FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide photographic material and more particularly
relates to a silver halide photographic material which is high sensitive and generates
less residual colors after processing.
BACKGROUND OF THE INVENTION
[0002] Every endeavor has been made for higher sensitization and reduction of residual colors
after processing of a silver halide photographic material. It is known that a sensitizing
dye which is used for spectral sensitization exerts a great influence on the capabilities
of a silver halide photographic material. A trace of structural difference of a sensitizing
dye largely affects photographic capabilities such as sensitivity, fog, storage stability
and residual colors after processing. Photographic performances are also largely influenced
by the combined use of two or more kinds of sensitizing dyes but it is difficult to
foresee its effect. Many engineers have hitherto synthesized various kinds of sensitizing
dyes, examined the combined use of sensitizing dyes and endeavored to investigate
photographic capabilities thereof, however, it is not possible to know photographic
capabilities in advance yet.
[0003] For that reason, a technique of spectral sensitization capable of improving sensitivity
of silver halide grains without causing adverse effects such as fog and residual colors
has been required.
[0004] Also, it is known that the present durability is deteriorated by adsorbing onto the
surface of silver halide grains the sensitizing dye used for the spectral sensitization.
Accordingly, a sensitizing dye in which the pressure durability is not deteriorated
is desired.
[0005] EP-A-341 958 describes a silver halide photographic material containing at least one cyanine dye
with a *H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-furopyrrole or 6H-furopyrrole
nucleus.
[0006] EP-A-1139164, which is prior art in accordance with Article 54(3) EPC, discloses a silver halide
photographic material containing a methine dye represented by the formula
SUMMARY OF THE INVENTION
[0007] An object of the present invention is to provide a silver halide photographic material
which is high speed and generates less residual colors after processing, and also
is to provide a silver halide photographic material not deteriorating the pressure
durability.
[0008] The present invention provides a silver halide photographic material which comprises
at least one methine dye represented by the following formula (XX):
wherein Y
51 represents an atomic group necessary to form a furan ring or a pyrrole ring, and
represents a structure selected from formulae (3a), (3b) and (3c) together with the
rings including X
51:
wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen
atom or a monovalent substituent; Va represents a monovalent substituent selected
from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents
a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent,
and at least one of Vc and Vd is a monovalent substituent selected from a methyl group,
a methoxy group, a cyano group and a halogen atom; X
51 and X
52 each represents an oxygen atom, a sulfur atom or a nitrogen atom;
Y
52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered
unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered
carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to
which Y
52 is condensed may be bonded by a single bond or a double bond; R
51 and R
52 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, or a substituted or unsubstituted heterocyclic group; L
51, L
52 and L
53 each represents a methine group; n
51 represents 0, 1, 2, 3 or 4; M
51 represents a counter ion; and m
51 represents a number of 0 or higher necessary to neutralize the charge in the molecule,
with the proviso that the methine dye is not
[0009] Preferred embodiments of the invention are set forth in the sub-claims.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The present invention will be described in detail below. In the first place, the
methine dye represented by formula (XX) will be described in detail below.
[0011] In formula (XX),
Y
51 represents an atomic group necessary to form a furan ring or a pyrrole ring, and
represents a structure selected from formulae (3a), (3b) and (3c) together with the
rings including X
51:
wherein Xa represents an oxygen atom or a nitrogen atom (N-Rw); Rw represents a hydrogen
atom or a monovalent substituent; Va represents a monovalent substituent selected
from a methyl group, a methoxy group, a cyano group and a halogen atom; Vb represents
a hydrogen atom; Vc and Vd each represents a hydrogen atom or a monovalent substituent,
and at least one of Vc and Vd is a monovalent substituent selected from a methyl group,
a methoxy group, a cyano group and a halogen atom; X
51 and X
52 each represents an oxygen atom, a sulfur atom or a nitrogen atom;
Y
52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered
unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered
carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to
which Y
52 is condensed may be bonded by a single bond or a double bond; R
51 and R
52 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, or a substituted or unsubstituted heterocyclic group; L
51 L
52 and L
53 each represents a methine group; n
51 represents 0, 1, 2, 3 or 4; M
51 represents a counter ion; and m
51 represents a number of 0 or higher necessary to neutralize the charge in the molecule.
Rw represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom,
a substituted alkyl group or an unsubstituted alkyl group. The substituents of the
substituted alkyl group are preferably substituents having higher hydrophilicity than
an iodine atom, more preferably substituents having the same or higher hydrophilicity
than a chlorine atom, and particularly preferably substituents having the same or
higher hydrophilicity than a fluorine atom. Rw more preferably represents a hydrogen
atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom
or a methyl group.
[0012] As the preferred substituents, an alkyl group (e.g., methyl), an aryl group (e.g.,
phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g.,
methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g.,
acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g.,
fluorine, chlorine, bromine, iodine) are exemplified, the more preferred substituents
are a methyl group, a methoxy group, a cyano group and a halogen atom, the still more
preferred is a halogen atom, the particularly preferred are a fluorine atom, a chlorine
atom and a bromine atom, and the most preferred is a chlorine atom.
[0013] Of (3a), (3b) and (3c), (3a) and (3b) are preferred. X
51 and X
52 each represents an oxygen atom, a sulfur atom, or a nitrogen atom, and preferably
an oxygen atom or a sulfur atom.
[0014] Y
52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered
unsaturated heterocyclic ring, which may further be condensed with other 5- or 6-membered
carbocyclic or heterocyclic ring or may have a substituent, and two carbon atoms to
which Y
52 is condensed may be bonded by a single bond or a double bond, preferably a double
bond. Y
52 represents an atomic group necessary to form a benzene ring or a 5- or 6-membered
unsaturated heterocyclic ring.
[0015] Examples of the 5-membered unsaturated heterocyclic rings formed by Y
52 include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan
ring, an oxazole ring, an isooxazole ring, a thiophene ring, a thiazole ring, an isothiazole
ring, a thiadiazole ring, a selenophene ring, a selenazole ring, an isoselenazole
ring, a tellurophene ring, a tellurazole ring, and an isotellurazole ring, and examples
of the 6-membered unsaturated heterocyclic rings formed by Y
52 include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a
pyran ring, and a thiopyran ring. Y
52 may further be condensed with other 5- or 6-membered carbocyclic ring or heterocyclic
ring to form, e.g., an indole ring, a benzofuran ring, a benzothiophene ring, or a
thienothiophene ring. The preferred 5- or 6-membered unsaturated heterocyclic rings
formed by Y
52 are a pyrrole ring, a furan ring, a thiophene ring, and a pyridine ring, and particularly
preferred is a pyrrole ring, a thiophene ring or a furan ring. Also, the bond between
two carbon atoms in which Y
52 is condensed may be a sigle bond or a double bond. Particularly, a double bond is
preferred.
[0016] Y
52 is preferably a benzene ring, a pyrrole ring, a furan ring, or a thiophene ring (as
the pyrrole and furan rings, the above-described (3a), (3b), and (3c) can be exemplified
and the similar ones are preferred), particularly preferably a benzene ring, a furan
ring or a pyrrole ring, and most preferably a benzene ring. The substituents are not
limited but preferably an alkyl group (e.g., methyl), an aryl group (e.g., phenyl),
an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g., methoxy),
an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl),
an alkoxycarbonyl group (e.g., methoxycarbonyl), and a halogen atom (e.g.,fluorine,chlorine,bromine,iodine)
are exemplified, more preferably a methyl group, a methoxy group, a cyano group and
a halogen atom, still more preferably a halogen atom, particularly preferably a fluorine
atom, a chlorine atom and a bromine atom, and most preferably a chlorine atom.
[0017] R
51 and R
52 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, or a substituted or unsubstituted heterocyclic group. The case where at
least one of R
51 and R
52 represents an alkyl group substituted with an acid radical is preferred, the case
where R
51 and R
52 both represent an alkyl group substituted with an acid radical is more preferred,
the case where at least one of R
51 and R
52, which are alkyl groups substituted with an acid radical, represents an alkyl group
substituted with an acid radical other than a sulfo group is particularly preferred,
and the case where one of R
51 and R
52 represents an alkyl group substituted with an acid radical other than a sulfo group
and the other represents an alkyl group substituted with a sulfo group is most preferred.
[0018] The alkyl group represented by R
51 or R
52 may be substituted or unsubstituted, for example, an unsubstituted alkyl group having
from 1 to 18, preferably from 1 to 7, and particularly preferably from 1 to 4, carbon
atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl,
octadecyl), and a substituted alkyl group having from 1 to 18, preferably from 1 to
7, and particularly preferably from 1 to 4, carbon atoms [examples of the substituents
include, e.g. , an aryl group having from 6 to 12 carbon atoms (e.g., phenyl, p-chlorophenyl,
p-tolyl), an unsaturated hydrocarbon group having from 2 to 6 carbon atoms (e.g.,
vinyl), a carboxyl group, a sulfo group, a sulfato group, a cyano group, a halogen
atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl group, a mercapto group,
an alkoxyl group having from 1 to 7 carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy,
benzyloxy), an aryloxy group having from 6 to 12 carbon atoms (e.g., phenoxy, 1-naphthoxy),
an alkylthio group having from 1 to 7 carbon atoms (e.g., methylthio), an arylthio
group having from 6 to 12 carbon atoms (e.g., phenylthio, 1-naphthylthio), an acyl
group having from 1 to 7 carbon atoms (e.g., acetyl, benzoyl), an alkoxycarbonyl group
having from 2 to 8 carbon atoms (e.g., ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl
group having from 7 to 13 carbon atoms (e.g., phenoxycarbonyl), an acyloxy group having
from 1 to 8 carbon atoms (e.g., acetyloxy), a carbamoyl group (e.g., morpholinocarbonyl),
a sulfamoyl group (e.g., N,N-dimethylsulfamoyl), a heterocyclic group (e.g., tetrahydrofuryl),
an alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbamoyl), an acylcarbamoyl
group (e.g., acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl), and
an alkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl)] can be exemplified.
[0019] The aryl group represented by R
51 or R
52 may be substituted or unsubstituted, for example, an unsubstituted aryl group having
from 6 to 20, preferably from 6 to 15, and more preferably from 6 to 10, carbon atoms
(e.g., phenyl, 1-naphthyl), and a substituted aryl group having from 6 to 26, preferably
from 6 to 21, and more preferably from 6 to 16, carbon atoms [examples of the substituents
include each substituent described above in the substituted alkyl group (an aryl group,
an unsaturated hydrocarbon group, a carboxyl group, a sulfo group, a sulfato group,
a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a hydroxyl
group, a mercapto group, an alkoxyl group, an aryloxy group, an alkylthio group, an
arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl
group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonyl sulfamoyl
group), and an alkyl group (which may be substituted) can be exemplified, and preferred
is a phenyl group.
[0020] The heterocyclic group represented by R
51 or R
52 may be substituted or unsubstituted, for example, an unsubstituted heterocyclic group
having from 1 to 20, preferably from 1 to 15, and more preferably from 1 to 10, carbon
atoms (e.g., pyrrole, furan, thiophene), and a substituted azole group having from
1 to 26, preferably 1 to 21, and more preferably 1 to 16, carbon atoms [examples of
the substituents include each substituent described above in the substituted alkyl
group (an aryl group, an unsaturated hydrocarbon group, a carboxyl group, a sulfo
group, a sulfato group, a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine,
iodine), a hydroxyl group, a mercapto group, an alkoxyl group, an aryloxy group, an
alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group,
an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an
alkylsulfonylsulfamoyl group), and an alkyl group (which may be substituted)] can
be exemplified.
[0021] R
51 and R
52 preferably represent, an alkyl group substituted with a group having an acid radical
or a dissociable proton (specifically, a carboxyl group, a sulfo group, a phosphoric
acid group, a boric acid group, an alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl),
an acylcarbamoyl group (e.g., acetylcarbamoyl), an acylsulfamoyl group (e.g., acetylsulfamoyl),
or an alkylsulfonylsulfamoyl group (e.g., methanesulfonylsulfamoyl)), and more preferably
represents a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl
group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.
[0022] L
51, L
52 and L
53 each represents a methine group, which may be a substituted or unsubstituted methine
group. Example of the substituents include the substituents described above in the
substituted alkyl group represented by R
51 or R
52. n
51 represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1. When
n
51 represents 2 or more, L
52 and L
53 are repeated but they may be or may not be the same. When n
51 represents 0, L
51 preferably represents an unsubstituted methine group, and when n
51 represents 1, L
51 and L
53 each preferably represents an unsubstituted methine group, and L
52 preferably represents a methine group substituted with an unsubstituted alkyl group
(e.g., methyl, ethyl, propyl). L
52 more preferably represents a methine group substituted with an ethyl group.
[0023] M
51 represents a counter ion, which is required for neutralizing the ion charge. M
51 is included in the formula for showing the presence of cation or anion. It is depended
on the substituent whether a dye is cation or anion, or the dye has a net ion charge
or not.
[0024] Examples of the cation include inorganic ions such as a hydrogen ion, alkali metal
ions (e.g., Na, K, and Li ions) and alkaline earth metal ions (e.g., Ca ion), organic
ions such as ammonium ions (e.g., ammonium, tetraalkyl ammonium, pyridinium and ethylpyridinium
ions) . Examples of the anion may be either of inorganic and organic ions, and include
halide ions (fluoride, chloride, bromide and iodide ions), substituted arylsulfonic
acid ions (e.g., p-toluene sulfonic acid ion, p-chlorobenzene sulfonic acid ion),
aryldisulfonic acid ions (e.g., 1, 3-benzene sulfonic acid ion, 2,6-naphthalenedisulfonic
acid ion), alkyl sulfonic acid ions (e.g., methyl sulfuric acid ion), a sulfonic acid
ion, a thiocyanic acid ion, a perchloric acid ion, a tetrafluoroboric acid ion, a
picric acid ion, an acetic acid ion, a trifluoromethane sulfonic acid ion.
[0025] Examples of the preferred cation include a sodium ion, a potassium ion, a triethylammonium
ion, a tetraethylammonium ion, a pyridinium ion, an ethylpyridinium ion and a methylpyridinium
ion. Examples of the preferred anion include a perchloric acid, a iodide ion, a bromide
ion, and a substituted arylsulfonic acid ion (e.g., p-toluen sulfonic acid ion).
[0026] m
51 represents a number of 0 or higher necessary to neutralize the charge in the molecule,
and when an inner salt is formed, m
51 represents 0. m
51 preferably represents a number of from 0 to 4.
[0027] The methine dye represented by formula (XX) is more preferably represented by the
following formula (XXI).
wherein Y
71 represents an atomic group necessary to form a furan ring or a pyrrole ring as defined
for Y
51. X
71 and X
72 each represents an oxygen atom, a sulfur atom, or a nitrogen atom. R
71 and R
72 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, or a substituted or unsubstituted heterocyclic group. L
71, L
72 and L
73 each represents a methine group. n
71 represents 0, 1, 2, 3 or 4. M
71 represents a counter ion, and m
71 represents a number of 0 or higher necessary to neutralize the charge in the molecule.
V
71, V
72, V
73 and V
74 each represents a hydrogen atom or a substituent.
[0028] Y
71 has the same meaning as Y
51 described above, and the similar ones are preferred, and two carbon atoms to which
Y
71 is condensed may be bonded by a single bond or a double bond, preferably a double
bond. X
71 and X
72 each has the same meaning as X5
1 and X
52 described above, and the similar ones are preferred. R
71 and R
72 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted
aryl group, or a substituted or unsubstituted heterocyclic group, each has the same
meaning as R
51 and R
52 described above, and the similar ones are preferred. L
71, L
72 and L
73 each represents a methine group, each has the same meaning as L
51, L
52 and L
53 described above, and the similar ones are preferred. n
71 represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and more preferably 0 or 1. The
case where the methine chain represented by =L
71-(L
72=L
73)
n71- represents the following LLa or LLb is particularly preferred.
Preferred methine chain
[0029]
LLa: |
=CH- |
LLb: |
|
-wherein A represents a methyl group, an ethyl group or a propyl group, preferably
an ethyl group.
[0030] M
71 represents a counter ion, and m
71 represents a number of 0 or higher necessary to neutralize the charge in the molecule,
and they have the same meaning as M
51 and m
51 described above. It is particularly preferred that M
71 represents a cation, and preferred cations are a sodium ion, a potassium ion, a triethylammonium
ion, a pyridinium ion and an N-ethylpyridinium ion.
[0031] V
71, V
72, V
73 and V
74 each represents a hydrogen atom or a substituent. Of these, two contiguous substituents
may be linked to each other to form a saturated or unsaturated condensed ring but
it is not preferred particularly to form an unsaturated condensed ring in view of
photographic performances. Further, it is also preferred not to form a saturated condensed
ring. It is preferred that both V
71 and V
74 represent a hydrogen atom, and V
72 and V
73 each represents a hydrogen atom, an alkyl group (e.g., methyl), an aryl group (e.g.,
phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxyl group (e.g.,
methoxy), an alkylthio group (e.g., methylthio), a cyano group, an acyl group (e.g.,
acetyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), or a halogen atom (e.g.,
fluorine, chlorine, bromine, iodine) . V
72 more preferably represents a hydrogen atom and V
73 more preferably represents a methyl group, a methoxy group, a cyano group, an acetyl
group, a methoxycarbonyl group, or a halogen atom, still more preferably a halogen
atom, particularly preferably a fluorine atom, a chlorine atom or a bromine atom,
and most preferably a fluorine atom or a chlorine atom.
[0032] When the methine dye represented by formula (XXI) is used in a red-sensitive emulsion
layer, it is preferred that the methine chain (L
71, L
72, L
73, n
71) represents theabove-describedLLb (wherein Apreferably represents an ethyl group),
either X
71 or X
72 represents an oxygen atom and the other represents a sulfur atom, and Y
71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably
a chlorine atom or a bromine atom).
[0033] It is preferred that R
71 and R
72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl
group, all of V
71, V
72 and V
74 represent a hydrogen atom, V
73 represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio
group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl
group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine,
iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl
group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen
atom, and most preferably a fluorine atom or a chlorine atom, M
71 represents an organic or inorganic monovalent cation, and m
71 represents 0 or 1.
[0034] When the methine dye represented by formula (XXI) is used in a green-sensitive emulsion
layer, it is preferred that the methine chain (L
71, L
72, L
73, n
71) represents the above-described LLb (wherein A preferably represents an ethyl group),
both of X
71 and X
72 represent an oxygen atom, and Y
71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably
a chlorine atom or a bromine atom).
[0035] It is preferred that R
71 and R
72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl
group, all of V
71, V
72 and V
74 represent a hydrogen atom, V
73 represents an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic
heterocyclic group (e.g., 2-thienyl), an alkoxyl group (e.g., methoxy), an alkylthio
group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl
group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine,
iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl
group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen
atom, and most preferably a fluorine atom or a chlorine atom, M
71 represents an organic or inorganic monovalent cation, and m
71 represents 0 or 1.
[0036] When the methine dye represented by formula (XXI) is used in a blue-sensitive emulsion
layer, it is preferred that the methine chain (L
71, L
72, L
73, n
71) represents the above-described LLa, both of X
71 and X
72 represent a sulfur atom, and Y
71 represents a pyrrole ring or a furan ring substituted with a halogen atom (preferably
a chlorine atom or a bromine atom).
[0037] It is preferred that R
71 and R
72 each represents a sulfoalkyl group, a carboxyalkyl group or an alkanesulfonylcarbamoylalkyl
group, all of V
71, V
72 and V
74 represent a hydrogen atom, V
73 represents an alkyl group (e.g., methyl), an alkoxyl group (e.g., methoxy), an alkylthio
group (e.g., methylthio), a cyano group, an acyl group (e.g., acetyl), an alkoxycarbonyl
group (e.g., methoxycarbonyl), or a halogen atom (e.g., fluorine, chlorine, bromine,
iodine), more preferably a methyl group, a methoxy group, a cyano group, an acetyl
group, a methoxycarbonyl group or a halogen atom, particularly preferably a halogen
atom, and most preferably a fluorine atom or a chlorine atom, M
71 represents an organic or inorganic monovalent cation, and m
71 represents 0 or 1.
[0038] In general, sensitizing dyes which are less in residual colors are poor in J-associative
property and low in sensitivity, but the sensitizing dyes used according to the present
invention are remarkably high in J-associative property and high in sensitivity, although
they generate less residual colors.
[0039] Only dyes S-66, S-106, S108, S-112, S-113, S-115, S-116, S-120, S-121, S-123, S-126,
S-127, S-128, S-139, S-140, S-141, S-142, S-143, S-144, S-148, S-149, S-150, S-151,
S-152, S-154 and S-157 are comprised by the formula (XX).
|
R1 |
R2 |
V |
S-98 |
CH2CONHSO2CH3 |
(CH2)3SO3- |
Br |
S-99 |
" |
" Cl |
|
S-100 |
" |
" |
F |
S-101 |
(CH2)3SO3- |
CH2CO2H |
Cl |
S-102 |
" |
" |
Br |
S-103 |
" |
" |
F |
S-104 |
CH2CO2H |
(CH2)3SO3- |
Br |
|
X |
Y |
Z1 |
Z2 |
R |
M |
S-105 |
F |
Y |
S |
S |
CH2CO2H |
- |
S-106 |
Br |
O |
O |
S |
(CH2)3SO3- |
|
S-107 |
Cl |
S |
O |
S |
CH2CONHSO2H3 |
- |
S-108 |
Cl |
NH |
O |
O |
CH2CO2H |
- |
S-109 |
Cl |
S |
S |
O |
(CH2)3SO3- |
K+ |
S-110 |
Br |
S |
S |
O |
(CH2)3SO3- |
K+ |
S-111 |
Cl |
S |
O |
O |
(CH2)3SO3- |
Na+ |
|
X |
Y |
Z1 |
Z2 |
R |
M |
S-112 |
Cl O |
|
S |
O |
CH2CO2H |
- |
S-113 |
Br |
O |
S |
S |
(CH2)3SO3- |
K+ |
S-114 |
H |
NH |
S |
O |
CH2CO2H |
- |
S-115 |
Cl |
NH |
S |
O |
CH2CONHSO2CH3 |
- |
S-116 |
Cl |
N-CH3 |
O |
S |
CH2CO2H |
- |
|
R |
M |
S-117 |
(CH2)4SO3- |
K+ |
S-118 |
CH2CONHSO2CH3 |
- |
S-119 |
CH2CO2H |
- |
|
X |
Y |
Z1 |
Z2 |
R |
M |
S-120 |
Cl |
O |
S |
S |
CH2CO2H |
- |
S-121 |
Cl |
NH |
S |
S |
CH2CONHSO2CH3 |
- |
S-122 |
Bar |
S |
O |
S |
(CH2)3SO3- |
|
S-123 |
Br |
O |
S |
S |
CH2CO2H |
- |
|
X |
Y |
Z1 |
Z2 |
R |
M |
S-124 |
Cl |
S |
O |
5 |
CH2CO2H |
- |
S-125 |
H |
NH |
S |
S |
(CH2)3SO3- |
|
S-126 |
Cl |
NH |
S |
S |
CH2SO2NHCOCH3 |
- |
S-127 |
Br |
O |
S |
S |
CH2CO2H |
- |
S-128 |
Cl |
N-CH3 |
S |
O |
(CH2)4SO3- |
H |
|
X |
R |
M |
S-129 |
Cl |
(CH2)3SO3- |
|
S-130 |
Cl |
CH2CONHSO2CH3 |
- |
S-131 |
Cl |
CH2CO2H |
- |
S-132 |
Br |
CH2CO2H |
- |
The methine dyes for use in the present invention can be synthesized according to
the methods described in the following literature.
- a) F.M. Hamer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds, John Wiley
& Sons, New York, London (1964)
- b) D.M. Sturmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry,
Chap. 8, Clause 4, pp. 482 to 515, John Wiley & Sons, New York, London (1977)
- c) Rodd's Chemistry of Carbon Compounds, 2nd Ed., Vol. 4, Part B, Chap. 15, pp. 369
to 422, Elsevier Science Publishing Company Inc., New York (1977)
[0041] For the incorporation of the methine dyes into the silver halide emulsion used in
the present invention, they may be directly dispersed in the emulsion, or they may
be dissolved in water, a single or mixed solvent of methanol, ethanol, propanol, acetone,
methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol,
3-methoxy-1-butanol, 1-methoxy-2-propanol, N,N-dimethylformamide, and then added to
the emulsion.
[0042] In addition, various methods can be used for incorporating dyes into the emulsion,
for example, a method in which dyes are dissolved in a volatile organic solvent, the
solution is dispersed in water or hydrophilic colloid and this dispersion is added
to the emulsion as disclosed in
U.S. Patent 3,469,987, a method in which water-insoluble dyes are dispersed in a water-soluble solvent
without being dissolved and this dispersion is added to the emulsion as disclosed
in
JP-B-46-24185 (the term "JP-B" as used herein means an "examined Japanese patent publication"),
a method in which dyes are dissolved in acid and this solution is added to the emulsion,
or dyes are added to the emulsion as an aqueous solution coexisting with acid or base
as disclosed in
JP-B-44-23389,
JP-B-44-27555 and
JP-B-57-22091, a method in which dyes are added to the emulsion as an aqueous solution or a colloidal
dispersion coexisting with a surfactant as disclosed in
U.S. Patents 3,822,135 and
4,006,026, a method in which dyes are directly dispersed in a hydrophilic colloid and the dispersion
is added to the emulsion as disclosed in
JP-A-53-102733 and
JP-A-58-105141, or a method in which dyes are dissolved using a compound capable of red-shifting
and the solution is added to the emulsion as disclosed in
JP-A-51-74624 can be used. Further, ultrasonic waves can also be used for dissolution.
[0043] The time of the addition of the methine dyes to the silver halide emulsion used in
the present invention may be at any stage of the preparation of the emulsion recognized
as useful hitherto. For example, they may be added at any stage if it is before coating,
i.e., before grain formation stage of silver halide grains and/or before desalting
stage, during desalting stage and/or after desalting and before beginning of chemical
ripening, as disclosed in
U.S. Patents 2,735,766,
3,628,960,
4,183,756,
4,225,666,
JP-A-58-184142 and
JP-A-60-196749, or immediately before or during chemical ripening, after chemical ripening and before
coating as disclosed in
JP-A-58-113920. Also, as disclosed in
U.S. Patent 4,225,666 and
JP-A-58-7629, the dyes can be used as a single compound alone or in combination with compounds
having foreign structures, and they may be divided and added separately, for example,
one part of them is added during grain formation stage and the remaining is added
during chemical ripening or after the completion of chemical ripening, otherwise one
part is added prior to chemical ripening or during ripening stage and the remaining
after completion of chemical ripening. The kinds of compounds added separately and
combinations of compounds may be varied.
[0044] The use amount of the methine dyes used according to the present invention varies
in accordance with the shape and the size of silver halide grains, but is preferably
from 1×10
-2 to 1×10
-8 mol per mol of the silver halide.
[0045] Other sensitizing dyes can be used in combination besides the methine dyes used according
to the present invention. Sensitizing dyes are often used in combination, in particular,
for the purpose of supersensitization. Representative examples thereof are disclosed
in
U.S. Patents 2,688,545,
2,977,229,
3,397,060,
3,522,052,
3,527,641,
3,617,293,
3,628,964,
3,666,480,
3,672,898,
3,679,428,
3,703,377,
3,769,301,
3,814,609,
3,837,862,
4,026,707, British Patents
1,344,281,
1,507,803,
JP-B-43-4936,
JP-B-53-12375,
JP-A-52-110618 and
JP-A-52-109925.
[0046] Any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
silver iodochloride, and silver chloroiodobromide can be used as silver halide grains
in the silver halide photographic material according to the present invention.
[0047] The silver halide grains contained in the silver halide emulsion for use in the present
invention have an average grain size (the grain size herein refers to the diameter
of the equivalent circle corresponding to the projected area of the grains, and the
number average is taken as the average grain size) of preferably from 0.1 to 2 µm.
[0048] With respect to the distribution of sizes of these grains, a so-called monodispersed
emulsion having a variation coefficient (the value obtained by dividing the standard
deviation of the grain size distribution by the average grain size) of 20% or less,
preferably 15% or less, and more preferably 10% or less, is preferred. For obtaining
a wide latitude, it is also preferred to blend the above described monodispersed emulsions
in the same layer or multilayer-coat the monodispersed emulsion.
[0049] The silver halide grains contained in a photographic emulsion may have a regular
crystal form, such as cubic, octahedral or tetradecahedral form, an irregular crystal
form, such as spherical or plate-like form, or a composite form of these forms. In
the present invention, the grains having the above described regular crystal forms
preferably account for 50% or more, preferably 70% or more, and more preferably 90%
or more.
[0050] Further, an emulsion in which the proportion of tabular grains having an average
aspect ratio (equivalent-circle diameter/thickness) of 5 or more, preferably 8 or
more, to the entire grains exceeds 50% as a projected area can also be preferably
used.
[0051] The emulsion for use in the present invention can be prepared according to the methods
disclosed, for example, in
P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967),
G. F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966),
V.L. Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press (1964). That is, any process, such as an acid process, a neutral process, and an ammoniacal
process, can be used. A single jet method, a double jet method, and a combination
of them may be used for reacting a soluble silver salt with a soluble halide, and
any of these methods can be used. A method in which silver halide grains are formed
in the atmosphere of excessive silver ions (a so-called reverse mixing method) may
also be used. Further, a so-called controlled double jet method, which is one form
of a double jet method, in which the pAg of the liquid phase in which the silver halide
is formed is maintained constant, may also be used. According to this method, a silver
halide emulsion having a regular crystal form and substantially an almost uniform
grain size can be obtained.
[0052] The silver halide emulsions for use in the present invention are generally chemically
sensitized. In chemical sensitization, chemical sensitization using chalcogen sensitizers
(typically, sulfur sensitization represented by the addition of labile sulfur compounds,
selenium sensitization by selenium compounds, and tellurium sensitization by tellurium
compounds can be exemplified), noble metal sensitization represented by gold sensitization,
and reduction sensitization are used alone or in combination. The compounds disclosed
in
JP-A-62-215272, from p. 18, right lower column to p. 22, right upper column are preferably used
in the chemical sensitization.
[0053] Various compounds and precursors thereof can be added to the silver halide emulsions
for the purpose of preventing generation of fog or stabilizing photographic performances
during production, storage or photographic processing of the photographic material.
The compounds disclosed in
JP-A-62-215272, from pp. 39 to 72 are preferably used. Further, 5-arylamino-1,2,3,4-thiatriazole
compounds (the aryl residue has at least one electron attractive group) disclosed
in European Patent
0447647 are also preferably used.
[0054] The silver halide emulsions used according to the present invention can be used in
both color photographic materials, such as color papers, color films for photographing,
and color reversal films , and black-and-white photographic materials, such as X-ray
films, general films for photographing, and photographic films for printing, and preferably
used as color photographic materials.
[0056] In addition to these, more specifically, for example, techniques and inorganic and
organic materials which can be used in the color photographic material to which the
silver halide photographic emulsion used in the present invention is applicable are
disclosed in the following places of
EP-A-436938 and the patents cited in the following places.
|
Item |
Place |
1) |
Layer Constitution |
line 34, page 146 to line 25, page 147 |
2) |
Silver Halide Emulsion |
line 26, page 147 to line 12, page 148 |
3) |
Yellow Coupler |
line 35, page 137 to line 33, page 146, lines 21 to 23, page 149 |
4) |
Magenta Coupler |
lines 24 to 28, page 149; line 5, page 3 to line 55, page 25 of EP-A- 421453 |
5) |
Cyan Coupler |
lines 29 to 33, page 149; line 28, page 3 to line 2, page 40 of EP-A- 432804 |
6) |
Polymer Coupler |
lines 34 to 38, page 149; line 39, page 113 to line 37, page 123 of EP-A-435334 |
7) |
Colored Coupler |
line 42, page 53 to line 34, page 137, lines 39 to 45, page 149 |
8) |
Other Functional Coupler |
line 1, page 7 to line 41, page 53, line 46, page 149 to line 3 page 150; line 1,
page 3 to line 50, page 29 of EP-A-435334 |
9) |
Preservative |
lines 25 to 28, page 150 |
10) |
Formalin Scavenger |
lines 15 to 17, page 149 |
11) |
Other Additives |
lines 38 to 47, page 153; line 21, page 75 to line 56, page 84 of EP-A- 421453 |
12) |
Dispersion Method |
lines 4 to 24, page 150 |
13) |
Support |
line 32 to 34, page 150 |
14) |
Film Thickness, Physical Properties of Film |
lines 35 to 49, page 150 |
15) |
Color Development Process |
line 50, page 150 to line 47, page 151 |
16) |
Desilvering Process |
line 48, page 151 to line 53, page 152 |
17) |
Automatic Processor |
line 54, page 152 to line 2, page 153 |
18) |
Washing and Stabilizing Processes |
lines 3 to 37, page 153 |
[0057] In the photographic material of the present invention, it is preferred to color a
hydrophilic colloid layer for the purpose of preventing irradiation and halation and
improving safelight stability. As water-soluble dyes which can be used as such a coloring
substance, the dyes capable of decoloration by processing (oxonol dyes and cyanine
dyes, above all) disclosed in
EP-A-0337490, pages 27 to 76, can be exemplified.
[0058] A coloring substance disperses regardless of the position where it is added and pervades
over the entire constitutional layers of the photographic material by such coloration.
[0059] Cyan, magenta and yellow couplers are preferably impregnated in a loadable latex
polymer (e.g., disclosed in
U.S. Patent 4, 203, 716) in the presence (or absence) of the high boiling point organic solvents described
in the above table, or dissolved in a polymer insoluble in water but soluble in an
organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution.
[0060] Examples of polymers insoluble in water but soluble in an organic solvent which can
preferably be used in the present invention include homopolymers or copolymers disclosed
in
U.S. Patent 4,857,449, from pages 12 to 30. Methacrylate based or acrylamide based polymers are more preferred,
in particular, acrylamide based polymers are preferred in the light of color image
stability.
[0061] In the photographic material of the present invention, it is preferred to use color
image preservability improving compounds disclosed in
EP-A-0277589 in combination with the couplers. In particular, the use in combination with pyrazoloazole
couplers or pyrrolotriazole couplers is preferred.
[0062] That is, the use of the compound disclosed in the above EP Patent which produces
a chemically inactive and substantially colorless compound upon chemically bonding
with an aromatic amine developing agent remaining after color development processing
and/or the compound disclosed in the above EP Patent which produces a chemically inactive
and substantially colorless compound upon chemically bonding with the oxidized product
of an aromatic amine color developing agent remaining after color development processing,
alone or in combination, is preferred for preventing the generation of stain due to
the formation of a colored dye caused by the coupling reaction of the coupler with
the color developing agent or the oxidized product thereof remaining in the film,
or preventing other side reactions, during preservation after processing.
[0063] The present invention will be illustrated specifically with reference to examples
below.
EXAMPLE 1
Synthesis of Methine Dye S-76
[0064] 5-Bromo-2-methylthieno[3,2-d]thiazole was obtained at a yield of 34% by reacting
3-acetylamino-2,5-dibromothiophene (synthesized according to
J. Am. Chem. Soc, 1954, 76, 2447) with phosphorous pentasulfide in toluene under heat-reflux.
[0065] 5-Bromo-2-methylthieno[3,2-d]thiazole (2.58 g), 1.61 g of 1,3 -propane sultone and
6.4 ml anisole were mixed and stirred with heating at 150°C for 3 hours. After cooling
the reaction mixture, the black precipitate generated was washed with acetone, the
supernatant was removed by decantation, and 5.21 g of 4-(5-chloro-2-sulfobutylthio-3-benzothiazolio)butanesulfonate
and 55 ml of acetonitrile were added thereto, followed by stirring with heating at
100°C.
Triethylamine (7.7 ml) was added to the reaction mixture and the mixture was refluxed
under heating with stirring for 1.5 hours, thereby yellow precipitate was generated.
The precipitate was filtered out by cooling with ice, washed with acetonitrile to
thereby obtain 2.27 g of yellow powder. The yellow powder was dissolved in 150 ml
of methanol, and then the solvent was distilled off to thereby obtain 1.34 g of Methine
Dye S-76 as powder. The structure of S-76 was confirmed by
1H-NMR, FAB-MS, and elemental analysis.
λ
max (MeOH) = 435.7 nm ( ε = 7.1×10
4)
EXAMPLE 2
Synthesis of Methine Dye S-31
[0066] 5-Bromo-2-methylthieno[3,2-d]thiazole (1.47 g), 0.93 g of 1,3-propanesultone and
3.7 ml of anisole were mixed and stirred with heating at 150°C for 3 hours. After
cooling the reaction mixture, the black precipitate generated was washed with acetone.
The supernatant was removed by decantation, and 3.28 g of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propane-sul
fonate and 45 ml of dimethylsulfoxide were added thereto, followed by stirring at
room temperature. 1,8-Diazabicyclo [5.4.0]-7-undecene (2.4 ml) was added to the reaction
solution and the solution was stirred for 30 minutes, and then 6 ml of acetic acid
and 600 ml of ethyl acetate were added thereto, thereby red precipitate was generated.
The precipitate was purified by column chromatography, and 1.0 g of potassium acetate
was added to methanol solution to distill off the solvent, thereby 1.03 g of Methine
Dye S-31 was obtained as green powder. The structure of S-31 was confirmed by
1H-NMR, FAB-MS, and elemental analysis.
λ
max (MeOH) = 524.3 nm ( ε = 7.8×10
4)
EXAMPLE 3
Synthesis of Methine Dye S-85
[0067] 5-Bromo-2-methylthieno[2,3-d]thiazole was obtained at a yield of 96% by adding dropwise
bromine to 2-methylthieno[2,3-d]thiazole (synthesized according to
J. Heterocyclic Chem., 1983, 20, 113) in the presence of sodium acetate in an acetic acid solvent.
[0068] 5-Bromo-2-methylthieno[3,2-d]thiazole (9.37 g), 10.37 g of methanesulfonylcarbamoylmethyl
bromide and 12 ml of cumene were mixed and stirred with heating at 150°C for 5 hours.
The temperature of the reaction mixture was lowered to 80°C, acetone was added thereto,
and the mixture was refluxed for 1 hour. The gray precipitate generated after cooling
was filtered out, washed with acetone to thereby obtain 18.45 g of 5-bromo-3-methanesulfonylcarbamoylmethyl-2-methylthieno[2,3-d
]thiazolium bromide as powder. The above-obtained compound (1.80 g), 1.78 g of 4-(5-chloro-2-sulfopropylthio-3-benzothiazolio)propanesulfonate,
and 16 ml of acetonitrile were mixed and stirred with heating at 40°C. Triethylamine
in an amount of 2 ml was added thereto and the reaction mixture was heated for 1 hour
to thereby generate yellow precipitate. After ice-cooling the reaction solution, the
precipitate was filtered out, washed with acetonitrile, thereby 1.61 g of yellow powder
was obtained. The obtained powder was dissolved in a mixed solvent of 20 ml of methanol,
20 ml of water and 1 ml of triethylamine, and then 3 ml of acetic acid was added thereto,
thereby precipitate was generated. The precipitate was filtered out and washed with
acetone to obtain 1.24 g of Methine Dye S-85 as powder. The structure of S-85 was
confirmed by
1H-NMR, FAB-MS, and elemental analysis.
λmax (MeOH) = 445.8 nm ( ε = 7.1×10
4)
EXAMPLE 4
Synthesis of Methine Dye S-96
[0069] 5-Chloro-2-methylthieno[2,3-d]thiazole was obtained by making trichloroisocyanuric
acid act on the above 2-methylthieno[2,3-d]thiazole in a dichloromethane solvent.
Yield: 98%.
[0070] 5-Chloro-2-methylthieno[2,3-d]thiazole (15.2 g), 13.3 g of bromoacetic acid and 24
ml of cumene were mixed and stirred with heating at outer temperature of 135°C for
8 hours. After cooling the reaction mixture, 100 ml of acetone was added thereto.
The crystals precipitated were filtered out by suction, washed with 50 ml of acetone,
dried under reduced pressure, thereby 15.6 g of 3-carboxymethyl-5-chloro-2-methylthieno[2,3-d]thiazolium
bromide (A) was obtained as yellow powder. To 7.4 g of (A), 18.5 g of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate
and 70 ml of benzyl alcohol were added and stirred at room temperature. After that,
10.1 ml of 1,8-diazabicyclo[5.4.0]-7-undecene was added to the above mixture and stirred
at outer temperature of 50°C for 20 minutes, 1,000 ml of ethyl acetate was then added
thereto, a supernatant was removed by decantation to obtain a residue. The residue
was dissolved in methanol and refined by Sephadex column chromatography. The refined
product was dissolved in 150 ml of methanol, 3 g of potassium acetate was added thereto,
after heating under reflux for 10 minutes, the mixture was allowed to be cooled, and
the crystals precipitated were filtered out by suction. Methanol (300 ml) was added
to the above-obtained powder, and the solution was heated under reflux for 50 minutes,
then the solution was concentrated by distilling off 100 ml of the solvent. After
cooling, the obtained crystals were recovered by suction filtration, the filtrate
was washed with 50 ml of methanol and dried under reduced pressure, thereby 2.65 g
of orange powder of S-96 was obtained. The structure of S-96 was confirmed by
1H-NMFt, FAB-MS, and elemental analysis. λmax (MeOH) = 535 nm (e = 8.3×10
4)
EXAMPLE 5
Synthesis of Methine-Dye S-97
[0071] Orange powder of S-97 was synthesized in the same manner as in Example 4 except for
using 3-[5-fluoro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate in place
of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate. The structure
of S-97 was confirmed by
1H-Wm, FAB-MS, and elemental analysis. λmax (MeOH) = 534 nm (ε = 8.2×10
4)
EXAMPLE 6
Synthesis of Methine Dye S-122
Synthesis of 2-Acetyl-3-hydroxythiophene
[0072] According to the description in
Synth. Commun., 1996, 26, 1083, methyl 2-acetyl-3-hydroxythiophene-5-carboxylate was synthesized
with chloroacetone, dimethyl acetylene dicarboxylate and sodium hydrosulfide as starting
materials (yield: 60%).
[0073] The above-obtained methyl 2-acetyl-3-hydroxythiophene-5-carboxylate was hydrolyzed
with an aqueous solution of sodium hydroxide, the hydrolyzate was heated with copper-quinoline
to be decarboxylated, thereby the objective 2-acetyl-3-hydroxythiophene was obtained
(yield: 58%).
Syntheses of 2-Methylthieno[2,3-d]oxazole
[0074] According to the description in
Arch. Pharm., (Weinheim) 1987, 320, 837, oxime was prepared using 2-acetyl-3-hydroxythiophene and hydroxylamine (yield: 88%),
and the oxime was further acetylated with acetic anhydride (yield: 69%). The oxime
acetate was subjected to treatment with sodium hydroxide in an N, N-dimethylformamide
solvent at room temperature, thereby the objective 2-methylthieno[2,3-d]oxazole was
obtained (yield: 57%).
Synthesis of 5-Bromo-2-methylthieno[2,3-d]oxazole
[0075] Sodium acetate (1.4 g) and 2 g of 2-methylthieno[2,3-d]-oxazole were dissolved in
24 ml of an acetic acid solvent, and a solution comprised of 15.8 ml of bromine and
7.2 ml of acetic acid was dropwise added thereto with stirring at room temperature.
After stirring at room temperature for 2.5 hours, the reaction solution was added
to 150 ml of water, followed by further stirring at room temperature for 2 hours.
The crystals precipitated were recovered by suction filtration, and dried under reduced
pressure, thereby 1.7 g of 5-bromo-2-methylthieno[2,3-d]oxazole was obtained as pale
yellow powder (yield: 54%).
Synthesis of Methine Dye S-122
[0076] 5-Bromo-2-methylthieno[2,3-d]oxazole (1.53 g) (7 mmol) and 0.94 g of 1,3-propanesultone
(7.7 mmol) were heated at 130°C with stirring for 6 hours. After cooling the mixture,
3.1 g of 3-[5-chloro-2-(3-sulfopropyl)thio-1-benzothiazolio]propanesulfonate (7 mmol),
5 ml of dimethyl sulfoxide and 5 ml of acetonitrile were added to the above reaction
mixture, and 3.9 ml of triethylamine (28 mmol) was added with stirring at 60°C, and
stirring was further continued for 1 hour. The solution was concentrated and refined
by column chromatography, thereby 0.51 g of the objective Dye S-122 was obtained.
Yield: 10%, λmax (MeOH) = 428.6 nm.
EXAMPLE 7
Synthesis of Methine Dye S-125
Synthesis of 2-Methylpyrrolo[3,2-d]thiazole
[0077] According to the description in
J. Heterocyclic Chem., 1979, 16, 1563, 4-chloromethyl-2-methylthiazole was synthesized with 1,3-dichloroacetone and thioacetamide
as starting materials. The above-obtained 4-chloromethyl-2-methylthiazole was converted
to a 4-hydroxymethyl body by dilute sulfuric acid, and then introduced into a 4-formyl
body by oxidation of manganese dioxide (yield to this point: 62%). 5-Ethoxycarbonyl-2-methylpyrrolo[3,2-d]thiazole
was obtained by making ethyl azidoacetate act on the above product in the presence
of sodium ethoxide and further heating in xylene (yield: 31%) .
[0078] Subsequently, according to the description in
Synth.Commun., 1992, 2077, the above-obtained 5-ethoxycarbonyl-2-methylpyrrolo[3,2-d]thiazole was
hydrolyzed with sodium hydroxide, and then heated in diphenylmethane at 230°C for
3.5 hours, thereby the objective decarboxylated2-methylpyrrolo[3,2-d]thiazole was
obtained (yield: 63%).
Synthesis of Methine Dye S-125
[0079] 2-Methylpyrrolo [3, 2-d] thiazole (0.70 g) (5 mmol) and 0.67 g of 1,3-propanesultone
(5.5 mmol) were stirred with heating at 130°C for 6 hours. After cooling, the crystals
precipitated were filtered out and washed with acetone, thereby 1.2 g of 3-[2-methyl-1-pyrrolo[3,2-d]thiazolio]propanesulfonate
was obtained (yield: 92%).
3-[5-Chloro-2-(3-sulfopropyl)thio-1-benzothiazolio]propanesulfonate (0.45 g) (1 mmol),
2 ml of dimethyl sulfoxide and 2 ml of acetonitrile were added to 0.26 g of the quaternary
salt of 3-[2-methyl-l-pyrrolo[3,2-d]thiazolio]propanesulfonate (1 mmol) and the mixture
was stirred at 50°C with adding 0.56 ml of triethylamine (4 mmol), followed by further
stirring for 1 hour. The solution was concentrated, and then refined with column chromatography,
thereby 0.10 g of the objective Methine Dye S-125 was obtained. Yield: 15%, λmax (MeOH)
= 447.5 nm.
EXAMPLE 8
Preparation of Sample No. 101
[0080] A multilayer color photographic material was prepared as Sample No. 101 by coating
each layer having the following composition on an undercoated cellulose triacetate
film support having a thickness of 127 µm. The numeral corresponding to each component
indicates the addition weight per m
2. The functions of the compounds added are not limited to the use described.
First Layer: Antihalation Layer |
Black Colloidal Silver silver amount: |
0.28 g |
Gelatin |
2.20 g |
Ultraviolet Absorber U-1 |
0.27 g |
Ultraviolet Absorber U-3 |
0.08 g |
Ultraviolet Absorber U-4 |
0.08 g |
High Boiling Point Organic Solvent Oil-1 |
0.29 g |
Coupler C-9 |
0.12 mg |
Second Layer: Interlayer |
Gelatin |
0.38 g |
Compound Cpd-K |
5.0 mg |
Ultraviolet Absorber U-2 |
3.0 mg |
High Boiling Point Organic Solvent Oil-3 |
0.06 g |
Dye D-4 |
10.0 mg |
Third Layer: Interlayer |
Yellow Colloidal Silver silver amount: |
0.007 g |
Gelatin |
0.40 g |
Fourth Layer: First Red-Sensitive Emulsion Layer |
Emulsion A silver amount: |
0.55 g |
Emulsion B silver amount: |
0.23 g |
Surface Fogged Fine Grain silver amount: Silver Iodobromide Emulsion (average grain
size: 0.11 µm) |
0.07 g |
Gelatin |
1.11 g |
Coupler C-1 |
0.04 g |
Coupler C-2 |
0.09 g |
Compound Cpd-A |
1.0 mg |
Compound Cpd-E |
0.14 g |
Compound Cpd-K |
2.0 mg |
Compound Cpd-H |
4.4 mg |
High Boiling Point Organic Solvent Oil-2 |
0.09 g |
Fifth Layer: Second Red-Sensitive Emulsion Layer |
Emulsion C silver amount: |
0.14 g |
Emulsion D silver amount: |
0.28 g |
Gelatin |
0.65 g |
Coupler C-1 |
0.05 g |
Coupler C-2 |
0.11 g |
Compound Cpd-E |
0.10 g |
High Boiling Point Organic Solvent Oil-2 |
0.09 g |
Sixth Layer: Third Red-Sensitive Emulsion Layer |
Emulsion E silver amount: |
0.50 g |
Gelatin |
1.56 g |
Coupler C-3 |
0.63 g |
Compound Cpd-E |
0.11 g |
Additive P-1 |
0.16 g |
High Boiling Point Organic Solvent Oil-2 |
0.04 g |
Seventh Layer: Interlayer |
Gelatin |
0.50 g |
Compound Cpd-D |
0.04 g |
High Boiling Point Organic Solvent Oil-3 |
0.08 g |
Eighth Layer: Interlayer |
Yellow Colloidal Silver silver amount: |
0.01 g |
Gelatin |
1.56 g |
Compound Cpd-A |
0.12 g |
Compound Cpd-1 |
0.04 mg |
Compound Cpd-J |
0.07 g |
High Boiling Point Organic Solvent Oil-3 |
0.15 g |
Ninth Layer: First Green-Sensitive Emulsion Layer |
Emulsion F silver amount: |
0.42 g |
Emulsion G silver amount: |
0.38 g |
Emulsion H silver amount: |
0.32 g |
Surface Fogged Core/Shell Type silver amount: Fine Grain Silver Bromide Emulsion (average
grain size: 0.11 µm) |
0.08 g |
Gelatin |
1.53 g |
Coupler C-7 |
0.07 g |
Coupler C-8 |
0.17 g |
Compound Cpd-B |
0.30 mg |
Compound Cpd-C |
2.00 mg |
Compound Cpd-K |
3.0 mg |
Polymer Latex P-2 |
0.02 g |
High Boiling Point Organic Solvent Oil-2 |
0.10 g |
Tenth Layer: Second Green-Sensitive Emulsion Layer |
Emulsion I silver amount: |
0.16 g |
Emulsion J silver amount: |
0.34 g |
Gelatin |
0.75 g |
Coupler C-4 |
0.20 g |
Compound Cpd-B |
0.03 g |
Polymer Latex P-2 |
0.01 g |
High Boiling Point Organic Solvent Oil-2 |
0.01 g |
Eleventh Layer: Third Green-Sensitive Emulsion Layer |
Emulsion K silver amount: |
0.44 g |
Gelatin |
0.91 g |
Coupler C-4 |
0.34 g |
Compound Cpd-B |
0.06 g |
Polymer Latex P-2 |
0.01 g |
High Boiling Point Organic Solvent Oil-2 |
0.02 g |
Twelfth Layer: Yellow Filter Layer |
Yellow Colloidal Silver silver amount: |
0.02 g |
Gelatin |
0.73 g |
Microcrystal Dispersion of Dye E-1 |
0.24 g |
Compound Cpd-G |
0.02 g |
Compound Cpd-J |
0.04 g |
High Boiling Point Organic Solvent Oil-3 |
0.08 g |
Polymer M-1 |
0.23 g |
Thirteenth Layer: First Blue-Sensitive Emulsion Layer |
Emulsion L silver amount: |
0.35 g |
Gelatin |
0.55 g |
Coupler C-5 |
0.20 g |
Coupler C-6 |
4.00 g |
Coupler C-10 |
0.02 g |
Compound Cpd-E |
0.07 g |
Compound Cpd-K |
0.03 mg |
Fourteenth Layer: Second Blue-Sensitive Emulsion Layer |
Emulsion M silver amount: |
0.06 g |
Emulsion N silver amount: |
0.10 g |
Gelatin |
0.75 g |
Coupler C-5 |
0.35 g |
Coupler C-6 |
5.00 g |
Coupler C-10 |
0.30 g |
Compound Cpd-E |
0.04 g |
Fifteenth Layer: Third Blue-Sensitive Emulsion Layer |
Emulsion O silver amount: |
0.20 g |
Emulsion P silver amount: |
0.02 g |
Gelatin |
2.40 g |
Coupler C-6 |
0.09 g |
Coupler C-10 |
0.90 g |
Compound Cpd-E |
0.09 g |
Compound Cpd-M |
0.05 mg |
High Boiling Point Organic Solvent Oil-2 |
0.40 g |
Additive P-2 |
0.10 g |
Sixteenth Layer: First Protective Layer |
|
Gelatin |
1.30 g |
Ultraviolet Absorber U-1 |
0.10 g |
Ultraviolet Absorber U-2 |
0.03 g |
Ultraviolet Absorber U-5 |
0.20 g |
Compound Cpd-F |
0.40 g |
Compound Cpd-J |
0.06 g |
Dye D-1 |
0.01 g |
Dye D-2 |
0.01 g |
Dye D-3 |
0.01 g |
Dye D-5 |
0.01 g |
High Boiling Point Organic Solvent Oil-2 |
0.37 g |
Seventeenth Layer: Second Protective Layer |
Fine Grain Silver Iodobromide silver amount: Emulsion (average grain size: 0.06 µm,
AgI content: 1 mol%) |
0.05 g |
Gelatin |
1.80 g |
Compound Cpd-L |
0.8 mg |
Polymethyl Methacrylate (average particle size: 1.5 µm) |
5.00 g |
Copolymer of Methyl Methacrylate/Methacrylic Acid in Proportion of 6/4 (average particle
size: 1.5 µm) |
0.10 g |
Silicone Oil SO-1 |
0.030 g |
Surfactant W-2 |
0.030 g |
[0081] Additives F-1 to F-11 were further added to every emulsion layer in addition to the
above components. Moreover, Gelatin Hardener H-1 and Surfactants W-1, W-3, W-4, W-5
and W-6 for coating and emulsifying were added to every layer in addition to the above
components.
[0082] In addition, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol,
and p-hydroxybenzoic acid butyl ester were added as antibacterial and antifungal agents.
Photosensitive emulsions used in Sample No. 101 are shown in Table 1 below.
TABLE 1
Emulsion |
Equivalent-Sphere Diameter
(µm) |
Variation Coefficient of Equivalent-Circle Diameter
(%) |
Average Aspect Ratio of Entire Grains |
Iodide Content
(mol%) |
Sensitizing Dye |
Sensitizing Dye |
Sensitizing Dye |
Kind |
Addition Amount
(×10-4mol/ mol-Ag) |
Kind |
Addition Amountv (×10-4mol/ mol-Ag) |
Kind |
Addition Amount
(×10-4 mol/ mol-Ag) |
A |
0.20 |
16 |
1.6 |
4.0 |
Sen-1 |
8.1 |
|
|
Sen-3 |
0.3 |
B |
0.25 |
15 |
3.0 |
4.0 |
Sen-1 |
8.9 |
|
|
Sen-3 |
0.3 |
C |
0.22 |
14 |
2.5 |
4.0 |
Sen-1 |
8.8 |
Sen-2 |
0.2 |
Sen-3 |
0.2 |
D |
0.35 |
10 |
3.6 |
4.0 |
Sen-1 |
9.8 |
Sen-2 |
0.3 |
Sen-3 |
0.2 |
E |
0.49 |
16 |
5.0 |
2.0 |
Sen-1 |
6.7 |
Sen-2 |
0.5 |
Sen-3 |
0.2 |
F |
0.15 |
15 |
1.0 |
3.5 |
Sen-4 |
15.1 |
Sen-5 |
1.5 |
|
|
G |
0.23 |
14 |
1.9 |
3.5 |
Sen-4 |
10.4 |
Sen-5 |
2.0 |
|
|
H |
0.32 |
11 |
2.4 |
3.5 |
Sen-4 |
7.5 |
Sen-5 |
1.4 |
|
|
I |
0.28 |
11 |
4.5 |
3.3 |
Sen-4 |
7.7 |
Sen-5 |
1.4 |
|
|
J |
0.40 |
16 |
4.0 |
3.3 |
Sen-4 |
7.2 |
Sen-5 |
1.4 |
|
|
K |
0.59 |
20 |
5.9 |
2.8 |
Sen-4 |
6.4 |
Sen-5 |
1.2 |
|
|
L |
0.24 |
14 |
3.4 |
4.6 |
Sen-6 |
6.5 |
Sen-7 |
2.5 |
|
|
M |
0.30 |
10 |
3.0 |
4.6 |
Sen-6 |
6.2 |
Sen-7 |
2.0 |
|
|
N |
0.40 |
9 |
4.5 |
1.6 |
Sen-6 |
5.6 |
Sen-7 |
1.8 |
|
|
O |
0.60 |
15 |
5.5 |
1.0 |
Sen-6 |
4 |
Sen-7 |
1.5 |
|
|
P |
0.80 |
18 |
2.5 |
1.0 |
Sen-6 |
3.4 |
Sen-7 |
1.1 |
|
|
Note 1) All of the above emulsions were silver iodobromide emulsions chemically sensitized
using gold, sulfur and selenium.
Note 2) All of the above emulsions were added with sensitizing dyes before chemical
sensitization.
Note 3) Appropriate amounts of Compounds F-5, F-7, F-8, F-9, F-10, F-11, F-12, F-13,
F-14 and F-15 were respectively added to the above emulsions.
Note 4) Emulsions A, B, I and J comprise triple structure tabular grains having main
planes comprising {100} faces and other emulsions comprise triple structure tabular
grains having main planes comprising {111} faces.
Note 5) Emulsions A, B, E, F, I and P are emulsions whose internal sensitivity is
higher than surface sensitivity.
Note 6) Emulsions E, I and P are emulsions comprising silver chloride grains epitaxially
grown after chemical sensitization.
Note 7) Emulsions other than A, E and F comprise grains having 50 or more dislocation
lines per one grain observed by a transmission electron microscope. |
Preparation of Dispersion of Organic Solid Dispersion Dye
[0083] Dye E-1 shown below was dispersed according to the following method. That is, water
and 70 g of W-4 were added to 1,400 g of a wet cake of the dye containing 30% of water,
and the mixture was stirred to obtain a slurry having 30% dye concentration. Next,
1,700 ml of zirconia beads having an average diameter of 0.5 mm was filled in an ultravisco
mill (UVM-2) manufactured by Imex Co., the slurry was passed and pulverized at a peripheral
speed of about 10 m/sec and discharge amount of 0.5 1/min for 8 hours. Beads were
removed by filtration and the resulting dispersion was heated at 90°C for 10 hours
for stabilization, then water and gelatin were added thereto to dilute the dispersion
to dye concentration of 3%. The average grain size of the obtained fine grains of
the dye was 0.4 µm and the extent of distribution of grain sizes [(standard deviation
of grain sizes)/(average grain size) × 100] was 18%.
Preparation of Sample Nos. 100, 102 to 130
Processing
[0085]
Processing Step |
Processing Time |
Processing Temperature |
Tank Capacity |
Replenishing Rate |
|
(min) |
(°C) |
(liter) |
(ml/m2) |
First Development |
6 |
38 |
12 |
2,200 |
First Washing |
2 |
38 |
4 |
7,500 |
Reversal |
2 |
38 |
4 |
1,100 |
Color Development |
6 |
38 |
12 |
2,200 |
Pre-bleaching |
2 |
38 |
4 |
1,100 |
Bleaching |
6 |
38 |
2 |
220 |
Fixing |
4 |
38 |
8 |
1,100 |
Second Washing |
4 |
38 |
8 |
7,500 |
Final Rinsing |
1 |
25 |
2 |
1,100 |
[0086] The composition of each processing solution used was as follows.
First Developing Solution |
Tank Solution |
Replenisher |
Pentasodium Nitrilo-N,N,N- |
1.5 g |
1.5 g |
trimethylenephosphonate |
|
|
Pentasodium Diethylene- |
2.0 g |
2.0 g |
triaminepentaacetate |
|
|
Sodium Sulfite |
30 g |
30 g |
Potassium Hydroquinone- |
20 g |
20 g |
monosulfonate |
|
|
Potassium Carbonate |
15 g |
20 g |
Sodium Bicarbonate |
12 g |
15 g |
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone |
1.5 g |
2.0 g |
Potassium Bromide |
2.5 g |
1.4 g |
Potassium Thiocyanate |
1.2 g |
1.2 g |
Potassium Iodide |
2.0 mg |
|
Diethylene Glycol |
13 g |
15 g |
Water to make |
1,000 ml |
1,000 ml |
pH (adjusted with sulfuric acid or potassium hydroxide) |
9.60 |
9.60 |
Reversal Solution |
Tank Solution |
Replenisher |
Pentasodium Nitrilo-N,N,N-trimethylenephosphonate |
3.0 g |
same as the tank solution |
Stannous Chloride |
1.0 g |
|
Dihydrate |
|
|
p-Aminophenol |
0.1 g |
|
Sodium Hydroxide |
8 g |
|
Glacial Acetic Acid |
15 ml |
|
Water to make |
1,000 ml |
|
pH (adjusted with acetic acid or sodium hydroxide) |
6.00 |
|
Color Developing Solution |
Tank Solution |
Replenisher |
Pentasodium Nitrilo-N,N,N-trimethylenephosphonate |
2.0 g |
2.0 g |
Sodium Sulfite |
7.0 g |
7.0 g |
Trisodium Phosphate |
36 g |
36 g |
Dodecahydrate |
|
|
Potassium Bromide |
1.0 g |
- |
Potassium Iodide |
90 mg |
- |
Sodium Hydroxide |
3.0 g |
3.0 g |
Citrazinic Acid |
1.5 g |
1.5 g |
N-Ethyl-N-(B-methanesulfonamidoethyl)-3-methyl-4-aminoaniline·Sesquisulfate· Monohydrate |
11 g |
11 g |
3,6-Dithiaoctane-1,8-diol |
1.0 g |
1.0 g |
Water to make |
1,000 ml |
1,000 ml |
pH (adjusted with sulfuric acid or potassium hydroxide) |
11.80 |
12.00 |
Pre-bleaching Solution |
Tank Solution |
Replenisher |
Disodium Ethylenediamine-tetraacetate Dihydrate |
8.0 g |
8.0 g |
Sodium Sulfite |
6.0 g |
8.0 g |
1-Thioglycerol |
0.4 g |
0.4 g |
Sodium Bisulfite Addition Product of Formaldehyde |
30 g |
35 g |
Water to make |
1,000 ml |
1,000 ml |
pH (adjusted with acetic acid or sodium hydroxide) |
6.30 |
6.10 |
Bleaching Solution |
Tank Solution |
Replenisher |
Disodium Ethylenediamine-tetraacetate Dihydrate |
2.0 g |
4.0 g |
Ammonium Ethylenediamine-tetraacetato Ferrate (III) |
120 g |
240 g |
Dihydrate |
|
|
Potassium Bromide |
100 g |
200 g |
Ammonium Nitrate |
10 g |
20 g |
Water to make |
1,000 ml |
1,000 ml |
pH (adjusted with nitric acid or sodium hydroxide) |
5.70 |
5.50 |
Fixing Solution |
Tank Solution |
Replenisher |
Ammonium Thiosulfate |
80 g |
same as the tank solution |
Sodium Sulfite |
5.0 g |
" |
Sodium Bisulfite |
5.0 g |
" |
Water to make |
1,000 ml |
" |
pH (adjusted with acetic acid or aqueous ammonia) |
6.60 |
|
Stabilizing Solution |
Tank Solution |
Replenisher |
1,2-Benzisothiazolin-3-one |
0.02 g |
0.03 g |
Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10) |
0.3 g |
0.3 g |
Polymaleic Acid (average molecular weight: 2,000) |
0.1 g |
0.15 g |
Water to make |
1,000 ml |
1,000 ml |
pH |
7.0 |
7.0 |
[0087] The results of sensitometry and evaluation of residual colors are shown in the following
Tables 2 and 3. Relative sensitivities of the blue-sensitive layer and the red-sensitive
layer were compared based on the relative exposure amount giving density of minimum
density plus 1.0.
TABLE 2
Sample No. |
Replacement of Sensitizing Dye Sen-7 in Emulsions L to P |
Relative Sensitivity of Blue-Sensitive Layer |
Yellow Stain Density |
100* (blank) |
None |
|
0 (control) |
101* |
Sen-7 |
100 (control) |
0.073 |
102* |
Comparative Dye Sen-12 |
92 |
0.055 |
103* |
Comparative Dye Sen-13 |
109 |
0.088 |
104* |
S-1 |
113 |
0.017 |
105* |
S-2 |
114 |
0.028 |
106* |
S-3 |
115 |
0.025 |
107* |
S-5 |
115 |
0.015 |
108* |
S-6 |
112 |
0.018 |
109* |
S-7 |
116 |
0.012 |
110* |
S-10 |
125 |
0.034 |
111* |
S-15 |
111 |
0.020 |
112* |
S-64 |
119 |
0.015 |
113 (invention) |
S-66 |
124 |
0.012 |
114* |
S-76 |
142 |
0.0260 |
115* |
S-78 |
133 |
0.018 |
116* |
S-79 |
135 |
0.019 |
117* |
S-80 |
140 |
0.022 |
118* |
S-81 |
123 |
0.013 |
119* |
S-84 |
127 |
0.016 |
120* |
S-85 |
125 |
0.017 |
TABLE 3
Sample No. |
Replacement of Sensitizing Dye Sen-2 in Emulsions C to F |
Relative Sensitivity of Red-Sensitive Layer |
Magenta Stain Density |
100* |
None |
|
0 (control) |
101* |
Sen-2 |
100 (control) |
0.085 |
121* |
Comparative Dye Sen-10 |
92 |
0.067 |
122* |
Comparative Dye Sen-11 |
83 |
0.044 |
123* |
S-31 |
118 |
0.031 |
124* |
S-39 |
106 |
0.026 |
125* |
S-65 |
117 |
0.030 |
126* |
S-69 |
112 |
0.020 |
127* |
S-87 |
110 |
0.026 |
128* |
S-88 |
125 |
0.028 |
129* |
S-89 |
115 |
0.021 |
130* |
S-90 |
121 |
0.016 |
[0088] As is apparent from the results in Tables 2 and 3, photographic materials showing
less residual colors and having high sensitivity can be obtained by using the compounds
and emulsions used according to the present invention. Thus, it is apparent that high
sensitivity and less residual colors are compatible for the first time by using the
constitution according to the present invention.
EXAMPLE 9
Preparation of Seed Emulsion a
[0089] An aqueous solution (1,164 ml) comprised of 0.017 g of KBr and 0.4 g of oxidation-processed
gelatin having an average molecular weight of 20,000 was stirred with maintaining
the temperature at 35°C. An aqueous solution containing 1.6 g of AgNO
3, an aqueous solution of KBr and an aqueous solution containing 2.1 g of oxidation-processed
gelatin having an average molecular weight of 20,000 were added to the above solution
by a triple jet method over 48 seconds. At this time, the silver potential was maintained
at 13 mV to the saturated calomel electrode. An aqueous solution of KBr was added
thereto, and the silver potential was adjusted to -66 mV, and the temperature was
raised to 60°C. After 21 g of succinated gelatin having an average molecular weight
of 100,000 was added to the above solution, an aqueous solution containing 5.1 g of
NaCl was added. An aqueous solution containing 206.3 g of AgNO
3 and an aqueous solution containing KBr were added thereto by a double jet method
over 61 minutes with accelerating the flow rate. At this time, the silver potential
was maintained at -44 mV to the saturated calomel electrode. After desalting, succinated
gelatin having an average molecular weight of 100 , 000 was added to the solution
to adjust pH to 5.8 and pAg to 8.8 at 40°C, thus a seed emulsion was obtained. The
seed emulsion was tabular grain emulsion containing 1 mol of Ag and 80 g of gelatin
per kg of the emulsion, and having an average equivalent-circle diameter of 1.46 µm,
an equivalent-circle diametyer variation coefficient of 28%, an average thickness
of 0.046 µm, and an average aspect ratio of 32.
Formation of Core
[0090] An aqueous solution (1,200 ml) comprised of 134 g of the above-prepared Seed Emulsion
a, 1.9 g of KBr and 22 g of succinated gelatin having an average molecular weight
of 100,000 was stirred with maintaining the temperature at 75°C. An aqueous solution
containing 43.9 g of AgNO
3, an aqueous solution containing KBr, and an aqueous solution containing gelatin having
a molecular weight of 20,000 were mixed just before addition in another chamber equipped
with a magnetic coupling induction stirrer disclosed in
JP-A-10-43570, and added to the above emulsion over 25 minutes. At this time, the silver potential
was maintained at -40 mV to the saturated calomel electrode.
Formation of First Shell
[0091] After the formation of the above core grains, an aqueous solution containing 43.9
g of AgNO
3, an aqueous solution containing KBr, and an aqueous solution containing gelatin having
a molecular weight of 20,000 were mixed just before addition in the same another chamber,
and added to the above emulsion over 20 minutes. At this time, the silver potential
was maintained at -40 mV to the saturated calomel electrode.
Formation of Second Shell
[0092] After the formation of the above first shell, an aqueous solution containing 42.6
g of AgNO
3, an aqueous solution containing KBr, and an aqueous solution containing gelatin having
a molecular weight of 20,000 were mixed just before addition in the same another chamber,
and added to the above emulsion over 17 minutes. At this time, the silver potential
was maintained at -20 mV to the saturated calomel electrode, and then the temperature
was lowered to 55°C.
Formation of Third Shell
[0093] After the formation of the above second shell, the silver potential was adjusted
to -55 mV, and an aqueous solution containing 7.1 g of AgNO
3, an aqueous solution containing 6.9 g of KI, and an aqueous solution containing gelatin
having a molecular weight of 20,000 were mixed just before addition in the same another
chamber, and added to the above emulsion over 5 minutes.
Formation of Fourth Shell
[0094] After the formation of the above third shell, an aqueous solution containing 66.4
g of AgNO
3 and an aqueous solution containing KBr were added to the above emulsion by a double
jet method over 30 minutes at constant flow rate. Potassium iridium hexachloride and
yellow prussiate of potash were added en route. At this time, the silver potential
was maintained at 30 mV to the saturated calomel electrode. The emulsion was subjected
to ordinary washing, and then gelatin was added to adjust pH to 5.8 and pAg to 8.8
at 40°C. The thus-obtained emulsion was designated Emulsion b. Emulsion b was a tabular
grain emulsion having an average equivalent-circle diameter of 3.3 µm, an equivalent-circle
diameter variation coefficient of 21%, an average thickness of 0.090 µm and an average
aspect ratio of 37. Tabular grains having an equivalent-circle diameter of 3.3 µm
or more and a thickness of 0.090 µm or less accounted for 70% or more of the entire
projected area of Emulsion b.
[0095] Emulsion b was heated at 56°C, and after the sensitizing dye shown in Table 4 was
added in an amount of 1.1×10
-3 mol/mol Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and
N,N-dimethylselenourea were added and the emulsion was optimally chemically sensitized,
and stirred for 60 minutes.
[0096] The sensitizing dye was used as the solid fine particle dispersion prepared according
to the method disclosed in
JP-A-11-52507. That is, 0.8 weight parts of sodium nitrate and 3.2 weight parts of sodium sulfate
were dissolved in 43 parts of ion exchange water, 13 weight parts of the sensitizing
dye was added to the above solution, and dispersed by means of dissolver blades at
2, 000 rpm for 20 minutes on the condition of 60°C, thereby a solid dispersion of
the sensitizing dye was obtained.
Preparation of Coated Sample
[0098] Samples shown in Table 5 were subjected to sensitometric exposure for 1/100 sec.
and to the following development process.
Processing Step |
Processing Step |
Processing Time |
Temperature |
Replenishment Rate* |
Tank Capacity |
|
|
(°C) |
(ml) |
(liter) |
Color Development |
2 min 45 sec |
38 |
33 |
20 |
Bleaching |
6 min 30 sec |
38 |
25 |
40 |
Washing |
2 min 10 sec |
24 |
1,200 |
20 |
Fixing |
4 min 20 sec |
38 |
25 |
30 |
Washing (1) |
1 min 05 sec |
24 |
countercurrent system from (2) to (1) |
10 |
Washing (2) |
1 min 00 sec |
24 |
1,200 |
10 |
Stabilization |
1 min 05 sec |
38 |
25 |
10 |
Drying |
4 min 20 sec |
55 |
|
|
Replenishment rate: per 1 meter of 35 mm wide |
[0099] The composition of each processing solution is described below.
Color Developing Solution |
|
Mother Solution |
Replenisher |
|
(g) |
(g) |
Diethylenetriaminepentaacetic Acid |
1.0 |
1.1 |
1-Hydroxyethylidene-1,1-diphosphonic Acid |
3.0 |
3.2 |
Sodium Sulfite |
4.0 |
4.4 |
Potassium Carbonate |
30.0 |
37.0 |
Potassium Bromide |
1.4 |
0.7 |
Potassium Iodide |
1.5 mg |
- |
Hydroxylamine Sulfate |
2.4 |
2.8 |
4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline Sulfate |
4.5 |
5.5 |
Water to make |
1.0 1 |
1.0 1 |
pH |
10.05 |
10.05 |
Bleaching Solution |
|
Mother Solution |
Replenisher |
|
(g) |
(g) |
Sodium Ethylenediaminetetra-acetato Ferrate Trihydrate |
100.0 |
120.0 |
Disodium Ethylenediamine-tetraacetate |
10.0 |
11.0 |
Ammonium Bromide |
140.0 |
160.0 |
Ammonium Nitrate |
30.0 |
35.0 |
Aqueous Ammonia (27%) |
6.5 ml |
4.0 ml |
Water to make |
1.0 1 |
1.0 1 |
pH |
6.0 |
5.7 |
Fixing Solution |
|
Mother Solution |
Replenisher |
|
(g) |
(g) |
Sodium Ethylenediaminetetra-acetate |
0.5 |
0.7 |
Sodium Sulfite |
7.0 |
8.0 |
Sodium Bisulfite |
5.0 |
5.5 |
Aqueous Solution of Ammonium Thiosulfate (70%) |
170.0 ml |
200.0 ml |
Water to make |
1.0 1 |
1.0 1 |
pH |
6.7 |
6.6 |
Stabilizing Solution |
|
Mother Solution |
Replenisher |
|
(g) |
(g) |
Formalin (37%) |
2.0 ml |
3.0 ml |
Polyoxyethylene-p-monononylphenyl Ether (polymerization degree: 10) |
0.3 |
0.45 |
Disodium Ethylenediaminetetra-acetate |
0.05 |
0.08 |
Water to make |
1.0 1 |
1.0 1 |
pH |
5.8-8.0 |
5.8-8.0 |
[0100] The density of each processed sample was measured, i.e., Sample Nos. 201 to 206 were
measured through a red filter, Sample Nos. 207 to 209 were measured through a green
filter, and Sample Nos. 210 to 214 were measured through a blue filter respectively
and sensitivity was evaluated.
[0101] The reciprocal of the exposure amount giving density of fog density + 0.2 is taken
as sensitivity, and sensitivity of each sample is shown in a relative value taking
the value of Sample No. 201 as 100 with Sample Nos. 201 to 206, taking the value of
Sample No. 207 as 100 with Sample Nos. 207 to 209, and taking the value of Sample
No. 210 as 100 with Sample Nos. 210 to 214.
[0102] The sensitizing dye formed a J-association body having absorption maximum at about
605 nm in Sample No. 206, and at about 487 nm in Sample No. 213, and each sensitizing
dye showed similar spectral sensitivity distribution to that of absorption.
[0103] For further evaluating residual colors of sensitizing dyes, samples in Table 5 were
subjected to color development processing in the same manner as above (ordinarily
processed samples) as one group, and the samples were subjected to sufficient washing
processing (that is, the same processing was performed except that the time of washing
(2) in the processing step was changed to 30 minutes) to completely remove the remaining
sensitizing dyes (washing-processed samples) as the other group, each sample was not
subjected to exposure. Since the samples did not undergo exposure, development did
not occur and image-forming dyes were not formed.
[0104] After processing each sample, the spectrum by transmission mode of from 360 to 700
nm of each sample was recorded with a spectrophotometer. After that, for evaluating
the remaining sensitizing dye of the ordinarily processed sample, the difference spectrum
of the ordinarily processed sample and the washing-processed sample was taken. The
absorption of the difference spectrum means the amount of the retained dye, i.e.,
the residual color of the sensitizing dye. The residual color of each sample is shown
in a relative value of the absorbance of the peak wavelength of each sample taking
the absorbance of the peak wavelength of Sample No. 201 as 100 with Sample Nos. 201
to 206, taking the absorbance of the peak wavelength of Sample No. 207 as 100 with
Sample Nos. 207 to 209, and taking the absorbance of the peak wavelength of Sample
No. 210 as 100 with Sample Nos. 210 to 214.
[0105] Further, pressure resistance test was performed as follows. A needle having a diameter
of 0.1 mm was put on the above sample before exposure and 5 g of load was applied
to the needle and the needle was moved at a rate of 600 mm/min. (pressure processing).
The difference in density between the part where pressure processing was performed
and the part where pressure processing was not performed (pressure marks) of the sample
which had been development-processed without undergoing exposure was measured with
a micro-densitometer having an aperture diameter of 10 µm.
[0106] The results of evaluation of sensitivity, residual color and pressure marks of each
sample are shown in Table 5.
TABLE 5
Sample No. |
Dye |
Coupler |
Sensitivity |
Residual Color |
Pressure Marks |
Remarks |
201 |
Sen-14 |
A |
100 (criterion) |
100 (criterion) |
0.225 |
* |
202 |
S-110 |
A |
155 |
50 |
0.131 |
* |
203 |
S-109 |
A |
155 |
48 |
0.123 |
* |
204 |
S-98 |
A |
161 |
25 |
0.055 |
* |
205 |
S-99 |
A |
162 |
18 |
0.046 |
* |
206 |
S-96 |
A |
161 |
18 |
0.046 |
* |
207 |
Sen-15 |
B |
100 (criterion) |
100 (criterion) |
0.210 |
* |
208 |
S-111 |
B |
153 |
35 |
0.105 |
* |
209 |
S-108 |
B |
155 |
19 |
0.041 |
Invention |
210 |
Sen-16 |
C |
100 (criterion) |
100 (criterion) |
0.225 |
* |
211 |
S-129 |
C |
135 |
50 |
0.151 |
* |
212 |
S-130 |
C |
144 |
20 |
0.061 |
* |
213 |
S-131 |
C |
142 |
21 |
0.063 |
* |
214 |
S-132 |
C |
142 |
36 |
0.066 |
* |
[0107] It can be seen from the results in Table 5 that the sample containing the sensitizing
dye used according to the present invention is high is sensitivity and conspicuously
low in residual color. In particular, sensitivity is markedly improved in trimethyl
cyanine dyes.
[0108] The sample containing the sensitizing dye used according to the present invention
is also excellent in pressure marks (i.e., pressure resistance).
EXAMPLE 10
Preparation of (111) high silver chloride tabular grains (A)
[0109] To 1.2 liters of water were added 1.0 g of sodium chloride and 2.5 g of inert gelatin
and the temperature of the reaction vessel was maintained at 27 °C. An aqueous solution
of silver nitrate (75 ml) (containing 18 g of silver nitrate) and 75 ml of an aqueous
solution of sodium chloride (containing 6.2 g of sodium chloride and 0.75 g of inert
gelatin) were added to the reaction vessel by a double jet method with stirring over
1 minute. One minutes after the completion of addition, 18.6 ml of an aqueous solution
containing 0.92 mmol of Crystal Phase Controlling Agent-1 was added to the reaction
solution. One minute after that, 450 ml of a 10% aqueous solution of oxidation-processed
gelatin was added thereto. Then, the temperature of the reaction vessel was raised
to 55 °C over 28 minutes, and ripening was performed for 27 minutes.
[0110] After ripening, 2.35 mg of sodium benzylthiosulfate was added to the reaction solution.
Thereafter, an aqueous solution of silver nitrate (containing 263 g of silver nitrate)
and an aqueous solution of NaCl (containing 96 g of NaCl and 0.016 mg of K
2IrCl
6) were added to the reaction solution at an accelerated flow rate over 32 minutes.
At the same time, 2.63 mmol of Crystal Phase Controlling Agent-1 was added at an accelerated
flow rate (in proportion to the addition amount of silver nitrate). After that, an
aqueous solution of silver nitrate (containing 71 g of silver nitrate) and an NaCl
aqueous solution (containing 24.2 g of NaCl, 1.39 g of KI and 12 mg of yellow prussiate
of potash) were added to the reaction mixture at an accelerated flow rate over 14
minutes. After addition was finished, the temperature of the reaction solution was
raised to 75 °C over 20 minutes, and an aqueous solution of silver nitrate (containing
2.9 g of silver nitrate) and a KBr aqueous solution (containing 2.25 g of KBr) were
added to the reaction solution at a constant flow rate over 1 minute.
[0111] The temperature was lowered to 40 °C and washing was performed according to ordinary
flocculation method. After washing, 175 g of inert gelatin, 34 ml of phenoxyethanol
(35%) and 700 ml of distilled water were added to the above mixture. pH and pAg were
adjusted to 6.2 and 7.5 respectively using sodium hydroxide and an aqueous solution
of sodium chloride. Thus, grains (A) was obtained, in which 99% of the entire projected
area was occupied by tabular grains having an average equivalent-circle diameter of
0.85 µm and an average thickness of 0.146 µm. The variation coefficient of thickness
was 16.8% and the variation coefficient of equivalent-circle diameter was 19.0%.
Crystal Phase Controlling Agent-1
[0112]
Chemical sensitization
Preparation of coated sample and evaluation of photographic properties and stability
[0114] The surface of a paper support both surfaces of which were laminated with polyethylene
resin was subjected to corona discharge treatment. The support was provided with a
gelatin undercoat layer containing sodium dodecylbenzenesulfonate, and further, photographic
constitution layers, from the first layer to the seventh layer, described below were
coated in order to prepare a silver halide color photographic material samples shown
below. The coating solution of each photographic constitution layer was prepared as
described below.
Preparation of coating solution
[0115] Each coupler, color image stabilizer and ultraviolet absorber were dissolved in a
solvent and ethyl acetate. The solution was emulsified and dispersed in a 10 weight%
gelatin aqueous solution containing a surfactant by means of a high speed dissolver,
thus an emulsified dispersion was prepared.
[0116] The above emulsified dispersion and silver chlorobromide emulsion were mixed and
dissolved to prepare a coating solution having the composition described below.
[0117] As the gelatin hardening agent in each layer, 1-oxy-3,5-dichloro-s-triazine sodium
salt was used.
[0118] Further, Ab-1, Ab-2 and Ab-3 were added to each layer so that the total amount became
15.0 mg/m
2, 60.0 mg/m
2 and 5.0 mg/m
2, respectively.
[0119] High silver chloride emulsion used in each photosensitive emulsion layer was as follows.
Blue-Sensitive Emulsion Layer
Green-Sensitive Emulsion Layer
[0121] To silver chlorobromide emulsion (a cubic form, a mixture in a ratio of 1/3 (silver
molar ratio) of a large grain size emulsion having an average grain size of 0.45 µm
and a small grain size emulsion having an average grain size of 0.35 µm, variation
coefficients of the grain size distribution were 10% and 8% , respectively, emulsions
of both sizes contained 0.4 mol% of silver bromide localized at a part of the grain
surface and the remaining substrate was comprised of silver chloride), Sensitizing
Dye D was added to the large grain size emulsion in an amount of 3.0×10
-4 mol per mol of the silver halide and to the small grain size emulsion in an amount
of 3.6×10
-4 mol per mol of the silver halide, and Sensitizing Dye E was added to the large grain
size emulsion in an amount of 4.0×10
-5 mol per mol of the silver halide and to the small grain size emulsion in an amount
of 2.8×10
-4 mol per mol of the silver halide.
Red-Sensitive Emulsion Layer
[0122] To silver chlorobromide emulsion (a cubic form, a mixture in a ratio of 1/1 (silver
molar ratio) of large grain size emulsion having an average grain size of 0.40 µm
and small grain size emulsion having an average grain size of 0.30 µm, variation coefficients
of the grain size distribution were 0.09 and 0.11, respectively, emulsions of both
sizes contained 0.5 mol% of silver bromide localized at a part of the grain surface,
and the remaining substrate was comprised of silver chloride), Sensitizing Dyes G
and H were added to the large grain size emulsion each in an amount of 9.0×10
-5 mol per mol of the silver halide, and to the small grain size emulsion each in an
amount of 1.2×10
-5 mol per mol of the silver halide.
[0123] Further, the following Compound I was added to a red-sensitive emulsion layer in
an amount of 3.0×10
-3 mol per mol of the silver halide.
[0124] Further, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to a blue-sensitive
emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer
in an amount of 3.3×10
-4 mol, 1.0×10
-3 mol and 5.9×10
-4 mol, respectively, per mol of the silver halide.
[0125] Further, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to the second layer,
the fourth layer, the sixth layer and the seventh layer in an amount of 0.2 mg/m
2, 0.2 mg/m
2, 0.6 mg/m
2 and 0.1 mg/m
2, respectively.
[0126] Further, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to a blue-sensitive
emulsion layer and a green-sensitive emulsion layer in an amount of 1x10
-4 mol and 2x10
-4 mol respectively, per mol of the silver halide.
[0127] Copolymer of methacrylic acid and butyl acrylate (weight ratio: 1/1, average molecular
weight: from 200,000 to 400,000) was added to a red-sensitive emulsion layer in an
amount of 0.05 g/m
2. Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth
layer and the sixth layer in an amount of 6 mg/m
2, 6 mg/m
2 and 18 mg/m
2, respectively.
Layer Constitution
[0129] The constitution of each layer is described below. The numeral represents the coating
amount (g/m
2). The numeral for an emulsion represents the coating amount in terms of silver.
Support
(UV-A)
[0131] A mixture of UV-1/UV-2/UV-3/UV-4 in the weight ratio of 4/2/2/3
(UV-C)
[0133] Coated Sample Nos. 301 to 304 were prepared by using emulsions shown in Table 6 in
the blue-sensitive layer of the photographic material having the above layer constitution.
Exposure
[0134] Gradation exposure by three color separation was performed with laser beams of three
colors of B, G and R using the following apparatus. At that time, laser output was
modulated so that each sample could obtain appropriate improvement.
Exposure Apparatus
[0135] Three types of laser beams were used as light sources, that is, the wavelength of
YAG solid state laser (oscillation wavelength: 946 nm) using a semiconductor laser
GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source converted
with SHG crystal of LiNbO
3 having reversal domain structure to 473 nm, the wavelength of YVO
4 solid state laser (oscillation wavelength: 1,064 nm) using a semiconductor laser
GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source converted
with SHG crystal of LiNbO
3 having reversal domain structure to 532 nm, andAlGaInP (oscillation wavelength: 680
nm, manufactured by Matsushita Densan Co., Ltd., Type No. LN9R20). Each of three laser
beams was made to be able to successively scanning expose a color photographic paper
transferring vertically to scanning direction by a polygonal mirror the intensity
of which was modulated by AOM. For restraining the fluctuation of light amount due
to the changes of temperature, the temperature of semiconductor laser was maintained
constant using Peltier element. At this time, scanning exposure was performed at 600
dpi, and every beam diameter of B, G and R measured with a beam diameter meter (1180GP
manufactured by Beam Scan Co., U.S.A.) was 65 µm (circular beams showing the difference
in diameters in the main scanning direction/sub scanning direction of within 1%).
(Development process, dry to dry: 180 seconds)
[0136] The thus-exposed samples were processed by CP45X processing (manufactured by Fuji
Photo Film Co., Ltd.).
[0137] The reflection density of each processed color sample was measured using a TCD type
densitometer (manufactured by Fuji Photo Film Co., Ltd.). Sensitivity was expressed
as the logarithm of the exposure amount required to give color density of fog density
+ 1.0. Sensitivity of the blue-sensitive layer of each sample is shown in Table 7.
In Table 7, sensitivity of each sample is shown in a relative value taking the value
of Sample No. 301 as 0.00. A positive value shows that sensitivity is high.
Test of pressure marks
[0138] Pressuremarks (i.e., pressure resistance) test was performed as follows. A needle
having a diameter of 0.1 mm was put on each of the above samples and 10 g of load
was applied to the needle and the needle was moved at a rate of 600 mm/min. (pressure
processing).
The difference in density between the part where pressure processing was performed
and the part where pressure processing was not performed (pressure marks) of the sample
which had been development-processed without undergoing exposure was measured with
a micro-densitometer having an aperture diameter of 10 µm. The results obtained are
shown in Table 7.
TABLE 7
Sample No. |
Grains |
Blue Light Exposure |
Pressure Marks |
Remarks |
Fog |
Sensitivity |
301 |
A |
0.04 |
0.00 |
0.185 |
* |
302 |
A |
0.04 |
0.02 |
0 160 |
* |
303 |
A |
0.03 |
0.08 |
0.090 |
* |
304 |
A |
0.03 |
0.05 |
0.105 |
* |
EXAMPLE 11
[0139] A tabular silver iodobromide emulsion was prepared according to the method of preparing
Emulsion D in Example 5 of
JP-A-8-29904 and this was designated Emulsion Q.
[0140] Multilayer color photographic materials were prepared according to the method of
preparation of Sample No. 101 in Example 5 of
JP-A-8-29904. Sample Nos. 401 and 402 were prepared by replacing Emulsion D in the fifth layer
of Sample No. 101 in Example 5 of
JP-A-8-29904 with Emulsion Q, and further replacing ExS-1, 2 and 3 with Sensitizing Dye Sen-10
(5.0×10
-4 mol/Ag mol) or Sensitizing Dye S-31 (5.0×10
-4 mol/Ag mol).
[0141] For examining the sensitivity of the thus-obtained samples, each sample was exposed
for 1/100 sec. through an optical wedge and a red filter with Fuji FW type sensitometer
(a product of Fuji Photo Film Co., Ltd.), color development processing was performed
using the same processing step and processing solutions as in Example 1 of
JP-A-8-29904 and cyan density was measured. Sensitivity was a reciprocal of exposure amount required
to give density of fog density + 0.2 and expressed as a relative value.
[0142] As a result, Sample No. 402 showed high sensitivity of 113 as compared with sensitivity
100 (control) of Sample No. 401. Sample No. 402 also showed less residual colors after
processing.
EXAMPLE 12
[0143] In Emulsion 1 in Example 1 of
JP-A-7-92601, the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-10 (8×10
-4 mol/Ag mol) or Sensitizing Dye S-31 (8×10
-4 mol/Ag mol) to prepare tetradecahedral silver iodobromide emulsions, the thus-obtained
emulsions were designated Emulsion R and Emulsion S. Further, in Emulsion 1 in Example
1 of
JP-A-7-92601, the silver potential during the second double jet was changed from +65 mV to +115
mV, further, the spectral sensitizing dyes were replaced with Sensitizing Dye Sen-12
(8×10
-4 mol/Ag mol) or Sensitizing Dye S-76 (8×10
-4 mol/Ag mol) to prepare cubic silver iodobromide emulsions, the thus-obtained emulsions
were designated Emulsion T and Emulsion U.
[0144] Multilayer color photographic materials were prepared according to the method of
preparation of Sample No. 401 in Example 4 of
JP-A-7-92601. Emulsion 1 in the ninth layer of Sample No. 401 in Example 4 of
JP-A-7-92601 was replaced with Emulsion R or Emulsion S, the thus-obtained samples were designated
Sample Nos. 411 and 412. Similarly, Emulsion 1 in the ninth layer of Sample No. 401
in Example 4 of
JP-A-7-92601 was replaced with Emulsion T or Emulsion U, and these samples were designated Sample
Nos. 413 and 414.
[0145] The sensitivity of the thus-obtained samples was evaluated. In the same manner as
in Example 4 of
JP-A-7-92601, samples were subjected to exposure for 1/50 sec. and color reversal development
processing, and magenta density was measured. Sensitivity was a reciprocal of exposure
amount required to give density of minimum density +0.2 which was obtained with sufficient
exposure and expressed as a relative value taking the sensitivity of Sample No. 411
as 100. As a result, Sample No. 412 showed high sensitivity of 129. Sample No. 412
also showed less residual colors after processing. Further, Sample No. 414 showed
such high sensitivity of 133 taking the sensitivity of Sample No. 413 as 100. Sample
No. 414 also showed less residual colors after processing.
EXAMPLE 13
[0146] Octahedral silver bromide internal latent image type direct positive emulsion and
hexagonal tabular silver bromide internal latent image type direct positive emulsion
were prepared in the same manner as in the preparation of Emulsions 1 and 5 in Example
1 of
JP-A-5-313297 and these emulsions were named Emulsion V and Emulsion W.
[0147] Color diffusion transfer photographic films were prepared in the same manner as in
the preparation of Sample No. 101 in Example 1 of
JP-A-5-313297. In the sixteenth layer of Sample No. 101 in Example 1 of
JP-A-5-313297, Emulsion-2 was replaced with Emulsion V and Sensitizing Dye (3) was replaced with
Sensitizing Dye Sen-12 (9×10
-4 mol/Ag mol) or Sensitizing Dye S-76 (9×10
-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 421 and 422. Also,
in the eleventh layer of Sample No. 101 in Example 1 of
JP-A-5-313297, Emulsion-2 was replaced with Emulsion W and Sensitizing Dye (2) was replaced with
Sensitizing Dye Sen-10(9×10
-4 mol/Ag mol) or Sensitizing Dye S-31 (9×10
-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 423 and 424
[0148] For examining the sensitivity of the thus-obtained samples, processing was carried
out using the same exposure, processing step and processing solutions as in Example
1 of
JP-A-5-313297 and transfer density was measured using a color densitometer. Sensitivity was a reciprocal
of exposure amount required to give density of 1.0 and expressed as a relative value.
The sensitivity of Sample No. 422 was as high as 123 taking the sensitivity of Sample
No. 421 as 100. Sample No. 422 also showed less residual colors after processing.
Also, the sensitivity of Sample No. 424 was as high as 115 taking the sensitivity
of Sample No. 423 as 100. Sample No. 424 also showed less residual colors after processing.
EXAMPLE 14
[0149] In the preparation of Emulsion F in Example 2 of
JP-A-4-142536, red-sensitive sensitizing dye (S-1) was not added before sulfur sensitization, in
addition to sulfur sensitization using triethylthiourea, chloroauric acid was used
in combination and optimally gold-sulfur sensitized, and after gold-sulfur sensitization,
Sensitizing Dye Sen-10 (2×10
-4 mol/Ag mol) or Sensitizing Dye S-31 (2×10
-4 mol/Ag mol) was added, the thus-obtained silver chlorobromide emulsions were designated
Emulsions X and Y.
[0150] Multilayer color photographic papers were prepared in the same manner as in the preparation
of Sample No. 20 in Example 1 of
JP-A-6-347944. The emulsion in the fifth layer of Sample No. 20 in Example 1 of
JP-A-6-347944 was replaced with Emulsion X or Y, these samples were designated Sample Nos. 431
and 432.
[0151] For examining the sensitivity of the thus-obtained samples, samples were exposed
for 1/10 sec. through an optical wedge and a red filter with Fuji FW type sensitometer
(a product of Fuji Photo Film Co., Ltd.), color development processing was carried
out using the same processing step and processing solutions as in Example 1 of
JP-A-6-347944. As a result, Sample No. 432 showed such high sensitivity of 136 taking the sensitivity
of Sample No. 431 as 100. Sample No. 432 also showed less residual colors after processing.
EXAMPLE 15
[0152] Tabular silver chloride emulsions were prepared in the same manner as in the preparation
of Emulsion A in Example 1 of
JP-A-8-122954. In chemical sensitization (B) in Example 1 of the same patent, Sensitizing Dye-1
and Dye-2 were replaced with Sensitizing Dye Sen-10 (2×10
-4 mol/Ag mol) or Sensitizing Dye S-31 (2×10
-4 mol/Ag mol), the thus-obtained emulsions were designated Emulsion ZA and Emulsion
ZB.
[0153] Coated samples were prepared by replacing the emulsion in Example 1 of
JP-A-8-122954 with Emulsion ZA or Emulsion ZB and an emulsion layer and a surface protective layer
were coated in combination on both sides of the support by a simultaneous extrusion
method similar to in Example 1, these samples were designated Sample Nos. 441 and
442. The coated silver amount per one side was 1.75 g/m
2.
[0154] For examining the sensitivity of the thus-obtained samples, samples were exposed
for 0.05 sec. from both sides through an X-ray ortho-screen HGM produced by Fuji Photo
Film Co., Ltd. and processed with the same automatic processor and processing solutions
as in Example 1 of
JP-A-8-122954. Sensitivity was a reciprocal of exposure amount required to give a density of fog
+ 0.1 and expressed as a relative value taking the sensitivity of Sample No. 441 as
100. As a result, Sample No. 442 showed such high sensitivity of 120, and also showed
less residual colors after processing.
[0155] When exposure was performed using HR-4 or HGH in place of X-ray ortho-screen HGM,
the same effects could be obtained.
EXAMPLE 16
[0156] Tabular silver chloride emulsion was prepared in the same manner as in the preparation
of Emulsion D in Example 2 of
JP-A-8-227117 except that Sensitizing Dye-2 and Dye-3 were not added. This emulsion was designated
Emulsion ZC.
[0157] Coated samples were prepared in the same manner as in the preparation of Coated Sample
No. F in Example 3 of
JP-A-8-227117. Emulsion F in Coated Sample No. F in Example 3 of
JP-A-8-227117 was replaced with Emulsion ZC, and Sensitizing Dye-1 in Coated Sample No. F in Example
3 was replaced with Sensitizing Dye Sen-12 (5×10
-4 mol/Ag mol) or Sensitizing Dye S-76 (5×10
-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 451 and 452.
[0158] For examining the sensitivity of the thus-obtained samples, samples were exposed
for 1/100 second through an optical wedge and a blue filter using Fuji FW type sensitometer
(a product of Fuji Photo Film Co., Ltd.), subjected to Fuji Photo Film CN16 processing
and photographic characteristics were compared.
[0159] Sensitivity was a reciprocal of exposure amount required to give a density of fog
+ 0.2 and expressed as a relative value taking the sensitivity of Sample No. 451 as
100. Sample No. 452 showed such high sensitivity of 124, and also showed less residual
colors after processing.
EXAMPLE 17
[0160] Octahedral silver chloride emulsion was prepared in the same manner as in the preparation
of Emulsion F in Example 3 of
JP-A-8-227117, this was designated Emulsion ZD.
[0161] Coated samples were prepared in the same manner as in the preparation of Coated Sample
No . F in Example 3 of
JP-A-8-227117. Emulsion F and Sensitizing Dye-1 in Coated Sample No. F in Example 3 of
JP-A-8-227117 were replaced with Emulsion ZD and Sensitizing Dye Sen-12 (5×10
-4 mol/Ag mol) or Sensitizing Dye S-76 (5×10
-4 mol/Ag mol), the thus-obtained samples were designated Sample Nos. 461 and 462.
[0162] For examining the sensitivity of the thus-obtained samples, samples were subjected
to exposure for 1/100 sec. through an optical wedge and a red filter using Fuji FW
type sensitometer (a product of Fuji Photo Film Co. , Ltd.), subjected to Fuji Photo
Film CN16 processing and photographic characteristics were compared. Sensitivity was
a reciprocal of exposure amount required to give a density of fog + 0.2 and expressed
as a relative value taking the sensitivity of Sample No. 461 as 100. Sample No. 462
showed such high sensitivity of 129, and also showed less residual colors after processing.
EXAMPLE 18
[0163] Tabular grain emulsions were prepared in the same manner as in the preparation of
Emulsion CC disclosed in European Patent
0699950, and in chemical sensitization Sensitizing Dye Sen-12 was added in an amount of 5×10
-4 mol/Ag mol and chemical sensitization was performed, then Sen-12 was added in an
amount of 3×10
-4 mol/Ag mol, thereafter, further, Sen-12 was added in an amount of 3×10
-4 mol/Ag mol, this emulsion was designated Emulsion ZE, or S-76 was added in an amount
of 5×10
-4 mol/Ag mol and chemical sensitization was performed, then S-76 was added in an amount
of 3×10
-4 mol/Ag mol, thereafter, further, S-76 was added in an amount of 3×10
-4 mol/Ag mol, this emulsion was designated Emulsion ZF.
[0164] Coated samples were prepared in the same manner as in the preparation of the coated
samples in the example of European Patent
0699950, and a sample in which Emulsion ZE was used was designated Sample No. 471, and ZF
was used was designated Sample No. 472. The thus-prepared samples were subjected to
exposure and development in the same manner as in European Patent
0699950 and photographic characteristics were compared. Sensitivity was a reciprocal of exposure
amount required to give a density of fog + 0.2 and expressed as a relative value taking
the sensitivity of Sample No. 471 as 100. Sample No. 472 showed such high sensitivity
of 136, and also showed less residual colors after processing.
EXAMPLE 19
Preparation of Sample No. 501
[0165] Sample No. 101 in Example 8 was prepared and designated Sample No. 501.
Preparation of Sample Nos. 500, 502 to 516
[0166] Sample Nos. 502 to 516 were prepared by replacing sensitizing dye Sen-2 or Sen-7
used in the emulsion of Sample No. 501 with equimolar amount of the dye shown in Table
8 and Table 9, and Sample No. 500 (blank sample) was prepared by excluding both dyes.
Each piece of the samples thus obtained was subjected to 20 CMS white light exposure
for 1/100 sec. through a gray wedge, then processed by the same processing step and
same processing solutions as in Example 8, and sensitometry was performed.
[0167] The yellow stain density and the magenta stain density of blank Sample No. 500 were
subtracted from the yellow stain density and magenta stain density of each piece of
the samples after processing and residual color was evaluated. The stain density was
measured using a densitometer Status A, a product of X-RITE Co.
[0168] Sensitometry and the results of evaluation of residual color are shown in Tables
8 and 9 below. BL relative sensitivity and RL relative sensitivity were compared on
the basis of relative exposure amount giving minimum density + 1.0.
TABLE 8
Sample No. |
Sensitizing Dye in Emulsions L to P and Replacement of Sen-7 |
Relative Sensitivity of Blue-Sensitive Layer |
Yellow Stain Density |
500* |
None |
- |
0 (criterion) |
501* |
Sen-7 |
100 (criterion) |
0.073 |
502* |
Comparative Dye Sen-12 |
92 |
0.055 |
503* |
Comparative Dye Sen-13 |
109 |
0.088 |
504 (Invention) |
S-139 |
113 |
0.022 |
505* |
S-145 |
126 |
0.032 |
506 (Invention) |
S-148 |
124 |
0.035 |
507 (Invention) |
S-154 |
122 |
0.017 |
508* |
S-156 |
134 |
0.044 |
509 (Invention) |
S-157 |
130 |
0.033 |
510* |
S-158 |
125 |
0.036 |
TABLE 9
Sample No. |
Sensitizing Dye in Emulsions C to E and Replacement of Sen-2 |
Relative Sensitivity of Red-Sensitive Layer |
Magenta Stain Density |
500* |
None |
- |
0 (criterion) |
501* |
Sen-2 |
100 (criterion) |
0.085 |
511 |
Comparative Dye Sen-10 |
92 |
0.067 |
512* |
omparative Dye Sen-11 |
83 |
0.044 |
513 (Invention) |
S-150 |
118 |
0.025 |
514 (Invention) |
S-151 |
128 |
0.038 |
515 (Invention) |
S-152 |
125 |
0.026 |
516* |
S-155 |
130 |
0.032 |
[0169] As is apparent from the results in Tables 8 and 9, photographic materials exhibiting
less residual color and high sensitivity can be obtained by using the compounds and
emulsions used according to the present invention. Thus, high sensitivity is compatible
with less residual color for the first time by using the constitution of the present
invention.
EFFECT OF THE INVENTION
[0170] High sensitivity and excellent residual color effect can be obtained by the constitution
of the present invention.