U.S. patent application number 09/733376 was filed with the patent office on 2001-07-19 for silver halide color photographic light sensitive material.
Invention is credited to Hoshino, Hiroyuki, Ishige, Osamu, Kataoka, Emiko.
Application Number | 20010008749 09/733376 |
Document ID | / |
Family ID | 18454453 |
Filed Date | 2001-07-19 |
United States Patent
Application |
20010008749 |
Kind Code |
A1 |
Ishige, Osamu ; et
al. |
July 19, 2001 |
Silver halide color photographic light sensitive material
Abstract
A silver halide color photographic light sensitive material is
disclosed, comprising a support having thereon a blue-sensitive
silver halide emulsion layer, a green-sensitive silver halide
emulsion layer and a red-sensitive silver halide emulsion layers,
wherein at least one of the silver halide emulsion layers contains
a coupler represented by the following formula: 1
Inventors: |
Ishige, Osamu; (Tokyo,
JP) ; Kataoka, Emiko; (Tokyo, JP) ; Hoshino,
Hiroyuki; (Tokyo, JP) |
Correspondence
Address: |
BIERMAN MUSERLIAN AND LUCAS
600 THIRD AVENUE
NEW YORK
NY
10016
|
Family ID: |
18454453 |
Appl. No.: |
09/733376 |
Filed: |
December 8, 2000 |
Current U.S.
Class: |
430/504 ;
430/505; 430/506; 430/544; 430/555 |
Current CPC
Class: |
G03C 7/30541 20130101;
G03C 7/3225 20130101; G03C 7/39236 20130101; Y10S 430/158 20130101;
C07D 231/52 20130101; G03C 7/384 20130101; Y10S 430/156 20130101;
G03C 7/3335 20130101 |
Class at
Publication: |
430/504 ;
430/506; 430/544; 430/505; 430/555 |
International
Class: |
G03C 001/46; G03C
007/26; G03C 007/333; G03C 007/384 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 16, 1999 |
JP |
357501/1999 |
Claims
What is claimed is:
1. A silver halide color photographic light sensitive material
comprising a support having thereon a blue-sensitive silver halide
emulsion layer, a green-sensitive silver halide emulsion layer and
a red-sensitive silver halide emulsion layers, wherein at least one
of the silver halide emulsion layers contains a coupler represented
by the following formula (I): 16wherein R.sub.11 represents a
secondary or tertiary alkyl group, or a cycloalkyl group; R.sub.12
represents an aryloxy group; R.sub.13 represents a hydrogen atom,
an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic
group; R.sub.14 represents a halogen atom or an alkoxy group;
R.sub.15, R.sub.16 and R.sub.17 independently represent a
substituent; k1 is an integer of 0 to 5; m1 and n1 are each an
integer of 0 to 4.
2. The silver halide color photographic material of claim 1,
wherein R.sub.11 is a secondary alkyl group.
3. The silver halide color photographic material of claim 1,
wherein R.sub.12 is a substituted phenoxy group.
4. The silver halide color photographic material of claim 3,
wherein R.sub.12 is a phenoxy group substituted by at least one
substituent selected from the group consisting of an alkyl group, a
cycloalkyl group, an alkoxy group, a halogen atom and an
alkoxycarbonyl group.
5. The silver halide color photographic material of claim 1,
wherein R.sub.13 is a hydrogen atom.
6. The silver halide color photographic material of claim 1,
wherein R.sub.14 is a chlorine atom or a methoxy group.
7. The silver halide color photographic material of claim 1,
wherein R.sub.15 is a halogen atom.
8. The silver halide color photographic material of claim 1,
wherein R.sub.16 is an acylamino group, an oxycarbonyl group, a
carbamoyl group, a sulfonyl group or a sulfamoyl group.
9. The silver halide color photographic material of claim 1,
wherein R.sub.17 is a halogen atom.
10. The silver halide color photographic material of claim 1,
wherein the compound of formula (I) is contained in an amount of
1.times.10.sup.-3 to 8.times.10.sup.-1 mol/mol Ag.
11. The silver halide color photographic material of claim 1,
wherein the silver halide emulsion layer containing the coupler
represented by formula (I) or another silver halide emulsion layer
having the same color-sensitivity as the silver halide emulsion
layer containing the coupler represented by formula (I) contains a
compound represented by the following formula (II): 17wherein
R.sub.21 and R.sub.24 represent a secondary or tertiary alkyl
group, or a cycloalkyl group; R.sub.22 and R.sub.25 represent an
aryloxy group; R.sub.23 and R.sub.26 represent a hydrogen atom, an
alkyl group, a cycloalkyl group, an aryl group or a heterocyclic
group; R.sub.27 and R.sub.28 independently represent a substituent;
m2 and n2 are each an integer of 0 to 4.
12. The silver halide color photographic material of claim 11,
wherein the compound of formula (II) is contained in an amount of
0.1 to 10% by weight, based on the compound of formula (1).
13. The silver halide color photographic material of claim 1,
wherein the silver halide emulsion layer containing the coupler
represented by formula (I) or another silver halide emulsion layer
having the same color-sensitivity as the silver halide emulsion
layer containing the coupler represented by formula (I) contains a
compound represented by the following formula (III): 18wherein W
represents a coupler moiety capable of forming a dye capable of
being leached out of the photographic material upon reaction with
an oxidation product of a color developing agent; TIME represents a
timing group capable of releasing an inhibitor residue DI after
being released from W upon reaction with an oxidation product of a
color developing agent; and n3 is an integer of 0, 1 and 2.
14. The silver halide color photographic material of claim 13,
wherein the compound of formula (III) is contained in an amount of
1.times.10.sup.-3 to 8.times.10.sup.-1 Ag.
15. The silver halide color photographic material of claim 1,
wherein the silver halide emulsion layer containing the coupler
represented by formula (I) or another silver halide emulsion layer
having the same color-sensitivity as the silver halide emulsion
layer containing the coupler represented by formula (I) contains a
compound represented by the following formula (IV): 19wherein Y
represents an yellow coupler moiety capable of forming an yellow
dye upon reaction with an oxidation product of a color developing
agent; TIME represents a timing group capable of releasing an
inhibitor residue DI after being released from Y upon reaction with
an oxidation product of a color developing agent; and n4 is an
integer of 0, 1 and 2.
16. The silver halide color photographic material of claim 15,
wherein the compound of formula (IV) is contained in an amount of
1.times.10.sup.-5 to 5.times.10.sup.-1 mol/mol Ag.
17. The silver halide color photographic material of claim 1,
wherein the silver halide emulsion layer containing the coupler
represented by formula (I) or another silver halide emulsion layer
having the same color-sensitivity as the silver halide emulsion
layer containing the coupler represented by formula (I) contains a
compound represented by the following formula (V): 20wherein
R.sub.51 and R.sub.52 independently represent a secondary or
tertiary alkyl group or a cycloalkyl group; R.sub.53 represents a
halogen atom or an alkoxy group; R.sub.54 and R.sub.55
independently represent a substituent; k5 is an integer of 0 to 5;
and m5 is an integer of 0 to 4.
18. The silver halide color photographic halide material of claim
17, wherein-the compound of formula (V) is contained in an amount
of 5 to 50 mol %, based on the coupler of formula (I).
Description
FIELD OF THE INVENTION
[0001] The present invention relates to sliver halide color
photographic light sensitive materials and in particular to silver
halide color photographic materials exhibiting enhanced
sensitivity, superior color forming properties and improved storage
stability.
BACKGROUND OF THE INVENTION
[0002] In conventional silver halide color photographic materials
(hereinafter, also denoted as color photographic materials or
simply as photographic materials), a subtractive color system is
employed and color images are formed by the combination of three
dyes derived from yellow, magenta and cyan couplers.
[0003] As magenta couplers used in conventional color photographic
materials are known 5-pyrazolone, pylazolinobenzoimidazole or
indanone type couplers, and of these, 5-pyrazolone derivatives are
broadly employed.
[0004] Substituents at the 3-position of the 5-pyrazolone ring of
the 5-pyrazolone derivatives include, for example, an alkyl group,
an aryl group, an alkoxy group described in U.S. Pat. Nos.
2,369,489 and 2,600,788, an acylamino group, and a ureido group
described in U.S. Pat. No. 3,558,319. However, such couplers had
the disadvantages that coupling activity with an oxidation product
of a developing agent was so low that sufficiently high magenta dye
image density could be& obtained, the magenta dye images
obtained through color development resulted in a relatively high
secondary absorption in the blue light region and the longer
wavelength-side absorption near edge of the main absorption was not
sharp.
[0005] Further, 3-anilino-5-pyrazolone couplers described in U.S.
Pat. Nos. 2,311,081, 3,677,764 and 3,684,514; British patent Nos.
956,261 and 1,173,513, exhibited a relatively high coupling
activity, giving a high color density and having advantages such as
unwanted absorption in the red light region being relatively low.
However, commonly known 3-anilino-5-pyrazolone type couplers have
disadvantages that solubility in organic solvents is relatively low
and when a color photographic material containing this coupler is
aged, precipitation of the coupler tends to easily occur in the
photographic material. Furthermore, color photographic materials
containing commonly known 3-anilino-5-pyrazolone couplers exhibited
a disadvantage that the magenta dye image density, after being
processed, varied after being aged.
[0006] In commercially available color photographic materials, as
is well known, a coupler is not used alone but is used in
combination with various functional couplers to improve image
quality and color reproducibility. As such functional couplers,
so-called DIR couplers and masking couplers (or colored couplers)
are generally employed. However, in cases when the
3-anilino-5-pyrazolone coupler is used in combination with a
functional coupler, it was shown that the foregoing disadvantages
tended to increase.
SUMMARY OF THE INVENTION
[0007] Accordingly, it is an object of the present invention to
provide a silver halide color photographic light sensitive material
exhibiting enhanced sensitivity, superior color forming property
and improved storage stability.
[0008] The above object of the invention can be accomplished by the
following constitution:
[0009] (1) A silver halide color photographic light sensitive
material comprising a support having thereon blue-sensitive,
green-sensitive and red-sensitive silver halide emulsion layers,
wherein at least one of the silver halide emulsion layers contains
a coupler represented by the following formula (I): 2
[0010] wherein R.sub.11 represents a secondary or tertiary alkyl
group, or a cycloalkyl group; R.sub.12 represents an aryloxy group;
R.sub.13 represents a hydrogen atom, an alkyl group, a cycloalkyl
group, an aryl group or a heterocyclic group; R.sub.14 represents a
halogen atom or an alkoxy group; R.sub.15, R.sub.16 and R.sub.17
independently represent a substituent; k1 is an integer of 0 to 5;
m1 and n1 are each an integer of 0 to 4;
[0011] (2) The silver halide color photographic material described
in (1) above, wherein the silver halide emulsion layer containing
the coupler represented by formula (I) or another silver halide
emulsion layer having the same color-sensitivity as the silver
halide emulsion layer containing the coupler represented by formula
(I) contains a compound represented by the following formula (II):
3
[0012] wherein R.sub.21 and R.sub.24 represent a secondary or
tertiary alkyl group, or a cycloalkyl group; R.sub.22 and R.sub.25
represent an aryloxy group; R.sub.23 and R.sub.26 represent a
hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or
a heterocyclic group; R.sub.27 and R.sub.28 independently represent
a substituent; m2 and n2 are each an integer of 0 to 4;
[0013] (3) The silver halide color photographic material described
in (1) or (2) above, wherein the silver halide emulsion layer
containing the coupler represented by formula (I) or another silver
halide emulsion layer having the same color-sensitivity as the
silver halide emulsion layer containing the coupler represented by
formula (I) contains a compound represented by the following
formula (III): 4
[0014] wherein W represents a coupler moiety capable of forming a
dye capable of being leached out of the photographic material upon
reaction with an oxidation product of a color developing agent;
TIME represents a timing group capable of releasing an inhibitor
residue DI after being released from W upon reaction with an
oxidation product of a color developing agent; and n3 is an integer
of 0, 1 and 2;
[0015] (4) The silver halide color photographic material described
in (1) or (2) above, wherein the silver halide emulsion layer
containing the coupler represented by formula (I) or another silver
halide emulsion layer having the same color-sensitivity as the
silver halide emulsion layer containing the coupler represented by
formula (I) contains a compound represented by the following
formula (IV): 5
[0016] wherein Y represents an yellow coupler moiety capable of
forming an yellow dye upon reaction with an oxidation product of a
color developing agent; TIME represents a timing group capable of
releasing an inhibitor residue DI after being released from Y upon
reaction with an oxidation product of a color developing agent; and
n4 is an integer of 0, 1 and 2;
[0017] (5) The silver halide color photographic material described
in any one of (1) through (4) above, wherein the silver halide
emulsion layer containing the coupler represented by formula (I) or
another silver halide emulsion layer having the same
color-sensitivity as the silver halide emulsion layer containing
the coupler represented by formula (I) contains a compound
represented by the following formula (V): 6
[0018] wherein R.sub.51 and R.sub.52 independently represent a
secondary or tertiary alkyl group or a cycloalkyl group; R.sub.53
represents a halogen atom or an alkoxy group; R.sub.54 and R.sub.55
independently represent a substituent; k5 is an integer of 0 to 5;
and m5 is an integer of 0 to 4.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The coupler (magenta coupler) represented by formula (I)
will be described in detail.
[0020] In formula (I), R.sub.1, represents a secondary or tertiary
alkyl group (e.g., i-propyl, sec-butyl, t-butyl, t-amyl, etc.) or a
cycloalkyl group (e.g., cyclopropyl, cyclopentyl, cyclohexyl,
etc.). The group represented by R.sub.11 may be substituted but
unsubstituted one is preferred. The group represented by formula
R.sub.11 preferably has 3 to 12 carbon atoms, and more preferably 3
to 6 carbon atoms. Specifically preferred R.sub.11 is a secondary
alkyl group and iso-propyl group is still more preferred. R.sub.12
represents an aryloxy group (e.g., phenoxy, naphthyloxy, etc.). The
aryloxy group may be substituted by substituents and examples of
the substituents include the following:
[0021] an alkyl group (e.g., t-amyl, t-octyl, dodcyl, etc), an
cycloalkyl group (e.g., cyclopropyl, cyclhexyl, etc), an aryl
(e.g., phenyl, naphthyl, etc), a heterocyclic group (e.g.,
2-tetrahydrofuryl, 2-thiophenyl, 4-imidazolyl, indoline-1-yl,
2-pyridyl, etc), a carbonyl group (e.g., alkylcarbonyl such as
acetyl, trifluoroacetyl and pivaloyl, and arylcarbonyl such as
benzoyl, pentafluorobenzoyl and 3,5-di-t-butyl-4-hydroxybenzoyl),
an oxycarbonyl group (e.g., alkoxycarbonyl such as methoxycarbonyl,
cyclohexyloxycarbonyl and dedecyloxycarbonyl, aryloxycarbonyl such
as phenoxycarbonyl, 2,4-di-t-amylphenoxycarbonyl and
1-naphthyloxycarbonyl, and heterocyclic-oxycarbonyl such as
2-pyridyloxycarbonyl and 1-phenylpyrazolyl-5-oxycarbonyl), a
carbamoyl group (e.g., alkylcarbamoyl such as dimethylcarbamoyl and
4-(2,4-di-t-amylphenoxy)butylcarbonyl, and arylcarbamoyl such as
1-naphthylcarbamoyl), a sulfonyl group (e.g., alkylsulfonyl such as
methanesulfonyl and trifluoromethanesulfonyl, and arylsulfonyl such
as p-toluenesulfonyl), a sulfamoyl (e.g., alkylsulfamoyl such as
dimethylsulfamoyl and 4-(2,4-di-t-amylphenoxy)buty- laminosulfonyl,
and arylsulfamoyl such as phenylsulfamoyl), a halogen atom, cyano
group, nitro group, an alkenyl group (e.g., 2-propylene, oleyl,
etc), hydroxy group, an alkoxy group (e.g., methoxy,
2-ethoxyethoxy, etc)an aryloxy group (e.g., phenoxy,
2,4-di-t-amylphenoxy, 4-(4-hydroxyphenylsulfonyl)phenoxy, etc), a
heterocyclic-oxy group (e.g., 4-pyridyloxy, 2-hexahydropiranyloxy,
etc), a carbonyloxy group (e.g., alkylcarbonyloxy such as
acetyloxy, trifluoroacetyloxy and pivaloyloxy, and aryoxy such as
benzoyloxy and pentfluorobenzoyloxy)a urethane group (e.g.,
alkylurethane such as N,N-dimethylurethane and arylurethane such as
N-phenylurethane, N-(p-cyanophenyl)urethane), a sulfonyloxy group
(e.g., alkylsulfonyoxy such as methanesulfonyloxy,
trifluoromethanesulfonyloxy and dodecanesulfonyloxy and
arylsulfonyloxy such as benzenesulfonyloxy and
p-toluenesulfonyloxy), an amino group (e.g., alkylamino such as
dimethylamino, cyclohexylamino and dodecylamino, and arylamino such
as anilino and p-t-octylanilino), a sulfonylamino group (e.g.,
alkylsulfonylamino such as methanesulfonylamino,
heptafluoropropanesulfon- ylamino and hexadecysulfonylamino, and
arylsulfonylamino such as p-toluenesulfonylamino and
pentafluorobenzenesulfonylamino), a sulfamoylamino group (e.g.,
alkylsulfamoylamino such as N,N-dimethylsulfamoylamino and
arylsulfamoylamino such as N-phenylsulfamoylamino), an acylamino
group (e.g., alkylcarbonylamino such as acetylamino and
myrystylamino and arylcarbonylamino such as benzoylamino), a ureido
group (e.g., alkylureido such as N,N-dimethylureido, and arylureido
such as N-phenylureido and N-(p-cyanophenyl)ureido), an alkylthio
group (e.g., methylthio, t-octylthio, etc), an arylthio group
(e.g., phenylthio, etc), and a heterocycli-thio group (e.g.,
1-phenyltetrazole-5-thio, 5-methyl-1,3,4-oxazole-2-thio, etc).
[0022] Of the groups represented by R.sub.12 is preferred a phenoxy
group having a substituent on the benzene ring, i.e., a substituted
phenoxy. The substituent is preferably an alkyl group, a cycloalkyl
group, an alkoxy group, a halogen atom and an alkoxycarbonyl group.
The total carbon number of the substituent(s) on the benzene ring
is preferably 4 to 20 and more preferably 8 to 12.
[0023] R.sub.13 represents a hydrogen atom, a cycloalkyl group, an
aryl-group or a heterocyclic group, of which a hydrogen atom is
preferred. R.sub.14 represents a halogen atom (e.g., chlorine,
bromine, iodine, etc.) or a alkoxy group (e.g., methoxy, I-propoxy,
etc.), of which R.sub.14 is preferably a chlorine atom or methoxy
group. R.sub.15 represents a substituent. Any group capable of
being substituted on a benzene ring may be included and exemplary
examples thereof are the same as cited as the substituents for
R.sub.12. R.sub.15 is prefrerably a halogen atom and a chlorine
atom is specifically preferred. Specifically, three chlorine atoms
being substituted at the 2, 4, 6-position is preferred.
[0024] R.sub.16 also represents a substituent. Any group capable of
being substituted on a benzene ring may be included and exemplary
examples thereof are the same as cited as the substituents for
R.sub.12. R.sub.16 is prefrerably an acylamino group, an
oxycarbonyl group, carbamoyl group, sulfonyl group and sulfamoyl
group. R.sub.17 also represents a substituent. Any group capable of
being substituted on a benzene ring may be included and exemplary
examples thereof are the same as cited as the substituents for
R.sub.12. R.sub.15 is prefrerably a halogen atom.
[0025] Representative examples of the coupler represented by
formula (I) are shown below but are not limited to these examples.
7
[0026] The compound represented by formula (II) will be described.
In formula (II), R.sub.21 and R.sub.24 independently represent a
secondary or tertiary alkyl group or a cycloalkyl group and
exemplary examples thereof are the same as cited as R.sub.11 of
formula (I). R.sub.22 and R.sub.25 each represent an aryloxy group
and exemplary examples thereof are the same as cited as R.sub.12 of
formula (I). R.sub.23 and R.sub.26 each represent a hydrogen atom,
an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic
group, and exemplary examples thereof are the same as cited as
R.sub.13 of formula (I). R.sub.27 and R.sub.28 each represent a
substituent and exemplary examples thereof are the same as cited as
R.sub.17 of formula (I). In formula (II), two --NHCO groups may be
substituted on any position of each benzene ring and substitution
at the ortho-position for the sulfur atom is preferred.
[0027] Representative examples of the compound represented by
formula (II) are shown below, but are by no means limited to these
examples. 8
[0028] Next, the compound represented by formula (III) will be
described. The compounds represented by formula (III) are a
so-called leachable decoloring DIR coupler, as described in JP-A
Nos. 58-160954, 63-37350, 4-356042, 5-61160 (hereinafter, the term,
JP-A means an unexamined published Japanese Patent Application);
and U.S. Pat. No. 4,482,629.
[0029] In formula (III), the coupler moiety represented by W may be
any coupler moiety having the same property as described above, and
is preferably a 1-naphthol substituted at the 2-position by an
unsubstituted carbamoyl group or an alkylcarbamoyl group
substituted with a water-solubilizing group (e.g., carboxy, sulfo,
hydroxy, methoxycarbonyl, ethoxycarbonyl, etc.), in terms of higher
reactivity and superior leachability.
[0030] The group represented by TIME is a so-called timing group
and a linkage group used for the purpose of adjustment of the
coupling reaction rate of the compound of formula (III) and an
oxidation product of a color developing agent, and of the releasing
rate of the inhibitor residue represented by DI. Representative
timing groups are described in U.S. Pat. Nos. 4,861,701, 4,248,962,
4,409,323, 4,482,629 and 4,857,447.
[0031] The inhibitor residue represented by DI refers to a compound
having a function of retarding the developing rate in the color
developing process, that is, a group in which a hydrogen atom is
removed from the inhibitor. Exemplary inhibitors include
mercaptotetrazoles, mercaptobenzothiazoles, mercaptobenzoxazoles,
mercaptobenzimidazoles, mercpatooxadiazoles, mercaptothiadiazoles,
benzoriazoles, and 1,2,3- or 1,2,4-triazoles. From the viewpoint of
reduction in contamination of processing solutions, the DI is
preferably a compound inhibiting development at the time of being
released from the active position of the coupler upon color
development reaction, which is decomposed to a compound
substantially having no photographic effect, after being leached
into a color developing solution. The compound releasing the DI
exhibiting such properties is a so-called deactivation type DIR
coupler. The deactivation type DIR coupler is systematically
defined in JP-A 57-151944, and exemplary compounds are described in
JP-A Nos. 58-205150, 60-218644, 60-221750, 60-233650, 61-11743,
2-48655, 3-18844, 3-228048, 4-211245, 4-308842; and U.S. Pat. No.
4,782,012.
[0032] The compounds represented by formula (III) can be
synthesized with reference to the methods described in the
above-cited patents. Exemplary examples of the compound of formula
(III) are shown below, but are by no means limited to these
examples. 9
[0033] The compound represented by formula )IV) will be described
below. In formula (IV), Y represents a coupler moiety capable of
forming a yellow dye upon reaction with an oxidation product of a
color developing agent in the color development process.
Representative yellow dye forming couplers are described in U.S.
Pat. Nos. 2,875,057, 2,407,210, 3,265,506, 2,298,433, 3,048,194,
3,447,928; and "Farbkuppler eine Literturiebersicht" (Affa
Mitteilungen, Vol. III page 112-126, 1961). Preferred Y is
acyacetoamides such as pivaloylacetoanilides and
benzoylacetoanilides. TIME represent a timing group capable of
releasing the DI after being released from Y upon reaction with an
oxidation product of a color developing agent, and examples thereof
are the same as cited as TIME and DI of formula (III).
[0034] The compounds represented by formula (IV) can be synthesized
with reference to the methods described in the above-cited patents.
Exemplary examples of the compound of formula (IV) are shown below,
but are by no means limited to these examples. 10
[0035] The compound represented by formula (V) will be described
below. The compound represented by formula (V) is a so-called
masking coupler or colored coupler, which is yellow-colored.
[0036] In formula (V), R.sub.51 and R.sub.52 represent a secondary
or tertiary alkyl group (e.g., i0propyl, sec-butyl, t-butyl,
t-amyl, etc.) or a cycloalkyl group (e.g., cyclopropyl,
cyclopentyl, cyclohexyl, etc.). R.sub.51 and R.sub.52 is preferably
a secondary or tertiary alky group having 6 or less carbon atoms or
a cycloalkyl group, and i-propyl or sec-butyl are specifically
preferred. R.sub.53 represents a halogen atom (e.g., chlorine,
fluorine, etc.) or an alkoxy group (e.g., methoxy, I-propoxy,
etc.). R.sub.53 is preferably a chlorine atom or methoxy group.
R.sub.54 represents a substituent. The substituent may be any group
capable of being substituted on a benzene ring and examples thereof
are the same as cited as substituent for R.sub.12 of formula (I).
R.sub.54 is preferably an acylamino group, an oxycarbonyl group, a
carbamoyl group, a sulfonyl group or a sulfamoyl group. R.sub.55
also represents a substituent. The substituent may be any group
capable of being substituted on a benzene ring and examples thereof
are the same as cited as substituent for R.sub.12 of formula (I).
R.sub.55 is preferably a halogen atom.
[0037] The compounds represented by formula (V) can be synthesized
with reference to the method described in JP-A 62-50830. Exemplary
examples of the compound of formula (V) are shown below but are by
no means limited to these examples. 11
[0038] Next, exemplary synthesis of the compound represented by
formulas (I) or (II) is described below.
SYNTHESIS EXAMPLE 1
(Synthesis of exemplified Compound II-1)
[0039] 12
[0040] In 620 ml of ethyl acetate, 122.8 g of raw material (A) was
dissolved and then cooled with ice. Subsequently, 53.8 g of 31%
hydrogen peroxide was dropwise added thereto at an internal
temperature of 15.degree.C. or lower (in about 20 min.). After
completing the addition, stirring continued further for 1 hr. at a
temperature at 20.degree.C. or lower. Then, to the reaction mixture
was added 194 g of potassium carbonate dissolved in 340 ml water.
Subsequently, 450 g of compound (C) dissolved in 450 ml of ethyl
acetate was dropwise added at an internal temperature of 20 to
25.degree.C. (in about 50 min.). After completing the addition,
stirring continued further for 8 hrs. at room temperature. As
crystals were precipitated, the reaction mixture was heated to an
internal temperature of 65.degree.C. with stirring and after
dissolving the crystals, a water phase was removed. The remaining
organic phase was washed with 390 ml of an aqueous 5% sodium
sulfite solution and then twice with 390 ml of hot water. Since
precipitation easily occurred, the above washing was carried out,
while being maintained at 65.degree.C. After distilling out ethyl
acetate under reduced pressure, obtained crude crystals were washed
1,160 ml of methanol, while boiling and suspending. After cooling
to room temperature, crystals were filtered and washed with 190 ml
of methanol, three times. After drying at 50.degree.C., 386.2 g of
exemplified compound II-1 was obtained. The structure was
identified by NMR and mass spectrum.
SYNTHESIS EXAMPLE 2
(Synthesis of exemplified Compound I-1)
[0041] 13
[0042] To 1.3 lit. of ethyl acetate, 130 g of exemplified compound
II-1 and 165 g of raw material (D) was added and after dissolved at
50.degree.C., the mixture was allowed to stand until cooled to room
temperature. Subsequently, 55.7 g of potassium carbonate dissolved
in 220 ml water was added thereto and 400 ml of dimethylformamide
was added. After stirring for 1 hr. at room temperature, 20 ml of
hypochlorous acid (measure effective chlorine concentration of
3.49%) was dropwise added five times at 30 min. intervals. As raw
material (D) still remained, 30 ml of hypochlorous acid was further
added thereto. After stirring for one night, an organic phase was
washed with 500 ml of hot water. Then, the organic phase was washed
successively with the following aqueous solutions having
composition described below.
1 Washing 1: 27 g sodium sulfite/550 ml water Washing 2: 550 ml
saturated sodium chloride solution Washing 3: 32 ml concentrated
hydrochloric acid/ 550 ml saturated sodium chloride solution
Washing 4: 550 ml saturated sodium chloride solution, 3 times.
[0043] After completion of washing, ethyl acetate was distilled out
under reduced pressure. Adding 290 ml of ethyl acetate, the
obtained crude crystals were dissolved and then recrystalized
adding 570 ml of acetonitrile. Further, through recrystalization in
a mixed solvent of 820 ml ethyl acetate and 260 ml acetonitrile was
obtained 123.6 g of exemplified compound II-1. No contamination of
exemplified compound II-1 was observed (less than 0.1%). The
structure was identified by NMR and mass spectrum.
[0044] The magenta coupler represented by formula (I) is used
preferably in an amount of 1.times.10.sup.-3 to 8.times.10.sup.-1,
and more preferably .times.10.sup.-2 to 3.times.10.sup.-1 mol/mol
AgX. The magenta coupler of formula (I) may be used in combination
with other kind of a magenta coupler. The compound represented by
formula (II) is used preferably in an amount of 0.1 to 10% by
weight, and more preferably 0.5 to 5% by weight, based on the
magenta coupler of formula (I). The DIR coupler represented by
formula (III) (I) is used preferably in an amount of
1.times.10.sup.-5 to 5.times.10.sup.-1, and more preferably
1.times.10.sup.-3 to 1.times.10.sup.-1 mol/mol AgX. The DIR coupler
of formula (III) may be used in combination with other kind of a
DIR coupler. The DIR coupler represented by formula (IV) (I) is
used preferably in an amount of 1.times.10.sup.-5 to
5.times.10.sup.-1, and more preferably 1.times.10.sup.-3 to
2.times.10.sup.-1 mol/mol AgX. The DIR coupler of formula (IV) may
be used in combination with other kind of a DIR coupler. The
colored coupler represented by formula (V) is used preferably in an
amount of 5 to 50% by weight, and more preferably 10 to 30% by
weight, based on the magenta coupler of formula (I).
[0045] The method for incorporating the compounds of formulas (I)
through (V) is not specifically limited and any of methods known in
conventional photographic materials are employable, including
dispersion as fine oil particles through dissolution in a high
boiling solvent, as described in U.S. Pat. No. 2,320,027;
dispersion through dissolution by introducing a ballast group and a
water-solubilizing group, as described in U.S. Pat. No. 2,186,849;
integrating into a polymeric compound as its component, as
described in U.S. Pat. No. 2,397,864; a method of filling in a
latex polymer and dispersing through mechanical crushing by the use
of a colloid mill or the like.
[0046] The color photographic material according to this invention
comprises on a support a green-sensitive silver halide emulsion
layer containing the compounds of formulas (I) through (V), as a
basic constitution, and a multicolor photographic material is
desirable. Thus, according to one of preferred embodiments of this
invention, the color photographic material comprises a support
provided thereon a green-sensitive silver halide emulsion layer
containing the compounds of formulas (I) through (V), which is in
combination a blue-sensitive silver halide emulsion layer
containing a yellow coupler (such as benzoylacetoanilide compounds
and pivaloylacetoanilide compounds) and a red-sensitive silver
halide emulsion layer containing a cyan coupler (such as naphthol
compounds, 2-ureido-5-acylaminophenol compounds). In addition
thereto, a filter layer, a protective layer, an interlayer, a
sublayer or a backing layer may be optionally provided. Further,
the silver halide emulsion layer having sensitivity within each of
the wavelength region may be comprised of two or more layers.
[0047] Silver halide emulsions used in this invention include not
only silver chloride, silver bromide and silver iodide, but also
mixed silver halide such as silver chlorobromide, silver
iodobromide, silver iodochloride or silver iodochlorobromide. These
silver halide emulsions can be prepared according to the
conventional methods, and ammoniacal precipitation, neutral
precipitation, acidic precipitaion, a halide conversion method,
variable addition and uniform precipitation are applicable. The
mean grain size is not specifically limited but is preferably 0.01
to 5 .mu.m. Two or more silver halide emulsions which have been
separately prepared may be blended. The silver halide emulsions
used in this invention can be chemically sensitized by the commonly
known methods, including a gold sensitization with a gold complex,
reduction sensitization with a reducing compound, sulfur
sensitization using a compound containing a reactive sulfur with a
silver ion or active gelatin, and sensitization with noble metal
salts of the VIII group of the periodical table. The silver halide
emulsions can be spectrally sensitized using cyanine dyes such as
monomethine cyanines, pentamethine cyanines, merocyanines and
carbocyanines, alone or in combination thereof, or in combination
with styryl dyes or aminostilbene compounds.
[0048] Furthermore, a commonly known stablilizer, antifoggant,
surfactant, defoaming agent, antistatic agent, hardener, agent for
improving physical properties of the layer, brightening agent,
anti-staining agent, UV absorbent, and anti-irradiation agent.
Compounds described in Research Disclosure (also denoted as RD vol.
176, No. 17643 (1978)can be employed as the foregoing
additives.
[0049] Supports used in the color photographic material of this
invention are optionally selected according to its purpose.
Examples of the supports include cellulose acetate film,
polyethylene terephthalate (PET) film, polystyrene (PS) film,
polycarbonate (PC) film, or their lamination materials; paper,
baryta paper, .alpha.-olefin polymer-laminated paper, synthetic
paper, glass and metals.
[0050] In the photographic material of this invention, gelatin is
advantageously employed as binder or protective colloid; and other
hydrophilic colloids including gelatin derivatives, graft polymers
of gelatin with other polymers, cellulose derivatives such as
hydroxyethyl cellulose, carboxymethyl cellulose and cellulose
sulfuric acid ester, and hydrophilic synthetic polymer compounds
such as polyvinyl alcohol, partial acetals of polyvinyl alcohol,
poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
polyacrylamide and their copolymers may be used in combination with
gelatin.
[0051] The color photographic materials, after exposure, are
subjected to conventional color development. The basic process of
the negative-positive method comprises color development, bleach
and fixing. The basic process of the reversal method comprises the
first development, followed by exposure to white light or treatment
in a foggant-containing bath, and the steps of color development,
bleach and fixing. Each of these steps may be independently carried
out. Alternatively, two or more steps may be conducted at one time
using a processing solution having such functions. Example thereof
include color processing with a monobath containing a color
developing agent, a ferric salt bleaching component and a
thiosulfate fixing component (as described in JP-B No. 35-1885);
and a monobath bleach-fixing method containing a bleaching
component of a ethylenediaminetetraacetate iron (III) complex and a
thiosulfate fixing component.
[0052] Photographic processing usable in this invention is not
specifically limited and any of photographic processing methods is
applicable. Representative examples thereof are as follows:
[0053] (1) color development, followed by bleach-fixing, and
optionally, washing and stabilization treatment;
[0054] (2) color development, followed by bleaching and fixing, and
further optionally washing and stabilization treatment;
[0055] (3) pre-hardening, followed by neutralization, color
development, stop-fixing, washing, bleaching, washing,
post-hardening and washing;
[0056] (4) color development, followed by washing, auxiliary color
development, stopping, bleaching, fixing, washing and
stabilization; and
[0057] (5) a method of processing a low silver coverage, silver
halide photographic material using an amplifier such as peroxides
or cobalt complex salts.
[0058] The processing may be conducted at a high temperature of
30.degree.C. or more, at room temperature or at a low temperature
of 20.degree.C. or less, but in general, carried out at a
temperature of 20 to 70.degree.C. The temperature of these steps
may be the same or different.
EXAMPLES
[0059] Embodiment s of this invention will be described based on
examples but are limited by no means to these examples.
Example 1
Preparation of Color Photographic Material
[0060] On a triacetyl cellulose film support were formed the
following layers containing composition as shown below to prepare a
multi-layered color photographic material Sample 101. The addition
amount of each compound was represented in term of g/m.sup.2,
provided that the amount of silver halide or colloidal silver was
converted to the silver amount and the amount of a sensitizing dye
was represented in mol/Ag mol.
2 1st Layer (Anti-Halation Layer) Black colloidal silver 0.16 UV
absorbent (UV-1) 0.30 Colored magenta coupler (CM-1) 0.12 Colored
cyan coupler (CC-1) 0.03 High boiling solvent (OIL-1) 0.24 Gelatin
1.33 2nd Layer (Intermediate Layer) Silver iodobromide emulsion j
0.10 Anti-staining agent (AS-1) 0.12 High boiling solvent (OIL-1)
0.15 Gelatin 0.67 3rd Layer (Low-speed Red-Sensitive Layer) Silver
iodobromide emulsion c 0.053 Silver iodobromide emulsion d 0.11
Silver iodobromide emulsion e 0.11 Sensitizing dye (SD-1) 2.2
.times. 10.sup.-5 Sensitizing dye (SD-2) 5.9 .times. 10.sup.-5
Sensiziting dye (SD-3) 1.2 .times. 10.sup.-4 Sensitizing dye (SD-4)
1.6 .times. 10.sup.-4 Sensitizing dye (SD-5) 1.6 .times. 10.sup.-4
Cyan coupler (C-1) 0.19 Colored cyan coupler (CC-1) 0.003 High
boiling solvent (OIL-2) 0.096 Anti-staining agent (AS-2) 0.001
Gelatin 0.44 4th Layer (Medium-speed Red-sensitive Layer) Silver
iodobromide emulsion b 0.28 Silver iodobromide emulsion c 0.34
Silver iodobromide emulsion d 0.50 Sensitizing dye (SD-1) 1.8
.times. 10.sup.-5 Sensitizing dye (SD-4) 2.6 .times. 10.sup.-4
Sensitizing dye (SD-5) 2.8 .times. 10.sup.-4 Cyan coupler (C-1)
0.74 Colored cyan coupler (CC-1) 0.081 DIR compound (DI-1) 0.020
DIR compound (DI-4) 0.008 High boiling solvent (OIL-2) 0.42
Anti-staining agent (AS-2) 0.003 Gelatin 1.95 5th Layer (High-speed
Red-Sensitive Layer) Silver iodobromide emulsion a 1.45 Silver
iodobromide emulsion e 0.076 Sensitizing dye (SD-1) 2.3 .times.
10.sup.-5 Sensitizing dye (SD-2) 1.1 .times. 10.sup.-4 Sensitizing
dye (SD-3) 1.5 .times. 10.sup.-5 Sensitizing dye (SD-4) 2.1 .times.
10.sup.-5 Cyan coupler (C-2) 0.087 Cyan coupler (C-3) 0.12 Colored
cyan coupler (CC-1) 0.036 DIR compound (DI-1) 0.021 DIR compound
(DI-3) 0.005 Bleach-accelerating agent releasing coupler 0.022
(BAR-1) High boiling solvent (OIL-2) 0.15 Anti-staining agent
(AS-2) 0.004 Gelatin 1.40 6th Layer (Intermediate Layer) Dye (F-1)
0.03 Anti-staining agent (AS-1) 0.18 High boiling solvent (OIL-1)
0.22 Gelatin 1.00 7th Layer (Low-speed Green-Sensitive Layer)
Silver iodobromide emulsion c 0.22 Silver iodobromide emulsion e
0.22 Sensitizing dye (SD-6) 4.7 .times. 10.sup.-5 Sensitizing dye
(SD-7) 2.6 .times. 10.sup.-4 Sensitizing dye (SD-8) 1.9 .times.
10.sup.-4 Sensitizing dye (SD-9) 1.1 .times. 10.sup.-4 Sensitizing
dye (SD-10) 2.4 .times. 10.sup.-5 Magenta coupler (M-1) 0.35
Colored magenta coupler (CM-1) 0.044 DIR compound (DI-2) 0.010 High
boiling solvent (OIL-1) 0.41 Anti-staining agent (AS-2) 0.001
Anti-staining agent (AS-3) 0.11 Gelatin 1.29 8th Layer
(Medium-speed Green-Sensitive Layer) Silver iodobromide emulsion b
0.90 Silver iodobromide emulsion e 0.048 Sensitizing dye (SD-6) 3.8
.times. 10.sup.-5 Sensitizing dye (SD-7) 2.6 .times. 10.sup.-5
Sensitizing dye (SD-8) 3.4 .times. 10.sup.-4 Sensitizing dye (SD-9)
1.6 .times. 10.sup.-4 Sensitizing dye (SD-10) 4.4 .times. 10.sup.-5
Magenta coupler (M-1) 0.15 Colored cyan couple (CM-1) 0.062 Colored
magenta coupler (CM-2) 0.030 DIR compound (DI-2) 0.032 High boiling
solvent (OIL-1) 0.28 Anti-staining agent (AS-2) 0.005 Anti-staining
agent (AS-3) 0.045 Gelatin (1.00) 9th Layer (High-speed
Green-Sensitive Layer) Silver iodobromide emulsion a 1.39 Silver
iodobromide emulsion e 0.073 Sensitizing dye (SD-6) 4.1 .times.
10.sup.-5 Sensitizing dye (SD-7) 2.6 .times. 10.sup.-5 Sensitizing
dye (SD-8) 3.7 .times. 10.sup.-4 Sensitizing dye (SD-10) 4.9
.times. 10.sup.-5 Magenta coupler (M-1) 0.071 Magenta coupler (M-2)
0.073 Colored magenta coupler (CM-2) 0.013 DIR compound (DI-2)
0.004 DIR compound (DI-3) 0.003 High boiling solvent (OIL-1) 0.27
Anti-staining agent (AS-2) 0.008 Anti-staining agent (AS-3) 0.043
Gelatin 1.35 10th Layer (Yellow Filter Layer) Yellow colloidal
silver 0.053 Anti-staining agent (AS-1) 0.15 High boiling solvent
(OIL-1) 0.18 Formalin scavenger (X-1) 0.06 Gelatin 0.83 11th Layer:
Low-speed Blue-sensitive Layer Silver iodobromide emulsion g 0.22
Silver iodobromide emulsion h 0.099 Silver iodobromide emulsion i
0.17 Sensitizing dye (SD-11) 2.4 .times. 10.sup.-4 Sensitizing dye
(SD-12) 5.7 .times. 10.sup.-4 Sensitizing dye (SD-13) 1.3 .times.
10.sup.-4 Yellow coupler (Y-1) 1.02 Bleach-accelerating agent
releasing coupler 0.022 (BAR-1) High boiling solvent (OIL-1) 0.42
Anti-staining agent (AS-2) 0.003 Formaline scavenger (X-1) 0.11
Formaline scavenger (X-2) 0.18 Gelatin 1.95 12th Layer (High-sped
Blue-sensitive Layer) Silver iodobromide emulsion f 1.52
Sensitizing dye (SD-11) 8.3 .times. 10.sup.-5 Sensitizing dye
(SD-12) 2.3 .times. 10.sup.-4 Yellow coupler (Y-1) 0.22 DIR
compound (DI-5) 0.11 High boiling solvent (OIL-1) 0.13
Anti-staining agent (AS-2) 0.003 Formaline scavenger (X-1) 0.15
Formaline scavenger (X-2) 0.20 Gelatin 1.20 13th Layer: First
Protective Layer Silver iodobromide emulsion k 0.30 UV absorbent
(UV-1) 0.11 UV absorbent (UV-2) 0.055 Liquid paraffin 0.28
Formaline scavenger (X-1) 0.079 Gelatin 1.00 14th Layer (Second
protective Layer) Matting agent PM-1 0.13 Matting agent PM-2 0.018
Lubricant (WAX-1) 0.021 Gelatin 0.55
[0061] Characteristics of silver iodobromide emulsions described
above are shown below, in which the average grain size refers to an
edge length of a cube having the same volume as that of the
grain.
3 Emul- Av. grain Av. AgI con- Diameter/thick- sion size (.mu.m)
tent (mol %) ness ratio a 0.85 4.2 7.0 b 0.70 4.2 6.0 c 0.50 4.2
5.0 d 0.38 8.0 Octahedral e 0.27 2.0 Tetradeca- hedral f 1.00 8.0
4.5 g 0.74 3.5 6.2 h 0.44 4.2 6.1 i 0.30 1.9 5.5 j 0.03 2.0 1.0
[0062] The thus prepared emulsions d and f were added with
sensitizing dyes afore-described and ripened, and then chemically
sensitized by adding triphenylphosphine selenide, sodium
thiosulfate, chloroauric acid and potassium thiocyanate until
relationship between sensitivity and fog reached an optimum point.
Silver iodobromide emulsions a, b, c, g, h, and i were each
spectrally and chemically sensitized in a manner similar to silver
iodobromide emulsions d and f.
[0063] In addition to the above composition were added coating aids
SU-1, SU-2 and SU-3; a dispersing aid SU-4; viscosity-adjusting
agent V-1; stabilizers ST-1 and ST-2; fog restrainer AF-1 and AF-2
comprising two kinds polyvinyl pyrrolidone of weight-averaged
molecular weights of 10,000 and 1.100,000; inhibitors AF-3, AF-4
and AF-5; hardener H-1 and H-2; and antiseptic Ase-1.
[0064] Chemical formulas of compounds used in the Samples described
above are shown below.
[0065] SU-1:
C.sub.8F.sub.17SO.sub.2N(C.sub.3H.sub.7)CH.sub.2COOK
[0066] SU-2:
C.sub.8F.sub.17SO.sub.2NH(CH.sub.2).sub.3N.sup.+(CH.sub.3).su-
b.3Br.sup.-
[0067] SU-3: Sodium di-(2-ethylhexyl) sulfosuccinate
[0068] SU-4: Tri-i-propylnaphthalenesuifonic acid sodium salt
[0069] ST-1: 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
[0070] ST-2: Adenine
[0071] AF-3: 1-Phenyl-5-mercaptotetrazole
[0072] AF-4: 1-(4-Carboxyphenyl)-5-mercaptotetrazole
[0073] AF-5: 1-(3-Acetoamidophenyl)-5-mercaptotetrazole
[0074] H-1:
[CH.sub.2.dbd.CHSO.sub.2CH.sub.2).sub.3CCH.sub.2SO.sub.2CH.sub-
.2CH.sub.2].sub.2NCH.sub.2CH.sub.2SO.sub.3K
[0075] H-2: 2, 4-Dichloro-6-hydroxy-s-triazine sodium salt
[0076] AS-1:
2,5-Bis(1,1-dimethyl-4-hexyloxycarbonylbutyl)-hydroquinone
[0077] As-2: Dodecyl gallate
[0078] AS-3: 1,4-Bis(2-tetradecyloxycarbonylethyl)piperazine
[0079] OIL-1: Tricresyl phosphate
[0080] OIL-2: Di(2-ethylhexyl)phthalate
[0081] X-1: Allantoin (5-ureidohydantoin)
[0082] X-2: Hydantoin 14
[0083] Samples 102 through 123 were prepared in the same manner as
Sample 101, except in the 7th layer (intermediate speed
green-sensitive layer), magenta coupler (M-1) was replaced by an
equimolar amount of a comparative coupler or an inventive coupler,
DIR coupler (DI-2) was replaced by an equimolar amount of a
comparative DIR coupler or the DIR coupler of formula (III) or
(IV), colored coupler (CM-2) was replaced by an equimolar amount of
a comparative colored coupler or the colored coupler of formula
(V), or the magenta coupler of formula (II) of 2% by weight was
added.
4 TABLE 1 Magenta Compd. of DIR Colored Sample No. Coupler Formula
(II) Coupler Coupler 101 (comp.) M-1 -- DI-2 CM-2 102 (comp.) M-A
-- DI-2 CM-2 103 (comp.) M-B -- DI-2 CM-2 104 (comp.) M-1 -- DI-A
CM-2 105 (comp.) M-1 -- DI-B CM-2 106 (comp.) M-1 -- DI-2 CM-A 107
(inv.) I-1 -- DI-2 CM-2 108 (inv.) I-2 -- DI-2 CM-2 109 (inv.) I-25
-- DI-2 CM-2 110 (inv.) I-1 II-1 DI-2 CM-2 111 (inv.) I-2 II-2 DI-2
CM-2 112 (inv.) I-25 II-1 DI-2 CM-2 113 (inv.) I-1 II-2 III-2 CM-2
114 (inv.) I-2 -- III-3 CM-2 115 (inv.) I-25 II-1 III-6 CM-2 116
(inv.) I-1 II-1 IV-1 CM-2 117 (inv.) I-2 II-2 IV-2 CM-2 118 (inv.)
I-25 -- IV-3 CM-2 119 (inv.) I-1 II-1 III-2 V-1 120 (inv.) I-2 II-2
IV-1 V-1 121 (inv.) I-25 -- IV-1 V-6 122 (inv.) I-1 II-1 IV-1 V-1
123 (inv.) I-1 -- DI-2 V-1
[0084] 15
[0085] The thus prepared Samples 101 through 123 were evaluated
with respect to photographic characteristics.
[0086] Sensitivity
[0087] Samples each were exposed to white light through an optical
wedge and processed following to the process described below to
determine sensitivity. Sensitivity is represented by a relative
value of the reciprocal of exposure giving a density of a minimum
density (or fog density) plus 0.7, based on the sensitivity of
Sample 101 being 100.
[0088] Raw stock stability
[0089] Samples each were cut to a 135-size, put into a patrone,
allowed to stand under an atmosphere of 22.degree.C. and 55% RH for
conditioning and then packed into a plastic resin case months, then
processed according to the process described below and evaluated
with respect to sensitivity. Results there of are shown by a
relative value, based on the sensitivity of Sample 101 before
storage being 100.
[0090] Image storage stability
[0091] After exposed to white light, samples each were processed
according to the process described below. The thus obtained samples
were kept for 3 days under an atmosphere of 50.degree.C. and 80% RH
and density variation was determined with respect to a magenta
density of 1.0 before storage. In this case, "+" refers to
sensitization and "-" refers to desensitization.
[0092] Evaluation results are shown in Table 2.
5 Processing: Temper- Replenish- Processing step Time ature ing
rate* Color developing 3 min. 15 sec. 38 .+-. 0.3.degree. C. 780 ml
Bleaching 45 sec. 38 .+-. 2.0.degree. C. 150 ml Fixing 1 min. 30
sec. 38 .+-. 2.0.degree. C. 830 ml Stabilizing 1 min. 38 .+-.
5.0.degree. C. 830 ml Drying 1 min. 55 .+-. 5.0.degree. C. --
*:Amounts per m.sup.2 of photographic material
[0093] A color developer, bleach, fixer and stabilizer each were
prepared according to the following formulas.
[0094] Color developer and replenisher thereof:
6 Worker Replenisher Water 800 ml 800 ml Potassium carbonate 30 g
35 g Sodium hydrogencarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g
5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg --
Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g --
4-Amino-3-methyl-N-(.beta.-hydroxyethyl)- 4.5 g 6.3 g aniline
sulfate Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium
hydroxide 1.2 g
[0095] Water was added to make 1 liter in total, and the pH of the
developer and its replenisher were each adjusted to 10.06 and
10.18, respectively with potassium hydroxide and sulfuric acid.
[0096] Bleach and replenisher thereof:
7 Re- Worker plenisher Water 700 ml 700 ml Ammonium iron (III)
1,3-diamino- 125 g 175 g propanetetraacetic acid
Ethylenediaminetetraacetic acid 2 g 2 g Sodium nitrate 40 g 50 g
Ammonium bromide 150 g 200 g Glacial acetic acid 40 g 56 g
[0097] Water was added to make 1 liter in total and the pH of the
bleach and replenisher thereof were adjusted to 4.4 and 4.0,
respectively, with ammoniacal water or glacial acetic acid.
[0098] Fixer and replenisher thereof:
8 Re- Worker plenisher Water 800 ml 800 ml Ammonium thiocyanate 120
g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g
Ethylenediaminetetraacetic acid 2 g 2 g
[0099] Water was added to make 1 liter in total and the pH of the
fixer and replenisher thereof were adjusted to 6.2 and 6.5,
respectively, with ammoniacal water or glacial acetic acid.
[0100] Stabilizer and replenisher thereof:
9 Water 900 ml p-Octylphenol/ethyleneoxide (10 mol) adduct 2.0 g
Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g
1,2-benzoisothiazoline-3-one 0.1 g Siloxane (L-77, product by UCC)
0.1 g Ammoniacal water 0.5 ml
[0101] Water was added to make 1 liter in total and the pH thereof
was adjusted to 8.5 with ammoniacal water or sulfuric acid
(50%).
10 TABLE 2 Raw Stock Image storage Sample No. Sensitivity
stability*.sup.1 stability*.sup.2 101 (comp.) 100 86 +0.06 102
(comp.) 98 82 +0.06 103 (comp.) 94 80 +0.08 104 (comp.) 103 85
+0.07 105 (comp.) 104 86 +0.06 106 (comp.) 98 86 +0.06 107 (inv.)
102 96 +0.03 108 (inv.) 103 95 +0.04 109 (inv.) 106 100 +0.04 110
(inv.) 100 96 +0.03 111 (inv.) 102 98 +0.04 112 (inv.) 104 101
+0.03 113 (inv.) 104 99 +0.02 114 (inv.) 106 100 +0.02 115 (inv.)
108 104 +0.02 116 (inv.) 110 106 +0.02 117 (inv.) 110 105 +0.02 118
(inv.) 106 101 +0.03 119 (inv.) 104 102 +0.02 120 (inv.) 109 106
+0.02 121 (inv.) 110 107 +0.02 122 (inv.) 110 108 +0.01 123 (inv.)
102 99 +0.03 *.sup.1: Sensitivity after storage *.sup.2: Density
variation after storage
[0102] As can be seen from Table 2, Samples Nos. 107 though 123
according to this invention exhibited little variation in
sensitivity after raw stock keeping and little variation in image
density after storage, as compared to Sample Nos. 101 through
106.
* * * * *