Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
l327sa~ ;
- METHOD OF PROCESSING SILVER HALIDE CO~OR PHOTOGRAP~IC
MATERIAL AND PHOTOGRAPHIC COLOR D~VELOPING COMPOSITION
FIELD OF THÆ INVENTION
The present invention relates to a method of
processing a silver halide color photographic material
and, more particularly, to a processing method which
ensures improvements in the stability and developability
of a color developer and marked reduction in the increase
of fog in a running color development process.
BACKGROUND OF THE INVENTION -
Color developers containing color developing
agents of the aromatic primary amine type have been used
from of old for formati-;n of color images and at present
have a primary role in the color photographic image-
forming process. However, the color developers described
above are exceedingly prove to air oxidation and oxidation
due to the presence of. It is well-known that then color
images are formed using oxidized developing solutions, and
increase in fog density and changes in photographic speed
and gradation are caused, which interfere with achieving
the intended photographic characteristics.
Therefore, various mean for enhancing
preservability of color developers have so far been
investigated. The most general means among them is the
-1- ~
. -.
. . , ~ , .
; ~
- -, ~ . .
~327~
combined use of hydroxylamine and sulfite ion. ~owever,
this method has the drawback that the hydroxylamine
produces ammonia by decomposition which causes for and the
sulfite ion competes against the developing agent to
impair developability. Accordingly, it is hard to say
that both of them are preferred as a compound capable of
enhancing the preservability of a color developer (or a
preservative).
In particular, sulfite ion, though it has been
used from of old as an a~ent capable of increasing the
preservability of various color developing agents or
preventing the decomposition of hydroxylamines,
drastically impair developability and lowers color density
of the developed image to a considerable extent,
especially when it is used in a system free of benzyl
alcohol. Benzyl alcohol is harmful from the standpoint of
environmental pollution and preparation of developers.
Alkanolamines described in Japanese Patent
Application (OPI) NO. 3532/79 (the term "OPI" as used
herein means an "unexamined published application") and
polyethylene imines described in Japanese Patent
Application (OPI) No. 94349/81 have been proposed as a
substitute for sulfites. However, these compounds cannot
produce sufficient effects.
'' ,, ,.,
: . ~, ~ ' ' .
'~ . . ' ," : . ' .
1327~
In addition, various kinds of preservatives and
chelating agents have been examined for the purpose of
improving the stability of color developers.
As examples of preservatives, aromatic
polyhydroxy compounds described in Japanese Patent
Application (OPI) Nos. 49828/77, 160142/84 and 47038/81,
U.S. Patent 3,746,544, and so on, hydroxycarbonyl
compounds described in U.S. Patent 3,615,503 and British
Patent 1,306,176, a-aminocarbonyl compounds described in
Japanese Patent Application (OPI) Nos. 143020/77 and
89425/78, metal salts described in Japanese Patent
Application (OPI) Nos. 44148/82 and 53749/82, hydroxamic
acids described in Japanese Patent Application (OPI) Nos.
27638/77, and so on, may be mentioned.
As examples of chelating agents, on the other
hand, mention may be made of aminopolycarboxylic acids
described in Japanese Patent Publication Nos. 30496/73 and
30232/69, organic phosphonic acids described in Japanese
Patent Application (OPI) No. 97347/81, Japanese Patent
Publication No. 39359/81 and West German Patent 2,227,639,
phosph~nocarboxylic acids described in Japanese Patent
Application (OPI) Nos. 102726/77, 42730/78, 121127/79,
126241/80 and 65956/80, and so on, and other compounds
described in Japanese Patent Application (OPI) Nos.
--3--
.
1327~
- 195845/83 and 203440/83, Japanese Patent Publication No.
40900/78, and so on.
However, sufficient preservability cannot be
obtained with any of the preservatives and chelating
agents described above and, what is worse, some of them
exert undesirable effects upon photographic
characteristices.
- For the foregoing reasons, satisfactory results
have not yet been achieved and the advent of excellent
preservatives, especially those capable of taking the
place of sulfites, have been desired.
Further, it is described in Japanese Patent
Application~OPI) Nos. 95345/83 and 232342/84 that a color
photographic material comprising a silver chlorobromide
emulsion with a high chloride content tends to generate
fog at the time of color development. When an emulsion of
the above-described kind is used, a preservative which has
low solubility in the emulsion and more excellent
preservability is essential to a color developer. Any
preservative which will suffice for the above-described
needs also has not been found until now.
SUMMARY OF THE INVENTION
Therefore, one object of the present invention is
to provide a method of processing a silver halide color
photographic material in which the color developer used is
--4--
,
. .
132793~
excellent in stability and the increase in fog density in
the running color development process is reduced to a
considerable extent.
~ nother object of the present invention is to
provide a method of processing a silver halide color
photographic material in which excellent developability
can be acquired, not-withstanding the fact that the color
developer is substantially free of benzyl alchol.
The above-described objects of the present
invention have been attained with a method of processing a
silver halide color photographic material in which the
development processing is performed using a developer
containing an aromatic primary amine color developing
agent and at least one compound represented by the
formula;
Rl
N X (I),
R ~
wherein X is a trivalent group necessary to complete a
condensed ring; and Rl and R2 may be the same as or different
from each other and R1 and R2 each represents an alkylene
group, an arylene group, an alkenylene group, or an aralky-
lene group.
.
,
~ . '" ,'.' . . ., '
13279~
DETAILED DESCRIPTION OF THE INVENTION
In formula (I), groups preferred as X as those
being a trivalent group containing not more than 20 carbon
atoms, preferably not more than 10 carbon atoms, and more
preferably not more than 6 carbon atoms. X may further
containg other atoms like nitrogen, oxygen, sulfur or so on.
X preferably represents a trivalent group contain-
ing not more than 6 carbon atoms, which may further contain
a nitrogen atom or an oxygen atom.
Each of the groups represented by Rl and R2
in formula (I) may be substituted by other groups, for
example, by a hydroxy group, an alkoxy group, etc. The
number of carbon atoms contained in Rl and R2, respectively,
is preferably 10 or less, more preferably 6 or less, and -
particularly preferably 3 or less. Rl and R2 each
preferably represents an alkylene group or an arylene group,
and particularly preferably represents an alkylene group.
- 6 -
. ~ , ,
:
,.
, , . . .: .
~ . .. t
13~79~5
The compound of formula (I) may be a bis or tris
body formed by connecting to each other through X.
Specific examples of groups represented by X in
formula (I) include
C=N-, -CH2CH2N ~, -cH2cH2cH , -CH2fHC~ , -CH2CH2-CH-C
OH o
OH
-CH21CCH , ~, -CH-C-CH , ~ H- ~ N ~
O OH OH ~ ~
so on.
Specific examples of groups represented by Rl
abnd R2 in formula ~I? include a methylene group, an
ethylene group, a propylene group, a butylene group, a
pentylene group, a 1,2-cyclohexylene group, a 1-
methylethylene group, a 1,2-dimethylethylene group, a 1-
carbocxyethylene group, a 1,2-phenylene group, a 1,2-
vinylene group, a 1,3-propenylene group, and so on. ~hese
groups each may further be substituted with an alkyl
group, a halogen atom, a carboxyl group, a sulfo group, a
hydroxyl group, an alkoxy group, an alkylthio group, an
amino group, an amido group, an acyl group, a carbamoyl
, : . : .: : , - . :
13279~
group, a a sulfamoyl group, a heterocyclyl group, or so
on.
Of the compounds represented by formula (I),
particularly preferred ones are represented by formulae
(I-a) and (I-b).
R 1
N - R3- Xl ~I-a)
~ R2~
In the above formula, Xl represents - N or - CH.
/
Rl and R2 may be the same or different and each have the
same meanings, respectively, as Rl and R in formula (I).
R3 repr~sents one of the groups represented by Rl and R2, or~CH2~-.
In formula (I-a), a preferred Xlis - N. The
number of carbon atoms contained in the groups represented
by each of Rl, RZ and R3, respectively, is preferably 6
or less, more preferably 3 or less, and particularly
preferably 2. Groups preferred as Rl, R2 and R3
respectively are an alkylene group and an arylene group,
and the most preferred one is an alkylene group.
~Rl~
b)
.
~. ;
,
132790a
,
In the above formula, Rl and R2 may be the same
or different and each have the same meaning, respectively,
as Rl and R2 in formula (I).
The number of carbon atoms in groups represented
by Rl and R2 , respectively, is preferably 8 or less,nDre
preferably 6 or less in the formwla (I-b). AmDng gr~ups represented by Rl and
R2, favored ones are an alkylene group and an arylene
group, and the most favored one is an alkylene group.
The compound represented by formula (I-a) are
preferable to those represented by formula (I-b).
Specific examples of the compounds of the present
invention, which are represented by the foregoing formula
(I), are illustrated below. However, the invention should
not be constured as being limited to the following
compounds.
,
~32790
I - ( 1 ) T
N ~~ B C O ) y~
I- (3) I- (4)
N~ ( DBN )
~OH
C HzOI~
I - ( 7 ) 1 ~
c~3 c~3
~1 N~~
/ , \ ~
CH3
I-- (q ) 1 ~
(DBU)
--10--
.
.
132790~
~)
0~
3 ~ 4)
-
$~ ~,'`J -
N,,~l
( 1 6 )
<~ .
-- ( 1 7 ) ~-- ( 1 8 )
--11--
-, . ,:
. . .
.
- . ~ ~ . ~. . ..
1327~3~
Many of the compounds represented by formula (I)
in the present invention are easily available as
commercial products.
Each of the compounds represented by formula (I)
is added in an amount of preferably 0.1 to 50 g,
particularly 0.2 to 20 g, per liter of color developer.
A color developer which can be used in the
present invention is described below.
The color developer to be used in the present
invention contains a known color developing agent of the
aromatic primary amine type.
Aromatic primary amines preferred as a color
developing agent are p-phenylene diamine derivatives, and
typical examples of the derivatives are cited below.
However, the invention should not be contrued as being
limited to the following example.
D-l N,N-diethyl-p-phenylenediamine.
D-2 4-[N-ethyle-N-(~-hydroxyethyl)amino]aniline.
D-3 2-methyl-4-~N-ethyl-N~ hydroxyethyl)amino]-
aniline
D-4 4-amino-3-methyl-[N-ethyl-N-(~-methanesulfon-
amidoethyl)]-aniline
These p-phenylenediamine derivatives may used in
Their salt form, such as ~ulfate, hydrochloride, sulfite, p-
toluene-sulfonate, etc, salts. A color developing agent
-12-
,
,
13279~
of the aromatic primary amine type is used in a quantity
of preferably about 0.1 g to about 20 g, more preferably
about 0.5 g to about 10 g, per liter of developing
solution.
It is particularly preferred to use the color
developing agent of D-4 in the presence of the compound of
formula (I) in respect that increase in fog is checked and
more desirable photographic characteristics are obtained.
In addition, the compounds of the present
invention can fully achieve their preservability when
used in combination with a compound capable of directly
stabilizing a color developing agent in the system using
an aromatic primary amine as the color developing agent.
In general, water-soluble antioxidants are known as the
compounds capable of directly stabilizing developing
agents, with specific examples including hydroxylamines
and other compound described hereinafter.
As the compound which can be used together with
the compounds of the present invention in the color
developer, hydroxylamines are preferred. In particular,
those represented by the formula
R21 N - R22 (II)
1H
are favored over others,
. ~.
.
1327~
- In formula (II), R2l, and ~22 each represents a
hydrogen atom, or an unsubstituted or substituted alkyl,
alkenyl or aryl group.
of groups represented by R21 and R22, an alkyl
group and an alkenyl group are preferred. When at least
one of R2l and R22 is a substituted alkyl or alkenyl
group, the compound can produce a more desirable effect.
Also, R21 and R22 may combine with each other to form a
nitrogen atom-containing herero ring.
Alkyl and alkenyl groups may assume any form,
such as a straight chain, a branched chain or a cyclic
group, and they may be substituted by a halogen atom, an
aryl group (e.g., phenyl, p-chlorophenyl, etc.), an alkoxy
group ~e.g., methoxy, ethoxy, methoxyethoxy, etc.), an
aryloxy group (e.g., phenoxy, etc.), a sulfonyl group
(e.g., methanesulfonyl, p-toluenesulfonyl, etc.), a
sulfonamido group (e.g., methanesulfonamido, benzene-
sulfonamido, etc.), a sulfamoyl group( e.g.,
diethylsulfamoyl, unsubstituted sulfamoyl, etc.), a
carbamoyl group (e.g., unsubstituted carbamoyl,
diethylcarbamoyl, etc.) , an amido group (e.g., acetamido,
benzamido, etc.), a ureido group (e.g., methylureido,
phenylureido, etc.), an alkoxycarbonylamino group (e.g.,
methoxycarbonyl amino, etc.), an aryloxycarbonylamino
group (e.g., phenoxycarbonylamino, etc.), a cyano group, a
-14-
.
: . . `: , ' ` ~ :
., .: - .
13279~
hydroxy group, a carboxy group, a sulfo group, a nitro
group, an amino group (e.g., unsubstituted amino,
diethylamino, etc.), an alkylthio group (e.g., methylthio,
etc.), an arylthio group (e.g.,phenylthio, etc.), or a
heterocyclyl group ~e.g., morpholyl, pyridyl, etc.), or so
on
The groups represented by R2l and R22 may be the
same or different and the substituent groups thereof may
be the same or different.
The number of carbon atoms contained in the
groups represented by R21 and R22 is preferably l to lO,
particularly preferably 1 to 5. Suitable examples of
nitrogen-containing heterocyclyl groups formed by
combining R2l and R22 include a piperidyl group, a
pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl
group, an indolinyl group, a benzotriazolyl group, and so
on.
Preferred substituent groups of R2l and R22
include a hydroxy group, an alkoxy group, a sulfonyl
group, an amido group, a carboxy group, a cyano group, a
sulfo group, a nitro group, and an amino group.
Specific examples of the compound represented by
formula (II) which can be used in the present invention
are illustrated below. However, the invention should not
be construed as being limited to the following compounds.
-15-
.
. . .
- `
II-l OH 132790-~
C2Hs -N-C2H40CH3
II-2 OH
CH3-N-C2H40C2H5
II-3 OH
CH30C2H4 -1-C2H4CH3
II-4 OH
C2H50C2H4 -N-C2H40C2Hs
II-5 OH
C2H50c2H4-b-C2H5
II-6 OH
I \
CH3 -N-CH2 -N~O
II-7 OH
CH3 N C 2H4 ~1
II-8 OH
C2H5S02C2H4 -N-C2H4s02c2H5
II -9
HO -N~02 -
0
HO - N~O
II-ll OH
HOOC-CH2-1~-CH2-COOH
II-12 OH
HOCH2CH21CH2CH20H
I I -13OH ~ .
CH3CH2NCH2CH3
I I - 1 4
NH20H
--16--
- ~ ~ - , . ..
1327~
- Other specific examples of the compound
represented by formula (II) and methods for synthesizing
the compounds of formula (II) are shown in U.S. Patents
3,661,996, 3,362,961 and 3,293,034, Japanese Patent
Publication No. 2794/67, and U.S. Patents 3,491,151,
3,655,764, 3,467,711, 3,455,916, 3,~87,125 and 3,287,124.'
Those compounds may form salts together with
various kinds of acids, such as hydrochloric acid,
sulfuric acid, nitric acid, phosphoric acid, oxalic acid,
acetic acid and so on.
As examples of "compounds capable of directly
stabilizing color developing agents", other than
hydroxylamines, which are preferably used in combination
with the compounds of the present invention, mention may
be made of hydrazines, hydrazides, phenols, sugars,
hydroxamic acids, a-aminoketones, ~-hydroxyketones, and so
on.
Details of these compounds are illustrated below.
The hydroxamic acids are preferably represented
by the formula
A31 -- X31 -- N -- O -- y31 ~III) .
R31
In formula (III), A31 represents a hydrogen atom,
an alkyl group, an aryl group, an amino group, a
-17-
1327~a
heterocycliC group, an alkoxy group, an aryloxy group, a
carbamoyl group, a sulfamoyl group, an acyl group, 2
carboxy group, a hydroxyamino group, or a
hydroxyaminocarbonyl group. These groups each may have a
substituent group, such as a halogen atom, an aryl group,
an alkyl group, an alkoxy group, an aryloxy group, a
hydroxy group, a sulfonyl group, a sulfonamido group, a
sulfamoyl group, a sulfo group, an amido group, an ureido
group, a cyano group, a hydroxyaminocarbonyl group, a
carboxy group, a nitro group, an amino group, an
alkoxycarbonyl group, an aryloxycarbonyl group, an
alkylthio group. an arylthio group, a heterocyclic group
(e.g., pyridyl, morpholino, etc.), or so on
Preferred examples of groups represented by A31
include substituted or unsubstituted alkyl, aryl, amino,
alkoxy and aryloxy groups. Particularly favorable ones
are substituted or unsubstituted amino, alkoxy and
aryloxy groups. The number of carbon atoms contained in
such groups may range from 1 to 10.
X31 represents ~ - 1_, -S02-, or -SO-.
O S
A preferred group represented by X31 is -C-.
O
R31 represents a hydrogen atom, an alkyl group, or
an aryl group. Further, R31 may combine with A31 to form
-18-
, .
,.~, .
.
,
- `
~327~a
a cyclic structure. These groups each may have a
substituent group. Suitable examples of such substituent
groups include the same as those cited with regard to A31.
A hydrogen atom is particularly preferred as R31.
y31 represents a hydrogen atom, or a group capable
of being converted to a hydrogen atom by hydrolysis.
As specific examples of such groups to be
converted to a hydrogen atom by hydrolysis, mention may be
made of the following ones.
1) Those protected by an ester linkage or an
urethane linkage, wherein y31 represents -Cl-R32- Suitable
examples of groups represented by R32 include alkyl, aryl
and amino groups.
2) Those protected by an imidomethyl blocking
group described in U.S. Patent 4,363,865,
Il
wherein y31 represents -CH2-N Z. In the blocking
\ ~
o
Il
group, J represents 9 or -6- and Z represents plural
O o
, . , ~ " ,.
, .
..
., : ,
13279~
- atoms necessary to complete a hetero ring having at least
one 5- to 6-membered ring.
Specific examples of hydroxamic acids are
illustrated below. However, the invention should not be
construed as bein~ limited to the following examples.
-20-
, ,
: ., :
,, , ~
13279~
(III)-l
HO- ~ -C-NH-OH
Il
O ~.
(III)-2
CH -C-NH-OH
3 11
o
(III)-3
C4H90-C-NH-OH
(III)-4
CH3 ~ S02NH-OH
(III)-S CH3
I
CH3-C-N-OH
!l . . . .
(III)-6
H N-C-NH-OH
2 11
o
-21-
.;
.
, ~ - ~ , .
. . - ,
.
1327~
Other specific examples of hydroxamic acids
include those described in ~apanese Patent Applicat o.. No.
186559/86 published as 63-43138, and such acids are available
on a basi~ of the description therein.
The hydrazines and hydrazides are preferably
represented by the formula
R41 \ R43
N - N (IV)
R42 / ~ X41 ~ R44
In formula lIV), R41, R42 and R43 each represents
a hydrogen atom, an alkyl group (containing l to 20 carbon
atoms, with examples including a methyl group, an ethyl
group, a sulfopropyl group, a carboxybutyl group, a
hydroxyethyl group, and the like), an aryl group
(containing 6 to 20 carbon atoms, with examples including
a phenyl group, a 2,5-dimethoxyphenyl group, a 4-
hydroxyphenyl group, a 2-carboxyphenyl group and the
like), or heterocyclic group ~containing l to 20 carbon
atoms, with examples including a pyridine-4-yl group and
so on)-
R44 represents a hydroxy group, a hydroxyaminogroup, an alkyl group (containing l to 20 carbon atoms,
with examples including a methyl group, an ethyl group, a
-22-
X
. .
. ' ''~' ~ ' '
~` 13279~
sulfopropyl group, a carboxybutyl group, a hydroxyethyl
group, a cyclohexyl group, a benzyl group and so on), an
aryl group lcontaining 6 to 20 carbon atoms, with examples
including a phenyl group, a 2,5-dimethoxyphenyl group, a
4-hydroxyphenyl group, a 2-carboxyphenyl group and so
on), a heterocyclic group (containing 1 to 20 carbon
atoms, with examples including a pyridin-4-yl group and
so on), an alkoxy group (containing 1 to 20 carbon atoms,
with examples including a methoxy group, an ethoxy group,
a methoxyethoxy group, a benzyloxy group, a cyclohexyloxy
group and so on), an aryloxy group (containing 6 to 20
carbon atoms, with examples including a phenoxy group, a
p-methoxyphenoxy group and so on), a carbamoyl group
(containing 1 to 20 carbon atoms, with examples including
an unsubstituted carbamoyl group, an N,N-diethylcarbamoyl
group, a hydrazinocarbonyl group and 30 on), or an amino
group (containing 0 to 20 carbon atoms, with examples
including an unsubstituted amino group, an N-phenylamino
group, a hydrazino and so on~.
X41 represents a divalent group selected from the
group consisting of -CO-, -SO2- and C=NH.
n represents 0 or 1. When n is 0, R44 represents
an alkyl group, an aryl group or a heterocyclic group
alone, or it may combine with R43 to form a hetero ring.
These groups R43 and R44 each may be substituted.
-23-
.
.
- ,: ,
,
. ' '
.
13279~5
In fo ~ la (rv)t R41 R4~ and ~43 preferably are each selected
from a hydrogen atom or an alkyl group. In particular,
R41 and R42 are each most preferably a hydrogen atom.
In formula (IV), R44 is preferably an alkyl group,
an aryl group, an alkoxy group, a carbamoyl group or an
amino group.
X41 is preferably -CO- or -S02-, and -CO- is
particularly favored.
Specific examples of compounds-of formula (IV)
which may be used in the present- invention are set forth
below. However, the present invention should not be
construed as being limited to the following examples.
(IV-l) C2H5
NH2N~
C2H5
(IV-2) H
NH2N
~ CH2)4 S03H
.' ~
:.
. ' ~,. : -.
1327~0J
(IV-3) H
NH2N
\~CH2~ OH
(IV-4)
2 \ 3
(IV-S) ~ C2H4H
NH2N
C2H40H
(IV-6)
NH2NHCOCH3
(IV-7)
NH2NHCOOC2H5
(IV-8)
NH2NHCO~
H
(IV-9)
NH2NHSO2 ~CH3
(IV-10)
NH2NHCONH2
(IV-ll)
NH2NHCONH-
~
(IV-12)
NH2NHS03H
(IV-13) NH
NH2NHCNH2
(IV-14)
NH2NHCOCONHNH2
--25--
- :- . -:
: .... . -. . . ~ -
. .,. . ., . . , . , -
~, ,
1327~9~
Other typical exz~ples of such compounds include
tho~e described in U.S. patent No. 4,801,521 issued
January 31, 1989, and they are available on the basi~ of the
description therein.
Preferred phenols are represented by the formula.
(oR52)
~,~ (V)
(RSl )
m
In the formula (V), R51 represents a hydrogen
atom, a halogen atom, an alkyl group ~e.g., a methyl group,
an ethyl group, a t-butyl group, etG), an axyl group (e.g.,
a phenyl group, etc.), an alkoxy group (e.g., a methoxy
group, an ethoxy group, etc.), an aryloxy group (e.g., a
phenoxy group, etc.), a carboxyl group, a sulfo group, a
carbamoyl group, a sulfamoyl group, an amido group (e.g.,
an acetamido group, a benzamido group, etc.), a sulfonamido
group ~e.g., a methanesulfonamido group, a benzenesulfon-
amido group, etc.), a ureido group, an alkylthio group (e.g.,
a methylthio group, etc~), an arylthio group (e.g., a
phenylthio group, etc.), a nitro group, a cyano group, an
amino group, a formyl group, an acyl group (e.g., an acetyl
group, etc.), a sulfonyl group (e.g., a methanesulfonyl
group, a benzenesulfonyl group, etc.), an alkoxycarbonyl
group (e.g., a methoxycarbonyl group, etc.), an aryloxy-
- 26 -
.:
., . . . -
13279~ .
carbonyl group ~e.s., a phenoxycarbonyl group, etc.), an
alkoxysulfonyl group (e.g., a methoxysulfonyl group, etc.),
or an aryloxysulfonyl group (e.g., a phenoxysulfonyl group,
etc.).
When R51 is further substituted, suitable examples
of groups by which it may be substituted include one or
more halogen atoms, alkyl groups, aryl groups, hydroxyl
groups, alkoxy groups, aryloxy groups, carboxyl groups,
sulfo groups, carbamoyl groups, sulfamoyl groups, amido
groups, sulfonamido groups, ureido groups, alkylthio groups,
arylthio groups, nitro groups, cyano groups, amino groups,
formyl groups, acyl groups, sulfonyl groups, alkoxycarbonyl
groups, aryloxycarbonyl groups, alkoxysulfonyl groups,
aryloxysulfonyl groups, and heterocyclic groups ~e.g.,
morpholyl, pyridyl, etc., groups).
When R51 i5 substituted by two or more of the
above-mentioned substituent groups, the two or more sub-
stituent groups may be the same or different.
When two or more R51 are present, they may be
the same or different.
When _oR52 and -R51 are adacent to each other,
they may combine with each other to form a ring. The ring
formed may be a 5- or 6-membered, saturated or unsaturated
ring, and may be comprised of atoms selected from carbon,
hydrogen, halogen, oxygen, nitrosen, sulfur and other atoms.
- 27 -
' ~ . ' ' ' ~ ' .
: ......... ' : . : ~ ...... . .
,:
. ~ . - . . . -
1~279~
In addition, when R 1 or its substituent group
represents carboxyl or sulfo group, the group may assume
the form of an alkali metal salt (e.g., Na, K or like salt),
and amino groups also may form salts together with various
acids, e.g., hydrochloric acid.
R52 represents a hydrogen atom or a hydrolyzable
group. The term hydrolyzable group refers to a group
capable of being replaced with a hydrogen atom by
hydrolysis. As an example of such a group, mention may be
made of -C-R53 (wherein R53 represents an alkyl group, an
aryl grou~, or an amino group). More specifically, R52
is a means for protecting the phenolic -OH group and forms
an ester or urethane linkage. As another example of the
protecting means, mention may be made of imidomethyl block-
ing groups described in U.S. Patent 4,363,865. That is, R52
represents 3
~ 55
-CH2N\ R54R:
wherein R represents -C- or -S-, and R55 represents
O O
the atoms necessary to complete a hetero ring having at
least on 5- or 6-membered ring).
m and n each represents an integer of 1 to 5.
In the foregoing formula (V), preferred groups
as R51 include an alkyl group, a halogen atom, an alkoxy
- 28 -
' " ' :
, . ~' ' ~"
.
13279~
group, an alkylthio group, a carboxyl group, a sulfo group,
a carbamoyl group, a sulfamoyl group, an amino group, an
amido group, a sulfonamido group, a nitro group, and a
cyano group. Of these groups, the alkoxy, alkylthio,
amino and nitro groups are particularly favored over the
others.
Each R51 group is preferably located in positions
ortho or para to the ~R52 group.
In addition, the number of carbon atoms contained
in R51 is preferably from 1 to 10, particularly preferably
from 1 to 6.
Preferred groups as R52 include a hydrogen atom
and hydrolyzable groups containing 1 to 5 carbon atoms.
When not less than two ~R52) groups are present, they are
preferably located in positions ortho or para to each other.
Specific examples of the phenols of formula (V)
are illustrated below. However, the invention should be
construed as being limited to these compounds.
- 29 -
13279~
V--~ OH
' . ~ , , ~
V--2
HO~S O 2 ~OH
- V--3
HO~NO 2
V--4
HO~S O 2 NH 2
V--s
~OOH
HO~
~OOH
V--6
HO~--OH
-- 30 --
'.
: ' . ' '; ' ' ' ' ' ' '
-~~ 13279~a
V--7
OH
~SO3Na
(t)C 4Hg--~J
OH
V--~
~OH
`OOH
OH
V--9
OH
NaO3 S~[~OH
SO3Na
S O 3 N a
V--/ o
OH
,NH2
~ ','
SO 3H
V-/ /
OH
,NH 2
J
(,'OOH
-- 31 --
,. ' . '
`~
1327905
Otner specific compounds are described in Ja~anese
Patent Application Nos. 188742/86 and 203253/86, published as
63-44657 and 63-58443 and available on the basi~ of the
de~cription therein.
a-hydroxyketones and -aminoketones are prefer-
ably those represented by the formula:
o X61
R61_ C - CH - R62 (VI)
In the above formula, R represents a hydrogen
atom, an alkyl group (containing 1 to 20 carbon atoms, e.g.,
a methyl group, an ethyl group, a hydroxymethyl group, a
methoxyethyl group, a cyclohexyl group, etc.), an aryl
group (containing 6 to 20 carbon atoms, e.g., a phenyl
group, a 2-hydroxyphenyl group, etc.), an alkoxy group
(containing l to 20 carbon atoms, e.g., a methoxy group, an
ethoxy group, a methoxyethoxy group, etc.), an aryloxy
group (containing 6 to 20 carbon atoms, e.g., a phenoxy
group, a 4-methoxyphenoxy group, etc.), or an amino group
(containing 0 to 20 carbon atoms, e.g., an unsubstituted
amino group, an N,~-diethylamino group, an N-phenylamino
group, etc.).
R62 represents a hydrogen atom, an alkyl group
(containing 1 to 20 carbon atoms, e.g., a methyl group, an
ethyl group, a hydroxymethyl group, etc.), or an aryl
group containing from 6 to 20 carbon atoms, e.g., a phenyl
group, a 2-hydroxyphenyl group, etc.).
- 13279~3
R61 and R62 may combine to form a carbon ring or
a hetero ring.
X61 represents a hydroxyl group or an amino
group (containing 0 to 20 carbon atoms, e.g., an unsub-
stituted amino group, an N,N-diethylamino group, a
morpholino group, etc.).
In the foregoing formula (Vl), preferred groups
as R61 include a hydrogen atom, an alkyl group, an aryl
group and an alkoxy group, while preferred groups as R62
include a hydrogen atom and an alkyl group.
Specific examples of the d-hydroxyketones and
~-aminoketones of formula (Vl) are illustrated below.
However, the present invention should not be construed as
being limited to these compounds.
- 33 -
.. , .. ~ . ~ .
- . .
.' ' ' " ' . ' . . ' ,' ' . ' ', ' ~ : . . . , : '
',~' ', ' ., ' ~ ~ .i, .
13279~
~-/ ) o
Il
(,'H3 c(~'H20H
--2 ) O OH
Il 1
CH 3 (~--(`H('H 3
3 ) O
Il
~H3t~CH2N O
O
CH 3 C CH 2 NHC 2 H 5
( ~il--s )
HC--CH 2 OH
-- 34 --
. ,, : ~ , ~-. .. .
' ~ ' . ! . . . ~ : ~
' ', ' ' ' ' ~,' ' ' :
13279~
.
( Vl- 6 )
[~_OH
(Vl--7 ) O
~(~CH2OH
OH
--8 )
O
HO~--C CH 2 NH4~ OOH
9 ) O OH
CH 3 O (~ (~HC 2 H 5
/ o ) o
(~H3 1~NH2
. ............ . `
. . .
. .
13279~.~
Other specific compounds are described in
Japanese Patent Application No. 188741/86, published as
63-44656 and available on the basis of the description
therein.
"Saccharides" are described in detail below.
Saccharides (which may also be called carbo-
hydrates) consist of monosaccharides and polysaccharides.
Many have the formula CnH2nOm. In general, aldehydes or
ketones of polyhydric alcohols (which are called aldoses
and ketoes), reduced derivatives thereof, oxidized
derivatives thereof, dehydrated derivatives thereof, amino
sugars, thio sugars are collectively called monosaccharide.
The term polysaccharides refers to the products obtained
by condensing two or more of the above-described mono-
saccharides through dehydration.
Of these saccharides, aldoses having a reductive
aldehyde group and derivatives thereof are preferred over
the others. In particular, the corresponding monosaccha-
rides of such aldoses are favored.
Specific examples of saccharides which can be
used are illustrated below. However, the invention should
not be construed as being limited to these compounds.
(Optical isomers of the exemplified saccharides can also
be used.)
- 36 -
X
13279~
VI I -1 D-xylose
ro\
HO ~ H
OH
VII-2 L-arabinose H O O
O H
OH
VI1-3 D-ribose H OH2 ~ OH
OH OH
VII-4 D-deoxyribose
HOH2(
~ ~ OH
HO
VII-S D-glucose ~H 2 OH
', ~0~
HO~H
0~1
-- 37 --
.
. .
. . .
, ~ ;
l327~a~
VII-6 D-galactose~H 2 OH
HO ~
H
OH
VII-7 D-mannose
~`H 2 OH
~ ~,0~
~7
VII-8 Glucosamine
~ _o2 OH
HO~
NH2
VII-9 L-sorbose HO~ ~ H
~J/ H20H
OH
VII-10 D-sorbite (sorbitol) CIH20H
H-C-OH
OH-C-H
H-C-OH
H-C-OH
CH20H
- 38 -
. .
.
.
'' :. - . . . t ' ' :,, ' ,
,: ''~ ': ' ' . '
,
1327~
The above cited compounds are easily available
as commercial products.
The compounds represented by the formulae (~ )
to ~VII), respectively, are added to a color developer in
an amount of preferably grom 0.01 to 20 g/l and more prefer-
ably from 0.5 to 10 g/l.
In addition, a sulfite, such as sodium sulfite,
potassium sulfite, sodium bisulfite, potassium bisulfite,
sodium metasulfite, potassium metasulfite, etc., or a
carbonyl/sulfurous acid adduct can be added to a color
developer as other preservatives, if desired. An addition
amount thereof is preferably 0 to 20 g/l, more preferably
0 to 5 g/l, and a more desirable result can be obtained
using the minimum addition amount necessary to preserve
the color developer.
Further, various kinds of metals described in
Japanese Patent Application (OPI) Nos. 44148/82 and
537g9/82, various kinds of saccharides described in
Japanese Patent Application (OPI) No. 102727/77,
dicarbonyl compounds described in Japanese Patent
Application (OPI) No. 160141/84, salicylic acids described
in Japanese Patent Application (OPI) No. 180588/84,
gluconic acid derivatives described in Japanese Patent
Application (OPI) No. 75647/81, and so on may be optionally
added to a color developer as preservatives. Two or more
- 39 -
.
13279~
-
of these preservatives may be used together, if desired.
In particular, addition of aromatic polyhydroxy compounds
is preferred.
A color developer which can be used in the present
invention is adjusted preferably to pH 9-12, more prefer-
ably to pH 9-11.0, and can contain other known developer
components.
In order to maintain the above-described pH,
various buffers may be used. Suitable examples of buffers
which can be used include carbonates, phosphates, borates,
tetraborates, hydroxybenzoates, glycine salts, N,N-
dimethylglycine salts, leucine salts, norleucine salts,
guanine salts, 3,4-dihydroxyphenylalanine salts, alanine
salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol
salts, valine salts, proline salts, trishydroxyaminomethane
salts, lysine salts, and so on.
Of these buffers, carbonates, phosphates, tetra-
borates, and hydroxybenzoates are particularly favored
over the others as they generally have excellent solubility
and buffering ability in the high pH region beyond 9.0, have
no adverse effect on photographic properties, such as fogging
etc., when added to a color developer, and are available at
low prices.
40 -
13279~5
-
Specific examples of the foregoing prererred
buffers include sodium carbonate, potassium carbonate,
sodium bicarbonate, potassium bicarbonate, trisodium
phosphate, tripotassium phosphate, disodium phosphate,
dipotassium phosphate, sodium borate, potassium borate,
sodium tetraborate (borax), potassium tetraborate, sodium
o-hydroxybenzoate (sodium salicylate), potassium o-
hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium
5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate
-(potassium 5-sulfosalicylate), and so on. However, the
invention should not be construed as being limited to the
above-mentioned compounds.
Such a buffer as described above is added to the
color developer in a concentration of preferably 0.1 mol/l
or more, particularly from 0.1 to 0.4 mol/lof color developer.
Furthermore, various kinds of chelating agents
can be used in the color developer for the purpose of pre
venting calcium and magnesium ions from precipitating or
for increasing the stability of the color developer.
Preferred chelating agents are organic acid com-
pounds, with examples including aminopolycarboxylic acids
described in Japanese Patent Publication Nos. 30496/6
organic phosphonic acids described in Japanese Patent
Application (OPI) No. 97347/81, Japanese Patent Publication
No. 39359/81 and West German Patent 2,227,639, phosphono-
- 41 -
' " ~ ' '
13279~J
carboxylic acids described in Japanese Patent Application
(OPI) Nos. 102726/77, 42730/78, 121127/79, 126241/80 and
659506/80, and so on, and the compounds described in
Japanese Patent Application (OPI~ Nos. 195845/83 and
203440t83, Japanese Patent Publication No. 40900/78, and
so on.
Specific examples of these chelating agents are
set forth below. However, the invention should not be
construed as being limited to these exemplified compounds.
Representatives of such chelating agents are
nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
ethylenediaminetetraacetic acid, N,N,N-trimethylenephos-
phonic acid, ethylenediamine-N,N,N',N'-tetramethylenephos-
phonic acid, transcyclohexanediaminetetraacetic acid, 1,2-
diaminopropanetetraacetic acid, glycol ether diminetetra-
acetic acid, ethylenediamine o-hydroxyphenylacetic acid,
2-phosphonobutane-1,2,4-tricarboxylic acid, l-hydroxy-
ethylidene~ diphosphonic acid, and N,N'-bis(2-hydroxy-
benzyl)ethylenediamine-N,N'-diacetic acid.
Two or more of these chelating agents may be
used together, if desired.
These chelating agents are added in amounts large
enough to block metal ions in the color developer, for
example from 0.1 to 10 g/l.
- 42 -
., , ,~ ,.
., . . , -: ,
- ~ ~,, : , . .
.
13279V~
Any development accelerator can be added to the
color developer, if needed. From the standpoint of prevent-
ing pollution, facility in preparation and prevention o~
fo~ generation, however, it is to be desired that the
color developer of the present invention should not con-
tain benzyl alcohol in any substantial amount~ The ex-
pression, "no benzyl alcohol in any substantial amount"
as used herein means benzyl alcohol contained in a con-
centration of 2 ml/l or less a~d, preferably, benzyl alcohol
is completely absent.
The foregoing compounds to be used in the present
invention have a remarkable effect even on the stability
of the color developer not containing benzyl alcohol in
any substantial amount.
As other development accelerators, thioether
compounds described in Japanese Patent Publication Nos.
16088/62, 5987/62, 7826/63, 12380/69 and 9019/70, U.S.
Patent 3,813,247, and so on, p-phenylenediamine compounds
described in Japanese Patent Application (OPI) Nos.
49829/77 and 15554/75, and so on, quaternary ammonium salts
descrlbed in Japanese Patent Application (OPI) No.
137726/75, Japanese Patent Publication No. 30074/69,
Japanese Patent Application (OPI) Nos. 156826j81 and
43429/77, and so on, amine compounds descrlbed in U.S.
Patents 2,494,903, 3,128,182, 4,230,796 and 3,253,919,
- 43 -
'` ' ', . : '. ', ' . ~ '
,:
. . .. . .
; ..
1327~
Japanese Patent Publication Wo. 11431/66, U.S. Patents
2,482,546, 2,596,926 and 3,582,346, and so on, polyalkylene
oxides described in Japanese Patent Publication Nos.
16088/62 and 25201/67, U.S. Patent 3,128,183, Japanese
Patent Publication Nos. 11431/66 and 23883/67, U.S. Patent
3,532,501, and so on, 1-phenyl-3-pyrazolidones, imidazoles
or the like can be added, if needed.
In the present invention, an arbitrary antifog-
gants can be added, if needed.
As typical examples of antifoggants which can be
used, mention may be made of alkali metal halides, such as
sodium chloride, potassium bromide and potassium iodide,
and organic antifoggants including nitrogen-containing
heterocyclic compounds, such as benzotriazole, 6-nitro-
benzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
S-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
thiazolyl-benzimidazole, 2-thiazoylmethyl-benzimidazole,
indazole, hydroxyazaindolidine and adenine.
The color developer which can be used in the
present invention preferably contains a brightening agent.
Preferred brightening agents are 4,4'-diamino-2,2'-di-
sulfostilbene compounds. The brightening agent may be added
in an amount of from 0 to S g/l and particularly from
0.1 to 4 g/l.
- 44 -
, :: ' ' ' '; ' ; . ~ .
. ~ ' .- . ~ : .
- . ... i .~ . . ... . .
:: ~ .. - , ~ . -
- 13279~
.
In addition, various kinds of surface active
agents, such as alkylsulfonic acids, arylphosphonic acids,
aliphatic carboxylic acids, aromatic caboxylic acid and
the like, may be added to the color developer, if desired.
The processing temperature of the color developer
of the present invention ranges from 20 to 50C, prefer-
ably from 30 to 40C and the processing time ranges from
20 seconds to 5 minutes, preferably from 30 seconds to 2
minutes. It is preferred to use a replenisher in a smaller
amount. Specifically, thè amount ranges from 20 to 600 ml,
preferably from 50 to 300 ml, and more preferably from 100
to 200 ml, per square meter of the light-sensitive materi-
al processed.
A bleaching bath, a bleach-fix bath, and a fixer,
which can be employed in the present invention, are de-
scribed below.
Any bleaching agent can be used in a bleaching
bath or a bleach-fix bath to be employed in the present
invention. In particular, Fe(m) complex salts of organic
aclds, such as aminopolycarboxylic acids (e.g., ethylene-
diaminetetraacetic acid, diethylenetriaminepentaacetic
acid, etc.), organic phosphonic acid (e.g., aminopoly-
phosphonic acids, phosphonocarboxylic acids, etc.), and
other organic acids (e.g., citric acid, tartaric acid, malic
acid, etc.); persulfates; hydrogen peroxide; and so on are
favored.
- 45 -
, ~.,, ,. ,,.."~,. ' :, :- -
.
1~279~
Of these bleaching agents, Fe(m) complex saltsof organic acids are especially preferred over others from
the standpoint of speeding up the development process and
preventing environmental pollution.
As specific examples of aminopolycarboxylic
acids, aminopolyphosphonic acid, organic phosphonic acids,
and salts thereof, which are useful for the formation of
organic complex salts of Fe(m), mention may be made of
ethylenediaminetetraacetic acid, diethylenetriaminepenta-
acetic acid, 1,3-diaminopropanetetraacetic acid, propylene-
diaminetetraacetic acid, nitrilotriacetic acie, cyclohexane-
diaminetetraacetic acid, methyliminodiacetic acid,- imino-
diacetic acid, glycol ether diaminetetraacetic acid, and
so on.
These compounds may také the form of a sodium,
potassium, lithium or ammonium salt. Of the foregoing
compounds, Fe(m) complex salts of ethylenediaminetetra-
acetic acid, diethylenetriaminepentaacetic acid, cyclo-
hexanediaminetetraacetic acid, 1,3-diaminopropanetetra-
acetic acid and methyliminodiacetic acid are favored over
the others because their high bleaching power.
These ferric ion complexes may be used in the
form of a complex salt or may be formed in the bath by
mixing a ferric salt, e.g., ferric sulfate, ferric chloride,
ferric nitrate, ammonium ferric sulfate, ferric phosphate,
- 46 -
: ~ -
- :
- , , . ~ , . ::
- ~,
132790.~ .
or so on, with a chelating agent, e.g., an aminopolycar-
boxylic acid, an aminopolyphosphonic acid, phosphonocarbox-
ylic acid, etc.
Further, the chelating agent may be used in excess
of the amount required for ferric ion complexation.
Of the Fe( m ) complex salts, aminopolycarboxylic
acid-Fe(m) complexes are favored over the others and they
are added in an amount of from 0.01 to 1.0 mol/l, preferably
frcm 0.05 to 0.50mal/1 of the bleaching solution or bleach-fixing solution.
In the bleaching bath, the bleach-fix bath and/or
prebaths thereof, various kinds of compounds can be used
as a bleach accelerator. Preferable examples of bleach
accelerators which can contribute to achievement of high
bleaching power include compounds containing a mercapto
group or a disulfide linkage described in U.S. Patent
3,893,859, German Patent 1,290,812, Japanese Patent
Application (OPI) No. 95630/78, and Research Disclosure,
No. 17129 (Jul. 1978), thiourea compounds described in
Japanese Patent Publication No. 8506/70, Japanese Patent
Application (OPI) Nos. 20832/77 and 32735/78, U.S. Patent
3,706,561, and so on, and halides such as iodine ion,
bromine ion, etc.
- 47 -
.
13279~.S
In addition, rehalogenating agents, such as
bromides (e.g., potassium bromide, sodium bromide, ammonium
bromide, etc.~, chlorides (e.g., potassium chloride, sodium
chloride, ammonium chloride, etc.) and iodide (e.g., am-
monium iodide~ can be added to the bleaching or bleach-fix
bath to be used in the present invention.
Optionally, one or more of an inorganic or
organic acid and an alkali metal or ammonium salt thereof,
which have a pH buffering abili~y; with specific examples
including boric acid, borax, sodium metaborate, acetic acid,
sodium acetate, sodium carbonate, potassium carbonate,
phosphorous acid, phosphoric acid, sodium phosphate, citric
acid, sodium citrate, tartaric acid, etc., corrosion in-
hibitors such as ammonium nitrate, guanidine, etc., and so
on can be added.
As for the fixing agent to be used in the bleach-
fix bath or the fixer in relation to the present invention,
known fixing agents or water-soluble silver halide dis-
solving agents, such as thiosulfates (e.g., sodium thio-
sulfate, ammonium thiosulfate, etc.), thiocyanates (e.g.,
sodium thiocyanate, ammonium thiocyanate, etc.), thioether
compounds (e.g., ethylenebisthioglycolic acid, 3,6-dithia-
1,8-octanediol, etc.), water soluble silver halide dissolving
agent (e.g.,) thioureas, etc., and so on, can be used alone
or as a mixture of two or more thereof.
- 48 -
,. .. . .
, . . .. ..
' ' ,'' ~ ' ~ ~
.", ~
.... .. .. ..
132790~
On the other hand, special bleach-fix baths, e.g.,
those which comprise combinations of fixing agents de-
scribed in Japanese Patent Application (OPI) No. 155354/80
and large quantities of halides like potassium iodide, can
be employed in the present invention.
However, it is particularly preferred to use
thiosulfates, especially ammonium thiosulfate, as a fixing
agent.
A preferable concentration of the fixing agent
ranges from 0.3 to 2 mol/l, particularly from 0.5 to 1.0
mol/l of bleach-fix solution or fixing solution.
A pH range of the bleach-fix bath or the fixer is
preferably 3 to 10, and more preferably 5 to 9.
In the bleach-fix bath, various additives, such
as a brightening agent, a defoaming agent, a surface
active agent, polyvinyl pyrrolidone, and an organic solvent
like methanol, can be added.
The bleach-fix bath or the fixer in the present
invention contains, as a preservative, sulfite ion-
releasing compounds, such as sulfites (e.g., sodium
sulfite, potassium sulfite, ammonium sulfite, etc.),
bisulfites (e.g., ammonium bisulfite, sodium bisulfite,
potassium bisulfite, etc.), metabisulfites (e.g., potassium
metabisulfite, sodium metabisulfite, ammonium metabisulfite,
etc.), and the like. A preferred concentration of these ,!,
- 49 -
13279~
preservatives ranges from about 0.02 to 0.50 mol sultite
ion/l, particularly 0.04 to 0.40 mol sulfite ion/l.
Although it is conventional to add sulfites as a
preservative, other preservatives, such as ascorbic acid,
carbonyl/bisulfite adducts, carbonyl compounds, etc., may
be added.
Further, buffers, brightening agents, chelating
agents, defoaming agents, antiseptics, and so on may be
added, if needed.
After a desilvering step, e.g., after a fixation,
bleach-fix or like step, the silver halide color photo-
graphic material of the present invention is, in general,
subjected to a washing step and/or a stabilizing step.
The volume of washing water required can be
determined based upon the characteristics of the photo-
sensitive materials to be processed (specifically, depend-
ing, e.g., on what kinds of the couplers are incorporated
therein), end-use purposes of the photosensitive materials
to be processed, the temperature of the washing water, the
number of washing tanks (stage number), how the washing
water is replenished (as to, e.g., whether or not a current
of water flows counter the direction, the photosensitive
materials are moved during development processing, and
other conditions.
_ 50
... ...
1~2730~
In particular, the relation between the number of
washing tanks and the volume of washing water in a multi-
stage counter current process can be determined using the
method described in Journal of the Society of Motion Pictur~
and Television Engineers, vol. 64, pages 248-253 (May 1955),
A preferred stage number in the multistage counter current
process is, in general, from 2 to 6, particularly from 2
to 4.
According to the multistage counter current pro-
cess, a volume of washing water can be sharply reduced,
for example, to below 0.5-1 liter per square meter of the
photosensitive material processed. However, the process - .
suffers from the disadvantage that bacteria propagate
themselves in the tanks because of an increase in staying
time of water in the tanks. Suspended matter produced from
the bacteria sticks to the photosensitive materials pro-
cessed therein.
As a means of solving such a problem in the
processing of the color photosensitive material of the
present invention, reducing the amount of calcium ! and
magne~ium, which is described ~n U.S. patent No. 5,055,381
issued October 8, 1991, can be employed to enormous advantage.
-- 51 --
X ,.
.
1327~
Further, bactericides such as isothiazolone
compounds and thiabendazoles described in Japanese Patent
Application (OPI) No. 8542/82, chlorine-containing
germicides such as the sodium salt of chlorinated iso-
cyanuric acid, benzotriazoles described in European
Patent 204197, copper ion, and other
germicides described in Hiroshi Horiguchi Bohkin Bohbai Zai
no Kagaku ~which means "Chemistry of Antibacteria and
Antimold"), Biseibutsu no Mekkin,-Sakkin, Bohbai no Kagaku
(which menas "Arts of sterilizing and pasteurizing microbe,
and proofing against mold") compiled by Eisei Gijutsu Kai,
and Bohkin Bobizai Jiten (which means "Thesaurus of Anti-
. _
bacteria and Antimold") compiled by Nippon Bohkin-Bohbi
Gakkai.
Further, a surface active agent as a water drain-
lng agent, and a chelating agent represented by EDTA as a
water softener can be used in washing water.
Washing water to be used in the processing of
the photosensitive material of the present invention is
adjusted to pH 4-10, preferably to pH 5-9. The temperature
of the washing water and the washing time can be set to
various values depending on, e.g., the characteristics
and the usage and the usage of the photosensitive material.
In general, the temperature and time are in the range of
from 15 to 45C and from 20 sec. to 10 min., preferably
from 25 to 40C and from 30 sec. to 5 min., respectively.
- 52 -
' ' ~ ' , . . .
- 13279~
Also, the photosensitive m~terial of the present
invention can b~ processed with a stabilizer with-
out using the above-described washing water.
In the stabilizer are added compounds having an
image-stabilizing function, for example, aldehyde compounds
represented by formaldehyde, buffers for adjusting the pH
in a film to a value suitable for stabilization of dyes,
ammonium compounds, and so on.
Further, the above-described antibacteria and
antimold agents can be used in the stabilizing bath in
order to prevent bacteria from propagating themselves in
the bath and to impart a mold proofing property to the
processed photosensitive material.
Furthermore, a surface active agent, a brighten-
ing agent and a hardener can be added to the stabilizer.
When stabilization is carried out directly
without a washing step in the processing of the sensitive
material of the present invention, all the methods de-
scribed, e.g., in Japanese Patent Application (OPI) Nos.
8543/82, 14834/83, 18434~/84, 220345/85, 238832/85,
239784/85, 239749/85, 4054/86 and 11879/86, and 50 on
can be employed.
In other preferred embodiments, chelating agents
such as l-hydroxyethylidene-l,l-diphosphonic acid, ethylene-
diaminetetramethylenephosphonic acid, magnesium compounds
and bismuth compounds are used in the stabilizer.
- 53 -
;:
: - ;.......... , -
1~279~
A solution used in the washing and/or the stabiliz-
ing step can further be used in a pre-step thereof. For
instance, the overflow of washing water, which is reduced
in amount by employing the multistage counter current
process, is streamed into a pre-bath or a bleach-fix bath.
Therein, the bleach-fix bath is replenished with a con-
centrated replenishing solution, resulting in a reduction
of waste.
The method of the present invention can be ap-
plied to any development process as long as a color
developer is used therein. For instance, it can be applied
to the processing of color paper, color reversal paper,
color direct-positive photosensitive materials, color
positive films, color negative films, color reversal films,
and so on. In particular, the application to color paper
and color reversal paper is preferred over other applications.
The silver halide emulsion in the photosensitive
materials which can be used in the present invention may
have any halide composition, e.g., silver iodobromide,
silver bromide, silver chlorobromide, silver chloride, etc.
More specifically, in the case of rapid process-
ing or low replenishment processing of color paper or the
llke, silver chlorobromide emulsions having a silver
chloride content of 60 mol~ or more and a silver chloride
emulsion are preferred and those having a chloride content
o~ 80 to 100 mol~ are particularly favored.
- 54 -
, . : , - ~ . :
.. .
. ~ .. .
.
': : ~' : "; ~. ' ,,. . :
13279~
When it is necessary to achieve high sensitivity
and to control generation of fog during preparation,
storage, and/or processing to a particularly low level,
silver chlorobromide emulsions having a bromide content of
50 mol~ or more and a silver bromide emulsion (which each
may have an iodide content of 3 mol% or less) are preferred,
and those having a bromide content o not less than 70 mol%
are more preferred. -
In color photographic materials for taking photo-
graphs, silver iodobrom~de and silver chloroiodobromide
are preferred, wherein the iodide content is preferably
from 3 to 15 mol%.
The interior and the surface of the silver halide
grains which can be employed in the photosensitive materi-
als to be used in the present invention may differ in
halide composltion. The silver halide grains may have a
conjunctlon structure or a multilayer structure, or the
silver halide grains may be uniform throughout.
The silver halide grains of the above-described
kinds may be present as a mixture.
A mean grain size of silver halide grains to be
employed in the present invention (the grain size herein
refers to the grain diameter when the grains are spherical
or approximately spherical in shape, while it refers to
the edge length when the grains are cubic grains. In both
- 55 -
, ' . : ' .
.
13279~5
cases, it is represented by the mean based on the projectionareas of grains and when the grains are tabular, it refers to
a projection areas calculated on a basis of area of circle)
ranges preferably from 0.1 micron to 2 microns, particularly
preferably from 0.15 micron to 1.5 micron.
The grain size distribution may be narrow or broad.
However, a so-called monodispersed silver halide emulsion
having a variation coefficient (which refers to the value
obtained by dividing the standard deviation in the
granularity distribution curve of the silver halide emul-
sions by the mean grain size) not exceeding 20%, particular-
ly preferably 15% or less, is preferred for use in the
photosensitive material employed in the present invention.
In order to obtain sufficient image density gradation,
two or more monodispersed silver halide emulsions (prefer-
ably having their variation coefficients in the above-
described range) having substantially the same color
sensitivity, but differing in grain size, can be coated in
a single layer as a mixed emulsion, or can be coated
separately in a multilayer form.
Also, a combination of two or more polydispersed
silver halide emulsions, or a combination of a monodispersed
emulsion and a polydispersed emulsion can be coated in a
single layer or in a multilayer.
- 56 -
- . . , ~. ~ .. .. , ~
1327~a
The silver halide grains to be employed in photo-
sensitive material used in the present invention may have
a regular crystal form, such as that of a cube, an octa- -
hedron, a rhombododecahedron or a tetradecahedron, or an
irregular crystal form, such as that of a sphere or so on.
Also, the grains may have a composite form of these crystal
forms. Moreover, the grains may have a tabular form in
which the diameter is greater than the thickness by a
factor of 5 or more, particularly 8 or more. An emulsion
which contains tabular grains as described above in a
fraction of 50% or more on a basis of the total projection
area of all the grains therein may be employed. An emulsion
which contains silver halide grains ha~ing various kinds
of crystal forms as a mixture may be employed. These
various kinds of emulsions may be either those which form
latent image predominantly at the surface of the grains,
or those which mainly form a latent image inside the grains.
Photographic emulsions which can be used in
photographic material employed in the present invention can
be prepared using methods described in Research Disclosure,
vol. 170, Item No.~17643, Section I, II, m (Dec. 1978).
The emulsions of photographic material employed
in the present invention are generally ripened physically
and chemically and further sensitized spectrally. Additives
to be used in these steps are described in Research
.
- ,
13279~
Disclosure, vol. 176, No. 17643 (Dec. 1978) and vol. 187,
No. 187I6 (Nov. 1979), and where descriptions thereof are
given are set forth together in the following table.
Photographic additives which can be used in the
present invention are also described in the above-described
two literatures, and where they are described are also
tabulated in the following table.
- 58 -
~ - 13279~5
.
Additives RD 17643 RD 18716
1. Chemical sensitizers p. 23 p. 643, right column
2. Sensitivity-increas- ditto
ing agents
3. Spectral sensitizers p. 23-24 p. 643, right column
4. Supersensitizers p, 649, right column^~
5. Brightening agents p. 24
6. Antifoggant and sta- p. 24-25 p. 649, right column
bll lzers
7. Coupler p. 25
8. Organic solvent p. 25
9. Light absorbents. p. 25-26 p. 649, right column to
Filter dyes p. 650, left column
10. UV-ray absorbents
11. Stain inhibitorp.25, right col.p. 650, left column
to right column
12. Dye image-stabil- p. 25
izing agents
13. Hardeners p. 26 p. 651, left column
14. Binders p. 26 ditto
15. Plasticizers andp. 27 p. 650, right column
Lubricants
16. Coating aids andp. 26-27 ditto
Surface active
agents
17. Antistatic agentsp. 27 ditto
. _ _
_ 59 _
,,
- , . : . .
.,. , '-.
-;~ .
13279~5
Various kinds of color couplers can be used in
photographic materials employed in the present invention.
The term color coupler as used herein refers to a compound
capable of producing a dye by a coupling reaction with
the oxidation product of an aromatic primary amine devel-
oping agent. Representatives of useful color couplers are
naphthol or phenol compounds, pyrazolone or pyrazoloazole
compounds, and open-chain or heterocyclic ketomethylene com-
pounds. Specific examples of such cyan, magenta and yellow
couplers which can be used in the present invention are de- -
scribed in the patents cited in Research Disclosure (RD)
No. 17643, Section VII-D ~Dec. 1978) and ibid., No. 18717
(Nov. 1979).
It is desirable that the color couplers to be
incorporated in the photosensitive material should be
rendered nondiffusible by containing a ballast group or
taking a polymerized form.
Moreover, two-equivalent color couplers which
have a coupling eliminable group at the coupling active
site are preferred to four-equivalent ones having a
hydrogen atom at that site, because the amount of silver
per unit area of photosensitive material can be reduced.
Couplers which can be converted to dyes having a moderate
diffusibility as the result of color development, colorless
'couplers, DIR couplers which can release development
- 60 -
.
: ~: , : . . - -
.~ , , ~ . . ..
\
l327sa~
inhibitors in proportion as the coupling reaction proceeds,
and couplers capable of releasing development accelerators
upon the coupling reaction can also be employed.
As representatives of the yellow couplers which
may be used in the present invention, mention may be made
of oil-protected acylacetoamide couplers. Specific ex-
amples of such couplers are described in U.S. Patents
2,407V210, 2,875,057 and 3,265,506, and so on.
In the present invention, two-equivalent yellow
couplers are preferably employed and typical representatives
thereof are yellow couplers of the type which have a split-
ting-off group attached to the coupling active site via
its oxygen, as described, e.g., in U.S. Patents 3,408,194,
3,447,928, 3,933,501 and 4,022,620, and yellow couplers of
the type which have a splitting-off group attached to the
coupling active site via its nitrogen, as described, e.g.,
in Japanese Patent Publication No. 10739180, U.S. Patents
4,401,752 and 4,326,024, RD 18053 ~Apr. 1979), British
Patent 1,425,020, and West German Patent Application (OLS)
Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812.
Of these yellow couplers, a-pivaloylacetoanilide
couplers are of great advantage in that they can produce
dyes excellent in fastness, especially to light, and ~-
benzoylacetoanllide couplers have an advantage in that
they can ensure high color density to developed image.
- 61 -
:: . . . .
. . . . ..
~32790~
Magenta couplers which may be employed in the
present invention include those of oil-protected indazolone
or cyanoacetyl type, and preferably those of pyrazoloazole
type, such as 5-pyrazolones, pyrazolotriazoles and the like.
Of 5-pyrazolone couplers, those having an arylamino group
or an acylamino group at the 3-position are preferred over
Gthers from the standpoint of the superiorities in hue and
color density of the developed dyes. Typical examples
thereof are described in U.S. Patents 2,311,082, 2,343,703,
2,600,788, 2,908,573, 3,062,655, 3,152,896 and 3,936,015,
and so on. As for the splitting-off groups of two-
equivalent 5-pyrazolone couplers, groups which can split
off at the nitrogen site, as described in U.S. Patent
4,310,619, and arylthio groups described in U.S. Patent
4,351,897 are particularly preferable. Also, ballast
group-containing 5-pyrazolone couplers described in European
Patent 73,636 can provide high color density of developed
images.
Specific examples of magenta couplers of the
pyrazoloazole type include pyrazolobenzimidazoles de-
scribed in U.S. Patent 3,369,879 and, preferably,
pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent
3,725,067, pyrazolotetrazoles described in RD 24220 (Jun.
1984), and pyrazolopyrazoles described in RD 24230 (Jun.
1984). From the viewpoint of smallness of yelllow side-
,
. ~ . - . ~ . .
- .. : ~ . .. . .
13279~
absorption and excellence of light fastness of the devel-
oped dyes, imidazo[1,2-b]pyrazoles described in European
Patent 119,741 are preferred, and pyrazolo[l,5-b][1,2,43-
triazoles described in European Patent 119,860 are par-
ticularly favored over others.
Cyan couplers which may be used in photosensitive
materials employed in the present invention include
couplers of the oil-protected naphthol and phenol types.
Representatives of the naphthol couplers
described in U.S. Patent 2,474,293, and more preferably
two-equivalent naphthol couplers of the type which have a
splitting-off group attached to the coupling active site
via its oxygen, as described in U.S. Patents 4,052,212,
4,146,396, 4,228,233 and 4,296,200. Specific examples of
phenol type cyan couplers are described in U.S. Patents
2,369,929, 2,801,171, 2,772,162 and 2,895,826, and so on.
Cyan couplers fast to moisutre and temperature
are preferably used in photosensitive materials employed
in the present invention. Typical examples thereof in-
clude phenol type cyan couplers which have an alkyl group
containing 2 or more carbon atoms at the meta-position of
the phenol nucleus as described in U.S. Patent 3,772,002,
couplers of 2,5-diacylamino-substituted phenol type as de-
scribed in U.S. Patents 2,772,162, 3,758,308, 4,126,396,
4,334,011 and 4,327,173, West German Patent Application
, ,
.
, - ~ . . ~ . , .
. , . , . ~. . ~ . .
1327~5
(OLS) No. 3,329,729, Japanese Patent Application ~OPI) No.
166956/84, and so on, and phenol couplers having a phenyl-
ureido group at the 2-position and an acylamino group at
the 5~position, as described in U.S. Patent 3,446,622,
4,333,999, 4,451,559, and 4,427,767, and so on.
In particular, low fog density and excellent
photographic properties can be obtained by using at least
one cyan coupler represented by the following general
formula (C-I) in the processing method of the present
invention.
Formula (C-I) is described in detail below.
OH
R73 ~NHCoR71
R72 ~J ~C-I)
z71
In the above formula, R71 represents an alkyl
group, a cycloalkyl group, an aryl group, an amino group,
or a heterocyclic group. R represents an acylamino
group or an alkyl group containing 2 or more carbon atoms.
R73 represents a hydrogen atom, a halogen atom, an alkyl
group, an alkoxy group, or may combine with R72 to form a
ring. z71 represents a hydrogen atom, a halogen atom, or
a group eliminable in the reaction with the oxidation
-- 64 --
~' ' ' ' ' ~ ' " ' ''' ''' ''' '' ': `'
,
- ~ .. , ' . :
.
.
.
1327~
product of an aromatic primary amine color developing
agent.
Alkyl groups preferred as R 1 in formula (C-l)
include those containing 1 to 32 carbon atoms, such as
methyl butyl, tridecyl, cyclohexyl, allyl, etc., preferred
aryl groups are, e.g., phenyl groups and naphthyl groups,
and preferred heterocyliC groups are, e.g., 2-pyridyl
groups, 2-furyl groups and the like.
As for the amino group represented by R71, phenyl
substituted àmino groups which may have a substituent
group are particularly preferred.
Further, groups represented by R71 may be
further substituted with a group selected from among an
alkyl group, an aryl group, an alkoxy group or an aryloxy
group (e.g., a methoxy group, a dodecyloxy group, a
methoxyethoxy group, a phenyloxy group, a 2,4-di-tert-
amylphenoxy group, a 3-tert-butyl-4-hydroxyphenyloxy
group, a nephthyloxy group, etc.), a carboxyl group, an
alkylcarbonyl or arylcarbonyl group (e.g., an acetyl group,
a tetradecanoyl group, a benzoyl group, etc.), an alkoxy-
carbonyl group or an aryloxycarbonyl group (e.g., a
methoxycarbonyl group, a phenoxycarbonyl group, etc.), an
acyloxy group (e.g., an acetyloxy group, a benzoyloxy group,
etc.), a sulfamoyl group (e.g., an N-ethylsulfamoyl group,
an N-octadecylsulfamoyl group, etc.), carbamoyl group
- 65
- ~ : . :
1 3 2 7 9 ~ ~
(e.g., an N-ethylcarbamoyl group, an N-methyl-dodecylcar-
bamoyl group, etc.), a sulfonamido group (e.g., a methane-
sulfonamideo group, a benzenesulfonamido group, etc.), an
acylamino group le.g., an acetylamino group, a benzamido
group, an ethoxycarbonylamino group, a phenylaminocarbonyl-
amino group, etc.), an imido group (e.g., a succinimido
group, a hydantoinyl group, etc.), a sulfonyl group (e.g.,
a methanesulfonyl group, etc.), a hydroxy group, a cyano
group, a nitro group, and a halogen atom.
z71 in formula (C-I) represents a hydrogen atom,
or a coupling eliminable group, with specific examples in-
cluding a halogen atom (e.g., a fluorine atom, a chlorine
atom, and a bromine atom, etc.), an alkoxy group (e.g., a
dodecyloxy group, a methoxycarbamoylmethoxy group, a
carboxypropyloxy group, a methylsulfonylethoxy group, etc.),
an aryloxy group (e.g., a 4-chlorophenoxy group, a 4-
methoxyphenoxy group, etc.), an acyloxy group (e.g., an
acetoxy group, a tetradecanoyloxy group, a benzoyloxy
group, etc.), a sulfonyloxy group (e.g., a methanesulfonyloxy
group, a toluenesulfonyloxy group, etc.), an amido group
~e.g., a cycloacetylamino group, a methanesulfonylamino
group, a toluenesulfonylamino group, etc.), an alkoxy-
carbonyloxy group (e.g., an ethoxycarbonyloxy group, a
benzyloxycarbonyloxy group, etc.), an aryloxycarbonyloxy
group (e.g., a phenoxycarbonyloxy group, etc.), an
- 66 -
.
.~ . . -
- . : .
~3279~5
aliphatic or aromatic thio group (e.g., phenylthio group,
a tetrazolylthio group, etc.), an imido group (e.g., a
succinimido group, a hydantoinyl group, etc-), an N-containing
heterocyclic group (e.g., a l-pyrazolyl group, a 1-benzo-
triazolyl group, etc.), an aromatic azo group (e.g., a
phenylazo group, etc.), and so on. These coupling
eliminable groups may contain a photographically useful
group.
The cyan coupler of formula (C-I) may form a
polymer (including a dimer) via R71 or R72.
Specific examples of cyan couplers represented
by the foregoing formula (C-I)are illustrated below.
However, the invention should not be construed as being
limited to the following examples.
( ~
CC~3~NH c O l~'H O ;~t)C s H l l
ce
.
1327g~
OH (~ gH9
C~NHCOCHO~(t)CsHI,
( ~ -- 3 )
0
~,NHCOC 13 H27 (n
C 2H5
ce
( ~--Y )
OH C 2H5
~NHCOCHO~(t)C sH
(t)C 4Hg~ (t~'5H
ce
( ~--S )
ce~, NHCO ~ CH ~ ) 3 O~(t)C 5 H
C 2H5 ce
O('Il2 CH 2 Cll 2 ('OOIl
-- 68 --
. . ~
.
13279~5
C--6 ) OH
C2H5 ~NH('0(,`3F7
(t~(~ 5 H 11 ~0( H~,`ONH
( )(~5H
~ (~--7 )
,' ~`12H25
(,' 4Hg SO2NH~O(,'HCONH/~
ce
( C--8 ) ,~ NH(,'~(t)(~4Hg
5 ,~
ce
( (~--9 ) OH
C6Hl3 ?
ce
-- 69 _
~. . - ~ -
.
: : . .: . .
13279~a
( (~ / ) F F
(i)C3H7 ~NHCO~F
(t)C 5H~ ICO~I F F
~ . ce
(t)C5Hl 1
( C~
(t)CsH"~ )~
ce
2 )
OH
~ NH(~o~9 ''
O ~O(,`H(,'ONH)~ HNSO 2 (~'H2 (~'H2 0(-~3
\= ~ ce
(t `' 6Hl 3
-- 70 --
` : . ` ; . ` , , . :
13279~
(`--/ 3 )
OH
~N~ H~
H HNSO2 (( H2 ) g t)c5H
ce \=/
( ~--/ Y )
0
~NH(,' 0~
H ce HNSO2(~l6H33
.
S )
O~H~_ NHCOCHO~(t)C5H
(t)(~ 5H
O H ce
-- 71 --
; ~
.. . . . ~ ,...... ~. .
.
: . . ~ . . .
: . . . ; : . ~ :
, . .. ., . ` . .
13279~ ^
( C-- / 6 ) OH
~NHC 04~)
O~NJ~ )=/ (t)C 8 H 17
ce - HNSO2~
O(,'H2 ~'H(' 4Hs
I
(~ 2Hs
)
NH(,'Ol_HO~
(t)~ sH
,NH(~ O~
H NHSO2Cl6H33(n)
ce
-- 72 --
, ,: .
, .~
'; ` ' '
^ 132790.3
/ 9 )
CH~NHc ~cl
N~ /~
H ce NHSO 2~0Cl 2H2s(n)
(~--.2 0 )
,OH
C 4Hg J~ NH(,`ONH:~ CN
(~)C5Hl l~O(,'H(,`ONH
'. (t)C5H, 1
OH
I 6Hl 3 )~
(t)( 8Hl7~ocH(~oNH
(t)(, 8~11 7
-- 73 --
,. :: -.. : - : :
. .
.
-
- 13279~a
(~- i 2
C2Hs )~ ~S02~8HI7
(t)C5Hl l~O(',H(~ONH
(tk,` 5H
2 3 )
OH
C4Hg J~--NH(~ONH~Ce
(t)CsHl l~O(CHCONH (~N
(t)C5H
C--2 Y )
OH
( ' H I~NH(, ONH~ CN
(t)C5Hl l~O('HCONH/~
(t)C5Hl 1
~ '.
OCH 3
-- 7 4
f
132790~
(~6HI3
(t)C8Hl r4~0(~ 0NH
~ O
(t~`8Hl 7 ~
.' ~
(t)(~8Hl 7
( C--2 6 )
~NHCONE~< S
(t)CsH"~ocHcoNH
(t)C5Hl 1
-- 7s --
:: .
-
- - ` . . . .. ... ...... . ................. . . .. .
-
l327sa3
The cyan couplers represented by the foregoing
formula (C-IJ can be synthesized on the basis of descriptions
in Japanese Patent Application (OPI) No. 166956/84, Japanese
Patent Publication No. 11572/74, and so on.
Couplers which can produce dyes having moderate
diffusibility can be used together with the above~described
couplers, whereby granularity can be improved. Specific
examples of the diffusible dye-producing magenta couplers -
are described in U.S. Patent 4,366,237 and British Patent
No. 2,125,570, while in European Patent No. 96,570 and West
German Patent Application (OLS) No. 3,234,533 are described
those of yellow, magenta and cyan couplers of the foregoing
kind. Dye forming couplers and the above-described special
couplers may assume a polymerized form (including a dimerized
form). Typical examples of polymerized couplers are de-
scribed in U.S. Patents 3,451,820 and 4,080,211. Further,
specific examples of polymerized magenta couplers are de-
scribed in British Patent 2,102,173 and U.S. Patent 4,367,282.
Two or more of various kinds of couplers which can
be employed in photosensitive material employed in the present
invention can ~e incorporated in the same light-sensitive -
layer or the same coupler can be incorporated in two or more
different layers, depending on characteristics required of
the photosensitive material to be produced.
- 76 -
.
-
13279~a
.
The couplers to be employed in the present inven-
tion can be incorporated into a photosensitive material using
various known dispersing methods. For instance, high boiling
organic solvents to be used in oil-in-water dispersion
methods are cited in U.S. Patent 2,322,027. Processes in
latex dispersion methods, effects of said methods, and
specific examples of latexes for impregnation are described
in U.S. Patent 4,199,363, West German Patent Application
(OLS) Nos. 2,541,274 and 2,541,230, and so on.
The standard amount of color coupler used ranges
from 0.001 to 1 mole per mole of light-sensitive silver
halide. A preferred amount of yellow coupler used range~
from 0.01 to 0.5 mole, that of magenta coupler from 0.003
to 0.3 mole, and that of cyan coupler from 0.002 to 0.3 mole.
The photographic material to be used in the present invention
comprises a support and atleast one photosensitive emulsion layer thereon.
~lsions are coated on a flexible support, such as a plastic film (e.g.,
a cellulose nitrate film, a cellulose acetate film, a poly-
ethylene terephthalate film, etc.), paper, etc., or a rigid
support like glass. Details of supports and coating methods
are described in Research Disclosure, vol. 176, Item 17643,
Section XV (p. 27), Section XVII ~p. 28) (Dec. 1978).
- 77 -
: .
; ' : '' ', . ~ , ,-
: . . -
132790~
In the present invention, a reflective support
is preferred.
A "reflective support" can render dye images
formed in silver halide emulsion layers clear through its
high reflectivity. Such a reflective support as described
above includes a support coated with a hydrophobic resin
in which a light-reflecting substance, e.g., titanium
oxide, zinc oxide, calcium carbonate, calcium sulfate, etc.,
is dispersed and a film of a hydrophobic resin containing
a light-reflecting substance in a dispersed condition.
The present invention is illustrated in more detail
by reference to the following examples. Unless stated
otherwise, all parts, percents and ratios are by weight.
EXAMPLE
A processing solution having the following formula
was prepared as a color developer.
Color Developer
Compound (A) ~Compound of the present invention)
described in Table 1
Compound (B) ~Hydroxylamines or the like)
described in Table 1
Sodium Sulfite 0.2 g
Potassium Carbonate 30 g
EDTA - 2Na 1 g
Sodium Chloride 1.5 g
4-Amino-3-methyl-N-ethyl-N-[~-(methane- 5.0 g
sulfonamido)ethyl~aniline Sulfate
- 78 -
.
,
' ' .' ' ' ' ' '
,;
13279~
Brightening Agent (of 4,4'-diminostilbene 3.0 g
type) ~ W ITEX-CK, produced by Ciba Geigy Ltd.
Water to make 1,000 ml
pH adjusted to 10.05
Samples of the thus prepared color developer (No.
1 to No. 20) were placed in separate test tubes designed
so as to have an aperture rate (aperture area/sample area)
of 0.05 cm 1, and allowed to stand for 4 weeks at 35C.
After the lapse of 4 weeks, each decrement due to evapora-
tion was supplemented with distilled water, and a residual
rate of the aromatic primary amine color developing agent in
each sample was determined by liquid chromatography.
The results are shown in Table 1 below.
~eho~S ~d ~ ~' J~'/C
- 79 -
- 13279~
Table 1
*1 *2 *3
Sample Compound (A) Compound (B) Residual Rate
No. 0.03 mol/l 0.04 mol/l Noteof Agent (~)
1 II-14 Comparison 7
2 II-13 ~' 15
3 Triethanolamine II-14 " 75
4 Polyethyleneimine 4 " " 63
Na S0 " " 75
6 I-l II-3 Invention 90
7 " II-13 " 91
8 1~ II-14 " 93
9 I-4 II-3 ~/ 87 .
'~ II-13 ~' 89
~ II-14 ~' 89
12 I-ll II-3 '~ 87
13 '~ II-13 " 87
14 " II-14 " 87
I-l N.N-diethyl- " 93
hydrazine
16 " Glucose ' 87
17 "Dihydroxyacetone " 86
18 - N,N-diethyl- Comparison 30
hydrazine
19 - Glucose ' ~ 0
~ Dihydroxyacetone " 11
- 80 -
- .
',: - '' ,,';
.; .
132793~
*l Indication by the number of the compound exemplified
in this specification.
*2 Indication by the number of the compound exemplified
in this specification.
.
*3 Concentration of re-
Residual rate of (,/,) _ sidual developin~ a~entXIOD
developing agent 5.0 g/l
4 -~CH2CH2NH~ n= SOO to 2,000
- 81 -
.. . . . . . . . .
. .. ~ . . . ,, . ~ ..
l327sas
As can be clearly seen from the data in Table 1,
the residual rate of the developing agent was improved by
additional use of such a compound as triethanol amine, poly-
ethyleneimine or sodium sulfite, (Sample No. 3, 4 or 5), ~
compared with the independent use of Compound (B), such as
hydroxylamine or diethylhydroxylamine, (Sample No. 1 or 2).
However, the improvement produced by such a combined use as
described above was insufficient.
On the other hand, as can be seen from the data -
of Samples Nos. 6 to 17, the use of the compound represented
by the formula (I) was able to raise remarkably the residual
rate of the developing agent, that is, effected the improve-
ment in preservability of the color developer.
EXAMP~E 2
An integral multilayer color paper was prepared by
coating layers so as to have the layer structure described
in Table A on a paper support laminated with polyethylene on
both sides thereof. The coating compositions employed there-
in were prepared in the following manner.
Preparation of Coating ComPOSition for First LaYer
To 19.1 g of the yellow coupler (a) and 4.4 g of
the color image stabilizer (b) were added 27.2 ml of ethyl
acetate and 7.7 ml of the solvent (c) to prepare a solution.
The solution was dispersed, in an emulsified condition,
into 185 ml of a 10~ aqueous gelating solution containing
8 ml of a 10~ solution of sodium dodecylbenzenesulfonate.
- 82 -
' ~ ' ' ; ,: ' , :
, . ~ :
- : -
-: , ' '
13279~.~
.
..
Separately, a blue sensitizing dye having the
chemical structure illustrated below was added to a silver
chlorobromide emulsion (having a bromide content of 1.0 mole%,
and containing 70 g of Ag per kg of emulsion) in an amount of
5.0 x 10 4 mole per mole of silver to prepare a blue-
sensitive emulsion.
The foregoing emulsified dispersion was mixed
with the blue-sensitive emulsion and dissolved therein.
Then, the resulting emulsion was so adjusted as to have the
composition shown in Table A.
Coating compositions for second to seventh layers
were prepared in analogy with that of the first layer. In
each of the constituent layers, sodium salt of l-oxy-3,5-
dichloro-s-triazine was used as gelatin hardener.
Spectral sensitizing dyes used in the respective
emulsion layers are as follows:
- 83 -
~, . . ...
~ , . . , ,, i .
.
13279~a
Blue-sensitive Emulsion Layer
CH ~ ~
b~J ( CH2 )4 S03 'i W
~5.0X10 4 mole per mole of silver halide)
Green-sensitive Bmulsion Layer
C2H5
+ ~ C H= C-CH
(CH2 )2 SO3 (Cl H2 )2
SO3H-N~
(4.0 X10 4 mole per mole of silver halide)
and
='<N1~3
( CH 2 ) 4 SO 3 ( I H 2 ) 4
SO3HN (C2~I5)3
(7.0X10 5 mole per mole of silver halide)
- 84 -
;
.
13279~
Red-sensitive E~ulslon La~-er
3 ~5
CH~CH=<
C2Hs I C2H5
(o.9x 10-4 mole per mole of silver halide)
In the red-sensitive emulsion layer, the following com-
pound was incorporated in an amount of 2.6X 10 3 mole per mole
of silver halide.
NH ~ CH=CH ~ NH ~ ~0
N ~ N S03H S03H ~ N
~/ ~ ,
In the blue-sensitive emulsion layer, the green-sensitive
emulsion layer and the red-sensitive emulsion layer was fur-
ther incorporated l-(S-methylureidophenyl)-5-mercaptotetrazole
in amounts of 8.5 xlO 5 mole, 7.7x 10 4 mole and 7.5 X 10 4
mole, respectively, per mole of silver halide.
The following dyes were added to the emulsion layers for
prevention of irradiation:
HOOC~,~CH--CH=C~;~COOH
N O H :
SO 3K SO 3K
-- 85 --
., . . ~. .
,
.
~3279~
and
H 5 C 2 OOC~K--CH=CH--CH----C~ COOC 2 ~ 5
SO 3K SO 3K
.
.. . . /
86
: . . .
,,
13279~
T-ble .~
Layer ~lain Ingredients Amount used
7th Layer Gelatin 1.33 glm2
(Protective Ac~yl-denatured polyvinyl 0.17
layer) alcohol (denaturing degree:
17 ~) -
Liquid paraffin 0.03 ~/
(Ultravio- Gelatin 0-53 g/m2
let absorb- Ultraviolet absorbent (i) 0.21 "
ing layer) Solvent (k) 0.08
~~Sth Layer. Silver halide emulsion
(Red sensi- (silver bromide: 1 mol%) silver: 0.23 g/m2
tive emul-~ Gelatin 1.34 ~
~sion layer) Cyan coupler (Q) 0.34 ~.
Color image stabilizer (m) 0.17
Polymer tn) 0.40
Solvent (o) 0.23 ~,
.
4th Layer Gelatin '1.58 g/m2
(Ultravio- Ultraviolet absorbent (i) 0.62 "
let absorb- Color stain inhlbitor (j) 0.05 1~
ing layer) Solvent (k), . 0.24 ~,
3rd Layer Silver halide emul-sion
(Green sen- (silver bromide: 0.5 mol$) sil~er: 0.36 g/m2
sitive emul- Gelatin 1.24 ~,
sion layer) Magenta coupler (e) 0.31
Color image stabilizer (f) 0.25
Color image stabilizer (g) 0.12 ~ :~
Solvent (h) 0.42 "
2nd Layer Gelatin 0.99 g/m2
(Color stain Colo~stain inhibitor (d) 0.08
inhibiting
layer)
1st Layer Silver halide emulsion
(Blue sensi- (silver bromide: 1.0 mol%) silver: 0.30 g/m2 .
tive emul- Gelatin 1.86
sion layer) Yellow coupler (a) 0.82
Color image stabilizer (b) 0.19 "
Solvent (c) 0.35 '~
Support Polyethylene-laminated paper (containing white
pigment tTi0~) and bluishe~pigment (ultramarine)
in polyethylene laminate on the 1st layer side)
- 87 -
'''
,, ~ ,
'~
. ~ ' ' ~: , . ' , '~' .
13279~
(a) Yellow Coupler
CH3 ce
_ - CH3-C CO-CH-CONH ~ C ~ (t)
- 3 NHCOCHO~,/ \tC5Hll(t)
N C 2 H 5
~C 2 H 5
(b) Color Image Stabilizer
(t)C4H9 ~3~H3
( HO ~ CH2~ C~COO ~ COCH=CH~
(c) Solvent
.
~COOC 4 H 9
~CO OC 4 H 9
-- 88 --
~, ~
.~. . : . . - . . . `
~, .. . .
., . . . ~ , .
132790~
(d) Color Stain Inhibitor '
. . .
OH
~C8Hl7 (SeC)
( s e c ) C 8H ~
OH
- (e) Magenta Coupler
ce .
Cl3H27coN~ ~ :
ce~,ce .
'
.... , ce
(f) C~lor Image Stabilizer
C 3H 7 O~<C~I3
C 3H 7 O~C sH 7
3 C~3
- 89 -
-
13279~ `
(g) Color Image Stabilizer
OH f
Cl~f~CH2~3COOC6Hl3
C6Hl300C~cH2~3 ~ CH3
CH3 OH
(h) Solvent
O=P~OCH2CHC4Hg)3 O=P~O ~ )3
1 : 1 Mixture (by volume)
.
. -- 90 --
. ' ~ '' '~
, , ' , . ~:
13279~
( i) Ultraviolet Absorbent
0~
C 4 H g(t)
CH 2 CH 2 COOC BH
OH
C 4 Hg(t)
.
OH
3'C~9(t)
4Hg(t)
2: 9: 8 Mixture tb.y weight)
-- 91 --
,
13279~
(j) Color Stain Inhibitor
OH
f~!~c 8Hl7(t)
(t)csH
OH
(k) Solvent
O=p~o-c9Hls(i S O ))3
(~) Cyan Coupler
OH C5H11(t)
~ ~ NHCOCHO ~ CsHI1(t) and
CH3 ~ C2Hs
ce
C6H18 ~ NHCO
(t)CsH11 ~ OCHCONH
ce , ce
l : l Mixture (by mole)
.
. - 92 -
. ., . - .. . . .
13279~.J
(m) Co 1 or Image St ab i 1 i z er
Ce~N\
~_ I N~C~Hg(t)
CH 2 CI~ 2 C oOC8H
... .
and
C~Hg(t) ~
[~ I h~c 4Hs (t)
C~Hg (t)
5: 8: 9 Mixture (by weight)
-- 93--
.. -: : -
1327~5
(n) Polymer
CH2-CH-~
CONHC~Hg(t)
mean molecular weight: 35,000
.
(o) Solvent
.
_ gg _
. . . .
l~279aa
The color photographic paper obtained was subjected to
the following p~ocessing steps~. in which color developers with
different compositions were used.
Processing Step Temperature Time
Color development - 35C 45 sec.
- Bleach-fix 35C 45 sec.
- Stabilization 1 35C 20 sec.
Stabilization 2 35C 20 sec.
Stabilization 3 35C 20 sec.
Drying 70-80C 60 sec.
The stabilization step was carried out according to the
three-stage counter current washing process, in which the sta-
bilizing solution flowed from Stabilization Table 3 to
Stabilization Tank 1. Processing solutions employed in the
.. . . . ... ...
foregoing steps, respectively, are described below.
Color Developer
Additive C (Hydroxylamines, etc.? described in Table 2
Additive D ~Compound of Invention) described in Table 2 -
Benzyl Alcohol described in Table 2
Diethylene Glycol described in Table 2
Sodium Sulfite 0.2 g
Potassium Carbonate 30 g
- 95 -
- . .
` 13279~
Nitrilotriacetic Acid 1 g
Sodium Chloride - 1.5 g
Color Developing Agent (described in Table 2) 0.01 mole
Brightening Agent ~UVITEX CK, produced by
Ciba Geigy Ltd.) - , 3.0 g
Water to make 1,000 ml
.pH adjusted to 10.05
Bleach-Fix Bath
EDTA Be(III)NH4~2H20 60 g
EDTA~2Na~2H20 - 4 g
Ammonium Thiosulfate (70 %~ 120 ml
Sodium Suifite 16 g
Glacial Acetic Acid 7 g
Water to make 1,000 ml
pH adjusted to . 5.5
Stabilizer ~~
Formaldehyde (37 %) 0.1 ml
l-Hydroxyethylidene-l,l-di-
phosphonic Acid (60 %) 1.6 ml
Bismuth Chloride 0.35 g
Aqueous Ammonia (26 %) 2.5 ml
Trisodium Nitrilotriacetate 1.0 g
BDTA~4H 0.5 g
Sodium Sulfite 1.0 g
5-Chloro-2-methyl-4-isothiazolin-3-one 50 mg
Water to make 1,000 ml
Separately, a portion of each color developer described
above was placed in l-liter beaker, allowed to stand in con-
- 96 -
. .
13279~ -
tact with the atmosphere for 21 days at 35C, and then
subjected to the foregoing p,rocessing steps.
The processing with the color developer which
had been allowed to stand for 21 days (aged developer was
called "aged developer tests,", and the processing carried
out using the color developer before storage was called
"fresh developer tests".
Photographic propertie,s obtained with the fresh
developer tests and the aged developer tests are shown in
Table 2.
The photographic properties were represented by
Dmin and gradation determined by magenta density measurements.
,., : ~:, Dmin refers to minimum-density and gradation is
represented by the difference in density between the point
of 0.5 and the point corresponding to log E which is 0.3
greater than that corresponding to the density of 0.5.
The results are shown in Table 2 below.
. .. . .............................................. , '
,- 97 -
. , . ~ .
.. .
2790~
~ -I
~ --I
~l I a ~ co N O .~ _~ ~ _ _ =, t~ _
.~ _ O O O O O O O _ o o o o -- o o 5 G O O O O O
- :~
_ _ ~ L'~ U~ L')
C .~ OOOOOOOOOOOOOOOOOO
b C ,.
b '` '
.,
b E ~1 ~
c~ a o o o o o o o o o o o o o o o o o o o o o o
~ o c
u~ o
.,~
~ a c
~ ~ ~ .
3 la ~
a ~ e a~ ~
o
e C _ C _l I N _~
~o oa~
e ~ b O b
E~
-
~ . C~
'1 ~
.C_
,
e .
:~
C C
Q~
_1 11
~ b-
O b a ~ 1 ~ ~ D O ~ ~ D l.J 'O ~J D U ~a ~
l o
~lz
I:L b~1 N r~ o C~ o ~ O
Ul ~
-- 98 --
, . ,.: . , : . .
.
1327905 - ^
As can be seen from tne data o~ Table 2, aging
of the color developers caused changes in Dmin and caused
gradation to increase contrast in experiments No. l to No. 4,
while in experiments No. S to No. 22 changes i~ Dmin and
gradation when using the aged developers were very small,
that is, the stability of photographic properties was
notably improved.
~~ In further detail, changes in Dmin and gradation
were smallest in experiments No. 8, No. 17 and No. 21 among
the experiments from No. 5 to No. 8 and from No. 14 to No.
21. Accordingly, it turned out that compound (d), the
structure of which was illustrated hereinafter, was the
most desirable color developing agent.
~ * Color developing agents (a) to (d) are illustrated below.
(a)/CH2CH3
\ ' H2S4
CH2CH3
tb)CH2CH3
H2 S04
CH2CH3
CH3
t c ) CH2C~3
H2N~-~/ H2S04
CH CH OH
CH3 2 2
td) ~CH2CH3
~ ~ 312 H2SO4
CH CH2CH2NHSO2CH3
_ 99 _
~ ' . ~ . ...
1~27~
EXAMPLE 3
Another color photographic paper was prepared in
the same manner as in Example 2, except the bromine ion
content in the green-sensitive emulsion was changed to 80
mol%. After wedgewise exposure, changes in photographic
properties caused by using aged color developers were
evaluated by reference to generation of fog.
As for the developers used for comparison, the
aged developers brought about a great increase in fog.
On the other hand, the increase in fog density
caused by the use of aged developers of the present inven-
tion was small and good photographic properties were
maintained.
EXAMPLE 4
After wedgewise exposure, the color photographic
paper prepared in the same manner as in Example 2 was sub-
jected to the following processing steps, wherein various
Xinds of color developers underwent a running development
process test in which the process was continued until the
amount of replenishe~ used became equal to three times the
tank volume.
.
-- 100 --
-
1327~35
Amount of
Processing Step Temperature Time Replenisher
Color Development 35C 45 sec. 160 ml/m2
Bleach-Fix 35C 45 sec. 100 ml/m2
Rinsing 1 30C 20 sec.
Rinsing 2 30~C 20 sec.
Rinsing 3 30C 20 sec. 200 ml/m2
Drying 60-70C 30 sec.
As water for the rinsing solution, ion exchange
water (calcium and magnesium concentrations were each below
3 ppm) was used. The rinsing step was carried out according
to the three-stage counter current process, in which the
rinsing solution flowed from Rinsing Tank 3 to Rinsing Tank 1.
Processing solutions employed in the foregoing
steps, respectively, are described below.
Color DeveloperTank Solution Replenisher
Additives C and Ddescribed in Table 3
Brightening Agent (4,4- 3.0 g 4.0 g
diaminostilbene type)
Ethylenediamine- 1.0 g 1.5 g
tetraacetic Acid
Potassium Carbonate30.0 g 30.0 g
Sodium Chloride 1.4 g 0.1 g
4-A~ino-3-methyl-N-ethyl- 5.0 g 7.0 g
N-[~-~methanesulfonamido)-
ethyl~aniline Sulfate
Benzyl alcoholdescribed in Table 3
--101
.
~: ~
13279~5
Diethylene Glycol described in Ta~le 3
1,2-Dihydroxybenzene- 300 mg 300 mg
3,4,6-trisulfonic Acid
. Water to make l,000 ml 1,000 ml
pH adjusted to lO.lO 10.50
Bleach-Fix Bath
(The replenisher was the same as the tank solution)
- E~TA~Fe(m)NH4-2H2O 60 g
EDTA-2Na 2H2O - 4 g
Ammonium Thiosulfate (70~) 120 ml
Sodium Sulfite 16 g
Glacial Acetic Acid 7 g
Water to make l,000 ml
pH adjusted to 5.5
.Rinsing Solution
(The replenisher was the same as the tank solution)
Formaldehyde (37~) 0.1 g
Adduct of Formaldehyde and 0.7 g
Sulfurous Acid
5-Chloro-2-methyl-4-isothiazoline- 0.02 g
3-one ~
2-Methyl-4-isothiazoline-3-one 0.01 g
Copper Sulfate
Water to make l,000 ml
pH (at 25C) adjusted to 4.0
The development process was carried out using the
foregoing processing solutions in accordance with the fore-
going processing steps, respectively. Blue(B), Green(G),. .
, - 102 -
.. . . .
.
.
:
13279~
and red(R) densities on the unexposed areas (stain densities)
were measured at the beginning and the conclusion of running
processing with a self-resistering densitometer produced by
Fuji Photo Film Co., Ltd.
In addition, samples which had received develop-
ment processing were allowed to stand (aged~ for one month,
starting from the conclusion of development processing, for
one month, at 80C (5 to 10%RH). Thereafter, B, G and R
densities on the unexposed areas wère measured again.
The results of changes in photographic properties
are shown in Table 3.
.
- 103 -
:~ ;'
..
` `` 13279~
" ~
1/~ ~: ~~ -- --e ~ U~ , e
_ G _ _ _ ~ -- -- -- _ _ _ _ _
C I ~ ~ ~ r~ _ O ~ -- _ O ~ ~ O
~C IOOO~OOO=~^----_O
~ 1/
C O ~ ~ ~ ~ ~ ~C7 0 ~ ~ r~ ~ ~
C ~ ~ ~ ~ ~ ~ _I ~ ~, ~ ~ ~ ~1 ~1
O'OOOOOOOOOOOO
,. C I+O'O`OOOO " "
C I ~O ~ o _~ o o O O
C I O O O o O o o O O O O O
_, - C ~ ~ 1 0 0 . O O O O O
OOOOOOOOOO.OOO
~_~ C C
_ C~ ~ ~ C
C~ C ~ C
C' ~ .
c~ c
~o
~ .~ .
. , C
~ ~ V
E ", ~. ~ 0 ~ J C
~1 0 ~ . ._~ ~ ~ . ~ ~ I ~ O
. ~:) Z-a h
_ ....
C C I O 1 ~0 0
:~
C C
- ~
C 3 I O l 00 1 0 ~
~ C
-
l zo
C~ C _~ ~ ~'1 ~ u~ ~o 1~ co C7~ o _I ~ r~
X ~
E
-1 04
,
~' ~ ' ' '
I
~, , ,
.
- 13279~
As can be seen from the data in Table 3, stains
were much increased in experiments No. l to No. 4 as the
result of the development process, while increments of
stains were very small in experiments No. 5 to No. 13.
As for the changes with the lapse of time after
the conclusion of photographic processing, increases of
stain in experiments No. 5 to No. 13 were very small com-
pared with those in experiments No. 1 to No. 4.
EXAMP~E 5
. .
As described in Table C below, an integral multi-
layer color paper was prepared by coating the first (the
lowest) layer to the seventh (uppermost) layer, in that order,
on a paper support which has been laminated with poly-
ethylene on both sides and has undergone a corona discharge
treatment. The coating compositions used therein were pre-
pared in the following manner (structural formulae of
couplers, names of color image stabilizers and so on which
were used in the coating compositions are described
hereinafter).
The coating composition for the first layer was
prepared in the following manner.
To 200 g of a yellow coupler, 93.3 g of a discolor-
ation inhibitor, lO g of the high boiling solvent (p) and
5 g of the solvent (q) was added 600 ml of ethyl acetate
as an auxiliary solvent. The resulting mixture was heated
- 105 -
' ~ ; ': '
: : . `, '
:
: ,
1327~3~
to 60C to make a solution. The solution was mixed with
3,3O ml of a 5 % aqueous gela ~n solution containing 330
ml of a 5% aqueous solution of Alkanol B (trade name of
- alkylnaphthalene sulfonate produced by Du Pont~.
Then the mixed solution was emulsified with a
colloid mill to prepare a coupler dispersion. From the
emulsion, ethyl acetate was distilled away under reduced
pressure.
- The resulting dispersion was added to 1,400 g of
an emulsion (containing 96.7 g of Ag and 170 g of gelatin)
to which a sensitizing dye for a blue-sensitive emulsion
layer and l-methyl-2-mercapto-5-acetylamino-1,3,4-triazole
had been added.
Further, 2,600 g of a 10% aqueous gelatin
solution was added to the resulting emulsion to prepare a
coating composition.
Coating compositions for the second to seventh
layers were prepared by analogy with that of the first
layer according to the formulae described in Table C.
As for the cyan coupler in the fifth layer, cyan
couplers set forth in Table 4 were employed respectively
for preparing each photographic paper.
ho~
- 106 -
;, .,
- : . .
1327905
Table C
Layer ~lain Ingredients Amount used
7th Layer Gelatin 600 mg/m2
(Protective
layer)
6th Layer Ultraviolet absorbent (n) . 260 mg/m2
(Ultravio- Ultraviolet absorbent (o)70 mg/m2
let absorb- Solvent (p) 300 mg/m2
ing layer) Solvent (q) 100 mg/m
Gelatin 700 mg/m2
5th Layer Silver chlorob~-omide emulsion 2
(~ed sensi- (silver bromide: 1 mol%)silver: 21~ mg/m
tive emul- Cyan coupler (See Table 4)5 ~10 mol/m22
sion layer) Color stain inhibitor (r)250 mg/m
Solvent (p) 160 mg/mz
Solvent (q) -- 100 mg/m
Gelatin 1800 mg/m2
4th Layer Color stain inhibitor (s) 65 mg/m2
(Color stain Ultraviolet absorbent (n)450 mg/m2
inhibiting Ultraviolet absorbent (o)230 mg/m2
layer) Solvent (p) 50 mg/m
Solvent (q) - 50 mg/m2
Gelatin 1700 mg/m2
3rd Layer Silver chlorobromide emulsion
(Green sen- ~silver bromide: 0.5 mol%) silver: 305 mg/m2
sitive emul- Magenta Coupler 670 mg/m
sion layer) Color stain inhibitor (t) 150 mg/m2
Color stain inhibitor (u) 10 mg/m2
Solvent (p) 200 mg/m2
Solvent (q) 10 mg/m2
Gelatln 1400 mg/m
2nd Layer SilveF bromide emulsion(e ~ sion has
(Color stain :not reoeived after-ripening and has an 2
inhibiting average grain size of 0.05 micr~n) silver: 10 mg/m2
layer) Color~ stain inhibitor (s)55 mg/m2
Solvent (p) 30 mg/m2
Solvent (q) 15 mg/m2
Gelatin 800 mg/m
1st Layer Silver chlorobromide emulsion
(Blue sensi- (silver bromide: 1.0 mol%)silver: 290 mg/m22
tive emul- Yellow coupler 600 mg/m
sion layer) Color stain inhibitor (r)280 mg/m22
Solvent (p) 30 mg/m2
Solvent (q) 15 mg/m2
Gelatin 800 mg/m
Support Paper support laminated with polyethylene on
both sides.
- 107 -
.
.
13279~
(n) 2-(2-Hydroxy-~,~-di-tert-amylphenyl)benzotriazole.
(o) 2-(2-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole.
(p~ Di-(2-ethylhexyl)phthalate.
(q) Dibutyl phthalate.
(r) 2,5-Di-tert-amylphenyl-3,5-di-tert-butylhydroxyb'enzo-
' ate.
(s) .2,5-Di-tert-octylhydroquinone.
(t) 1,4-Di-tert-amyl-2,5-dioctyloxybenzene.
---(u) 2,2'-Methylenebis(4-methyl-6-tert-butylphenol).
The following compounds were used as sensitizing dyes for
their respective emulsion layers.
Blue-sensitive emulsion layer: Anhydro-5-methoxy-5'-methyl-3,
3'-disulfopropylselenacyanine hydroxide.
Green-sensitive emulsion layer: Anhydro-9-ethyl-5,5'-diphenyl
-3,3'-disulfoethyloxacarbocyanine hydroxide.
Red-sensitive emulsion layer: 3,3'-diethyl-5-methoxy-9j9'-(2,
' ' 2-dimethyl-1,3-propano)thiadicarbocyanine iodide.
As a stabilizer for each emulsion layer, l-methyl-2-mer-
capto- 5-acetylamino-1,3,4-triazole was used.
,
' As lrradiation inhibiting dyes, dipotassium 4-(3-carboxy-
5-hydroxy-4-(3-(3-carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyra-
zolin-4-ylidene)-1-propenyl)-1-pyrazolyl)benzenesulfonate
and tetrasodlum N,N-(4,8-dihydroxy-9,10-dioxo-3,7-disulfonato-
anthracen-1,5-diyl)bis(aminomethanesulfonate) were used.
As a hardener, 1,2-bis(vinylsulfonyl)ethane was used.
The structural formulae of the couplers used are illus-
trated below.
- 108 -
- , - . .
- . , , , ,: ! ' . ~ '-
~'. ~ : ' . : ' .
1327~
Yellow Coupler
ce
CH3
CH 3--C--COCHCONH~ C~(t)
CH 3 N NHCO ( CH 2 ) 3 O~ C 5 H ll(t)
0~ ~0 .
~ N--CH2~)
Magenta Coupler - -
.
C16~33C~=C~
H
~0
,,, , . ' ce~
~q
ce
Cyan Coupler
See Table 4
After wedgewise exposure, the integral multilayer color
photographic paper obtalned was subjected to the following
processing steps.
Processing Step Time Temperature
Color development3 min. 30 sec. 33C
Bleach-fix 1 min. 30 sec. 33C
-- 109 --
~\
13279~3
Rinsing (3-tank
cascade) 2 min. 30C
Drying 1 min. 80C
Processing solutions-employed in the foregoing steps, re-
spectively, are described below.
Color Developer
Water 800 ml
Sodium sulfite See Table 4
--~N,N'-bis(2-hydroxybenzyl)ethylene-
diamine-N,N'-diacetic Acid 0.1 g
Nitrilo-N,N,N-trimethylenephospho-
nic Acid (40 ~) . 1.0 g
Potassium Bromide 1.0 g
Additives C and D See Table 4
Potassium Carbonate 30 g
N-ethyl-N-(~-methanesulfonamidoethyl)
-3-methyl-4-aminoaniline Sulfate 5.5 g
Brightening Agent (4,4'-diamino-
stilbene type) 1.0 g
Water to make 1,000 ml
KOH to adjust pH to 10.10
Bleach-Pix Bath..
Ammonium Thiosulfate (70 ~) 150 ml
Sodium Sulfite 15 g
Ammonium Pthylenediamineferrate (III) 60 g
~thylenediaminetetraacetic Acid 10 g
Brightening Agent (4,4'-diamino-
stilbene type) 1.0 g
2-Mercapto-5-amino-3,4-thiadiazole 1.0 g
Water to make 1,000 ml
--110 -- .
. ' :
:' . .: - . ' ' .
:. : ,
.. ' ' . : ,' . , . .,' :'~ , '',''
13279~
Aqueous Ammonia to adjus L pH LO 7.0
Rinsing Solution
5-Chloro-2-methyl-4-isothiazolin- 3-one 40 mg
2-Methyl-4-isothiazolin -3-one 10 mg
2-Octyl-4-isothiazolin -3-one 10 mg -
Bismuth Chloride (40 ~) 0.5 g
Nitrilo-N,N,N-trimethylenephosphonic Acid(40~) 1.0 g
l-Hydroxyethylidene-l,l-diphosphonic Acid (60%J 2.5 g
Brightening Agent (4,4'-diamino-
stilbene type) 1.0 g
Aqueous Ammonia (26 %) 2.0 ml
Water to make 1,000 ml
KOH to adjust pH to 7.5
,.
In the foregoing color development step, the fresh
developer and the aged developer, obtained by a allowing
a portion of the fresh developer to stand ~or 21 dayes,
were used separately. Dmin and the gradation of the cyan
dye image in each photographic development process were
examined in the same manner as in Example 2.
Increases in Dmin and gradation, respectively,
using~.the aged developer over those using the fresh developer
are shown in Table 4.below.
-- 111 --
. ' : ' . :. '
...
. . , ~ . .
-
13279~.~
. ~
..,
C C~ _
~ ~ ooooooooC~oooo
r h O O O O O O O O O O OO O O O
C ~ ~
C o o o o o o o o ' O ~
C Z
S
_,- ' 0~
a ~
~r C
_,a ~ ~ ~ ,~,
_l _, ..
:~ o o
V s ,_,
C o . ~
~ o
C~- ,Co~ V -
. 3
,~ ~ o
U h
~ W W t~ CO C~ WW O O ~ ~ )
~,~ O oooo oooa~ O
cqo ~ ~ ' ¢l ~
h , e~
C ' C
. C~
I O
L. ~ ~ ~ .
C~ C ~ o ~ W o~ O ~ D 1~ W
X C) ~
~I E
- 112 -
.. ..
. . -
- .. . - ~ :
`-`` 13279~
As can be seen from the data in Table 4, changes in
Dmin and gradation resulting from using the developer allowed
to stand for 21 dayes were small in experiments Nos. 4 to
No. 18 compared those in experiments No. 1 to No. 3. That
is, the photographic properties have turned out to be highly
stabilized in experiments No. 4 to No. 18.
In particular, it has been found that hte preserv-
ability of the developer was higher and the photographic
properties were more highly stabilized when using C-9 or C-l -
as a cyan coupler (in experiment Nos. 6, 7, 10, 11, 13, 15, 17
and 18) and when the developer contained sulfurous acid in
low concentration (in experiment Nos. 10, 11, 17 and 18).
EXAMPLE 6
An integral multilayer color paper was prepared by
coating layers so as to have the layer structure described
in Table D below on a paper support laminated with poly-
ethylene on both sides thereof. The coating compositions
employed therein were prepared in the following manner.
Preparation of the Coating Composition for First Layer:
To 19.1 g~of the yellow coupler (a) and 4.4 g of
the color image stabilizer ~b) were added 27.2 ml of ethyl
acetate and 7.7 ml of the solvent (c) to prepare a solution.
The solution was dispersed, in an emulsified condition, into
185 ml of a 10% aqueous gelatin solution containing 8 ml of
a 10% solution of sodium dodecylbenzenesulfonate.
-113 -
, .
,
-
: '
:: : :.
i3279~
Separately, the blue sensitizing dye having thechemical structure illustrated bellow was added to a silver
chlorobromide emulsion (having a bromide content of 90.0
mol%, and containing 70 g of Ag per kg of emulsi~on) in an
amount of 5.0 x lO 4 mole per mole of silver to prepare a
blue-sensitive emulsion.
The foregoing emulsified dispersion was mixed with
the blue-sensitive emulsion, and dissolved therein. Then,
the resulting emulsion was so adjusted as to have the compo-
sition shown in Table D.
Coating compositions for the second to seventh layers
were prepared in analogy with that of the first layer.
In each of the constituent layers, sodium salt of
l-oxy 3,5-dichloro-s-triazine was used as gelatin hardener.
Spectral sensitizing dyes used in the respective
emulsion layers are as follows:
- 114 -
.- : - - - ; ~
13279~;~
Blue-sens it ive Emulsion Layer
~ ~ ~ N ~
(cH2)4so3 (CH2)4S03H-N ~C2H5)3
(5.0 ~10 4 mole per mole of silver halide)
Green-sensitive Emulsion Layer
C2Hs ~3
(cH2)3so3 (CH2)2
` SO3H- N (C2H5 )3
(4.0X 10 4 mole per mole of silver halide)
and
+~CH=< ~3
(cH2)4so3 ( IH2)4
SO3HN (C2H5 )3
(7.0X 10 5 mole per mole of silver halide)
-- 115 --
: , .
13279~5
Red-sensitive Emulsion La~-er
H3C~ ,CH3
~CH~LCH=<~
C2H5 I C2H5
(0.9x 10 4 mole per mole of silver halide)
In the red-sensitive emulsion layer, the following com-
pound was incorporated in an amount of 2.6X 10 3 mole per mole
of silver halide.
~,O~NH~CH= CH~NH~0
03H S03H
~v 0~
In the blue-sensitive emulsion layer, the green-sensitive ~ -
emulsion layer and the red-sensitive emulsion layer were fur-
ther incorporated l-(S-methylureidophenyl)-5-mercaptotetrazole
in amounts of 8.5X 10 5 mole, 7.7 xlO 4 mole and 2.5 X 10 4
mole, respectively, per mole of silver halide.
Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene
was added to the blue-sensitive emulsion layer and the green
-sensitive emulsion layer in amounts of 1.2X 10 2 mole and 1.1
10 2 mole, respectively, per mole of silver hallde.
The fo~lowing dyes were added to the emulsion layers for
prevention of irradiation:
- 116 -
.
- , ,,
- 13273~
:
HOH,I C2NHCO~oCH--CH=CH~hCONHC2H ~ OH
CIH2
~SO3N a
and
HOH~C2NHCO~;CH--CH=CH--CH=CH~CONH2C2H60H
CXa CH2
~_SO3Na g3~SO3Na
-- 117 --
'
~ l327sas
Table D
Layer ~lain Ingredients Amount used
7th Layer Gelatin 1.33 g/m2
(Protective ACryl-denatured polyvinyl 0.17 .,
layer) alcohol (denaturing degree:
17 ~)
Liquid paraffin 0.03 ~
6th Layer Gelatin 0-53 g/m2
(Ultravio- Ultraviolet absorbent (i) 0.21 ~,
let absorb- Solvent (k) 0.08 "
ing layer)
5th Layer Silver halide emulsion Silver: 0.23 g/m2
(Red sensi- Gelatin 1.34
tive emul- Cyan coupler (~) 0.34
sion layer) Color image stabilizer (m) 0.17 '~
Polymer (n) - 0.40
Solvent (o) 0.23 ~
4th Layer Gelatin . 1.58 g/m2
(Ultravio- Ultraviolet absorbent (i) 0.62 ~;
let absorb- Color stain inhibitor (j) 0.05 ~,
ing layer) Solvent (k) 0.24 ~,
3rd Layer Silver halide emulsion silver: 0.16 g/m2
(Green-sen- Gelatin 1.79
sitive emul- Magenta coupler te) 0.32
sion layer) Color image stabilizer (f) 0.20
Color image stabilizer (g) 0.01 ~'
Solvent (h) 0.65
Additive (v) 0.023 "
. Additive (w) 0.036 ~,
2nd Layer Gelatin 0.99 g/m2
(Color stain Color stain inhibitor (d) 0.08 "
inhibiting
layer)
1st Layer Silver halide emulsion silver: 0.26 g/m2
(Blue sensi- Gelatin 1.83 "
tive emul- Yellow coupler (a) 0.83 ,
sion layer) Color image stabilizer (b) 0.19
Solvent (c) 0.35 ~,
Support Polyethylene-laminated paper (containing white
pigment (TiO ) and bluish~ pigment (ultramarine)
in polyethylene laminate on the 1st layer side)
- 118 -
, . .
... ... . . . . . - ~ . . .
^`` 13279~
(a) Yellow Coupler
CH3 ~
--~ CH3-C-CO-CH-CONH ~ C ~ l(t)
- O 1 0 - NHColHO ~ CsHll(t)
Y; ~ C2H5
~3C / ~
.
(b) Color Image Stabilizer
( HO~CH2~C~COO~cocH=cH~)
(t)C4Hs C 3
,
~c) Solvent
~COOC4Hg
~C OO C 4 H g
-- 119 --
.
. .; : . ~ , . .
. ~ . . . . - , .. . . . .
1327~
(d) Color Stain Inhibitor -
OH
~C8Hl7 (SeC)
( S e c ) C 8H 17
OH
(e) Maqenta Coupler ^-
CH3 ~
HS02 ~ 7
NHS0
CgH17(t)
(f) Color Image Stabilizer
Cy3 CH3
C3H70 ~
C 3~7 O~OC 3H7
C ~ OC3H7
- 120 -
:
~, . .
. .,, ~ . .
.; , ~;
1327~5
(g) Color Ima~e Stabilizer
OH
s o 3 N a
OC lS H
OH
(h) Solvent
CzHs
~ O=P~OCH2CHC4Hg)3
and
O=P~O-~ )
2: / Mixture (by volume)
- 121.-
. ~. . ., ,. . .. -
1327~5
(1) Ultraviolet Absorbent
OH
C4Hs(t)
CH2CH2COOC8Hl7
OH
and
4Hs(t)~
~\N~C 4 H g(t)
C 4Hg(t)
2 : 9 : 8 Mixture (by weight)
(;) Color Stain Inhibitor
OH
f~,C8Hl7(t)
(t)csH
OH
(k) Solvent
O=P~O~CsH1s(iso))3
- 122 -
,; , ,
.
:
~:: ., ., .:
` 13279~
(~) Cyan Coupler
See Table 5
(m) Color Image Stabilizer
5 : 8 : 9 Mixture (by weight) of
OH
4Hs(t)
CH2cH2cooc8Hl7
- OH
C 4 H g(t)
and
C ~ H g~t)
C4Hg(t~
(n) Polymer
-~ CH2 ICH ~ mean molecular weight: 35,000
CONHC4Hg(t)
~o) Solvent CH
o = P{ O- ~ 3)3
.
- 123 -
. .
13279~
(v) Additive
O ..
11
CH3CH2CH2CHCH2--OCO
CH3--CH2 ~3
- :' 1~1
~ C l6 H 33 ( ~ )
(w) Additive
SO2Na
~CH2 CH3 H ~ H ~Ha CH3
CH3 CH2 CH2~0 ( CH2 ) 3 NC~CN ( CH2 ~ 3 O~CH2 CH3
O
The color photographic paper obtained was processed in
the same manner~ as in Example 5. The results obtained are
shown in Table 5.
- 124 -
., .
l~27~as
u~
-
o~ o
L~ ~1 O O~ 00 ~ ~ O ~ ~ ~ ~
~; o o o o o- o o o o o o o
o ~ o o oo o o o o o o o o o o o o o
s la ++++++++++++++ +++
e COo O O rO O O O~0 ~0 ~0Yo~ ~0 0 0 0
.,, . . . . . . . . . O O . . . O
. E o o o o o o o o o o o o o o o
_~
C'
~ O ~: .
O Id ` C ~ ~ ~' ~ ; ` ` ' ` ` ' ~ `
,
E
Q~ O C
U7 C ' ' ' ..
O ...
_I _ E
~ o _l _~
E~ :~ o o
E C ~
a ~ _,
¢ o . E
C ~ -l . X
t C
~o ~ ~ ~ U~
O C~
' ' ' ' O
,1 ~`
U ~ CO o~
o o ~ o O o O O O o O O o O
o ~,, ~n
~ . s
O O~
~ ~ ~ ¢ c4 ~ ¢
. ~d
~zo ~ .
~ . .'.
-- 125 --
,, :, .
.
. . . .
.
. .: ~ ..: .: , .
. . .
~` 1327~
As can be seen from the data in Tcble i, reduced
changes in Dmin and gradation were achieved in the embodi-
ments of the present invention.
In particular, more desirable results were obtained
when the color developer contained sodium sulfite in a low
concentration, and the compound of formula (C-I) was
employed as a cyan coupler.
~, ,
.
- 126 -
; - ~
: ,, ,
- .
- , - : ,. -
- - ., - ~
- . .-. .. .
13279~
~XAMPLE 7
A color photographic paper was prepared in the same man-
ner as in Example 6, (except only the compound represented by
formula (C-l) was used as a cyan coupler).
After imagewise exposure, the color photographic paper
was subjected to the following processing steps using a Fuji
Color Paper Processer PP-600, wherein various kinds of color
developers underwent a running process test in which the process
was continued until the amount of replaenisher became equal to
two times the volume of the color development tank.
Amount sup- Volume
Processing Step Temperature Time plemented* of Tank
Color Developement 38C 100 sec.290 ml 17
Bleach-Fix 33C60 sec. 150 ml 9
Rinsing 1 30-34C20 sec. - 4
Rinsing 2 30-34C20 sec. 4 ~
Rinsing 3 . 30-34C, 20 sec. 364 ml 4 Q
Drying i 70-80OC50 sec.
* per 1 m of the color paper.
The rinsing step was carried out according to the three
-stage counter current process, in which the rinsing solution
flowed from Rinsing Tank 3 to rinsing Tank 1.
- 127 _
132790~
Processing solutions em?loved in the foreaoing steps, re-
spectively, are described below.
Color Developer
- Tank Solution Replenisher
Water . 800 ml 800 ml
Compound of the InventionSee ~able 6
Ethylenediamine-N,N,N'N'-tetra-
methylenephosphonic Acid 3.0 g 3.0 g
Brightening Agent (UVITEX CK,
produced by Ciba Geigy Ltd.) 2.5 g 4.0 g
Sodium Sulfite 0.1 g 0.2 g
Potassium Bromide 0.5 g
Potassium Carbonate 30 g 30 g
N-ethyl-N-(~-methanesulfonamido-
ethyl)-3-methyl-4-aminoaniline
Sulfate 5.5 g 7.5 g
N,N-diethylhydroxyamine Sulfate. 2.0 g 2.5 g
. Water to make 1,000 ml 1,000 ml
pH (at 25C) adjusted to 10.20 10.60
Bleach-Fix Bath
Tank Solution Replenisher
Water 400 ml 400 ml
Ammonium Thiosulfate (70%)200 ml 300 ml
Sodium Sulfite 20 g 40 g
Ammonium Ethylenediamine-
tetraacetatoferrate(III) 60 g 120 g
Disodium Ethylenediamine-
tetraacetate 5 g 10 g
Water to make 1,000 ml 1,000 ml
pH (at 25C) adjusted to 6.70 6.30
- 128 -
. .
.. . .
. . F `'
1327~
~7 nsinq Solution
Ion exchange water (in which the calcium and magnesium
concentrations.were below 3 ppm).
Changes in photographic characteristics (Dmin and
gradation) between the start and the finish of the running
process for each processing formula is shown in Table 6.
In accordance with the present invention, changes
in photographic characteristics resulting from the running
process were remakably reduced. -
.
- 129 -
, , : ,
: ~ .
,~ , , ,
:: . . ~ . : . .,
1327~05
O O ~ o o r~ ~ ~
,, ~ o ~ ~ o o o
~d o o o c) o O O O O
+ .. + + + + + +
~ o~ I~ ~ oo ~ , ~ ~
C~ o o ~ o o o o o
C~
C o o o o o o ~9 o ~ o
.,, + + + + + + + +.
~ O~ I~ J OD ~-1 ~ _I ~ ~1 ~
t~4 O 0 ~1 0 0 0 0 0 0 0
C ~ . . . ..
~ O . O O O O ~O O O O
.-: + + + + + +++++
_
. ~ ~ ~
O O O
C: C~
. o o o o o ooooo
C)
~' t~ ' _~ ~ ,
C: O O O O
._1 ~ . ~ ~ ~
~O ~ C~ O O O O O O O O O
C x Lr~ ~ ~l ~1 ~ ~ f~l ~ _I
~:1~:: C~ O O O O O O O O O O
E-l . .o o+ O C;
tll c , a~ c
~ o - - ~
C ~_I -- -- _
C~ ~ ,~
_I C~
~ I I C
a~_
~ c ~ . ~~ c ~
E _ c E
et O E ~ C '~
C .rl
L~ _~ O ~ O--
¢ C E~ ou~ cn
I C
-1 Z
a~ I ~ O
x a
E
-- 130 --
..
,.: , . ..
~:
.
13279~
EXAMPLE 8
The following color photographic paper was pre-
pared. The procedures of Nos. 1 to 18 in Example 2 were
applied to the color photographic paper thus ob.ained instead
of the color photographic paper used in E~ample 2.
An integral multilayer color pa~e- wzs ~reoared
by coating lavers so as to have the layer struc.ure desc~ised
below on a paDer suppor- laminated r~ith oolyethvlene on
both slaes thereoî. The coating liauld wzs oreoared by
mixing to dissolve an emulsion, additives and emulsified
disoersion of couplers, according to the following manner.
Preparation or Coupler Emulsion:
To 19.1 g of the yellow couoler (ExY) and 4.4
g of the color image stabilizer (Cpd-l) we-e added 27.2
ml of ethyl acetate and 7.7 ml of the solvent (Solv.-l)
to prepare a solution. The solution was dispersed, in an
emulsified condition, into 185 ml of a 10% aqueous gelating
solution containing 8 ml of a 10% solution of sodim dodecyl-
benzenesulfonate. In the same way,~lsions for magenta layer,
cyan layer and an intermediate layer were prepared. ComFounds used in
the resp ~ ive e ~ sion layers are as follows:
(ExY) Yellow Coupler
C~3 C~ .
CH3--C--C0~C0N~ CsHl l(t)
CH3 ~ NWC0CHO~CsHl l('G)
o~,~N~_ o
toc 2Hs
- 131 -
.. . . .
:
. "', . ~ ' ' . ' '
.. . . . ..
' ~ : '' ' ' . ' ''
.' ` ; ~ ~'". ', , :
1327~
( ExMl ) Magenta Coupler
~e .
~N~1
C131-127COH N
ce~ .,
c~
( ExC1 )
OH 1 aH6
ct~NE~CO - CHO~(t,C 6 H
CH .3,~ (t)C 6 H i
ce
( ExC2 )
PH
C ~ 3 ~N~lCo~)t)CslII l~OCHCONH~ ce
ce .
- 132 --
. . . , - . , . : . . . : . - . - . , - ., . - -, ,,
13279~5
( ExC4 )
01-1 ,
HCOR
C 2 l-l 5~ R=-CHO~ 15 31(
ce ,
( EXC5 )
011 , '
lHC O R
C 21-l 5 /~/ 15 31
ce , .
(Cpd-l) Color Image Stabilizer
( tlO~Ctl~--C-~COO ~3CH=CH2)
C~Hg(t) H3
(Cpd-2) Color Mixing Preventing Agent
OH
~ R=C8H17(SeC)
H
- 133 --
.. . . . . . .. , .. ~ . - . ` . .
.
.
: ~ : . . . ..
.
- ..
~ , . . .
13279~5
( Cpd-3 )
C~ CH3
C3H70~
C 3 H 7 o,bl--~c 3 H 7
3 CH3
( Cpd-4 )
OH H3
CH~C~CH2~3 COOC 6Hl3
C 6Hl300C~CH2~3 ¢~ CH3
'
( Cpd-5 ) Color Mixing Preventing Agent
OH
R
OH 8 17( )
-- 134 -- .
- ~ ,
. , . . '~ .
132790~
(Cpd-6) Color Image Stabilizer
(Mixture of 6a, 6b and 6c compounds;
6a:6b:6C=5:8:9 by weight)
6a
/N~C~Hg(t)
CH2CH2COOc~Hl 7
~ . .
6b
Of~
N
~H9(tJ~
6C
OH
I /N~ C ~H9 ~ S . C )
C4~lg(t)
~Cpd-7) Polymyer
CONHC4Hg(t) mean molecular weight: 80,000
- 135 -
. . . . . .
13279~
(UV-l) Ultraviolet Absorbent
Mixture of Cpd-6a, CPd-6b and Cpd-6c
l2:9:8 by weight)
(Solv-l) Solvent
~ COOC4Hg
W~C
4 9
(Solv-2) Solvent
O=P (O-C8H17(iso))
(Solv-3) Solvent
O=P--~O-CgHlg(iso))3
(Solv-4) Solvent CH3
O=P~ ~ )3
The following dyes were added to the emulsion
layers for prevention of irradation.
- 136 -
. :
'
:~ ' '' ,-''
-~,
13279~
Red sensitive layer
Dye-R
- HO . O H
~;o l~;C NCHzCIlzOH
CHz CHz
~SO3Na ~3~SO3Na
wherein. n is an integer of 2
Green sensitive layer
Dye-R (which is the same dye as above except for n being
an integer of 1)
In the red-sensitive emulsion layer, the following
compound was incorporated in an amount of 2.6 x 10 3 mole
per mole of silver halide.
O ~ NH ~ CH=CH ~ NH
- 137 -
-
- , ~ . :. . .
13 2 7 ~ 0 ~
,
The e~ulsions used in the Example were prepared
in the following manner.
Blue Sensitive emulsion:
By following the conventional procedure, mono-
dipsered cubic silver chloride emulsion having 1.1 ~m of
average particle size, 0.10 of variation coefficient which
is designated as a value of s/d (s~andard deviation is devided
by average particle size) and containing K2IrC16 and 1,3-
dimethylimidazaoline-2-thion was prepared. To 1.0 kg of e ~ sion
thus obtained were added 26 ml of 0.6~ solution containing
blue spectral sensitizing dye (s-1) and an emulsion contain-
ing silver bromide fine particles having average diameter
of 0.05 ~ m in an amount of 0.5 mol% based on the host silver
chloride emulsion. After ripening, sodium thiosulfate
was added to the emulsion thus obtained to perform an appropri-
ate chemical sensitization. Then, stabilzer(Stb-l) was added
in an amount of 10 4 mol per mol of Ag to prepare a blue
sensitive emulsion.
Green Sensitive Emulsion:
By following the conventional procedure, silver
chloride particles containing R2IrC16 and 1,3-dimethylimidazoline-
2-thion were prepared. The sensitizing dye ts-2) in an amount of
of 4 x 10 4 mol per mol of Ag and KBr were added to the
emulsion thus obtained, After repening, sodium thiosulfate
was added to the emulsion to perform an appropriate chemical
sensitization, and subs~quently, stabilizer (Stb-l) was added
in an amount of 5 x 10 4 mol per mol of Ag to prepare
- 138 -
..
,
,
-
13279~5
-mono-disperse cubic silver chloride emulsion having 0.48~(m
of average particle diameter and 0.10 of variation coefficient.
Red Sensitive Emulsion
-
A Red sensitive emuilsion was prepared in the
same manner as a preparation of a gree sensitive emulsion
except for using a sensitizing dye (s-3) in an amount
of 1.5 x 10 4 mol per mol of Ag instead of the sensitizing
dye (s-2).
- 139 -
' . , , ' . , . .. . .. "
~ . .
~3279~
. Compounds used in the Example are as follows.
(S-1) Sensitizing Dye
>C CH~
H2)3 (1H2~3~J
S 0 K 1
(S-2) Sensitizing Dye
>=CH--C----CH~
( I HZ)2 t ( I H2)2
.. 503H N~) SO3~
(S-3) Sensitizing Dye .... _
C~3 CH3
~c Cl~--CH~
C2H6 1~ C2H5
(stb-1) Stabilizer
N--N
S~f HCOl`lHH 3
- 140 -
: - ' . ' : ' :
~. . ' ~ :
. :
13279~
Layer Structure
Coating compositions for each layer are as follows.
.As a hardening agent, l-oxy-3,5-dichloro-s-triazine
sodium salt was used.
Photographic properties of the color photographic
paper which were applied by the procesure Nos. 5 to 18 were
hardly varied to be sufficient enough to exert superior
effects.
- 141 -
.:
,, . ` ..
~-"
132793~
,
Layer ~lain Ingredients Amount used
7th Layer - Gelatin 1.33 g/m2
(Protective Acryl-denatured polyvinyl 0.17 ~,
layer) alcohol (denaturing degree:
17 %)
Liquid paraffin 0.03 ~
6th Layer Gelatin 0.53 g/m2
(Ultravio-
let absorb- Ultraviolet absorbent ~UV-1) 0.21 "
- ing layer) Solvent ~ Solv-3) 0.08 "
5th Layer Silver halide emulsion
(Red sensi- silver: 0.23 g/m2
tive emul- Gelatin - 1 34
sion layer) Cyan coupler (l:lm~ ~ E~a~ ~) 0 34
Color image stabilizer (Cpd-6) 0.17
Polymer (cpd-7 ?
Solvent (Solv-i) 0.23 ~,
4th Layer Gelatin 1.58 g/m2
(Ultravio- Ultraviolet absorbent (UV-l) 0.62 "
let absorb- Color stain inhibitor (Cpd-5) 0.05 ~
ing layer) Solvent ( Solv-3) 0. 24 ~,
3rd Layer Silver halide emulsion
tGreen sen- Silver: silver: 0.36 g/m2
sitive emul- Celatin 1.24 ,
sion layer) Magenta coupler ( ExM1) 0. 31
Color image stabilizer (Cpd-3) 0.25
Color image stabilizer (Cpd-4) 0.12
Solvent ( Solv-2) 0. 42 ~,
2nd Layer Gelatin 0.99 g/m2
(Color stain Color muxmg inhibitor (Cpd-2) 0.08
inhibiting
layer)
1st Layer Silver halide emulsion
(Blue sensi- silver: 0.30 g/m2
tive emul- Gelatin 1.86 ~
sion layer) Yellow coupler (ExY) 0.82 '~ -
Color image stabilizer (cpd-l) 0.19 "
Solvent (Solv-1) 0.35 "
Support Polyethylene-laminated paper (containing white
pigment (TiO~) and bluish pigment (ultramarine)
in polyethylene laminate on the 1st layer side)
- 142 -
; . : ' ' , ''. ,
,
, ~ ' ' ' ''
1327~3~
In accordance with the embodiments of the present
invention, the stability and the color developability of
color developers were remarkably enhanced. Therefore, an
increase in fog and a change in gradation were considerably
suppressed, that is, color images with excellent photographic
characteristics were obtained, even when aged color developers
were used in photographic development processing.
The above-described effect of the present invention
was prominetn particularly when color developers not contain-
ing a substnatial amount of benzyl alcohol were used. This
has the advantage of reducing the high pollution load caused
by disposal of used developer solution containing benzyl
alcohol.
Further, the effect of the present invention was
also remarkable when sensitive materials containing cyan
couplers represented by formula (C-I) were processed.
Furthermore, the increase in fog was considerably
reduced in the running development process and the color
image obtained was also excellent in keeping stability.
While the invention has been described in detail and
with reference to specific embodiments thereof, it will be
apparent to one skilled in the art that various changes and
modifications can be made therein without departing from
the spirit and the scope thereof.
- 143 -
` ' ' ~'',` ~
