FIELD OF THE INVENTION
The present invention relates to a light-sensitive
silver halide photographic material. More particularly,
it relates to a light-sensitive silver halide photographic
material that can form a dye image having been improved in
fastness to light and also having been prevented from
being stained.
BACKGROUND OF THE INVENTION
Dye images obtained using light-sensitive silver
halide photographic materials (hereinafter often "light-sensitive
material(s)") are desired not to undergo
discoloration or fading even after they have been subject
to light for a long time or stored in an environment of
high temperature and high humidity. They are also desired
to be free from yellowing (hereinafter "Y-stain") that may
occur at their non-image portions because of light,
humidity or heat.
A metal complex having a singlet oxygen quenching
rate constant kq of not less than 3 x 107 M-1s-1 is used
to improve the fastness to light of dye images, as
disclosed in Japanese Patent Publications Open to Public
Inspection (hereinafter referred to as "Japanese Patent
O.P.I. Publication(s)") No. 262740/1986, No. 267049/1986,
No. 175754/1987, No. 187348/1987, No. 182741/1987, No.
183459/1987, etc.
Japanese Patent O.P.I. Publication No. 958/1990 also
discloses that the storage stability can be improved when
a compound with kq of not less than 1 x 107 M-1s-1 is made
present in a heat-developable color light-sensitive
element having a dye-providing compound capable of forming
or releasing a diffusible dye, corresponding or reverse
corresponding with the reaction in which a light-sensitive
silver halide, a binder and a silver halide are reduced to
silver.
Sole use of the compound having the above kq,
however, can not be said to be satisfactory for preventing
the fading and discoloration of color images against
light.
On account of the problem on color reproduction
quality, pyrazoloazole couplers improved in the prevention
of unpreferable secondary absorption inherent in
5-pyrazolone couplers conventionally used as magenta dye
forming couplers have been recently developed and put into
use.
Such pyrazoloazole magenta couplers have been
advantageous in that the Y-stain at the non-image portions
may hardly occur against light, heat and humidity, but on
the other hand disadvantageous in that the azomethin dye
formed has a very low fastness to light and also tends to
undergo the discoloration by light, to seriously damage
the performances of, in particular, light-sensitive color
photographic materials for printing. No satisfactory
effect has been obtainable even when the compound having
the above kq is solely used together with any of these
couplers.
Japanese Patent O.P.I. Publication No. 3995/1991
discloses a technique by which the fastness to light is
improved and the Y-stain due to light, humidity and heat
is prevented from occurring, by using a pyrazoloazole
coupler in combination with an amine compound and a phenol
compound. Nevertheless, no satisfactory effect of
preventing fading for a long period of time was found to
be obtained even by this method.
In addition, in recent years, emulsions layers are
desired to be made smaller in layer thickness from the
viewpoints of cost, sharpness, etc. As a measure for
settling this matter, it has been proposed to decrease the
amount of gelatin used as a binder. The decreasing of the
amount of gelatin, however, causes the problem that the
storage stability of dye images is deteriorated.
Meanwhile, in continuous methods wherein light-sensitive
materials are running processed, they are
commonly running processed while the respective processing
solutions are replenished using replenishing solutions.
In such instances, a large quantity of overflowing
solution is produced with supply of the replenishing
solutions, causing a great problem from the viewpoints of
environmental pollution and cost.
Thus, it is strongly desired in recent years to
decrease the amount of replenishment of color developing
solution (i.e., to achieve low-replenishment). When,
however, conventional light-sensitive color photographic
material are continuously processed using a low-replenished
color developing solution, the deterioration
of storage stability of dye images has clearly come into
question.
SUMMARY OF THE INVENTION
Accordingly, a first object of the present invention
is to provide a light-sensitive silver halide photographic
material that can form a dye image causing less
discoloration against light.
A second object of the present invention is to
provide a light-sensitive material that has prevented the
Y-stain at the non-image portions from occurring against
light, heat and humidity.
A third object of the present invention is to
provide a light-sensitive material that is free from the
secondary absorption of magenta dyes and has been improved
in color reproduction quality.
The above objects of the present invention can be
achieved by a light-sensitive silver halide photographic
material comprising a support carrying a silver halide
emulsion layer containing a dye forming coupler,
characterised in that the silver halide emulsion layer
contains a compound having a singlet oxygen-quenching
ability with a quenching rate constant Kq of not less than
1 X 10
8 M
-1 s
-1 and having the Formula II-a-2;
wherein Y' is a group of non-metallo atoms necessary to
complete a heterocyclic ring having from 5 to 8 members;
R
10 is an alkyl group, a cycloalkyl group, an alkenyl
group, an aryl group, a heterocyclic group, an acyl group.
a bridged hydrocarbon group, an alkylsulfonyl group or an
arylsulfonyl group; R
11 and R
13 are each an electron
donating group having a Hammett's σ p value of not more
than 0; and R
12 and R
14 are each hydrogen atoms; and
a compound represented by the Formula R;
wherein R
15 is a substituent and l is an integer in the range 0
to 5; provided that the value of Kq is determined as follows:
singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)proprionic
acid in ethanol as
solvent at 35 C; 2,5-diphenyl-3,4-benzofuran (DPBF), as a
standard substance for quenching, is made present together with
the substance to be measured; then both the substances are
brought into competitive reaction with the singlet oxygen the
changes with time of light absorption at the absorption
wavelength of the DPBF (λ max: 411 nm) are followed up to
determine the Kq.
The present invention can be particularly effective when
the dye forming coupler comprises a couple represented by the
following Formula M-I
In the formula, Z represents a group of non-metal
atoms necessary to complete a nitrogen-containing
heterocyclic ring. The ring formed by X may have a
substituent.
X represents a hydrogen atom or a group capable of
being split off upon reaction with an oxidized product of
a color developing agent.
R represents a hydrogen atom or a substituent.
DETAILED DESCRIPTION OF THE INVENTION
The kq is determined by the measurement according to
the method disclosed in Daifuku, Mukai et al., Ehime
University, the Faculty of Science, SUMMARY COLLECTIONS OF
THE 22ND OXIDATION FORUM, page 7.
More specifically, singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)propionic
acid (EP) in an ethanol solvent at 35°C according to the
Inoue et al's Method disclosed in Tetrahedron Letter,
41,
pp.2177-2181 (1985). Using 2,5-diphenyl-3,4-benzofuran
(DPBF) as a standard substance for quenching, a substance
to be measured is made present together with this
substance. Both the substances are brought into
competitive reaction with the singlet oxygen, and changes
with time of light absorbance at the absorption wavelength
(λmax: 411 nm) of the DPBF are followed up to determine
the kq.
wherein Y' represents a group of non-metallo atoms
necessary to complete a heterocyclic ring having from 5 to
8 members; R
10 represents an alkyl group, a cycloalkyl
group, an alkenyl group, an aryl group, a heterocyclic
group, an acyl group, a bridged hydrocarbon group, an
alkylsulfonyl group or an arylsulfonyl group.
R11 to R14 each represent an electron donative group
having a Hammett's σp value of not more than 0.
The alkyl group represented by R10 may preferably be
a straight-chain or branched alkyl group having 1 to 24
carbon atoms, as exemplified by groups such as methyl,
ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, t-octyl
and benzyl.
The cycloalkyl group may preferably be a cycloalkyl
group having 5 to 24 carbon atoms, as exemplified by
groups such as cyclopentyl and cyclohexyl.
The alkenyl group may preferably be an alkenyl group
having 3 to 24 carbon atoms, as exemplified by groups such
as aryl and 2,4-pentadienyl.
The aryl group may include, for example, groups such
as phenyl and naphthyl.
The heterocyclic group may include, for example,
groups such as pyridyl, imidazolyl and thiazolyl.
The acyl group may include, for example, groups such
as acetyl and benzoyl.
The bridged hydrocarbon group may include, for
example, groups such as bicyclo[2.2.1]heptyl.
The alkylsulfonyl group may include, for example,
groups such as dodecylsulfonyl and headecylsulfonyl. The
arylsulfonyl group may include, for example, groups such
as phenylsulfonyl.
These groups may each include those having a
substituent. For example, the substituent of the alkyl
group may include a halogen atom and groups such as
hydroxyl, alkoxyl, aryl, acylamino, sulfonamide, aryloxy,
alkylthio, carbamoyl, sulfamoyl, alkylsulfonyl, nitro,
cyano, arylsulfonyl, carboxyl, amino, arylamino,
alkylamino, alkoxycarbonayl, acyl and acyloxy. The
substituent of the group represented by R10 except for the
alkyl group may include the substituents described above
and an alkyl group.
R10 preferably represents an alkyl group.
R11 to R14 each represent an electron donative group
having a Hammett's σp value of not more than 0. R12 and
R14 each represent a hydrogen atom.
Typical examples of these compounds are shown below.
The compounds usable in the present invention are by no
means limited by these.
The kq of the compound
having a singlet oxygen quenching rate constant
kq of not less than 1 x 108 M-1 s-1may preferably be
within the range of from 1 x 108 M-1 s-1to 1 x 109 M-1s-1.
The compound
having a radical-scavenging ability may preferably be a
compound having a radical-scavenging rate constant Ks of
10-1 to 2 x 104 M-1 s-1.
The above Ks is determined by the measurement
according to the method disclosed in Mukai et al., Bull.
Chem. Soc. Jpn., 59, pp.3113-3116.
More specifically, 2,6-di-t-butyl-4-(4'-methoxyphenyl)phenoxyl
radical (PhO·) is mixed in an
ethanol solvent at 25.0°C. Using a stopped-flow
spectrophotometer, changes with time at the maximum
absorption wavelength (λmax: 375 nm) of the PhO· are
followed up to determine the Ks.
The quenching compound
having the above ks of 10
-1 to 2 x 10
4 M
-1 s
-1
has the structure of the following Formula R.
In the formula, R15 represents a substituent that
can be substituted on the benzene ring, and ℓ represents
an integer of 0 to 5. When ℓ is 2 or more, a plurality of
R15 may be the same or different one another, and R15's
may mutually combine to form a ring.
The group represented by R15 in Formula R may
preferably include an alkyl group, a cycloalkyl group, an
alkenyl group, an aryl group, an acylamino group, a
sulfonamide group, an alkylamino group, an alkylthio
group, an arylthio group, an alkoxycarbonyl group, an
aryloxycarbonyl group, a halogen atom and a group -OR16.
Here, R
16 represents an alkyl group, a cycloalkyl
group, an alkenyl group, an aryl group, a heterocyclic
group or a group
wherein R
16a, R
16b and R
16c may be the same or different
one another, and each represent an alkyl group, an alkenyl
group, an aryl group, an alkoxyl group, an alkenoxy group
or an aryloxy group.
The alkyl group represented by R15 may include a
straight-chain or branched alkyl group having 1 to 24
carbon atoms as exemplified by groups such as methyl,
ethyl, i-propyl, t-butyl, octyl, 2-ethylhexyl, dodecyl,
tetradecyl, hexadecyl, eicocyl and benzyl.
The cycloalkyl group represented by R15 may include
a cycloalkyl group having 5 to 24 carbon atoms as
exemplified by groups such as cyclopentyl and cyclohexyl.
The alkenyl group may include an alkenyl group
having 2 to 24 carbon atoms as exemplified by groups such
as ethenyl, propenyl, butenyl, octenyl, decenyl and oleyl.
The aryl group represented by R15 may include a
phenyl group and a naphthyl group.
The halogen atom may include, for example, atoms
such as fluorine, chlorine, bromine and iodine.
The acylamino group may include, for example,
groups such as acetylamino and benzoylamino.
The sulfonamide group may include, for example,
groups such as methylsulfonylamino and
benzenesulfonylamino.
The alkyl component that constitutes the alkylamino
group and alkylthio group may include the same as those of
the alkyl group previously described.
The aryl component that constitutes the arylthio
group may include the same as those of the aryl group
previously described.
The alkoxycarbonyl group may include, for example,
groups such as methoxycarbonyl, ethoxycarbonyl,
benzyloxycarbonyl. The aryloxycarbonyl group may include,
for example, a phenoxycarbonyl group.
In Formula R, among the respective substitutents,
the alkyl group, the cycloalkyl group, the aryl group or
the heterocyclic group, or a group having any of these
groups even in part, may further has a substituent.
For example, the substituent for the alkyl group or
cycloalkyl group may include a halogen atom and groups
such as hydroxyl, alkoxyl, alkylthio, acylamino,
sulfonamide, aryl, aryloxy, carboxyl, amino, alkylamino,
arylamino, carbamoyl, sulfamoyl, alkylsulfonyl,
arylsulfonyl, nitro, cyano, alkoxycarbonyl, acyl and
acyloxy.
The substituents other than the alkyl group may
include the substituents set forth above and an alkyl
group.
The substitutents the aryl group and heterocyclic
group may have may include a halogen atom and groups such
as alkyl, aryl, alkoxyl, aryloxy, alkylthio, arylthio,
acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl,
ureido, alkoxycarbonyl, amino, sulfonyl, nitro, cyano and
carboxyl.
When ℓ is two or more, the ring that may be formed
by any mutual combination of a plurality of R15 may
include an indane ring, a cumarane ring, a naphthalene
ring and a chromane ring. The spiro ring may include a
spirobiindane ring, a spirobicumaran ring and a
spirobichroman group.
These compounds include the compounds disclosed in
the patent publications as set forth in the description on
Formula I.
However, when R15 is a hydroxyl group, the compound
represented by Formula R is not preferable because of its
properties that it reacts with an oxidized product of a
developing agent to inhibit the dye formation of the dye
forming coupler.
Of the compound represented by Formula R, preferred
compounds are those represented by the following Formulas
R-a and R-b.
In the formula, R
15 and R
15' each have the same
definition for R
15 in Formula R, and A represents a
divalent connecting group. Letter symbols a and a' each
represent an integer of 0 to 4. In the case when a or a'
is two or more, a plurality of R
15 or R
15' may be the same
or different one another. R
15 and R
15' may also combine
to form a ring.
In the formula, R15' and R15" each have the same
definition for R15 in Formula R, and may be the same or
different each other. Letter symbols b and b' each
represent an integer of 0 to 3. In the case when b or b'
is two or more, a plurality of R15' or R15" may be the
same or different one another, and may also combine to
form a ring. B and B' each represent a group of non-metal
atoms necessary to complete a heterocyclic ring of 5 to 7
members together with the carbon atoms and C=C.
Of the compound represented by Formula R-a,
particularly preferred compounds are those with the
structures represented by the following Formulas R-a-1 and
R-a-2 .
In the formula, R
15 and R
15' may be the same or
different each other, and each have the same definition
for R
15 in Formula R. Letter symbols a' and a" each
represent an integer of 0 to 4. The letter symbol A
represents a divalent connecting group.
In the formula, R16, R16' , a', a" and A have the
same definitions for R16, R16' , a', a" and A,
respectively, in Formula R-a-1.
In the above Formulas R-a-1 and R-a-2, the
substituents represented by R16 and R16' may include the
groups detailed for R15 in Formula R.
The A represents a divalent connecting group, as
exemplified by an alkylene group,
etc.
wherein R
17 represents a hydrogen atom or a substituted or
unsubstituted alkyl group or phenyl group in all
instances.
The alkylene group may have a single or plural
number of substituent(s). Such substituent(s) may
include, for example, an aryl group, a cyano group, a
halogen atom, a heterocyclic group, a cycloalkyl group, an
alkoxyl group, a hydroxyl group and an aryloxy group.
This alkylene group may also be those in which the
alkylene chain itself constitutes a cycloalkyl ring, as in
the following:
The A may also include those in which the above
divalent connecting groups are arbitrarily connected in
plurality.
The compound represented by Formula R-b will be
described below in greater detail.
Of the compound represented by Formula R-b,
particularly preferred compounds may include structures
represented by Formula R-b-1 or R-b-2.
In the formula, R
15, R
15' , b and b' have the same
definitions for R
15, R
15' , b and b', respectively, in
R
18, R
18' , R
19 and R
19' each represent a hydrogen atom, a
substituted or unsubstituted aliphatic group, a
substituted or unsubstituted aromatic group or a
substituted or unsubstituted heterocyclic group.
In the formula, R15' , R15", b, b' and D have the
same definitions for R15' , R15", b, b' and D,
respectively, in Formula R-b-1.
Typical examples of the compound represented by
Formula R are shown below. The compounds usable in the
present invention are by no means limited by these.
The compound
having a radical-scavenging ability is not the same as the
compound having a singlet oxygen quenching rate constant
kq of not less than 1 x 108 M-1 s-1.
The compound having a radical-scavenging ability may
preferably have a radical-scavenging rate constant Ks in
the range of from 10-1 M-1 s-1 to 2 x 104 M-1 s-1, and more
preferably from 10-1 M-1 s-1to 103 M-1 s-1.
In the coupler
represented by Formula M-1 as previously set forth,
Z represents a group of non-metal atoms necessary to
complete a nitrogen-containing heterocyclic ring. The
ring formed by said Z may have a substitutent.
X represents a hydrogen atom or a group capable of
being split off upon reaction with an oxidized product of
a color developing agent.
R represents a hydrogen atom or a substituent.
There are no particular limitations on the
substituent represented by R. It may typically include
groups such as alkyl, aryl, anilino, acylamino,
sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl.
Besides these, it may also include a halogen atom, groups
such as cycloalkenyl, alkynyl, a heterocyclic ring,
sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl,
sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy,
siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido,
ureido, sulfamoylamino, alkoxycarbonylamino,
aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and
heterocyclic thio, a spiro compound residual group, and a
bridged hydrocarbon compound residual group.
The alkyl group represented by R may preferably
include those having 1 to 32 carbon atoms, which may be
either straight-chain or branched.
The aryl group represented by R may preferably
include a phenyl group.
The acylamino group represented by R may include an
alkylcarbonylamino group and an arylcarbonylamino group.
The sulfonamide group represented by R may include
an alkylsulfonylamino group and an arylsulfonylamino
group.
The alkyl component or aryl component in the
alkylthio group or arylthio group represented by R may
include the alkyl group or aryl group represented by R.
The alkenyl group represented by R may preferably
include those having 2 to 32 carbon atoms; and the
cycloalkyl group, those having 3 to 12 carbon atoms, and
particularly 5 to 7 carbon atoms. The alkenyl group may
be either straight-chain or branched.
The cycloalkenyl group represented by R may
preferably include those having 3 to 12 carbon atoms, and
particularly preferably 5 to 7 carbon atoms.
The sulfonyl group represented by R may include an
alkylsulfonyl group and an arylsulfonyl group;
the sulfinyl group may include an alkylsulfinyl
group and an arylsufinyl group; the phosphonyl group may include an alkylphosphonyl
group, an alkoxyphosphonyl group, an aryloxyphosphonyl
group and an arylphosphonyl group; the acyl group may include an alkylcarbonyl group
and an arylcarbonyl group; the carbamoyl group may include an alkylcarbamoyl
group and an arylcarbamoyl group; the sulfamoyl group may include an alkylsulfamoyl
group and an arylsulfamoyl group; the acyloxy group may include an alkylcarbonyloxy
group and arylcarbonyloxy group; the carbamoyloxy group may include an
alkylcarbamoyloxy group and an arylcarbamoyloxy group; the ureido group may include an alkylureido group
and an arylureido group; the sulfamoylamino group may include an
alkylsulfamoylamino group and an arylsulfamoylamino group; the heterocyclic group may preferably include those
of 5 to 7 members, specifically including a 2-furyl group,
a 2-thienyl group, a 2-pyrimidinyl group and a 2-benzothiazolyl
group; the heterocyclic oxy group may preferably include
those having a heterocyclic ring of 5 to 7 members,
including, for example, a 3,4,5,6-tetrahydropyranyl-2-oxy
group and a 1-phenyltetrazole-5-oxy group; the heterocyclic thio group may preferably include a
heterocyclic thio group of 5 to 7 members, including, for
example, a 2-pyridylthio group, a 2-benzothiazolylthio
group and a 2,4-diphenoxy-1,3,5-triazole-6-thio group; the siloxy group may include a trimethylsiloxy
group, a triethylsiloxy group and a dimethylbutylsiloxy
group; the imido group may include a succinimido group, a 3-heptadecylsuccinimido
group, a phthalimido group and a
glutalimido group; the spiro compound residual group may include
spiro[3.3]heptan-1-yl; and the bridged hydrocarbon compound residual group may
include bicylo[2.2.1]heptan-1-yl, tricyclo[3.3.1.13.7]
decan-1-yl and 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl.
The group represented by X, capable of being split
off through the reaction with an oxidized product of a
color developing agent, may include, for example, a
halogen atom such as a chlorine atom, a bromine atom or a
fluorine atom, and groups such as alkoxy, aryloxy,
heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy,
aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy,
alkylthio, arylthio, heterocyclic thio,
alkyloxythiocarbonylthio, acylamino, sulfonamido, a
nitrogen-containing heterocyclic ring bonded with a N
atom, alkyloxycarbonylamino, aryloxycarbonylamino,
carboxyl, and
wherein R
1' has the same definition for the above R, and
Z', the same definition for the above Z; and R
2' and R
3'
each represent a hydrogen atom, an aryl group, an alkyl
group or a heterocyclic group. It may preferably include
a nitrogen-containing heterocyclic group substituted via a
nitrogen atom, or a halogen atom, in particular, a
chlorine atom.
The nitrogen-containing heterocyclic group formed by
Z or Z' may include a pyrazole ring, an imidazole ring, a
triazole ring or a tetrazole ring, and the substituent the
above ring may have may include those described for the
above R.
The coupler represented by Formula M-I is more
specifically represented, for example, by the following
Formulas M-II to M-VII.
In the above Formulas M-II to M-VII, R1 to R8 and X
have the same definitions for the above R and X,
respectively.
Among Formula M-I, preferred is the one represented
by Formula M-VIII shown below.
In the formula, R1, X and Z1 have the same
definitions for R, X and Z, respectively, in Formula M-I.
Among the magenta couplers represented by Formulas M-II
to M-VII, particularly preferred magenta couplers are
the magenta couplers represented respectively by Formulas
M-II and M-III.
Among the substituents on the above heterocyclic
ring, at least one of them may preferably be a substituent
represented by the following Formula M-IX. Particularly
preferably, R
1 is the substituent of Formula M-IX.
In the formula, R9, R10 and R11 each have the same
definitions for the above R.
Any two of the above R9, R10 and R11, for example,
R9 and R10, may also combine to form a saturated or
unsaturated ring as exemplified by cycloalkane,
cycloalkene and a heterocyclic ring, and the ring thus
formed and R11 may further combine to form a bridged
hydrocarbon compound residual group.
Particularly preferred in Formula M-IX are (i) the
case when at least two of R9 to R11 are alkyl groups, and
(ii) the case when one of R9 to R11, for example, R11, is
a hydrogen atom, and other two, R9 and R10, combine to
form cycloalkyl together with the route carbon atom.
Still particularly preferred in (i) is the case when
any two of R9 to R11 are alkyl groups and the remaining
one is a hydrogen atom or an alkyl group.
The substituent the ring formed by Z in Formula M-I
or the ring formed by Z1 in Formula M-VIII may have, and
R2 to R8 in Formulas M-II to M-VI may preferably include
those represented by Formula M-X shown below.
Formula M-X -R12-SO2-R13
In the formula, R12 represents an alkylene group,
and R13 represents an alkyl group, a cycloalkyl group or
an aryl group.
The alkylene group represented by R12 may preferably
have two or more, more preferably 3 to 6, carbon atoms at
the straight-chain moiety, and may be straight-chain or
branched.
Typical examples of the compounds
are shown below.
In addition to the above typical examples of the
compounds employed in the present invention, examples of
the compounds which can be used in the present invention may also
be the compounds shown as Nos. 1 to 4, 6, 8 to 17, 19 to
24, 26 to 43, 45 to 59, 61 to 104, 106 to 121, 123 to 162
and 164 to 223 among the compounds disclosed in Japanese
Patent O.P.I. Publication No. 166339/1987, pages 66 to
122.
The magenta coupler represented by the above Formula
M-I
can be readily synthesized by those
skilled in the art, by making reference to Journal of the
Chemical Society, Perkin I (1977), 2047-2052, U.S. Patent
No. 3,725,067, Japanese Patent O.P.I. Publications No.
99437/1984, No. 42045/1983, No. 162548/1984, No.
171956/1984, No. 33552/1985, No. 43659/1985, No.
172982/1985 and No. 190779/1985, etc.
The magenta couplers can be
used usually in the range of from 1 x 10-3 mol to 1 mol,
and preferably from 1 x 10-2 mol to 8 x 10-1 mol, per mol
of silver halide.
The use couplers can also be
used in combination with magenta couplers of different
types.
Based on the magenta coupler
represented by Formula M-I, the compound having
a singlet oxygen quenching rate constant kq of not less
than 108 M-1s-1and the compound having a radical-scavenging
ability may each preferably be used in an
amount of from 5 mol % to 400 mol %, and more preferably
from 10 mol % to 250 mol %.
The compound having kq of not less than 108 M-1s-1
and the compound having a radical-scavenging ability may
be used in their total amount of from 10 mol % to 500 mol
%, and more preferably from 20 mol % to 400 mol %, based
on the magenta coupler
represented by Formuia M-I.
The compound having kq of not less than 108 M-1 s-1
and the compound having a radical-scavenging ability,
according to the present invention, may preferably be used
in a proportion of from 0.1 to 10, and more preferably in
the range of from 0.25 to 4.0, in molar ratio of the
former to the latter.
The magenta coupler
represented by Formula M-I, the compound having kq of not
less than 108 M s-1s-1and the compound having a radical-scavenging
ability (serving as stabilizing agents)
are used in the same layer. They may also be
used in such a way that the stabilizing agents are used in
a layer adjoining to the layer in which the coupler is
present.
The magenta coupler represented by Formula M-I, the
compound having kq of not less than 108 M-1s-1 and the
compound having a radical-scavenging ability, according to
the present invention can be added to the light-sensitive
material by various methods such as the solid-state
dispersion, the latex dispersion and the oil-in-water
emulsification dispersion.
For example, according to the oil-in-water
emulsification dispersion, hydrophobic additives such as
the magenta coupler may usually be dissolved in a high-boiling
organic solvent having a boiling point of 150°C or
more or a water-insoluble polymeric compound, optionally
together with a low-boiling and/or water-soluble organic
solvent to effect emulsification dispersion in a
hydrophilic binder such as an aqueous gelatin solution
using a surface active agent, and thereafter the resulting
emulsion may be added to the intended hydrophilic colloid
layer.
The light-sensitive material of the present
invention can be applied to, for example, color negative
and positive films and color photographic papers. The
present invention can be remarkably effective particularly
when applied to color photographic papers used for direct
viewing.
The silver halide used in the present invention may
include any silver halides such as silver chloride, silver
bromide, silver iodide, silver chlorobromide, silver
iodobromide and silver chloroiodide.
Silver halide grains preferably used in the present
invention may preferably have a silver chloride content of
not less than 90 mol %, a silver bromide content of not
more than 10 mol % and a silver iodide content of not more
than 0.5 mol %. They may more preferably be silver
chlorobromide grains having a silver bromide content of
from 0.1 mol % to 2 mol %.
The silver halide grains may be used alone, or may
also be used in combination with other silver halide
grains having different composition. They may also be
used in combination with silver halide grains having a
silver chloride content of not more than 90 mol %.
In the silver halide emulsion layer containing
silver halide grains having a silver chloride content of
not less than 90 mol %, the silver halide grains having a
silver chloride content of not less than 90 mol % are held
in a proportion of not less than 60 % by weight, and
preferably not less than 80 % by weight, in the whole
silver halide grains contained in the emulsion layer.
The composition of silver halide grains may be
uniform throughout a grain, from its inside to its outer
portion, or may be different between the inside and outer
portion of a grain. In the case when the composition of
the grain is different between the inside and the outer
portion, the composition may change continuously or
discontinuously.
There are no particular limitations on the grain
size of the silver halide grains according to the present
invention. Taking account of the rapid processing
performance and speed, and also other photographic
performances, it may be preferably in the range of from
0.2 µm to 1.6 µm, and more preferably from 0.25 µm to 1.2
µm. The above grain size can be measured by various
methods generally used in the present technical field.
Typical methods are described in Loveland, "Grain Size
Analytical Methods", A.S.T.M. Symposium on Light
Microscopy, 1955, pp.94-122, or Mees and James, "The
Theory of The Photographic Process", 3rd Ed., 2nd Chapter,
Macmillan Publishing Co., Inc. (1966).
This grain size can be measured by use of the
projected area or diameter approximate value of a grain.
If the grains are of substantially uniform shape, the
grain size distribution can be represented fairly
accurately as the diameter or projected area.
The grain size distribution of the silver halide
grains according to the present invention may be
polydisperse or monodisperse. Prefered are monodisperse
silver halide grains wherein, in the grain size
distribution of the silver halide grains, its coefficient
of variation is 0.22 or less, and preferably 0.15 or less.
Here, the coefficient of variation is a coefficient
indicating the breadth of the grain size distribution, and
can be defined by the following formula:
Coefficient of variation (S/r) = Standard deviation of grain size distribution Average grain size
Standard deviation (S) of grain size distribution = Σ(r - ri)2ni Σni
Average grain size (r) = ΣniriΣni
Here, ri represents the grain size of the individual
grains; and ni, its number. The grain size herein
mentioned indicates the diameter when a silver halide
grain is spherical; and, when it is cubic or of the form
other than the spherical, the diameter obtained by
calculating a projected image thereof as a round image
having the same area.
In the present invention, the silver halide grains
used in emulsions may be those obtained by any of the acid
method, the neutral method and the ammoniacal method. The
grains may be grown at one time, or may be grown after
making seed grains.
The method of making seed grains and the method of
growing them may be the same or different.
The manner by which soluble silver salts are reacted
with readily soluble halogen salts may be any of those
including the normal precipitation, the reverse
precipitation, the double-jet precipitation, and the
combination of any of these. Preferred are grains
obtained by the double-jet precipitation. As one manner
of the double-jet precipitation, it is also possible to
use the pAg-controlled double-jet precipitation described
in Japanese Patent O.P.I. Publication No. 48521/1979.
If necessary, a silver halide solvent such as
thioethers may also be used. A mercapto group-containing
compound, a nitrogen-containing heterocyclic compound or a
compound like a spectral sensitizer may also be used by
adding them at the time the silver halide grains are
formed or after the formation of grains has been
completed.
As the silver halide grains used in the present
invention, those of any shape can be used. A preferable
example thereof is a cube having { 100} face as a crystal
surface. It is also possible to prepare grains of the
shape such as an octahedron, a tetradecahedron or a
dodecahedron, according to the methods as disclosed in
publications such as U.S. Patents No. 4,183,756 and No.
4,225,666, Japanese Patent O.P.I. Publication No.
26589/1980, Japanese Patent Publication No. 42737/1980,
and The Journal of Photographic Science, 21, 39 (1973),
and put them into use. Grains with twin planes may also
be used.
The silver halide grains used in the present
invention may be comprised of grains having a single
shape, or comprised of a mixture of grains having various
shapes.
In the present invention, to the silver halide
grains used in emulsions, metal ions may be added using a
cadmium salt, a zinc salt, a lead salt, a thallium salt,
an iridium salt or a complex salt thereof, a rhodium salt
or a complex salt thereof, an iron salt or a complex salt
thereof, in the course the grains are formed and/or in the
course they are grown, whereby they can be incorporated in
the insides of the grains and/or the surfaces thereof.
Alternatively, the silver halide grains may be placed in a
reducing atmosphere, whereby reduction sensitization
nuclei can be imparted to the insides of the grains and/or
the surfaces of the grains.
From emulsions containing the silver halide grains,
excess soluble salts may be removed after the growth of
the silver halide grains has been completed, or they may
remain unremoved. In the case when the slats are removed,
they can be removed by the method described in Research
Disclosure No. 17643.
In the present invention, the silver halide grains
used in emulsions may be those in which a latent image is
mainly formed on the surfaces, or those in which it is
formed in the insides of grains. It is preferred to use
grains in which the latent image is mainly formed on the
surfaces.
In the present invention, the emulsions are
chemically sensitized by conventional methods. More
specifically, the sulfur sensitization making use of a
compound containing sulfur capable of reacting with silver
ions or an active gelatin, the selenium sensitization
making use of a selenium compound, the reduction
sensitization making use of a reducing substance and the
noble metal sensitization making use of a compound of
noble metal such as gold or the like can be used alone or
in combination.
The emulsions can also be spectrally sensitized to
the desired wavelength region, using a spectral
sensitizer. The spectral sensitizer that can be used may
include cyanine dyes, merocyanine dyes, composite cyanine
dyes, composite merocyanine dyes, holopolar cyanine dyes,
hemicyanine dyes, styryl dyes and hemioxanol dyes.
The dye forming couplers used in the light-sensitive
silver halide photographic material of the present
invention are usually so selected that the dye capable of
absorbing spectrum light to which an emulsion layer is
sensitive is formed with respect to each emulsion layer.
Thus, a yellow dye forming coupler is used in a blue-sensitive
emulsion layer, a magenta dye forming coupler in
a green-sensitive emulsion layer, and a cyan dye forming
coupler in a red-sensitive emulsion layer. However,
depending on the purpose, the light-sensitive silver
halide photographic material may be prepared by a method
in which the couplers are used in the manner different
from the above combination.
In the present invention, as the yellow dye forming
coupler, acylacetoanilide couplers can be preferably used.
In particular, benzoyl acetanilide compounds and pivaroyl
acetanilide compounds are advantageous, and those
particularly preferably usable are the exemplary compounds
Y-1 to Y-146 disclosed in Japanese Patent O.P.I.
Publication No. 85631/1988, the exemplary compounds Y-1 to
Y-98 disclosed in Japanese Patent O.P.I. Publication No.
97951/1988, the exemplary compounds I-1 to I-50 disclosed
in Japanese Patent O.P.I. Publication No. 298943/1990, and
the exemplary compounds Y-1 to Y-24 disclosed in Japanese
Patent Application No. 316996/1987.
In the present invention, in addition to the magenta
coupler represented by Formula M-I previously set forth, a
magenta coupler represented by the following Formula M-II
may also be used in combination.
In the formula, Ar represents an aryl group; X
represents a halogen atom, an alkoxyl group or an alkyl
group; and R represents a group capable of being
substituted on the benzene ring. The letter symbol n
represents 1 or 2. In the case when n is 2, the groups
R's may be the same or different. Y represents a group
capable of being split off upon reaction with an oxidized
product of an aromatic primary amine color developing
agent.
In Formula M-II, the group represented by Y, capable
of being split off upon reaction with an oxidized product
of an aromatic primary amine color developing agent may
include, for example, a halogen atom, an alkoxyl group, an
aryloxy group, an acyloxy group, an arylthio group, an
alkylthio group, and -N Z' wherein Z' represents a
group of atoms necessary to complete a ring of 5 or 6
members formed by an atom selected from a carbon atom, an
oxygen atom, a nitrogen atom and a sulfur atom, together
with the nitrogen atom. Here, Y does not represent a
hydrogen atom.
Examples of the group represented by Y are shown
below.
Halogen atom: Atoms such as chlorine, bromine and
fluorine.
Alkoxyl group: An ethoxy group, a benzoyloxy group,
a methoxyethylcarbamoylmethoxy group, a
tetradecylcarbamoylmethoxy group, etc.
Aryloxy group: A phenoxy group, a 4-methoxyphenoxy
group, a 4-nitrophenoxy group, etc.
Acyloxy group: An acetoxy group, a myristoyloxy
group, a benzoyloxy group, etc.
Arylthio group: a phenylthio group, a 2-butoxy-5-octylphenylthio
group, a 2,5-dihexyloxyphenylthio group,
etc.
Alkylthio group: A methylthio group, an octylthio
group, a hexadecylthio group, a benzylthio group, a 2-(diethylamino)ethylthio
group, an ethoxycarbonylmethylthio
group, an ethoxydiethylthio group, a phenoxyethylthio
group, etc.
-N Z': A pyrazolyl group, an imidazolyl group, a
triazolyl group, a tetrazolyl group, etc.
The coupler represented by Formula M-II may include,
for example, the exemplary compounds No. 218 to No. 244
disclosed in Japanese Patent O.P.I. Publication No.
52138/1988. It may further include those disclosed in
U.S. Patents No. 2,600,788, No. 3,061,432, No. 3,062,653,
No. 3,127,269, No. 3,311,476, No. 3,152,896, No.
3,419,391, No. 3,519,429, No. 3,555,318, No. 3,684,514,
No. 3,888,680, No. 3,907,571, No. 3,928,044, No.
3,930,861, No. 3,930,866 and No. 3,933,500, Japanese
Patent O.P.I. Publications No. 29639/1974, No.
111631/1974, No. 129538/1974, No. 13041/1975, No.
58922/1977, No. 62454/1980, No. 118034/1980, No.
38043/1981, No. 35858/1982, No. 2953/1985, No. 23855/1985,
No. 60644/1985, British Patent No. 1,247,493, Belgian
Patents No. 789,116 and 792,525, West German Patent No. 21
56 111, Japanese Patent Examined Publications No.
60479/1971 and No. 36577/1982.
The cyan coupler used in the present invention may
include naphthol type, phenol type and imidazole type
compounds.
The cyan coupler particularly preferably used in the
present invention may include cyan couplers represented by
the following Formulas C-I and C-II.
In the formula, Rc1 represents an alkyl group having
2 to 6 carbon atoms.
Rc2 represent a ballast group. Zc represents an
atom or group capable of being split off upon reaction
with an oxidized product of a color developing agent.
The alkyl group represented by Rc1 may be straight-chain
or branched, and may include those having a
substituent.
The ballast group represented by Rc2 is an organic
group having the size and shape that impart to coupler
molecules a bulkiness large enough for the coupler to be
substantially undiffusible from the layer to which the
coupler is applied, to other layer.
A group preferred as the ballast group is a group
represented by the following formula:
Rc3 represents an alkyl group having 1 to 12 carbon
atoms, Arc represents an aryl group such as a phenyl
group. This aryl group includes those having a
substituent.
The cyan coupler represented by Formula C-I can be
exemplified by the exemplary compounds PC-1 to PC-19
disclosed in Japanese Patent O.P.I. Publication No.
156748/1989, page 30, right upper column to page 31, left
upper column, the exemplary compounds C-1 to C-28
disclosed in Japanese Patent O.P.I. Publication No.
249151/1987, and also the cyan couplers as disclosed in
Japanese Patent Examined Publication No. 11572/1974,
Japanese Patent O.P.I. Publications No. 3142/1986, No.
9652/1986, No. 9653/1986, No. 390465/1986, No. 50136/1986,
No. 99141/1986 and No. 105545/1986. Examples are by no
means limited to these.
In the formula, Rc1 represents an alkyl group or an
aryl group. Rc2 represents an alkyl group, a cycloalkyl
group, an aryl group or a heterocyclic group. Rc3
represents a hydrogen atom, a halogen atom, an alkyl group
or an alkoxyl group. Rc3 and Rc1 may also combine to form
a ring. Zc represents a hydrogen atom or a group capable
of being split off upon reaction with an oxidized product
of a color developing agent.
In the cyan coupler represented by the above Formula
C-II, the alkyl group represented by Rc1 may preferably be
an alkyl group having 1 to 32 carbon atoms, these of which
may be straight-chain or branched, and may also include
those having a substituent.
The aryl group represented by Rc1 may preferably be
a phenyl group, and may include those having a
substituent.
The alkyl group represented by Rc2 may preferably be
an alkyl group having 1 to 32 carbon atoms. Such alkyl
group may be straight-chain or branched, and may include
those having a substituent.
The cycloalkyl group represented by Rc2 may
preferably be a cycloalkyl group having 3 to 12 carbon
atoms. Such cycloalkyl group may include those having a
substituent.
The aryl group represented by Rc2 may preferably be
a phenyl group, and may include those having a
substituent.
The heterocyclic group represented by Rc2 may
preferably be a heterocyclic ring of 5 to 7 members, and
may include those having a substituent. It may also be of
a condensed form.
Rc3 represents a hydrogen atom, a halogen atom, an
alkyl group or an alkoxyl group, where the alkyl group and
the alkoxyl group may include those having a substituent.
Rc3 may preferably be a hydrogen atom.
The ring formed by the combination of R
c1 and R
c3
may preferably include rings of 5 or 6 members, which can
be exemplified by the following:
The group represented by Zc, capable of being split
off upon reaction with an oxidized product of a color
developing agent may include a halogen atom, an alkoxyl
group, an aryloxy group, an acyloxy group, a sulfonyloxy
group, an acylamino group, a sulfonylamino group, an
alkoxycarbonyoxy group, an aryloxycarbonyloxy group and an
imide group, all of which may include those having a
substituent. It may preferably be a halogen atom, an
aryloxy group or an alkoxyl group.
Of the cyan couplers described above, a particularly
preferred one is a cyan coupler represented by the
following Formula C-II-A.
In the formula, RA1 represents a phenyl group
substituted with at least one halogen atom. Such a phenyl
group may include a phenyl group further having a
substituent other than the halogen atom. RA2 has the same
definition for Rc1 in Formula C-II previously described.
XA represents a halogen atom, an aryloxy group or an
alkoxyl group, and may include those having a substituent.
Typical examples of the cyan coupler represented by
Formula C-II are the exemplary compounds C-1 to C-25
disclosed in Japanese Patent O.P.I. Publication No.
96656/1985, the exemplary compounds PC-II-1 to PC-II-31
disclosed in Japanese Patent O.P.I. Publication No.
156748/1989, pages 32, left lower column to page 34, left
upper column, and besides the 2,5-diacylamino cyan
couplers as disclosed in Japanese Patent O.P.I.
Publication No. 178962/1987, page 7, right lower column to
page 9, left lower column, Japanese Patent O.P.I.
Publication No. 225155/1985, page 7, left lower column to
page 10, right lower column, Japanese Patent O.P.I.
Publication No. 222853/1985, page 6, left upper column to
page 8, right lower column, and Japanese Patent O.P.I.
Publication No. 185335/1984, page 6, left lower column to
page 9, left upper column. They can be synthesized
according to the method disclosed in these publications.
Hydrophobic compounds such as the dye forming
couplers as described above may usually be dissolved in a
high-boiling organic solvent having a boiling point of
about 150°C or above or a water-insoluble polymeric
compound, optionally together with a low-boiling and/or
water-soluble organic solvent to effect emulsification
dispersion in a hydrophilic binder such as an aqueous
gelatin solution using a surface active agent by the use
of a dispersion means such as a homogenizer, a colloid
mill, a flow-jet mixer and an ultrasonic apparatus, and
thereafter the resulting emulsion may be added to the
intended hydrophilic colloid layer. The step of removing
the low-boiling organic solvent at the same time of
carrying out the dispersion may also be inserted.
In the present invention, a solvent with a
dielectric constant of less than 6.0 may preferably be
used as the high-boiling organic solvent.
Any compounds can be used as the high-boiling
organic solvent preferably used in the present invention
so long as they are compounds with a dielectric constant
of less than 6.0. No particular limitation may be
required for its lower limit. In a preferred embodiment,
the compounds may have a dielectric constant of 1.9 or
more. They can be exemplified by esters such as phthalate
and phosphate, organic acid amides, ketones and
hydrocarbon compounds having dielectric constant of less
than 6.0.
In the present invention, it is preferred to use a
high-boiling organic solvent having a vapor pressure of
preferably not more than 0.5 mmHg at 100°C. It is more
preferred to use phthalates or phosphates among such high-boiling
organic solvents. The organic solvent may be
comprised of a mixture of two or more kinds. In this
instance, the mixture may have the dielectric constant of
less than 6.0. The dielectric constant herein referred to
indicates a dielectric constant measured at 30°C.
The phthalate advantageously used in the present
invention may include a compound represented by the
following Formula HA.
In the formula, RH1 and RH2 each represent an alkyl
group, an alkenyl group or an aryl group, provided that
the total sum of the carbon atom number of the groups
represented by RH1 and RH2 is from 9 to 32. More
preferably, the total sum of the carbon atom number is
from 16 to 24.
The alkyl group represented by RH1 and RH2 in the
above Formula HA may be straight-chain or branched. The
aryl group represented by RH1 and RH2 may include a phenyl
group, a naphthyl group, etc., and the alkenyl group, a
hexenyl group, a heptenyl group, an octadecenyl group,
etc. These alkyl group, alkenyl group and aryl group may
each have a substituent or substituents.
In the present invention, the phosphate
advantageously used in the present invention may include a
compound represented by the following Formula HB.
In the formula, RH3, RH4 and RH5 each represent an
alkyl group, an alkenyl group or an aryl group, provided
that the total sum of the carbon atom number of the groups
represented by RH3, RH4 and RH5 is from 24 to 54.
The alkyl group, alkenyl group and aryl group may
each have a substituent or substituents. Preferably, RH3,
RH4 and RH5 are each an alkyl group, which may include a
nonyl group, a n-decyl group, a sec-decyl group, a sec-dodecyl
group and a t-octyl group.
The above high-boiling organic solvent can be
exemplified by the exemplary organic solvents 1 to 22
disclosed in Japanese Patent O.P.I. Publication No.
166331/1987, page 41.
The polymer used for dispersing the couplers, which
is insoluble in water and soluble in an organic solvent,
may include the following:
(1) Vinyl polymers and copolymers. (2) Condensation polymers of polyhydric alcohols with
polybasic acids. (3) Polyesters obtained by ring-opening polymerization. (4) Others: Polycarbonate resins, polyurethane resins,
polyamide resins, etc.
There are no particular limitations on the number
average molecular weight of these polymers. It may
preferably be not more than 200,000, and more preferably
from 5,000 to 100,000. The proportion of the polymer to
the hydrophobic compounds such as couplers may preferably
be 1:20 to 20:1, and more preferably 1:10 to 10:1.
Examples of the polymer preferably used are shown
below. Copolymers are shown together with their weight
ratios.
(PO-1) Poly(N-t-butylacrylamide) (PO-2) N-t-butylacrylamide/methyl methacrylate copolymer
(60:40) (PO-3) Polybutyl methacrylate (PO-4) Methyl methacrylate/styrene copolymer (90:10) (PO-5) N-t-butylacrylamide/2-methoxyethyl acrylate
copolymer (55:45) (PO-6) ω-Methoxypolyethylene glycol acrylate (addition
molar number n = 9)/N-t-butylacrylamide copolymer
(25:75) (PO-7) 1,4-Butanediol-adipic acid polyester (PO-8) Polypropiolactam
As the binder (or protective colloid) used in the
light-sensitive silver halide photographic material of the
present invention, it is advantageous to use gelatin.
Besides gelatin, it is also possible to use hydrophilic
colloids such as gelatin derivatives, graft polymers of
gelatin with other macromolecules, proteins, sugar
derivatives, cellulose derivatives, and homopolymer or
copolymer synthetic hydrophilic polymeric substances.
In the light-sensitive silver halide photographic
material of the present invention, it is also possible to
optionally use additives such as hardening agents, color
contamination preventives, image stabilizers, ultraviolet
absorbents, plasticizers, latexers, surface active agents,
matting agents, lubricants and antistatic agents.
The gelatin coated on a support of the light-sensitive
material of the present invention may preferably
be in an amount of less than 7 g/m2 in total. No
particular limitation is required for its lower limit. In
general, it may preferably be not less than 3 g/m2 in view
of physical properties or photographic performance. The
amount of gelatin can be determined in terms of the weight
of gelatin containing 11.0 % of water, according to the
method of measuring water content as described in the PAGI
method.
The gelatin contained in the light-sensitive
material of the present invention is hardened using a
hardening agent. There are no particular limitations on
the hardening agent that can be used. It may include
hardening agents known in the photographic industrial
field, as exemplified by aldehyde type hardening agents,
active vinyl type hardening agents, active halogen type
hardening agents, epoxy type hardening agents,
ethyleneimine type hardening agents, methane sulfonate
type hardening agents, carbodiimide type hardening agents,
isooxazole type hardening agents, and polymeric hardening
agents.
The present invention can be particularly effective
when the light-sensitive material of the present invention
is used in direct-view light-sensitive materials such as
color photographic papers or color copying light-sensitive
materials on which there are severe demands for image
storage stability.
In the light-sensitive material of the present
invention, images can be formed by carrying out color
development processing known in the present industrial
field.
In the present invention, the color developing agent
used in the color developing solution may include
aminophenol derivatives and p-phenylenediamine derivatives
widely used in various color photographic processes.
To the color developing solution applied in the
processing of the light-sensitive material of the present
invention, known developing solution component compounds
can be added in addition to the primary aromatic amine
color developing agent previously mentioned.
The color developing solution may have a pH value of
not less than 9, and preferably from about 10 to about 13.
Color developing may be carried out at a temperature
of usually not lower than 15°C, and generally in the range
of from 20°C to 50°C.
For rapid processing, the color developing may
preferably be carried out at 30°C or above.
Development processing may generally be carried out
in 10 seconds to 4 minutes. When the rapid processing is
intended, the processing may preferably be carried out in
the range of from 10 seconds to 1 minute. When more rapid
processing is required, the processing may preferably be
carried out in the range of from 10 seconds to 30 seconds.
In instances in which the light-sensitive material
of the present invention is running processed while
continuously supplying a color developing solution
replenisher, the color developing solution may preferably
be replenished in an amount of from 20 ml to 150 ml, more
preferably from 20 ml to 120 ml, and still more preferably
from 20 ml to 100 ml, per 1 m2 of the light-sensitive
material. The present invention can be more effective
when such low-replenishment running processing is carried
out.
After the color developing has been completed, the
light-sensitive material of the present invention is
subjected to bleach-fixing.
After the bleach-fixing has been completed, the
light-sensitive material is usually subjected to washing
or stabilizing, or both of them in combination.
EXAMPLES
Specific examples of the present invention will be
given below. Embodiments of the present invention are by
no means limited to these.
Structures of additives used in the examples are
shown together in the last.
Example 1
(Preparation of silver halide emulsions)
Six kinds of silver halide emulsions shown below
were prepared by neutral and double-jet precipitation.
Emulsion No. | AgCl | AgBr | Av. grain size | Chemical sensitizer | Spectral sensitizer |
| (mol%) | (mol%) | (µm) |
Em-1 | 10 | 90 | 0.67 | Sodium thiosulfate | SD-1 |
Em-2 | 30 | 70 | 0.46 | " | SD-2 |
Em-3 | 30 | 70 | 0.43 | " | SD-3 |
Em-4 | 99.5 | 0.5 | 0.67 | Sodium thiosulfate + Sodium chloroaurate | SD-1 |
Em-5 | 99.5 | 0.5 | 0.46 | " | SD-2 |
Em-6 | 99.5 | 0.5 | 0.43 | " | SD-3 |
The respective silver halide emulsions were
chemically sensitized. After completion of the
sensitization, STB-1 was added as an emulsion stabilizer
in an amount of 2 x 10-4 mol per mol of silver halide.
(Preparation of light-sensitive silver halide color
photographic materials)
On a laminated support comprising a paper support
one side of which was coated with polyethylene and the
first layer side on the other side of which was coated
with polyethylene containing titanium oxide, layers with
the constitution as shown below were formed by coating to
give a multilayer light-sensitive silver halide color
photographic material. Coating solutions were prepared in
the following way.
First layer coating solution:
To a mixture of 26.7 g of a yellow coupler (Y-1),
0.67 g of an anti-stain agent (HQ-1) and 13.3 g of a high-boiling
organic solvent (DNP), 60 ml of ethyl acetate was
added to effect dissolution. The resulting solution was
emulsifyingly dispersed in 200 ml of an aqueous 10 %
gelatin solution containing 10 ml of 10 % sodium
alkylnaphthalenesulfonate, using a homogenizer to produce
a yellow coupler dispersion.
The dispersion thus obtained was mixed together with
a blue-sensitive silver chlorobromide emulsion (Em-1, 10 g
in terms of silver) and a coating gelatin solution to give
a first-layer coating solution.
Second-layer to seventh-layer coating solutions were
also prepared in the same manner as the first-layer
coating solution.
As hardening agents, a compound (H-1) was added to
the second and fourth layers, and (H-2) to the seventh
layer. As coating aids, surface active agents (SU-2), (SU-3)
were added to make adjustment of surface tension.
Layer | Constitution | Amount |
| | (g/m2) |
Seventh layer (Protective layer) | Gelatin | 1.00 |
Sixth layer (UV absorbing layer) | Gelatin | 0.40 |
Ultraviolet absorbent (UV-1) | 0.10 |
Ultraviolet absorbent (UV-2) | 0.04 |
Ultraviolet absorbent (UV-3) | 0.16 |
Anti-stain agent (HQ-1) | 0.01 |
DNP | 0.20 |
PVP | 0.03 |
Fifth layer (Red-sensitive layer) | Gelatin | 1.30 |
Red-sensitive silver chlorobromide |
emulsion (Em-3) | 0.21 |
Cyan coupler (C-1) | 0.24 |
Cyan coupler (C-2) | 0.08 |
Dye image stabilizer (ST-1) | 0.20 |
Anti-stain agent (HQ-1) | 0.01 |
| HBS-1 | 0.20 |
| DOP | 0.20 |
Fourth layer (UV absorbing layer) | Gelatin | 0.94 |
Ultraviolet absorbent (UV-1) | 0.28 |
Ultraviolet absorbent (UV-2) | 0.09 |
Ultraviolet absorbent (UV-3) | 0.38 |
Anti-stain agent (HQ-1) | 0.03 |
DNP | 0.40 |
Third layer (Green-sensitive layer) | Gelatin | 1.40 |
Green-sensitive silver chlorobromide |
emulsion (Em-2) | 0.17 |
Magenta coupler (MM-1) | 0.35 |
Dye image stabilizer (1) (as shown in |
Table 1) | 0.20 |
Dye image stabilizer (2) (as shown in |
Table 1) | 0.20 |
DNP | 0.20 |
Second layer (Intermediate layer) | Gelatin | 1.20 |
Anti-stain agent (HQ-2) | 0.12 |
DIDP | 0.15 |
First layer | Gelatin | 1.20 |
(Blue-sensitive layer) | Blue-sensitive silver chlorobromide |
emulsion (Em-1) | 0.26 |
Yellow coupler (Y-1) | 0.80 |
Dye image stabilizer (ST-1) | 0.30 |
Dye image stabilizer (ST-2) | 0.20 |
Anti-stain agent (HQ-1) | 0.02 |
DNP | 0.20 |
Support | Polyethylene-laminated paper |
The amounts of silver halide emulsions added are expressed
in terms of silver.
- DOP:
- Dioctyl phthalate
- DNP:
- Dinonyl phthalate
- DIDP:
- Diisodecyl phthalate
- PVP
- Polyvinyl pyrrolidone
The dye image stabilizers (1) and (2) were changed
as shown in Table 1 to produce samples 102 to 140.
Samples thus obtained were subjected to wedge
exposure using green light by means of a sensitometer KS-7
(manufactured by Konica Corporation), and were processed
according to the following color processing steps. After
the processing was completed, evaluation was made on the
items shown later.
Processing steps | Time | Temp. |
Color developing | 3 min. 30 sec. | 33°C |
Bleach-fixing | 1 min. 30 sec. | 33°C |
Washing | 3 min. | 33°C |
Formulation of color developing solution |
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- |
aminoaniline sulfate | 4.9 g |
Hydroxylamine sulfate | 2.0 g |
Potassium carbonate | 25.0 g |
Sodium bromide | 0.6 g |
Anhydrous sodium sulfite | 2.0 g |
Benzyl alcohol | 13.0 ml |
Polyethylene glycol (average degree of polymerization: 400) | 3.0 ml |
Made up to 1 liter by adding water, and adjusted to pH 10.0 using sodium hydroxide. |
Formulation of bleach-fixing solution |
Ferric sodium ethylenediaminetetraacetate | 6.0 g |
Ammonium thiosulfate | 100 g |
Sodium bisulfite | 10 g |
Sodium metabisulfite | 3 g |
Made up to 1 liter by adding water, and adjusted to pH 7.0 using ammonia water |
On the samples 101 to 140 thus processed, densities
were measured using a densitometer (Type KD-7R,
manufactured by Konica Corporation) under the following
conditions.
The above samples having been processed were stored
for 2 weeks under sunlight (on an exposure stand) to
examine fastness to light of dye images.
The fastness to light of dye images was evaluated on
the following items.
- Retention -
Percentage of the dye remaining after light fastness
tests, with respect to the initial density 1.0.
- Degree of discoloration -
A value obtained by subtracting the (yellow
density)/(magenta density) before light fastness tests
from the (yellow density)/(magenta density) after light
fastness tests started at the initial density 1.0. The
larger this value is, the more the color tends to change
from magenta to a yellowish tone.
Results obtained are shown in Table 1.
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks M-1 s-1 | Retention (2 w.) (%) | Discoloration |
101(X) | - | - | - | - | 65 | 0.59 |
102(X) | - | - | Cp.RH-1 | 0 | 67 | 0.14 |
103(X) | - | - | Ex.R-47 | 3x10 1 | 81 | 0.17 |
104(X) | - | - | Ex.R-29 | 8 | 78 | 0.18 |
105(X) | - | - | Ex.R-1 | 3x10 | 80 | 0.16 |
106(X) | - | - | Ex.R-23 | 1x102 | 79 | 0.18 |
107(X) | - | - | Ex.R-4 | 5x103 | 77 | 0.17 |
108(X) | Cp.QH-1 | 2x106 | - | - | 68 | 0.18 |
109(X) | Cp.QH-1 | 2x106 | Cp.RH-1 | 0 | 70 | 0.19 |
110(X) | Cp.QH-1 | 2x106 | Ex.R-47 | 3x10 1 | 85 | 0.14 |
111(X) | Cp.QH-1 | 2x106 | Ex.R-29 | 8 | 82 | 0.13 |
112(X) | Cp.QH-1 | 2x106 | Ex.R-1 | 3x10 | 83 | 0.13 |
113(X) | Cp.QH-1 | 2x106 | Ex.R-23 | 1x102 | 82 | 0.14 |
114(X) | Cp.QH-1 | 2x106 | Ex.R-4 | 5x102 | 80 | 0.16 |
115(X) | Cp.QH-2 | 8x107 | - | - | 79 | 0.17 |
X: Comparative Example, Y: Present Invention |
Cp.: Comparative, Ex.: Exemplary |
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1s-1) | Retention (2 w.) (%) | Discoloration |
116(X) | Cp.QH-2 | 8x107 | Cp . RH-1 | 0 | 80 | 0.19 |
117(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | 88 | 0.07 |
118(X) | Cp.QH-2 | 8x107 | Ex.R-29 | 8 | 89 | 0.08 |
119(X) | Cp.QH-2 | 8x107 | Ex.R-1 | 3x10 | 88 | 0.08 |
120(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | 89 | 0.07 |
121(X) | Cp.QH-2 | 8x107 | Ex.R-4 | 5x103 | 84 | 0.10 |
122(X) | EX.Q-48 | 1x108 | - | - | 77 | 0.16 |
123(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | 78 | 0.15 |
124(X) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | 94 | 0.05 |
125(X) | EX.Q-48 | 1x108 | Ex.R-29 | 8 | 92 | 0.05 |
126(X) | EX.Q-48 | 1x108 | Ex.R-1 | 3x10 | 93 | 0.06 |
127(X) | EX.Q-48 | 1x108 | Ex.R-23 | 1x102 | 92 | 0.05 |
128(X) | EX.Q-48 | 1x108 | Ex.R-4 | 5x103 | 90 | 0.08 |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | Retention (2 w.) (%) | Discoloration |
133(Y) | Ex.Q-34 | 7x108 | Ex.R-47 | 3x10-1 | 92 | 0.06 |
134(Y) | Ex.Q-34 | 7x108 | Ex.R-29 | 8 | 89 | 0.07 |
135(Y) | Ex.Q-34 | 7x108 | Ex.R-1 | 3x10 | 91 | 0.05 |
136(Y) | Ex.Q-34 | 7x108 | Ex.R-23 | 1x102 | 92 | 0.06 |
X: Comparative Example, Y: Present Invention |
As is clear from the results shown in Table 1,
improvements have been achieved, but less effectively, in
both the dye retention and the prevention of discoloration
in the light fastness tests when the compound according to
the present invention having the radical-scavenging
ability is used alone. Improvements have been also
achieved, but less effectively, in both the dye retention
and the prevention of discoloration in the light fastness
tests when the compound according to the present invention
having the singlet oxygen quenching rate constant kq of
not less than 108 M-1s-1 is used alone. In the instances
in which the compound according to the present invention
having the radical-scavenging ability and the comparative
compound QH-1 with kq of 2 x 106 M-1s-1 are used in
combination (Samples 108 to 114), improvements can be seen
compared with the instances in which they are not used in
combination, but the effect is unsatisfactory.
On the other hand, in the instances where the
compound according to the present invention having the
radical-scavenging ability and the compound according to
the present invention having the kq of not less than 108
M-1s-1 are used at the same time (Samples 124 to 140),
improvements have been achieved in both the dye retention
and the prevention of discoloration in the light fastness
tests, to the extent that can not be expected when the
compound having the radical-scavenging ability and the
compound having the kq of not less than 108 M-1s-1 are
respectively used alone (Samples 102 to 107 and 122).
Improvements are also found to have been
particularly remarkably achieved in both the dye retention
and the prevention of discoloration in the light fastness
tests when the compound having the radical-scavenging rate
constant Ks of 10-1 to 103 M-1s-1 and the compound having
the kq of not less than 108 M-1s-1 are used at the same
time.
Example 2
Multilayer light-sensitive silver halide color
photographic materials were produced in the same manner as
in Example 1 except that the blue-sensitive silver
chlorobromide emulsion Em-1 in the first layer, the green-sensitive
silver chlorobromide emulsion Em-2 in the third
layer and the red-sensitive silver chlorobromide emulsion
Em-3 in the fifth layer were replaced with Em-4, Em-5 and
Em-6, respectively.
Samples thus obtained were subjected to wedge
exposure in the same manner as in Example 1, and were
processed according to the following color processing
steps. Thereafter, evaluation similar to that in Example
1 was also made.
Results obtained are shown in Table 2.
Processing steps | Temp. | Time |
Color developing | 35.0 ±0.3°C | 45 sec. |
Bleach-fixing | 35.0 ±0.5°C | 45 sec. |
Stabilizing | 30 to 34°C | 90 sec. |
Drying | 60 to 80°C | 60 sec. |
Bleach-fixing solution |
Ferric ammonium ethylenediaminetetraacetate dihydrate | 60 g |
Ethylenediaminetetraacetic acid | 3 g |
Ammonium thiosulfate (aqueous 70 % solution) | 100 ml |
Ammonium sulfite (aqueous 40 % solution) | 27.5 ml |
Made up to 1 liter by adding water, and adjusted to pH 6.2 using potassium carbonate or glacial acetic acid. |
Stabilizing solution |
5-Chloro-2-methyl-4-isothiazolin-3-on | 1.0 g |
Ethylene glycol | 1.0 g |
1-Hydroxyethylidene-1,1-diphosphonic acid | 2.0 g |
Ethylenediaminetetraacetic acid | 1.0 g |
Ammonium hydroxide (aqueous 20 % solution) | 3.0 g |
Ammonium sulfite | 3.0 g |
Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative) | 1.5 g |
Made up to 1 liter by adding water, and adjusted using to pH 7.0 sulfuric acid or potassium hydroxide. |
Color developing solution |
Pure water | 800 ml |
Triethanolamine | 10 g |
N,N-diethylhydroxyamine | 5 g |
Potassium bromide | 0.02 g |
Potassium chloride | 2 g |
Potassium sulfite | 0.3 g |
1-Hydroxyethylidene-1,1-diphosphonic acid | 1.0 g |
Ethylenediaminetetraacetic acid | 1.0 g |
Disodium catechol-3,5-diphosphonate | 1.0 g |
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate | 4.5 g |
Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative) | 1.0 g |
Potassium carbonate | 27 g |
Made up to 1 liter in total by adding water, and adjusted to pH 10.10. |
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1s-1) | Retention (2 w.) (%) | Discoloration |
201(X) | - | - | - | | 64 | 0.60 |
202(X) | - | - | Cp.RH-1 | 0 | 66 | 0.13 |
203(X) | - | - | Ex.R-47 | 3x10-1 | 80 | 0.16 |
204(X) | - | - | Ex.R-29 | 8 | 78 | 0.17 |
205(X) | - | - | Ex.R-1 | 3x10 | 80 | 0.17 |
206(X) | - | - | Ex.R-23 | 1x102 | 80 | 0.16 |
207(X) | - | - | Ex.R-4 | 5x103 | 76 | 0.16 |
208(X) | Cp.QH-1 | 2x106 | - | - | 67 | 0.18 |
209(X) | Cp.QH-1 | 2x106 | Cp.RH-1 | 0 | 69 | 0.20 |
210(X) | Cp.QH-1 | 2x106 | Ex.R-47 | 3x10-1 | 84 | 0.13 |
211(X) | Cp.QH-1 | 2x106 | Ex.R-29 | 8 | 81 | 0.14 |
212(X) | Cp.QH-1 | 2x106 | Ex.R-1 | 3x10 | 82 | 0.13 |
213(X) | Cp.QH-1 | 2x106 | Ex.R-23 | 1x102 | 82 | 0.14 |
214(X) | Cp.QH-1 | 2x106 | Ex.R-4 | 5x103 | 80 | 0.15 |
215(X) | Cp.QH-2 | 8x107 | - | - | 78 | 0.19 |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | Retention (2 w.) (%) | Discoloration |
216(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | 80 | 0.18 |
217(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | 88 | 0.07 |
219(X) | Cp.QH-2 | 8x107 | Ex.R-1 | 3x10 | 87 | 0.08 |
220(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | 88 | 0.08 |
221(X) | Cp.QH-2 | 8x107 | Ex.R-4 | 5x103 | 84 | 0.11 |
222(X) | Ex.Q-48 | 1x108 | - | - | 78 | 0.15 |
223(X) | Ex.Q-48 | 1x108 | Cp.RH-1 | 0 | 79 | 0.14 |
224(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10 1 | 93 | 0.04 |
225(Y) | Ex.Q-48 | 1x108 | Ex.R-29 | 8 | 93 | 0.05 |
226(Y) | Ex.Q-48 | 1x108 | Ex.R-1 | 3x10 | 93 | 0.06 |
227(Y) | Ex.Q-48 | 1x108 | Ex.R-23 | 1x102 | 92 | 0.05 |
228(Y) | Ex.Q-48 | 1x108 | Ex.R-4 | 5x103 | 91 | 0.07 |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | Retention (2 w.) (%) | Discoloration |
233(Y) | Ex.Q-34 | 7x108 | Ex.R-47 | 3x10-1 | 92 | 0.06 |
234(Y) | Ex.Q-34 | 7x108 | Ex.R-29 | 8 | 90 | 0.08 |
235(Y) | Ex.Q-34 | 7x108 | Ex.R-1 | 3x10 | 91 | 0.06 |
236(Y) | Ex.Q-34 | 7x108 | Ex.R-23 | 1x102 | 92 | 0.07 |
X: Comparative Example, Y: Present Invention |
As is clear from Table 2, improvements have been
achieved in both the dye retention and the prevention of
discoloration in the light fastness tests even when the
silver halide emulsion having a silver chloride content of
99.5 % is used and the rapid processing is carried out in
the developing time of 45 seconds, if the compound
according to the present invention having the radical-scavenging
ability and the compound having the kq of not
less than 108 M-1s-1 are used as dye image stabilizers at
the same time.
Example 3
The dye image stabilizers (1) and (2) in Example 2
were replaced as shown in Table 3. The light-sensitive
materials obtained were subjected to wedge exposure in the
same manner as in Example 1, and were processed according
to the color development processing steps like those in
Example 2. Thereafter, the light-sensitive materials thus
processed were stored for a month under sunlight, and then
the same evaluation as in Example 1 was made.
Results obtained are shown in Table 3.
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1s-1) | Retention (1 m.) (%) | Discoloration |
301(X) | - | - | - | - | 48 | 0.90 |
302(X) | Cp.QH-2 | 8x107 | - | - | 53 | 0.54 |
303(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | 56 | 0.52 |
304(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | 65 | 0.46 |
305(X) | Cp.QH-2 | 8x107 | Ex.R-29 | 8 | 63 | 0.45 |
306(X) | Cp.QH-2 | 8x107 | Ex.R-1 | 3x10 2 | 62 | 0.44 |
307(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x10 | 63 | 0.43 |
308(X) | Cp.QH-2 | 8x107 | Ex.R-4 | 5x103 | 62 | 0.45 |
309(X) | Ex.Q-48 | 1x108 | - | - | 56 | 0.42 |
310(X) | Ex.Q-48 | 1x108 | Cp.RH-1 | 0 | 57 | 0.43 |
311(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | 78 | 0.32 |
312(Y) | Ex.Q-48 | 1x108 | Ex.R-29 | 8 | 77 | 0.31 |
313(Y) | Ex.Q-48 | 1x108 | Ex.R-1 | 3x10 | 78 | 0.32 |
314(Y) | Ex.Q-48 | 1x10-8 | Ex.R-23 | 1x102 | 77 | 0.34 |
315(Y) | Ex.Q-48 | 1x108 | Ex.R-4 | 5x103 | 74 | 0.32 |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1s-l) | Retention (1 m.) (%) | Discoloration |
316(Y) | Ex.Q-34 | 7x108 | Ex.R-47 | 3x10 -1 | 77 | 0.32 |
317(Y) | Ex.Q-34 | 7x108 | Ex.R-29 | 8 | 75 | 0.33 |
318(Y) | Ex.Q-34 | 7x108 | Ex.R-1 | 3x10 | 77 | 0.35 |
319(Y) | Ex.Q-34 | 7x108 | Ex.R-23 | 1x102 | 78 | 0.32 |
X: Comparative Example, Y: Present Invention |
As is clear from Table 3, improvements have been
achieved, but less effectively, in both the dye retention
and the prevention of discoloration in the light fastness
tests continued for as long as one month, when the
comparative compound QH-2 with kq of 8 x 107 M-1s-1 and
the compound having the radical-scavenging ability are
used at the same time.
On the other hand, in the instances where the
compound according to the present invention having the kq
of not less than 108 M-1s-1 and the compound having the
radical-scavenging ability are used at the same time,
surprising improvements have been achieved in both the dye
retention and the prevention of discoloration.
From the above results, it is understood that a
superior fastness to light can be promised when the
compound according to the present invention having the kq
of not less than 108 M-1s-1 and the compound having the
radical-scavenging ability are used at the same time.
Example 4
The magenta coupler MM-1 and the dye image
stabilizers (1) and (2) in Example 2 were replaced as
shown in Table 4. The same evaluation as in Example 1 was
made.
Results obtained are shown in Table 4.
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | [1] | [2] (%) | [3] |
401(X) | - | - | - | - | MM-1 | 64 | 0.59 |
402(X) | Cp.QH-2 | 8x107 | - | - | MM-1 | 79 | 0.20 |
403(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | MM-1 | 80 | 0.19 |
404(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | MM-1 | 88 | 0.07 |
405(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | MM-1 | 89 | 0.08 |
406(X) | EX.Q-48 | 1x108 | - | - | MM-1 | 79 | 0.16 |
407(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | MM-1 | 80 | 0.15 |
408(Y) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10 -1 | MM-1 | 95 | 0.04 |
409(Y) | EX.Q-48 | 1x108 | Ex.R-23 | 1x10-2 | MM-1 | 92 | 0.06 |
410(X) | EX.Q-48 | 1x108 | - | - | MM-2 | 73 | 0.55 |
411(X) | EX.QH-2 | 8x107 | - | - | MM-2 | 81 | 0.17 |
412(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | MM-2 | 84 | 0.16 |
413(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | MM-2 | 91 | 0.06 |
414(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | MM-2 | 91 | 0.07 |
415(X) | EX.Q-48 | 1x108 | - | - | MM-2 | 81 | 0.13 |
[1]: Magenta coupler, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | [1] | [2]
(%) | [3] |
416(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | MM-2 | 82 | 0.12 |
417(Y) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10 -1 | MM-2 | 94 | 0.04 |
418(Y) | EX.Q-48 | 1x108 | Ex.R-23 | 1x10-2 | MM-2 | 92 | 0.04 |
419(X) | EX.Q-48 | 1x108 | - | - | MM-3 | 71 | 0.57 |
420(X) | Cp.QH-2 | 8x107 | - | - | MM-3 | 81 | 0.17 |
421(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | MM-3 | 84 | 0.16 |
422(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | MM-3 | 90 | 0.05 |
423(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x10-2 | MM-3 | 90 | 0.06 |
424(X) | EX.Q-48 | 1x108 | - | - | MM-3 | 80 | 0.13 |
425(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | MM-3 | 80 | 0.14 |
426(Y) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10 -1 | MM-3 | 95 | 0.04 |
427(Y) | EX.Q-48 | 1x108 | Ex.R-23 | 1x10-2 | MM-3 | 93 | 0.04 |
428(X) | EX.Q-48 | 1x108 | - | - | MM-4 | 66 | 0.58 |
429(X) | EX.QH-2 | 8x107 | - | - | MM-4 | 80 | 0.19 |
430(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | MM-4 | 80 | 0.17 |
[1]: Magenta coupler, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | [1] | [2]
[%] | [3] |
431(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | MM-4 | 88 | 0.06 |
432(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | MM-4 | 88 | 0.07 |
433(X) | EX.Q-48 | 1x108 | - | - | MM-4 | 80 | 0.14 |
434(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | MM-4 | 80 | 0.13 |
435(Y) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10 -1 | MM-4 | 94 | 0.05 |
436(Y) | EX.Q-48 | 1x108 | Ex.R-23 | 1x102 | MM-4 | 93 | 0.06 |
[1]: Magenta coupler, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
As is clear from Table 4, improvements have been
achieved in both the dye retention and the prevention of
discoloration in the light fastness, when the magenta
coupler was replaced with the 5-pyrazolone coupler MM-2
and when the compound according to the present invention
having the kq of not less than 108 M-1s-1 and the compound
having the radical-scavenging ability are used at the same
time.
Also when the pyrazolotriazole couplers MM-1, MM-3
and MM-4 are used, which have a superior color
reproduction quality to conventionally used 5-pyrazolone
couplers but have an inferior fastness to light,
improvements have been achieved particularly in both the
dye retention and the prevention of discoloration in the
light fastness when the compound according to the present
invention having the kq of not less than 108 M-1s-1 and
the compound having the radical-scavenging ability are
used at the same time.
Example 5
Samples produced in Example 3 were subjected to
wedge exposure in the same manner as in Example 1, and
thereafter processed according to the following processing
steps until a color developing solution was replenished
with a color developing solution replenisher in the amount
three times the tank capacity of the color developing
solution.
Processing steps | Temp. | Time |
Color developing | 35.0 ±0.3°C | 45 sec. |
Bleach-fixing | 35.0 ±0.3°C | 45 sec. |
Stabilizing | 30 to 34°C | 90 sec. |
Drying | 60 to 80°C | 60 sec. |
Processing solutions each had the composition as
shown below.
The color developing solution was replenished in an
amount of 160 ml in the case of A, 110 ml in the case of B
or 80 ml in the case of C, per 1 m2 of the light-sensitive
silver halide photographic material.
Color developing solution
(a) Pure water
(b) Triethanolamine
(c) N,N-diethylhydroxyamine
(d) Potassium chloride
(e) 1-Hydroxyethylidene-1,1-diphosphonic acid
(f) N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline
sulfate
(g) Fluorescent brightening agent (4,4'-diaminostilbene
disulfonic acid derivative)
(h) Potassium carbonate
(i) By adding water, made up to:
(j) pH
Tank solution |
Replenishing solution |
|
A |
B |
C |
A |
B |
C |
(a) |
800 ml |
800 ml |
800 ml |
800 ml |
800 ml |
800 ml |
(b) |
10 g |
10 g |
10 g |
13 g |
15 g |
18 g |
(c) |
5 g |
5 g |
5 g |
7 g |
8 g |
9 g |
(d) |
2 g |
2.2 g |
2.4 g |
0.1 g |
- |
- |
(e) |
1.0 g |
1.0 g |
1.0 g |
1.3 g |
1.5 g |
1.8 g |
(f) |
5.0 g |
5.2 g |
5.4 g |
7.2 g |
7.6 g |
8.2 g |
(g) |
1.0 g |
1.0 g |
1.0 g |
1.3 g |
1.5 g |
1.8 g |
(h) |
27 g |
27 g |
27 g |
27 g |
27 g |
27 g |
(i) |
1 lit |
1 lit |
1 lit |
1 lit |
1 lit |
1 lit |
(j) |
10.10 |
10.10 |
10.10 |
10.10 |
10.10 |
10.10 |
Bleach-fixing solution |
(Common to the tank solution and the replenishing solution) |
Ferric ammonium ethylenediaminetetraacetate dihydrate |
60 g |
Ethylenediaminetetraacetic acid |
3 g |
Ammonium thiosulfate (aqueous 70 % solution) |
100 ml |
Ammonium sulfite (aqueous 40 % solution) |
27.5 ml |
Made up to 1 liter in total by adding water, and adjusted to pH 5.7 using potassium carbonate or glacial acetic acid. |
Stabilizing solution |
(Common to the tank solution and the replenishing solution) |
5-Chloro-2-methyl-4-isothiazolin-3-on |
1.0 g |
Ethylene glycol |
1.0 g |
1-Hydroxyethylidene-1,1-diphosphonic acid |
2.0 g |
Ethylenediaminetetraacetic acid |
1.0 g |
Ammonium hydroxide (aqueous 20 % solution) Fluorescent brightening agent (4,4'-diaminostilbene |
3.0 g |
disulfonic acid derivative) |
1.5 g |
Made up to 1 liter in total by adding water, and adjusted to pH 7.0 using sulfuric acid or potassium hydroxide. |
Using the samples having been continuously
processed, evaluation was made in the following way.
On the samples 501 to 542, densities were measured
using a densitometer (Type KD-7R, manufactured by Konica
Corporation) under he following conditions.
The above samples having been processed were stored
for 2 weeks under sunlight (on an exposure stand) to
examine the fastness to light of dye images.
The fastness to light of dye images was evaluated on
the following items.
- Retention -
Percentage of the dye remaining after light fastness
tests, with respect to the initial density 1.0.
- Stain -
An increase in green density at the minimum density
portions of dye images with respect to its initial
density.
Results obtained are shown in Table 5.
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | [1] | [2]
(%) | [3] |
501(X) | - | - | - | - | A | 64 | 0.15 |
502(X) | Cp.QH-2 | 8x107 | - | - | A | 79 | 0.08 |
503(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | A | 80 | 0.07 |
504(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | A | 88 | 0.05 |
505(X) | Cp.QH-2 | 8x107 | Ex.R-29 | 8 | A | 88 | 0.06 |
506(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | A | 88 | 0.05 |
507(X) | EX.Q-48 | 1x108 | - | - | A | 77 | 0.08 |
508(X) | EX.Q-48 | 1x108 | Cp.RH-1 | 0 | A | 78 | 0.08 |
509(Y) | EX.Q-48 | 1x108 | Ex.R-47 | 3x10 -1 | A | 93 | 0.05 |
510(Y) | EX.Q-48 | 1x108 | Ex.R-29 | 8 | A | 92 | 0.04 |
511(Y) | EX.Q-48 | 1x108 | Ex.R-23 | 1x102 | A | 91 | 0.04 |
515(X) | - | - | - | - | B | 62 | 0.18 |
[1]: Processing, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye image stabilizer (1) | Kq (M-1 s-1) | Dye image stabilizer (2) | Ks (M-1 s-1) | [1] | [2]
(%) | [3] |
516(X) | Cp.QH-2 | 8x107 | - | - | B | 73 | 0.11 |
517(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | B | 76 | 0.10 |
518(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10 -1 | B | 84 | 0.07 |
519(X) | Cp.QH-2 | 8x107 | Ex.R-29 | 8 | B | 83 | 0.09 |
520(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | B | 84 | 0.07 |
521(X) | Ex.Q-48 | 1x108 | - | - | B | 73 | 0.10 |
522(X) | Ex.Q-48 | 1x108 | Cp.RH-1 | 0 | B | 75 | 0.09 |
523(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | B | 92 | 0.05 |
524(Y) | Ex.Q-48 | 1x108 | Ex.R-29 | 8 | B | 91 | 0.06 |
525(Y) | Ex.Q-48 | 1x108 | Ex.R-23 | 1x102 | B | 89 | 0.04 |
529(X) | - | - | - | - | C | 60 | 0.23 |
530(X) | Cp.QH-2 | 8x107 | - | - | C | 70 | 0.15 |
[1]: Processing, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
Sample No. | Dye stabilizer (1) | Kq (M-1 s-1 ) | Dye image stabilizer (2) | Ks (M-1 s-1 ) | [1] | [2]
(%) | [3] |
531(X) | Cp.QH-2 | 8x107 | CP.RH-1 | 0 | C | 73 | 0.16 |
532(X) | CP.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | C | 81 | 0.11 |
533(X) | Cp.QH-2 | 8x107 | Ex.R-29 | 8 | C | 80 | 0.12 |
534(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | C | 81 | 0.13 |
535(X) | Ex.Q-48 | 1x108 | - | - | C | 70 | 0.12 |
536(X) | Ex.Q-48 | 1x108 | CP.RH-1 | 0 | C | 72 | 0.10 |
537(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | C | 91 | 0.05 |
538(Y) | Ex.Q-48 | 1x108 | Ex.R-29 | 8 | C | 89 | 0.06 |
539(Y) | Ex.Q-48 | 1x108 | Ex.R-23 | 1x102 | C | 88 | 0.05 |
[1]: Processing, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
As is clear from Table 5, the decreasing of the
amount of the replenishing solution causes a great
deterioration of the fastness to light in the light
fastness tests and also results in a lowering of the dye
retention. However, unexpectedly great improvements have
been achieved when the compound according to the present
invention having the kq of not less than 108 M-1s-1 and
the compound having the radical-scavenging ability are
used at the same time.
Example 6
The amounts of gelatin as used in the first to
seventh layers in Example 3 were changed as shown below,
and also the dye image stabilizers (1) and (2) were
replaced as shown in Table 6. Processing was carried out
in the same manner as in Example 2, and evaluation was
also made in the same manner as in Example 1.
Amount of gelatin (g/m2) |
| Samples 601 to 609 | Samples 610 to 618 |
Seventh layer | 1.00 | 0.80 |
Sixth layer | 0.40 | 0.35 |
Fifth layer | 1.30 | 1.10 |
Fourth layer | 0.94 | 0.90 |
Third layer | 1.40 | 1.20 |
Second layer | 1.20 | 1.00 |
First layer | 1.20 | 1.00 |
Total | 7.44 | 6.35 |
Results obtained are shown in Table 6.
Sample No. | Dye image stabilizer (1) | Kq (M-1s-1) | Dye image stabilizer (2) | Ks (M-1s-1) | [1]
(g/m2) | [2]
(%) | [3] |
601(X) | - | - | - | - | 7.44 | 64 | 0.61 |
602(X) | Cp.QH-2 | 8x107 | - | - | 7.44 | 77 | 0.20 |
603(X) | Cp.QH-2 | 8x107 | Cp.RH-1 | 0 | 7.44 | 80 | 0.19 |
604(X) | Cp.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | 7.44 | 87 | 0.07 |
605(X) | Cp.QH-2 | 8x107 | Ex.R-23 | 1x102 | 7.44 | 88 | 0.08 |
606(X) | Ex.Q-48 | 1x108 | - | - | 7.44 | 79 | 0.16 |
607(X) | Ex.Q-48 | 1x108 | Cp.RH-1 | 0 | 7.44 | 79 | 0.14 |
608(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | 7.44 | 93 | 0.05 |
609(Y) | Ex.Q-48 | 1x108 | Ex.R-23 | 1x102 | 7.44 | 92 | 0.05 |
610(X) | Ex.Q-48 | 1x108 | - | - | 6.35 | 60 | 0.68 |
611(X) | Ex.QH-2 | 8x107 | - | - | 6.35 | 73 | 0.24 |
612(X) | CP.QH-2 | 8x107 | Cp.RH-1 | 0 | 6.35 | 76 | 0.22 |
613(X) | CP.QH-2 | 8x107 | Ex.R-47 | 3x10-1 | 6.35 | 81 | 0.10 |
614(X) | CP.QH-2 | 8x107 | Ex.R-23 | 1x102 | 6.35 | 81 | 0.11 |
615(X) | Ex.Q-48 | 1x108 | - | - | 6.35 | 72 | 0.18 |
616(X) | Ex.Q-48 | 1x108 | Cp.RH-1 | 0 | 6.35 | 76 | 0.17 |
617(Y) | Ex.Q-48 | 1x108 | Ex.R-47 | 3x10-1 | 6.35 | 92 | 0.05 |
618(Y) | Ex.Q-48 | 1x108 | Ex.R-23 | 1x102 | 6.35 | 90 | 0.06 |
[1]: Amount of gelatin, [2]: Retention (2 weeks) |
[3]: Discoloration |
X: Comparative Example, Y: Present Invention |
As is clear from Table 6, the decreasing of the
amount of gelatin causes a great deterioration of the
fastness to light in the light fastness tests and also
results in a lowering of the dye retention. However,
unexpectedly great improvements have been achieved when
the compound according to the present invention having the
kq of not less than 108 M-1s-1 and the compound having the
radical-scavenging ability are used at the same time.
As having been described above, the present
invention has made it possible to provide a light-sensitive
silver halide photographic material improved in
the fastness to light, of dye images and the prevention of
stain on account of the feature that the compound having a
singlet oxygen quenching rate constant kq of not less than
10
8 M
-1s
-1 is contained and also the compound having a
radical-scavenging ability is contained.