqueous ammonium thiosulfate
solution ~70%) 175 m Q 200 m ~
Sodium sulfate 4.5 g 4-5 9
Ammonia water (28%) 12 m Q 13 m~
Wa~er ~o 1 ~
pH 6.8 pH 7.0
- 86 -
~ 2
Fixing solution
Initial
solution Replenisher
Sodium tetrapolyphosphate 2.0 9 2.0 g
Sodium sulfite 4.0 g 5.0 g
Aqueous ammonium thiosulfate
solutton (70%~ 175 m ~ 200 m Q
Sodium bisulfite 4.6 g 5 g
Water to 1.~
pH 606 pH 6.6
Stabilizing solution
Initial
solution Re~Ien~he,
Formalin (40%) 5 m~ 7 m~
(polyoxyethylene para- 5 m~ 7 m~
monononylphenyL ether, 0.3 g/
water to , 1 Q 1 æ
- 87 -
.
.
Table 3
Processing Steps Amount of Replenisher per 1 meter
of film
Process 1 Process 2
(Comparative~ (This invention)
Color development 40 m~ 40 m~
Bleaching 15 m~ 15 m~
Fixing 40 m~ -
Blixing - . 40 m~
Stabilizing 40 m~ 40 m~
The amoun~ of residual silver in the ma~imum color
density area of the film samples which were subjected to ;he
wedge-exposure, followed by the processings of Processes 1 and
~, was measured by X-ray fluor~scence analysis. Photographic
properties of the films thus processed were compared wi h
those of the control sample. The differences in gradation and
relative sensitivity ~etween the samples and the control are
as shown in Table 4.
~0 Table 4 shows that in the process of ~his inven~ion, a
good de-silvering effect and good quality photographic
reproduction were obtained and maintained for a long time even
when the process was crried out using an automatic developing
. processor, whereas in the comparative process in which the
time for bleaching was 5 minutes, de-silvering effect and
photographic reproduction became worse with time and no de-
silvering was effected on the 10th day. Namely, the process
of this invention provides stable de-silvering effect and good
.
- 88
,
- ' : ,
~. .
6Z8
quality photographic reproduction which are superior to those
provided by the comparative process in which the working time
for bleaching was the same (5 minutes) as in the process of
this inventionO
` - 89 -
;` `
: . , .` , ' ` :. ,
:~ ' ' ", '
' ~ ,' ~ ' , `: '; '
~ _ ~ +1 +l +l +l
~ ---- ~
.~-l c~ o o o o o o o o
~0 ~1 + + + ~1 +1
C _ . _,_ _ _ ___.__ m. _ ____
u~ m +1 0 0 0 +l ~1 +1
. ~ ,+ + +
o ~ o ~ o o o o
" +l o o o +l +l +l +l
~ _ + + + _
. ~ _ ~1 ~ o ~ +1 ~ +1 o
c~ ~1
~a o o o o o o o c~
o O ~ O. o O O O
++++ ++~+
_ .~ . _ ._ _ .
. ~ u~ ~
~ ~ . . . , a,.c:.
~~ ~ C~ o
.. ~ u~,
_ _ --
.
.~ _
Ul ~ ~
U
O JJ ~ ~ ~ J~
a ~ ~q
_ ~ ~ ~ _
U O ~ O C~l Ul O
_~ .
_ . _.__ _-. ... ... ~.
a~ o
bq .~ .
~a v
ùU ~ C~ ~
o ~
. . ~ . . ~
- , : ' .:
'' '
,
6~ i
Example 3
The color negative film No. 10 as described in Table 1
was exposed through a wedge in a similar manner to that of
Example 1, followed by color development at 38~C according to
the following steps.
Process 1 (Comparative)
Color development 3 min. 15 sec.
Bleaching The time as de~cribed in Table 5
Fixing The time as described in Table 5
Washing 3 min. 15 sec.
Stabilizing 1 min. 5 sec.
Process 2 (This invention)
Color development 3 min~ 15 sec.
~leaching The time as described in Table 5
Blixing The time as described in Table 5
Washing 3 min. 15 sec.
` Stabilizing 1 min. 5 sec.
Compositions of the solutions used in the processes
described above were the same as those described in Example 1,
except that the bleaching solution contained a bleach
accelerating agent ~bleach accelerator) as shown in Table 5 in
an amount as shown also in Table 5.
--91--
.
,. : '' '' ~
,~
The amount of residual silver in the maximum color
density area of each of ~he samples thus processed was
measured by X-ray fluorescence analysis.
Table 5 shows that the addition of the bleach
accelerating agent to the bleaching solution had an excellent
effect on the process of this invention which comprises
bleaching and blixing steps but it had only a small effect on
the comparative process which comprises bleaching and fixing
steps.
` -92 -
~8
_
In ~ O c
.~ _l ~ a~ ~ O ~ ~ ~ co ~ _I ~ ~P ~ ~ ~ ~ U~ U~
~ ~ ~ r~
~ o
Ul X ~ : 2: S C~
C C ~ O O .
~ m ~ ~S S . ~ S
o c ~ ~ _
E~ J~ C .~ O
u~ a~ ~ e E~ 8 :~
~ _ ~ _ _ trl
E~ ~: ~ _ a~ ~
C ~i -- o _I s ~ D Z X X
~U ~ _ _ _ _ .
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Example 4
The same film samples as those described in Example 1
were prepared in a similar manner to ~hat of Example 1, except
that the couplers used in the 3rd and 4~h layers in Example 1
were replaced by the following couplers, respectively.
3rd layer: Low speed red-sensitive emulsion layer
Comparative compound ~ of Example 1 ... per 1 mole of silver
0.04 mole
Coupler EX~ O~per 1 mole of silver
0.003 mole
Coupler EX-2 ~ O per 1 mole of silver
0.0006 mole
4th layer: High speed red-sensitive emulsion layer
Comparative compound ~ of Example 1 ... per 1 mole of silver
0.02 mole
Coupler EX-l .............. ~........... per 1 mole of silver
0.0016 mole
~ The film samples thus prepared were cut into 35 mm-
wide film which was then exposed to tungsten light at 25 cms
(the color temperature of which had been adjusted to 4,800K
through a filter) through a wedge, followed by the processing
according to FUJI COLOR PROCESS CN-16 of FUJI PHOTO FILM CO.,
LTD. (color development 3 min. 15 sec., bleaching 6 min. 30
sec, washing 2 min. 10 sec., fixing 4 min. 20 sec., washing 3
min. 15 sec., stabilizing 1 min~ 5 sec., followed by drying;
the processing temperature was 38C~ using an automatic
-94 -
~ 2 ~
developing processor to prepare a control sample. separatelyt
the same film samples were exposed through a wedge, followed
by the three different processings as described in Table 6
using the automatic developing processor at 38C.
_ 95 0
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,
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E~ ~ u~ ~ u~ u~
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u~ ~ E~ .c E~ ~ E3 ~ E3 _1 ~
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o ~1 ~ x ~c: .n
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u~ ~ E~ . . C N~ .
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_I ~ ~ ~ C~: C ~1 C
tQ ~ ~ 3 . . N -
a~ O ~ ~ ~~ ~ ~ ~ -~
~0 O ,-1 '.~C IU a~
~ ~ m 3
2~
Compositions of the solutions used in
the processes described above were as follows:
Color developing solution (Processes ll to 13)
Sodium nitrilo~riace~ate l.9 9
Sodium sulfite 4.0 g
Potassium carbonate 30.0 g
Potassium bromide 1~4 9
Potassium iodide 1.3 mg
Hydroxylamine sulfate .2.4 g
4-(N-ethyl-N-~-hydroxyethylamino)-
2-methylaniline sulfate 4.5 9
Water to l.0 ~
p~l 10.0
Bleaching solution ~Processes 11 and 13)
Ethylenediaminetetraacetic acid, ferric 100.0 g
ammonium-salt
Ethylenediaminetetraacetic acldf disodium salt 8.0 g
Ammonium bromide 150.0 9
Ammonia water ~2~%) 7.0 mQ
Water to 1.0 R
pH 6.0
g7
.
'
.
,
Fixing solution ~Process 11)
Sodium tetrapolyphosphate 2.0 g
Sodium sulfite 4.0 g
Aqueous ammonium thiosulfate solution (70%)175.0 m~
S Sodium bisulfite 4.6 g
Water to 1.0
p~ 6.6
Blixing solution (Processes 12 and 13)
Ethylenediaminetetraacetic acid,
ferric ammonium salt 100.0 9
Ethylenediaminetetraacetic acid,
disodium salt 4.0 9
Aqueous ammonium thiosulfate solution (70%)17500 m
Sodium sulfite 4.5 9
Ammonia water (28~) 15 m
Water to l.OR
pH 6.8
Stabilizing solution (Processes 11 to 13)
Formalin (40%) 8.0 m~
(Polyoxyethylene para- 5.0 m~
monononylphenyl ether, 0.3 g/~
water to 1.0
Gradation and relative sensitivity of each of the
samples thus processed and the control were measured. An
` - 98 -
z~
amount of residual silver in the maximum color density area
was measured by X-ray fluorescence analysis.
In Process 13, the upper part of ~he bleaching bath of
the automatic developing processor was connected to the lower
part of the blixing bath by a tube so that the overflow
solution from the bleaching bath was introduced into the
blixing bath when the replenisher is added to the bleaching
bath. For ten sucGessive days, the 35 mm-wide film (100 m per
day) was used for outdoor photography, and were then subjected
to the processing according to Process 13 while replenishing
the following processing solutions. At the same time, the
samples exposed through a wedge were also processed every day.
<Amount of each of the solutions replenished per 1 meter ~f
tbe 35 mm-wide film ~
Replenisher to the color developing bath 40 m 2
Replenisher to the bleaching bath 20 m~
Replenisher (containing the fixing agent)
to the blixing bath 20 m~
Replenisher to the stabilizing bath 40 m~
<Compositions o the replenishers ~
Replenisher to the color developing bath
Sodium nitrilotriacetate 1.1 g
Sodium sulfite 4.~ g
Sodium carbonate 32.0 g
Potas~ium bromide 0.7 g
Hydroxylamine sulfate 2.6 g
_ 99 _
.
'
~8~
4-(N-ethyl-N-~-hydroxye~hylamino)-
2-methylaniiine-sulfate 5 0 g
Water to 1.0 ~
pH 10.2
Replenisher to the bleaching bath
Ammonium bromide 175.0 g
Ammonia water ~28%) 4.0 m~
Ethylenediaminetetraacetic acid,
erric ammonium salt 110.0 9
Ethylenediaminetetraacetic acid,
disodium salt 10 9
Water to 1.0
. pH S.7
Replenisher (containing the ~ixing agent) to
the blixing bath
Aqueous ammonium thiosulfate solution (70%)400 m~
Sodium sulfite 9 9
Ammonia water ~28%) 12 m~
Sodium bisulfite 10~2 9
Sodium tetrapolyphosphate 4.4 9
Water to 1.0
pH 8.1
-- 100 --
8~6~:~
Replenisher to the s~abilizing bath
Formalin (40~) 9 m 2
(Polyoxyethylene para- 7 m~
monononylphenyl ether, 0.3 g/
water to 1.0~'
Results of the processings are as shown in Table 7.
-- 101 -- .
.
.
.
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,
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~ O _ O N __ ~
~ ~]
: ~1 ~
_ ~ ~ e
~ . .
~8~62~
The difference in relative sensitivity and the
difference in gradation as shown in Table 7 are differences
between the control sample and the examples, respectively.
Table 7 shows that the process of this invention
provides good quality photographic reproductions and good de-
silvering in a shortened ~ime, which are comparable to those
obtain~d by the control process and that these effects of the
process of this invention are long-lasting.
Example 5
The procedure of Example 4 was repeated to prepare a
35 mm - wi~e film, except that Comparative compound A of
Example 1 used in Example 4 was replaced by the coupler o~ ~;e
following formula:
OH
C~3
(tlCsH~ Cl~
(~C 5Hl I
-- 103 --
.
6~3
The color negative pho~ographic element thus prepared
was subjected to the same exposure through a wedge as
described in Example 4, followed by the processing according
to the Process CN-16 as described in Example 4 using the
automatic developing processor.
Separately, the films exposed through a wedge were
processed by Processes 14 and 15 as described in Table 8.
Tabl~ 8
, . _ , _
Process 14 (Comparative) Process 15 (This invention)
-- _ r ,
Color development Color development
3 min. 15 secu 3 min. 15 sec.
Bleaching 40 sec.Bleaching 40 sec.
Fixing 3 min. 15 sec. Blixing 3 min. 15 sec.
Washing 3 min. 15 sec. Washing 3 min. 15 sec.
Stabilizing 20 sec. ~ =
Various bleach accelerating agents were used in the
processes as described in Table 8.
The processing solutions used in the processes of
Table 8 were the same as those used in Processes 11 and 13 of
Example 4, except for the following solutions.
-- 10~ --
Bleaching solution
Ethylenediaminetetraacetic acid,
ferric ammonium salt lO0.0 g
Ethylenedieminetetraacetic acid,
disodium salt 8.0 g
Ammonium bromide 80.0 g
Ammonia water (28%) 7.0 m
Bleach accelerating agent (as described in Table 9)
Water to l.0 ~
pH 6.0
Blixing solution
lS The same as the bleaching solution described
above except that any bleach accelerating
agents were not contained 500 m
Aqueous ammonium thiosulfate solution (70%) 175 m~
Sodium sulfite 4.0 g
20. Sodium bisulfite 4.6 g
Ammonia water (28%) 6.0 m
Sodium tetrapolyphosphate 2.0 g
For ten successive days, the 35 mm - wide films of the
Example (lO0 m per day) were used for outdoor photography, and
were then subjected to the processing according to Process 15,
while replenishing the following processing solutions. At the
same time, the samples exposed through a wedge were also
processed e~ery day.
- 105 -
82t~2~
The solution which overflowed from the bleaching bath
when the replenisher was added thereto was introduced into the
blixing bath in a manner similar to that of Example 4.
~Amount of each of ~he replenishers>
The same as in Example 4O
~Compositions of the replenlshers>
The same as those used in Process 13 of Example 4,
except for the following solutionsO
Replenisher to the bleaching bath
Ethylenediaminetetraacetic aoid,
~erric ammonium salt 110 g
Ammonium bromide 90 g
Ammonia water ~28~) . 4 m~
Ethylenediaminete~raacetic acid,
disodium salt - 10 g
20 ~ Bleach accelerating agent As described in Table 9
Water to 1.0 ~
pH 5.7
The results of the processings are as shown in Table
9. Table 9 shows that the process of this invention provides
good quality photographic reproduction and promotes the effect
of the bleach accelerating agent to enable rapid de-silvering.
- 106 -
.~ , . . . ..
,
~'~8~6Z8
Further, it shows tha~ these excellent effects are long-
lesting by the introduction of the overflow solution out of
the bleaching bath to the blixing bath.
- - 107 -
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Example 6
The photographic elements prepared according to
Example S were subj~cted to the exposure ~hrough a wedge in a
similar manner to that of Example 4, followed by the Process
CN-16 using the automa~ic developing procéssor to prepare a
control sample.
For ten successive days, the photographic element (100
m per day) were used for outdoor photography, ~ollow~d ~y the
processing according to Process 15 as described in Table 8 of
Example 5, while replenishing the following processing
solutions. A~ the same time, ~he samples exposed through a
wedge were also processed every day. Pipework was set up 50
that the solution which overflowed out of the bleaching b~
was introduced into the blixing bath.
<Compositions of the processing solutions>
Color developing solution and Replenisher
The same as described in Example 4.
Bleaching solution and Replenisher
Diethylenetriaminepentaacetic acid 174 g
Ferric chloride hexa hydrate 108 9
Ammonium ~romide 90 g
Ammonia water (37%) 190 m
Ammonium nitrate ~S g
Bleach accelerating agent (Compound IV-1) 2 9
Water ~o 1~0 Q
pH 5.8
-- 110 --
:
:. :
z~
Blixing solution
The bleaching solution described above 500 m
Sodium sulfate 10 g
Aqueous ammonium thiosulfate solution (70~)200 m æ
Water to 1.0
pH 7.3
Replenisher to the blixing bath
The same as described in Example 4.
Stabilizing solution and Replenisher
rhe same as described in Example 4.
Amounts of replenishers added
The same as described in Example 4.
The results are as shown in Table lO, which shows ~hat
the process of this invention provides good quality
pohotographic reproduction and enables good de-silvering.
Table 10 also shows that these effects of this invention are
comparable to. those of the control sample and are long-
lasting~ .
Table 10
. .
Difference in Difference in
relative gradation Residual
. Days of sensitivity silver
processing _ ~ (~g/cm2)
. B G R G R
0 (start) ~0.02 +0.01 -0.01 +0.02 ~0 ~0 1.6
10 days +0.01 + L + + . 02 +o . ol +o . ol 1. 4
Differences in relative sensitivity and in gradation
are between the sample of this invention and the control
sample, respectivelyO
- 112 -
