Title: Silver halide photographic emulsion and silver halide photographic material containing said silver halide photographic emulsion
Abstract: A silver halide photographic emulsion which contains silver halide grains having light absorption strength of 100 or more.
Patent Number: 6,875,562 Issued on 04/05/2005 to Yamashita, et al.
| Inventors:
|
Yamashita; Katsuhiro (Kanagawa, JP);
Kobayashi; Katsumi (Kanagawa, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
| Appl. No.:
|
352106 |
| Filed:
|
January 28, 2003 |
Foreign Application Priority Data
| Oct 24, 1996[JP] | 8-282595 |
| Dec 26, 1996[JP] | 8-348524 |
| Current U.S. Class: |
430/505; 430/502; 430/543; 430/567; 430/569; 430/572; 430/573; 430/574; 430/577; 430/580 |
| Intern'l Class: |
G03C 001//46; G03C 001//00.5 |
| Field of Search: |
430/572,569,567,573,574,577,580,505,502,543
|
References Cited [Referenced By]
U.S. Patent Documents
| 3622316 | Nov., 1971 | Bird et al.
| |
| 3973969 | Aug., 1976 | Shiba et al.
| |
| 5302499 | Apr., 1994 | Merrill et al.
| |
| 5541047 | Jul., 1996 | Kashiwagi et al. | 430/522.
|
| 5561039 | Oct., 1996 | Ochiai.
| |
| 5573894 | Nov., 1996 | Kodama et al.
| |
| 5604088 | Feb., 1997 | Asami et al.
| |
| 5637446 | Jun., 1997 | Yamashita.
| |
| 6117629 | Sep., 2000 | Yamashita et al.
| |
| 6143486 | Nov., 2000 | Parton et al.
| |
| 6165703 | Dec., 2000 | Parton et al.
| |
| 6180332 | Jan., 2001 | Yamashita et al.
| |
| Foreign Patent Documents |
| 63-108335 | May., 1988 | JP.
| |
Other References
Thomas L. Penner et al., "Spectral Shifts and Physical Layering of
Sensitizing Dye Combinations in Silver Halide Emulsions," Photographic
Science and Engineering, vol. 20, No. 3, (1976), pp. 97-106.
|
Primary Examiner: Chea; Thorl
Attorney, Agent or Firm: Sughrue Mion, PLLC
Parent Case Text
This is a divisional of application Ser. No. 09/987,373 filed Nov. 14,
2001, now U.S. Pat. No. 6,537,742 which is a divisional of application
Ser. No. 09/739,884, filed Dec. 20, 2000, now issued as U.S. Pat. No.
6,387,610, which is a continuation of application Ser. No. 09/469,226,
filed Dec. 22, 1999, now issued as U.S. Pat. No. 6,180,332 B1, which is a
continuation of application Ser. No. 08/956,027, filed Oct. 22, 1997, now
issued as U.S. Pat. No. 6,117,629; the disclosures of which are
incorporated herein by reference.
Claims
What is claimed is:
1. A silver halide color photographic material containing a cyan coupler, a
magenta coupler and a yellow coupler, and comprising a silver halide
photographic emulsion comprising silver halide grains that have been
spectrally sensitized with sensitizing dyes that are multilayer adsorbed
onto a surface of said silver halide grains,
wherein said sensitizing dyes comprise an anionic dye and a cationic dye;
said sensitizing dyes are selected from the group consisting of a cyanine
dye, a merocyanine dye, a complex cyanine dye, a holopolar cyanine dye, a
hemicyanine dye, a styryl dye and a hemioxonol dye; and
said silver halide grains are tabular grains having an aspect ratio of 10
or more and have a halogen composition of the outermost surface such that
iodide content is 0.1 mol % or more.
2. The silver halide color photographic material according to claim 1,
wherein the total addition amount of said sensitizing dyes is 160% or more
of the saturated coated amount of said silver halide grains.
3. The silver halide color photographic material according to claim 1,
wherein 30% or more of the total addition amount of said sensitizing dyes
is the anionic dye, and 30% or more of the total addition amount of said
sensitizing dyes is the cationic dye.
4. The silver halide color photographic material according to claim 1,
wherein at least one of said sensitizing dyes comprises a merocyanine or
complex merocyanine dye having a nucleus having a ketomethylene structure.
5. A method for producing a silver halide color photographic material
containing a cyan coupler, a magenta coupler and a yellow coupler, and
comprising a silver halide photographic emulsion comprising silver halide
grains that have been spectrally sensitized with sensitizing dyes that are
multilayer adsorbed onto a surface of said silver halide grains,
wherein said sensitizing dyes comprise an anionic dye and a cationic dye;
said silver halide grains are tabular grains having an aspect ratio of 10
or more and have a halogen composition of the outermost surface such that
iodide content is 0.1 mol % or more,
wherein said silver halide photographic emulsion is prepared by adding the
anionic dye and the cationic dye differently; and
at least one of the anionic dye and the cationic dye is a) directly
dispersed in a hydrophilic colloid to form a dispersion and the dispersion
is added to a silver halide emulsion, or b) dissolved by a compound
capable of red-shifting an absorption of said dye to form a solution and
the solution is added to a silver halide emulsion.
6. The method for producing a silver halide color photographic material
according to claim 5, wherein 30% or more of the total addition amount of
said sensitizing dyes is the anionic dye, and 30% or more of the total
addition amount of said sensitizing dyes is the cationic dye.
7. The method for producing a silver halide color photographic material
according to claim 5, wherein the total addition amount of said
sensitizing dyes is 160% or more of the saturated coated amount of said
silver halide grains.
Description
FIELD OF THE INVENTION
The present invention relates to a spectrally sensitized silver halide
photographic emulsion and a method for producing the same and, further,
relates to a silver halide photographic material containing said emulsion.
BACKGROUND OF THE INVENTION
The sensitivity of a silver halide photographic material is determined by
the light absorption factor of a grain, latent image forming efficiency
including spectral sensitization efficiency and a minimum size of a latent
image.
Of these factors, as to techniques of improving the light absorption factor
of a grain, some which are known heretofore are shown below.
Techniques of high aspect ratio tabular grain emulsions disclosed in U.S.
Pat. No. 5,494,789, etc., are techniques capable of increasing a dye
adsorption amount per one grain because a tabular grain has a larger grain
surface area, as a result, the light absorption factor can be improved.
However, there are limitations in the increase of the surface area of a
grain by heightening an aspect ratio and the like, therefore, a larger
sized grain is necessary to improve the light absorption factor of one
grain.
In addition to the above, as methods of increasing the grain surface area
per one grain, methods of making a pore at a part of a grain are disclosed
in JP-A-58-106532 (the term "JP-A" as used herein means an "unexamined
published Japanese patent application") and JP-A-60-221320, and a ruffled
grain is disclosed in U.S. Pat. No. 4,643,966. However, the forms of
grains according to these methods are unstable and accompanied by extreme
difficulties in practical use.
Further, U.S. Pat. No. 5,302,499 discloses that a light absorption factor
can be improved by constituting the layer structure having spectral
sensitization characteristics and optimal grain thicknesses. But the
improvement of a light absorption factor by the optimization of the grain
thicknesses is at most 10% or so.
Accordingly, for markedly improving a light absorption factor of one grain
while maintaining a grain size small with a stable grain form, it is
necessary to improve the light absorption factor per unit surface area of
a grain. For that sake, it is necessary to heighten the adsorption density
of a sensitizing dye, but a generally used spectral sensitizing dye is
adsorbed onto a monolayer with almost the closest charging and is adsorbed
no more.
Methods which have been proposed for a sensitizing dye to be multilayer
adsorbed onto a grain surface are shown below.
In P. B. Gilman, Jr., et al., Photographic Science and Engineering, Vol.
20, No. 3, p. 97 (1976), a cationic dye is adsorbed onto the first layer
and an anionic dye is adsorbed onto the second layer using electrostatic
power.
Further, G. B. Bird, et al., in U.S. Pat. No. 3,622,316, a plurality of
dyes are multilayer adsorbed onto silver halide and sensitized by Forster
type excitation energy transfer.
However, even these above-described methods could not sufficiently improve
the light absorption factor per unit surface area of a silver halide
grain, therefore, a further technical development has been required.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method for producing a
silver halide emulsion having a high light absorption factor per unit area
of a grain surface and a photographic material of high sensitivity using
said emulsion.
The above object of the present invention has been achieved by the
following (1), (2), (3), (4), (5), (6), (7) and (8).
(1) A silver halide photographic emulsion which contains silver halide
grains having light absorption strength of 100 or more, wherein said
silver halide grains are preferably spectrally sensitized.
(2) A silver halide photographic material which has at least one silver
halide photographic emulsion layer containing the silver halide
photographic emulsion described in (1) above.
(3) A silver halide photographic emulsion which contains silver halide
grains having a spectral absorption maximum wavelength of 500 nm or less
and light absorption strength of 60 or more and less than 100, wherein
said silver halide grains are preferably spectrally sensitized.
(4) A silver halide photographic material which has at least one silver
halide photographic emulsion layer containing the silver halide
photographic emulsion described in (3) above.
(5) A silver halide photographic emulsion which contains at least one dye
represented by the following formula (1) or (2) in an amount equivalent to
the amount of 80% or more of the saturated coated amount and the total
addition amount of sensitizing dyes is equivalent to the amount of 160% or
more of the saturated coated amount:
##STR1##
wherein R.sub.11 and R.sub.12 each represents an alkyl group, at least one
of R.sub.11 and R.sub.12 is an alkyl group represented by R.sub.13, where
R.sub.14 represents a single bond or a divalent linking group and Y.sub.11
represents an aryl group or a heterocyclic aromatic group, and neither
R.sub.11 nor R.sub.12 has an anionic substituent; Z.sub.11 and Z.sub.12,
which may be the same or different, each represents a 5- or 6-membered
nitrogen-containing heterocyclic nucleus-forming atomic group; L.sub.11,
L.sub.12, L.sub.13, L.sub.14, L.sub.15, L.sub.16 and L.sub.17 each
represents a methine group; p.sub.11 and p.sub.12 each represents 0 or 1,
n.sub.11 represents 0, 1, 2 or 3; X.sub.11 represents a counter ion for
balancing a charge; and m.sub.11 represents a number of from 0 to 8
necessary for neutralizing a charge in the molecule;
##STR2##
wherein R.sub.21 and R.sub.22 each represents an alkyl group, at least one
of R.sub.21 and R.sub.22 is an alkyl group represented by R.sub.23, where
R.sub.24 represents a single bond or a divalent linking group and Y.sub.21
represents an aryl group or a heterocyclic aromatic group, and both
R.sub.21 and R.sub.22 have an anionic substituent; Z.sub.21 and Z.sub.22,
which may be the same or different, each represents a 5- or 6-membered
nitrogen-containing heterocyclic nucleus-forming atomic group; L.sub.21,
L.sub.22, L.sub.23, L.sub.24, L.sub.25, L.sub.26 and L.sub.27 each
represents a methine group; p.sub.21 and p.sub.22 each represents 0 or 1,
n.sub.21 represents 0, 1, 2 or 3; X.sub.21 represents a counter ion for
balancing a charge; and m.sub.21 represents a number of from 0 to 8
necessary for neutralizing a charge in the molecule.
(6) A silver halide photographic material which has at least one silver
halide photographic emulsion layer containing the silver halide
photographic emulsion described in (5) above.
(7) A silver halide photographic emulsion which contains at least one dye
represented by formula (1) and at least one dye represented by formula (2)
described in (5) above.
(8) A silver halide photographic material which has at least one silver
halide photographic emulsion layer containing the silver halide
photographic emulsion described in (7) above.
A sensitizing dye can be multilayer adsorbed onto the surface of a silver
halide grain according to the above method, and light absorption strength
by a sensitizing dye per unit area of a silver halide grain surface can be
made 100 or more, only when a grain has a spectral absorption maximum
wavelength of 500 nm or less, light absorption strength of 60 or more.
"Light absorption strength" in the above (1) and (3) means the light
absorption strength per unit surface area by a sensitizing dye except for
absorption by a silver halide grain. "The light absorption strength per
unit surface area by a sensitizing dye" used herein is defined as the
value obtained by integrating optical density Log (I.sub.0 /(I.sub.0 -I))
to wave number (cm.sup.-1), taking the light amount incident on the unit
surface area of a grain as I.sub.0 and the light amount absorbed by the
sensitizing dye at said surface as I, and the integrated range is from
5,000 cm.sup.-1 to 35,000 cm.sup.-1.
When a silver halide photographic emulsion contains silver halide grains
having light absorption strength of 100 or more (or light absorption
strength of 60 or more when the grains have spectral absorption maximum
wavelength of 500 nm or less), it is preferred that 1/2 or more of the
entire amount of silver halide grains contained in the emulsion be silver
halide grains having light absorption strength of 100 or more (or light
absorption strength of 60 or more when the grains have spectral absorption
maximum wavelength of 500 nm or less). Further, light absorption strength
is preferably from 100 to 100,000, provided that light absorption strength
of a grain having a spectral absorption maximum wavelength of 500 nm or
less is preferably from 80 to 100,000, more preferably from 100 to
100,000. With respect to a grain having a spectral absorption maximum
wavelength of 500 nm or less, a spectral absorption maximum wavelength is
preferably 350 nm or more.
According to the kinds of photographic materials, as it is required to have
strong absorption in a narrower wave number range, it is more preferred to
select the kinds of dyes so as to 90% or more of light absorption strength
is concentrated within the integrated range of from x cm.sup.-1 to x+5,000
cm.sup.-1 (where x is the value to make the above range of light
absorption strength maximum, 5,000 cm.sup.-1 <x<30,000 cm.sup.-1).
The saturated coated amount in the present invention is the amount of a
sensitizing dye which completely coats the grain surface of an emulsion
taking the molecular occupancy area of the sensitizing dye as 80
.ANG..sup.2.
In the method in (6) above, the total addition amount of sensitizing dyes
is preferably equivalent to the amount of 160% or more of the saturated
coated amount, more preferably the sum total of the addition amount of the
dyes represented by formulae (1) and (2) is equivalent to the amount of
160% or more of the saturated coated amount, and particularly preferably
the addition amount of each of the dyes represented by formulae (1) and
(2) is equivalent to the amount of 80% or more of the saturated coated
amount.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
In formula (1), preferred examples of nitrogen-containing heterocyclic
nuclei represented by Z.sub.11 and Z.sub.12 include thiazole,
benzothiazole, naphthothiazole, dihydronaphthothiazole, selenazole,
benzoselenazole, naphthoselenazole, dihydronaphthoselenazole, oxazole,
benzoxazole, naphthoxazole, benzimidazole, naphthoimidazole, pyridine,
quinoline, imidazo[4,5-b]quinoxaline and 3,3-dialkylindolenine. More
preferred nitrogen-containing heterocyclic nuclei are benzothiazole,
naphthothiazole, dihydronaphthothiazole, benzoselenazole,
naphthoselenazole, dihydronaphthoselenazole, benzoxazole, naphthoxazole;
benzimidazole or naphthoimidazole.
The above nitrogen-containing heterocyclic nuclei represented by Z.sub.11
and Z.sub.12 may have one or more substituents. Substituents are not
particularly limited, and preferred examples of substituents, when the
nitrogen-containing heterocyclic nuclei represented by Z.sub.11 and
Z.sub.12 are other than benzimidazole and naphthoimidazole, include a
lower alkyl group (which may be branched or may further have a substituent
(e.g., a hydroxyl group, a halogen atom, an aryl group, an aryloxy group,
an arylthio group, an alkoxyl group, an alkylthio group, an alkoxycarbonyl
group, etc.), more preferably an alkyl group having 8 or less total carbon
atoms, e.g., methyl, ethyl, butyl, chloroethyl, 2,2,3,3-tetrafluoropropyl,
hydroxyl, benzyl, methoxyethyl, ethylthioethyl, ethoxycarbonylethyl), a
lower alkoxyl group (which may further have a substituent, e.g., those
described above as substituents for the alkyl group, more preferably an
alkoxyl group having 8 or less total carbon atoms, e.g., methoxy, ethoxy,
pentyloxy, ethoxymethoxy, methylthioethoxy, phenoxyethoxy, hydroxyethoxy,
chloropropoxy), a hydroxyl group, a halogen atom, an aryl group (e.g.,
phenyl, tolyl, anisyl, chlorophenyl), a heterocyclic group (e.g., thienyl,
furyl, pyridyl), an aryloxy group (e.g., tolyloxy, anisyloxy, phenoxy,
chlorophenoxy), an arylthio group (e.g., tolylthio, chlorophenylthio,
phenylthio), a lower alkylthio group (which may further have a
substituent, e.g., those described above as substituents for the lower
alkyl group, more preferably an alkylthio group having 8 or less total
carbon atoms, e.g., methylthio, ethylthio, hydroxyethylthio,
chloroethylthio, benzylthio), an acylamino group (more preferably an
acylamino group having 8 or less total carbon atoms, e.g., acetylamino,
benzoylamino, methanesulfonylamino, benzenesulfonylamino), a carboxyl
group, a lower alkoxycarbonyl group (more preferably an alkoxycarbonyl
group having 6 or less total carbon atoms, e.g., ethoxycarbonyl,
butoxycarbonyl), a perfluoroalkyl group (more preferably a perfluoroalkyl
group having 5 or less total carbon atoms, e.g., trifluoromethyl,
difluoromethyl), and an acyl group (more preferably an acyl group having 8
or less total carbon atoms, e.g., acetyl, propionyl, benzoyl,
benzenesulfonyl). When the nitrogen-containing heterocyclic nuclei
represented by Z.sub.11 and Z.sub.12 are benzimidazole or
naphthoimidazole, preferred examples of substituents include a halogen
atom, a cyano group, a carboxyl group, a lower alkoxycarbonyl group (more
preferably an alkoxycarbonyl group having 6 or less total carbon atoms,
e.g., ethoxycarbonyl, butoxycarbonyl), a perfluoroalkyl group (more
preferably a perfluoroalkyl group having 5 or less total carbon atoms,
e.g., trifluoromethyl, difluoromethyl), and an acyl group (more preferably
an acyl group having 8 or less total carbon atoms, e.g., acetyl,
propionyl, benzoyl, benzenesulfonyl).
Specific examples of nitrogen-containing heterocyclic nuclei represented by
Z.sub.11 and Z.sub.12 include, e.g., benzothiazole, 5-methylbenzothiazole,
6-methylbenzothiazole, 5-ethylbenzothiazole, 5,6-dimethylbenzothiazole,
5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-butoxybenzothiazole,
5,6-dimethoxybenzothiazole, 5-methoxy-6-methylbenzothiazole,
5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole,
5-phenylbenzothiazole, 5-acetylaminobenzothiazole,
6-propionylaminobenzothiazole, 5-hydroxybenzothiazole,
5-hydroxy-6-methylbenzothiazole, 5-ethoxycarbonylbenzothiazole,
5-carboxybenzothiazole, naphtho[1,2-d]thiazole, naphtho[2,1-d]thiazole,
5-methylnaphtho[1,2-d]thiazole, 8-methoxynaphtho[1,2-d]thiazole,
8,9-dihydronaphthothiazole, 3,3-diethylindolenine, 3,3-dipropylindolenine,
3,3-dimethylindolenine, 3,3,5-trimethylindolenine, benzoselenazole,
5-methylbenzoselenazole, 6-methylbenzoselenazole,
5-methoxybenzoselenazole, 6-methoxybenzoselenazole,
5-chlorobenzoselenazole, 5,6-dimethylbenzoselenazole,
5-hydroxybenzoselenazole, 5-hydroxy-6-methylbenzoselenazole,
5,6-dimethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole,
naphtho[1,2-d]selenazole, naphtho[2,1-d]selenazole, benzoxazole,
5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole,
5-phenethylbenzoxazole, 5-phenoxybenzoxazole, 5-chlorobenzoxazole,
5-chloro-6-methylbenzoxazole, 5-phenylthiobenzoxazole,
6-ethoxy-5-hydroxybenzoxazole, 6-methoxybenzoxazole,
naphtho[1,2-d]oxazole, naphtho[2,1-d]oxazole,
1-ethyl-5-cyanobenzimidazole, 1-ethyl-5-chlorobenzimidazole,
1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-6-chloro-5-cyanobenzimidazole,
1-ethyl-6-chloro-5-trifluoromethylbenzimidazole,
1-ethyl-6-fluoro-5-cyanobenzimidazole,
1-propyl-5-butoxycarbonylbenzimidazole,
1-benzyl-5-methylsulfonylbenzimidazole,
1-allyl-5-chloro-6-acetylbenzimidazole, 1-ethyl-naphtho[1,2-d]imidazole,
1-ethylnaphtho[2,1-d]imidazole, 1-ethyl-6-chloronaphtho[2,1-d]imidazole,
2-quinoline, 4-quinoline, 8-fluoro-4-quinoline, 6-methyl-2-quinoline,
6-hydroxy-2-quinoline, 6-methoxy-2-quinoline, etc.
R.sub.11 and R.sub.12 in formula (1) each represents a substituted or
unsubstituted alkyl group which may contain an oxygen atom, a nitrogen
atom or a sulfur atom in the main chain thereof, and further may contain a
double bond or a triple bond. Preferred substituents include the
substituents described for Z.sub.11 and Z.sub.12 above, but an anionic
substituent is not included. The anionic substituent in the present
invention means a substituent having negative electric charge, i.e., an
atomic group liable to be dissociated under a neutral or slightly alkaline
condition, in particular, a substituent having a hydrogen atom. For
example, a sulfo group (--SO.sub.3 --), a sulfuric acid group (--OSO.sub.3
--), a carboxyl group (--CO.sub.2 --), a phosphoric acid group (--PO.sub.3
--), an alkylsulfonylcarbamoylalkyl group (e.g.,
methanesulfonylcarbamoylmethyl), an acylcarbamoylalkyl group (e.g.,
acetylcarbamoylmethyl), an acylsulfamoylalkyl group (e.g.,
acetylsulfamoylmethyl), or an alkylsulfonylsulfamoylalkyl group (e.g.,
methanesulfonylsulfamoylmethyl) can be cited.
Specific examples of R.sub.11 and R.sub.12 include, e.g., methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl,
benzyl, 2-phenylethyl, allyl, 2-hydroxyethyl, 3-hydroxypropyl,
2-methoxyethyl, 2-phenoxyethyl, 2-(1-naphthoxy)ethyl,
ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylpropyl,
2-acetylethyl, 2-(pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl, etc.
Both R.sub.11 and R.sub.12 are more preferably represented by R.sub.13.
The divalent linking group represented by R.sub.14 in R.sub.13 is more
preferably an alkylene group having 10 or less total carbon atoms, which
may contain an oxygen atom, a nitrogen atom or a sulfur atom in the main
chain thereof, or may contain a double bond or a triple bond. The alkylene
group may be branched, or may further have a substituent but an anionic
substituent is not included (those described above as examples of anionic
substituents can be cited, e.g., a sulfo group or a carboxyl group).
Substituents cited above as preferred substituents for Z.sub.11 and
Z.sub.12 can be cited as examples of preferred substituents for the
alkylene group, e.g., a halogen atom, a hydroxyl group, an alkoxyl group
having 6 or less carbon atoms, an aryl group having 8 or less carbon atoms
which may be substituted (e.g., phenyl, tolyl), a heterocyclic group
(e.g., furyl, thienyl), an aryloxy group having 8 or less carbon atoms
which may be substituted (e.g., chlorophenoxy, phenoxy, hydroxyphenoxy),
an acyl group having 8 or less carbon atoms (e.g., benzenesulfonyl,
methanesulfonyl, acetyl, propionyl), an alkoxycarbonyl group having 6 or
less carbon atoms (e.g., ethoxycarbonyl, butoxycarbonyl), a cyano group,
an alkylthio group having 6 or less carbon atoms (e.g., methylthio,
ethylthio), an arylthio group having 8 or less carbon atoms which may be
substituted (e.g., phenylthio, tolylthio), a carbamoyl group having 8 or
less carbon atoms which may be substituted (e.g., carbamoyl,
N-ethylcarbamoyl), an amino group, an ammonium group, or an acylamino
group having 8 or less carbon atoms (e.g., acetylamino,
methanesulfonylamino). The alkylene group may have one or more
substituents.
Specific examples of the groups represented by R.sub.14 include, e.g.,
methylene, ethylene, trimethylene, allylene, tetramethylene,
pentamethylene, hexamethylene, methoxyethylene, ethoxyethylene,
ethyleneoxy, ethylenethio, phenethylene, 2-trifluoromethylethylene,
2,2,3,3-tetrafluoroethylene, carbamoylethylene, hydroxyethylene, and
2-(2-hydroxyethoxy)ethylene, preferably methylene, ethylene, trimethylene,
tetramethylene, pentamethylene, 3-methyltetramethylene, and ethyleneoxy.
Y.sub.11 preferably represents an aryl group of condensed 5-membered or
less ring or a heterocyclic aromatic group, which may further have a
substituent, but an anionic substituent is not included (those described
above as examples of anionic substituents can be cited, e.g., a sulfo
group or a carboxyl group). Preferred examples of the aryl groups are
phenyl, naphthyl, anthracenyl, etc. Preferred examples of the heterocyclic
aromatic groups are pyridinium, quinoline, imidazole, benzimidazole, etc.
Substituents cited above as preferred substituents for Z.sub.11 and
Z.sub.12 can be cited as examples of preferred substituents for the aryl
and heterocyclic aromatic groups, e.g., a lower alkyl group having 6 or
less carbon atoms, e.g., methyl, ethyl, propyl, a halogen atom, a hydroxyl
group, an alkoxyl group having 6 or less carbon atoms, an aryl group
having 8 or less carbon atoms which may be substituted, a heterocyclic
group (e.g., furyl, thienyl), an aryloxy group having 8 or less carbon
atoms which may be substituted (e.g., chlorophenoxy, phenoxy,
hydroxyphenoxy), an acyl group having 8 or less carbon atoms (e.g.,
benzenesulfonyl, methanesulfonyl, acetyl, propionyl), an alkoxycarbonyl
group having 6 or less carbon atoms (e.g., ethoxycarbonyl,
butoxycarbonyl), a cyano group, an alkylthio group having 6 or less carbon
atoms (e.g., methylthio, ethylthio), an arylthio group having 8 or less
carbon atoms which may be substituted (e.g., phenylthio tolylthio), a
carbamoyl group having 8 or less carbon atoms which may be substituted
(e.g., carbamoyl, N-ethylcarbamoyl), an amino group, an ammonium group, or
an acylamino group having 8 or less carbon atoms (e.g., acetylamino,
methanesulfonylamino), and the aryl and heterocyclic aromatic groups may
have one or more substituents.
In formula (1), L.sub.11, L.sub.12, L.sub.13, L.sub.14, L.sub.15, L.sub.16
and L.sub.17 each independently represents a methine group. The methine
groups represented by L.sub.11 to L.sub.16 each may have a substituent,
e.g., a substituted or unsubstituted alkyl group having from 1 to 15,
preferably from 1 to 10, and more preferably from 1 to 5, carbon atoms
(e.g., methyl, ethyl, 2-carboxyethyl), a substituted or 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, o-carboxyphenyl), a substituted
or unsubstituted heterocyclic group having from 3 to 20, preferably from 4
to 15, and more preferably from 6 to 10, carbon atoms (e.g.,
N,N-diethylbarbituric acid), a halogen atom (e.g., chlorine, bromine,
fluorine, iodine), an alkoxyl group having from 1 to 15, preferably from 1
to 10, and more preferably from 1 to 5, carbon atoms (e.g., methoxy,
ethoxy), an alkylthio group having from 1 to 15, preferably from 1 to 10,
and more preferably from 1 to 5, carbon atoms (e.g., methylthio,
ethylthio), an aryloxy group having from 6 to 20, preferably from 6 to 15,
and more preferably from 6 to 10, carbon atoms (e.g., phenoxy), an
arylthio group having from 6 to 20, preferably from 6 to 15, and more
preferably from 6 to 10, carbon atoms (e.g., phenylthio), an amino group
having from 0 to 15, preferably from 2 to 10, and more preferably from 4
to 10, carbon atoms (e.g., N,N-diphenylamino, N-methyl-N-phenylamino,
N-methylpiperazino), etc. L.sub.11 to L.sub.16 may form a ring with other
methine groups or an auxochrome.
X.sub.11 represents a charge balancing ion which is necessary for
neutralizing an ionic charge of a dye. Examples of representative cations
include an inorganic cations such as a hydrogen ion (H.sup.+), an alkali
metal ion (e.g., a sodium ion, a potassium ion, a lithium ion), and an
alkaline earth metal ion (e.g., a calcium ion), and an organic ion such as
an ammonium ion (e.g., an ammonium ion, a tetraalkylammonium ion, a
pyridinium ion, an ethylpyridinium ion). Anions may be inorganic or
organic, e.g., a halogen ion (e.g., a fluoride ion, a chloride ion, an
iodide ion), a substituted arylsulfonate ion (e.g., a p-toluenesulfonate
ion, a p-chlorobenzenesulfonate ion), an aryldisulfonate ion (e.g., a
1,3-benzenedisulfonate ion, a 1,5-naphthalenedisulfonate ion, a
2,6-naphthalenedisulfonate ion), an alkylsulfate ion (e.g., a
methylsulfate ion), a sulfate ion, a thiocyanate ion, a perchlorate ion, a
tetrafluoroborate ion, a picrate ion, an acetate ion, or a
trifluoromethanesulfonate ion. Anions are preferably used. Further, ionic
polymers or other dyes having a counter charge can also be used.
Specific examples of dyes for use in the present invention are shown below.
##STR3##
##STR4##
##STR5##
##STR6##
##STR7##
##STR8##
##STR9##
##STR10##
##STR11##
##STR12##
In formula (2), Z.sub.21 and Z.sub.22, which may be the same or different,
each represents a 5- or 6-membered nitrogen-containing heterocyclic
nucleus-forming atomic group, and preferred nitrogen-containing
heterocyclic rings formed by Z.sub.11 and Z.sub.12 cited above can be
cited as preferred nitrogen-containing heterocyclic rings formed by
Z.sub.21 and Z.sub.22. The nitrogen-containing heterocyclic nuclei
represented by Z.sub.21 and Z.sub.22 may have one or more substituents,
and those cited above as preferred substituents for Z.sub.11 and Z.sub.12
can be cited as examples of preferred substituents for Z.sub.21 and
Z.sub.22. As specific examples of the nitrogen-containing heterocyclic
nuclei represented by Z.sub.21 and Z.sub.22, those cited above as specific
examples of the nitrogen-containing heterocyclic nuclei represented by
Z.sub.11 and Z.sub.12 can be cited.
R.sub.21 and R.sub.22 each represents an alkyl group, provided that it is
essential for both R.sub.21 and R.sub.22 to have at least one anionic
substituent (those enumerated above as examples of anionic substituents
can be cited, e.g., a sulfo group or a carboxyl group).
As examples of preferred alkyl groups, the same alkyl groups as preferred
alkyl groups represented by R.sub.11 and R.sub.12 in formula (1) can be
mentioned.
At least one of R.sub.21 and R.sub.22 is preferably represented by
R.sub.23, and more preferably each of R.sub.21 and R.sub.22 is represented
by R.sub.23. R.sub.24 in R.sub.23 represents a single bond or a divalent
linking group, and as preferred linking groups thereof, the same linking
groups cited as preferred linking groups represented by R.sub.14 can be
cited except that R.sub.24 may have an anionic substituent (those
described above as examples of anionic substituents can be mentioned,
e.g., a sulfo group or a carboxyl group).
Y.sub.21 represents an aryl group or a heterocyclic aromatic group, and as
preferred aryl groups and heterocyclic groups, the same aryl groups and
heterocyclic groups cited as preferred aryl groups and heterocyclic groups
represented by Y.sub.11 can be cited except that Y.sub.21 may have an
anionic substituent (those described above as examples of anionic
substituents can be mentioned, e.g., a sulfo group or a carboxyl group).
In R.sub.23, the position of substitution of an anionic substituent may be
either of R.sub.24 or Y.sub.21, or both may be substituted with anionic
substituents. Moreover, either one of R.sub.24 or Y.sub.21 may have a
plurality of anionic substituents.
L.sub.21, L.sub.22, L.sub.23, L.sub.24, L.sub.25, L.sub.26 and L.sub.27
each independently represents a methine group. The methine groups
represented by L.sub.21 to L.sub.26 each may have a substituent, e.g., and
as preferred substituents, those cited above as preferred substituents
represented by L.sub.11 to L.sub.16 can be cited. L.sub.21 to L.sub.26 may
form a ring with other methine groups or an auxochrome.
X.sub.21 represents a charge balancing ion which is necessary for
neutralizing an ionic charge of a dye. Those cited as examples of X.sub.11
can be used as a charge balancing ion. Cations are preferably used.
m.sub.21 represents a number of from 0 to 8 necessary for neutralizing a
charge in the molecule.
Specific examples of dyes for use in the present invention are shown below.
##STR13##
##STR14##
##STR15##
##STR16##
##STR17##
##STR18##
##STR19##
##STR20##
##STR21##
##STR22##
##STR23##
The structure of a sensitizing dye is not particularly limited in the
present invention, and a cyanine dye, a merocyanine dye, a complex cyanine
dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a
hemioxonol dye can be used. Of the above dyes, a particularly useful
sensitizing dye is a cyanine dye for the present invention.
Nuclei which are usually utilized as basic heterocyclic nuclei in cyanine
dyes can be applied to these dyes. For example, a pyrroline nucleus, an
oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole
nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a
tetrazole nucleus, a pyridine nucleus; the above nuclei to which alicyclic
hydrocarbon rings are fused; the above nuclei to which aromatic
hydrocarbon rings are fused, that is, an indolenine nucleus, a
benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a
naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus,
a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline
nucleus can be applied. These heterocyclic nuclei may be substituted on
the carbon atoms.
As a nucleus having a ketomethylene structure, a 5- or 6-membered
heterocyclic nucleus, such as a pyrazolin-5-one nucleus, a thiohydantoin
nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione
nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, or a
2-thio-selenazoline-2,4-dione can be applied to a merocyanine dye or a
complex merocyanine dye.
For example, the compounds described in Research Disclosure, 17643, p. 23,
Item IV (December, 1978), or compounds described in the literature cited
therein can be used.
Specifically, the following compounds (dyes) can be used.
a: 5,5'-Dichloro-3,3'-diethylcyanine bromide
b: 5,5'-Dichloro-3,3'-di(4-sulfobutyl)thiacyanine Na salt
c: 5-Methoxy-4,5-benzo-3,3'-di(3-sulfopropyl)thiacyanine Na salt
d: 5,5'-Dichloro-3,3'-diethylselenacyanine iodide
e: 5,5'-Dichloro-9-ethyl-3,3'-di(3-sulfopropyl)-thiacarbocyanine pyridinium
salt
f: Anhydro-5,5'-dichloro-9-ethyl-3-(4-sulfobutyl)-3'-ethyl hydroxide
g: 1,1-Diethyl-2,2'-cyanine bromide
h: 1,1-Dipentyl-2,2'-cyanine perchloric acid
i: 9-Methyl-3,3'-di(4-sulfobutyl)thiacarbocyanine pyridinium salt
j: 5,5'-Diphenyl-9-ethyl-3,3'-di(2-sulfoethyl)-oxacarbocyanine Na salt
k:
5-Chloro-5'-phenyl-9-ethyl-3-(3-sulfopropyl)-3'-(2-sulfoethyl)oxacarbocyan
ine Na salt
l: 5,5'-Dichloro-9-ethyl-3,3'-di(3-sulfopropyl)-oxacarbocyanine Na salt
m:
5,5'-Dichloro-6,6'-dichloro-1,1'-diethyl-3,3'-di(3-sulfopropyl)imidacarboc
yanine Na salt
n: 5,5'-Diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)-thiacarbocyanine Na salt
For the inclusion of the sensitizing dyes for use in the present invention
in the silver halide photographic emulsion of 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,
acetonitrile, tetrahydrofuran, N,N-dimethylformamide, etc., and then added
to the emulsion.
In addition, various methods can be used for the inclusion of the
sensitizing dyes in 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. Pat. No. 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 the
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 colloidal dispersion
coexisting with a surfactant as disclosed in U.S. Pat. Nos. 3,822,135 and
4,006,025, 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 be used for dissolution.
The sensitizing dyes represented by formulae (1) and (2) for use in the
present invention can be synthesized by referring to, for example,
JP-A-52-104917, JP-B-43-25652, JP-B-57-22368, F. M. Hamer, The Chemistry
of Heterocyclic Compounds, Vol. 18, The Cyanine Dyes and Related
Compounds, A. Weissberger ed., Interscience, New York, 1964, D. M.
Sturmer, The Chemistry of Heterocyclic Compounds, Vol. 30, A. Weissberger
and E. C. Taylor ed., John Wiley, New York, p. 441, and JP-A-270,164.
It is preferred that 30% or more of the total addition amount of the
sensitizing dyes for use in the present invention is anionic cyanine dyes
and 30% or more is present invention is anionic cyanine dyes and 30% or
more is cationic cyanine dyes.
Several kinds of dyes can be previously mixed and added to an emulsion but
cationic cyanine dyes and anionic cyanine dyes are preferably added
differently. Further, preferably cationic cyanine dyes are added first,
more preferably cationic dyes represented by formula (1) are added in an
amount equivalent to the amount of 80% or more of the saturated coated
amount, subsequently anionic cyanine dyes are added, and particularly
preferably cationic dyes represented by formula (1) are added in an amount
equivalent to the amount of 80% or more of the saturated coated amount,
then anionic cyanine dyes represented by formula (2) are added in an
amount equivalent to the amount of 50% or more of the saturated coated
amount.
When dyes are added differently, the fluorescent yield of the later added
dye in a gelatin dry film is preferably 0.5 or more, more preferably 0.8
or more.
It is also preferred that the reduction potential of the dye added later is
equal to or base than that of the dye added first, more preferably the
reduction potential of the dye added later is base by 0.03 V or more than
that of the dye added first. Further, it is preferred that the oxidation
potential of the dye added later is base by 0.01 V or more than that of
the dye added first, more preferably by 0.03 V or more.
Dyes may be added at any time of the emulsion preparation. The addition
temperature of dyes may be any degree but the emulsion temperature at the
time of dye addition is preferably from 10.degree. C. to 75.degree. C.,
and particularly preferably from 30.degree. C. to 65.degree. C.
The emulsion for use in the present invention may not be chemically
sensitized but is preferably chemically sensitized. The total addition
amount of dyes may be added before chemical sensitization or after
chemical sensitization, but optimal chemical sensitization can be obtained
by conducting chemical sensitization after a part of the dye is added and
adding the remaining part of the dyes after the chemical sensitization.
As chemical sensitizing methods, a gold sensitizing method using gold
compounds (e.g., U.S. Pat. Nos. 2,448,060, 3,320,069), a sensitizing
method using metals such as iridium, platinum, rhodium, palladium, etc,
(e.g., U.S. Pat. Nos. 2,448,060, 2,566,245, 2,566,263), a sulfur
sensitizing method using sulfur-containing compounds (e.g., U.S. Pat. No.
2,222,264), a selenium sensitizing method using selenium compounds, or a
reduction sensitizing method using tin salts, thiourea dioxide, polyamine,
etc. (e.g., U.S. Pat. Nos. 2,487,850, 2,518,698, 2,521,925) can be used
alone or in combination of two or more.
For the silver halide photographic emulsion of the present invention, gold
sensitization or sulfur sensitization, or a combination of them is
preferred. The preferred addition amount of a gold sensitizer and a sulfur
sensitizer is from 1.times.10.sup.-7 to 1.times.10.sup.-2 mol, more
preferably from 5.times.10.sup.-6 to 1.times.10.sup.-3 mol, per mol of the
silver, respectively. The preferred proportion of a gold sensitizer to a
sulfur sensitizer in the case of a combined use of gold sensitization and
sulfur sensitization is 1/3 to 3/1, and more preferably 1/2 to 2/1, in
molar ratio.
The temperature of chemical sensitization of the present invention can be
arbitrarily selected between 30.degree. C. and 90.degree. C. The pH at
chemical sensitization is from 4.5 to 9.0, preferably from 5.0 to 7.0. The
time of chemical sensitization cannot be determined unconditionally as it
varies depending upon the temperature, the kind and the amount of the
chemical sensitizer, pH, etc., but can be arbitrarily selected between
several minutes and several hours, generally from 10 minutes to 200 hours.
As silver halide for the photographic emulsion which rules light sensitive
mechanism in the present invention, any silver halide such as silver
bromide, silver iodobromide, silver chlorobromide, silver iodide, silver
iodochloride, silver iodobromochloride, and silver chloride can be used,
but by using silver halide having the halogen composition of the outermost
surface of the emulsion of iodide content of 0.1 mol % or more, more
preferably 1 mol % or more, and particularly preferably 5 mol % or more,
stronger multilayer adsorption structure can be constructed.
Grain size distribution may be broad or narrow, but narrow distribution is
preferred.
Silver halide grains in a photographic emulsion may have a regular crystal
form such as a cubic, octahedral, tetradecahedral, or rhombic dodecahedral
form, an irregular crystal form such as a spherical or plate-like form, a
form which has higher planes such as {hkl} plane, or a form which is a
composite of grains having these forms, but tabular grains having an
aspect ratio of 10 or more, more preferably 20 or more, are preferably
used. An aspect ratio is defined as the value obtained by dividing the
equivalent-circle diameter by the thickness of a grain. With respect to
grains having higher planes, Journal of Imaging Science, Vol. 30, pp. 247
to 254 (1986) can be referred to.
Silver halide photographic emulsions for use in the present invention may
comprise alone or the mixtures of two or more of these grains. The
interior and the surface layer of silver halide grains may be comprised of
different phases, grains may be a multiphase structure having a joined
structure, may have a local phase on the grain surface, may be comprised
of uniform phase, or may be the mixtures of these forms.
These various types of emulsions may be of the superficial latent image
type wherein the latent image is primarily formed on the surface, or of
the internal latent image type wherein the latent image is formed within
the grains.
The photographic emulsions for use in the present invention can be prepared
using 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), F. H. Claes et al., The
Journal of Photographic Science, (21) 39-50 (1973), F. H. Claes et al.,
ibid., (21) 85-92 (1973), JP-B-55-42737, U.S. Pat. Nos. 4,400,463,
4,801,523, JP-A-62-218959, JP-A-63-213836, JP-A-63-218938, and Japanese
Patent Application No. 62-291487. That is, any of an acid process, a
neutral process and an ammoniacal process may be used. Any of a single jet
method, a double jet method and a combination of these methods can be used
for the reaction of a soluble silver salt with a soluble halide. A method
in which grains are formed in the presence of excess silver ions (a
so-called reverse mixing method) can also be used. A method in which the
pAg in the liquid phase in which the silver halide is formed is kept
constant, that is, the controlled double jet method, can also be used as
one type of the double jet method. A silver halide photographic emulsion
having a regular crystal form and an almost uniform grain size can be
obtained with this method.
Further, an emulsion prepared by a so-called conversion method which
contains the process of converting grains to silver halide already formed
until the termination of the silver halide grain formation process, or an
emulsion subjected to the same halogen conversion after the termination of
the silver halide grain formation process can also be used.
In the preparation of silver halide grains for use in the present
invention, a silver halide solvent may be used.
As silver halide solvents which are frequently used, for example, thioether
compounds (e.g., disclosed in U.S. Pat. Nos. 3,271,157, 3,574,628,
3,704,130, 4,276,347), thione compounds and thiourea compounds (e.g.,
disclosed in JP-A-53-144319, JP-A-53-82408, JP-A-55-77737), and amine
compounds (e.g., disclosed in JP-A-54-100717) can be cited and these can
be used in the present invention. In addition, ammonia can also be used
within the range not being accompanied by a mal-effect.
A method in which the feeding rate, the addition amount and the addition
concentration of a silver salt solution (e.g., a silver nitrate solution)
and a halide solution (e.g., a sodium chloride solution) to be added are
increased on time schedule with a view to accelerating the grain growth is
preferably used in the preparation of silver halide grains. With respect
such methods, e.g., British Patent 1,335,925, U.S. Pat. Nos. 3,672,900,
3,650,757, 4,242,445, JP-A-55-142329, JP-A-55-158124, JP-A-55-113927,
JP-A-58-113928, JP-A-58-111934, JP-A-58-111936, etc., can be referred to.
During the process of forming silver halide grains or physical ripening,
cadmium salts, zinc salts, lead salts, thallium salts, rhenium salts,
ruthenium salts, iridium salts or complex salts thereof, rhodium salts or
complex salts thereof, iron salts or complex salts thereof may be present.
Rhenium salts, iridium salts, rhodium salts and iron salts are
particularly preferred.
The addition amount thereof can be arbitrarily selected according to
necessity, for example, the preferred addition amount of an iridium salt
(e.g., Na.sub.3 IrCl.sub.6, Na.sub.2 IrCl.sub.6, Na.sub.3 Ir(CN).sub.6,
etc.) is from 1.times.10.sup.-8 to 1.times.10.sup.-5 mol, per mol of the
silver, and that of a rhodium salt (e.g., RhCl.sub.3, K.sub.3
Rh(CN).sub.6, etc.) is from 1.times.10.sup.-8 to 1.times.10.sup.-6 mol,
per mol of the silver.
Various color couplers can be used in the present invention, and specific
examples are disclosed in the patents cited in the above Research
Disclosure, No. 17643, VII-C to G and ibid., No. 307105, VII-C to G.
Non-diffusible couplers having a hydrophobic group called a ballast group
or polymerized couplers are preferably used. Couplers may be either
2-equivalent or 4-equivalent to a silver ion. Colored couplers which have
the effect of correcting colors or couplers which release development
inhibitors upon development reaction (so-called DIR couplers) may be
contained. Further, colorless DIR coupling compounds which produce a
colorless coupling reaction product and release a development inhibitor
may be contained.
Examples of preferred cyan couplers for use in the present invention
include, e.g., naphthol based couplers and phenol based couplers, and
preferred are those disclosed in U.S. Pat. Nos. 2,369,929, 2,772,162,
2,801,171, 2,895,826, 3,446,622, 3,758,308, 3,772,002, 4,052,212,
4,126,396, 4,146,396, 4,228,233, 4,254,212, 4,296,199, 4,296,200,
4,327,173, 4,333,999, 4,334,011, 4,343,011, 4,427,767, 4,451,559,
4,690,889, 4,775,616, West German Patent Publication No. 3,329,729,
EP-A-121365, EP-A-249453, and JP-A-61-42658.
As magenta couplers, imidazo[1,2-b]pyrazoles disclosed in U.S. Pat. No.
4,500,630 and pyrazolo[1,5-b]-[1,2,4]triazoles disclosed in U.S. Pat. No.
4,540,654 are particularly preferably used. Other preferred magenta
couplers include pyrazolotriazole couplers in which a branched alkyl group
is directly bonded to the 2-3- or 6-position of the pyrazolotriazole ring
disclosed in JP-A-61-65245, pyrazoloazole couplers having a sulfonamido
group in the molecule disclosed in JP-A-61-65246, pyrazoloazole couplers
having an alkoxyphenylsulfonamido ballast group disclosed in
JP-A-61-147254, and pyrazolotriazole couplers having an alkoxyl group or
an aryloxy group at the 6-position disclosed in European Patents
(Publication) 226849 and 294785, in addition, couplers disclosed in U.S.
Pat. Nos. 3,061,432, 3,725,067, 4,310,619, 4,351,897, 4,556,630, European
Patent 73636, JP-A-55-118034, JP-A-60-35730, JP-A-60-43659,
JP-A-60-185951, JP-A-61-72238, WO 88/04795, Research Disclosure, No. 24220
and ibid. No. 24230 are more preferably used.
Preferred yellow couplers are those disclosed, for example, in U.S. Pat.
Nos. 3,933,501, 3,973,968, 4,022,620, 4,248,961, 4,314,023, 4,326,024,
4,401,752, 4,511,649, EP-A-249473, JP-B-58-10739, British Patents
1,425,020, and 1,476,760, and the use pivaloylacetanilide is more
preferred.
The above-described couplers which can be preferably used in the present
invention are the same as those disclosed in detail in JP-A-2-248945 as
preferred couplers, and as specific examples of the above couplers which
can preferably be used in the present invention, specific examples of
couplers disclosed in JP-A-2-248945, pp. 22 to 29 can be cited.
Typical examples of polymerized dye-forming couplers are disclosed in U.S.
Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, 4,576,910,
EP-A-341188 and British Patent 2,102,137 and they are more preferably
used.
The couplers disclosed in U.S. Pat. No. 4,366,237, European Patent 96570,
British Patent 2,125,570, and West German Patent Publication No. 3,234,533
are preferred as couplers the colored dyes of which have an appropriate
diffusibility.
The preferred colored couplers for correcting the unnecessary absorption of
colored dyes are disclosed in the patents described in Research
Disclosure, No. 17643, item VII-G, ibid., No. 307105, item VII-G, U.S.
Pat. Nos. 4,004,929, 4,138,258, 4,163,670, British Patent 1,146,368, and
JP-B-57-39413. Moreover, it is also preferred to use couplers for
correcting the unnecessary absorption of colored dyes by fluorescent dyes
released upon coupling disclosed in U.S. Pat. No. 4,774,181, and couplers
having a dye precursor group capable of forming a dye upon reacting with a
developing agent as a releasable group disclosed in U.S. Pat. No.
4,777,120.
Compounds which release photographically useful residual groups upon
coupling can also preferably be used in the present invention. The
preferred DIR couplers which release development inhibitors are disclosed
in the patents cited in the foregoing Research Disclosure, No. 17643, item
VII-F, ibid., No. 307105, item VII-F, JP-A-57-151944, JP-A-57-154234,
JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, U.S. Pat. Nos. 4,248,962 and
4,782,012.
Couplers disclosed in JP-A-59-157638, JP-A-59-170840, British Patents
2,097,140, and 2,131,188 are preferred as couplers which imagewise release
nucleating agents or development accelerators at the time of development.
Further, compounds which release fogging agents, development accelerators,
silver halide solvents, etc., upon oxidation reduction reaction with the
oxidation products of developing agents disclosed in JP-A-60-107029,
JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687 are also preferred.
Other compounds which can be used in the photographic material of the
present invention include competitive couplers disclosed in U.S. Pat. No.
4,130,427, multiequivalent couplers disclosed in U.S. Pat. Nos. 4,283,472,
4,338,393 and 4,310,618, DIR redox compound-releasing couplers, DIR
coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR
redox-releasing redox compounds disclosed in JP-A-60-185950 and
JP-A-62-24252, couplers which release dyes which restore colors after
separation disclosed in EP-A-173302 and EP-A-313308, bleaching
accelerator-releasing couplers disclosed in the patents cited in Research
Disclosure, No. 11449, ibid., No. 24241 and JP-A-61-201247,
ligand-releasing couplers disclosed in U.S. Pat. No. 4,553,477, leuco
dye-releasing couplers disclosed in JP-A-63-75747, and fluorescent
dye-releasing couplers disclosed in U.S. Pat. No. 4,774,181.
Two or more of the above couplers, etc., can be used in combination in the
same layer for satisfying the characteristics required of the photographic
material, or, of course, the same compound can be added to two or more
different layers.
The above couplers are contained in a silver halide photographic emulsion
layer which constitutes a light-sensitive layer generally in an amount of
from 0.1 to 1.0 mol, preferably from 0.1 to 0.5 mol, per mol of the silver
halide.
In the present invention, various known methods can be used to incorporate
the above couplers into a light-sensitive layer. In general, an
oil-in-water dispersing method known as an oil-protect method is
effectively used for the addition. That is, the coupler is dissolved in a
solvent, then dispersed in an aqueous solution of gelatin containing a
surfactant. Alternatively, couplers may be added as oil-in-water
dispersion accompanied by phase inversion by adding water or an aqueous
solution of gelatin to a coupler solution containing a surfactant. In
addition, alkali-soluble couplers can be dispersed according to a
so-called Fischer dispersing method. After a low boiling point organic
solvent is removed from the coupler dispersion by distillation, noodle
washing or ultrafiltration, couplers may be mixed with a photographic
emulsion.
As a dispersion medium of couplers, it is preferred to use a high boiling
point organic solvent having a dielectric constant of from 2 to 20 at
25.degree. C. and a refractive index o
