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Description  |
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FIELD OF THE INVENTION
The present invention relates to a silver halide light-sensitive material
containing a novel streptocyanine dye. More specifically, the present
invention relates to a silver halide light-sensitive material containing a
linking-type streptocyanine dye that comprises streptocyanine dyes
connected with each other through two divalent linking groups at two
positions of each of the dyes.
BACKGROUND OF THE INVENTION
Streptocyanine dye is an important photographic sensitizing dye. However,
in the present state of the art, absorbability of the dye to a silver
halide emulsion (grains) is weak. Consequently, the absorptivity of the
dye in the silver halide emulsion is low and insufficient.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a silver
halide light-sensitive material that exhibits high absorptivity
(light-absorption factor).
Other and further objects, features, and advantages of the invention will
appear more fully from the following description.
DETAILED DESCRIPTION OF THE INVENTION
The above-described object of the present invention has been attained by a
silver halide light-sensitive material containing a streptocyanine dye
represented by the following general formula (1):
General formula (1)
##STR2##
wherein A1, A2, and A3 each represent a streptocyanine dye; L1, L2, L3,
and L4 each represent a divalent linking group, and n1 represents an
integer of not less than 0.
In particular, a silver halide light-sensitive material containing a
streptocyanine dye represented by general formula (2) as shown below, is
effective. General formula (2)
##STR3##
wherein R1, R2, R3, and R4 each represent an alkyl group or an aryl group;
E1, E2, E3, E4, E5, E6, E7, E8, and E9 each represent a methine group; L5,
L6, L7, and L8 each represent a divalent linking group; m1, m2, m3, and n2
each represent an integer of not less than 0, and M represents an ion for
charge neutralization.
Streptocyanine dyes represented by general formula (1) or (2) are explained
below in detail.
A1, A2, and A3 each represent a streptocyanine dye. The streptocyanine dye
is a general term of compounds having a conjugated system represented by
general formula (3) as shown below.
##STR4##
wherein Y1, Y2, and Y3 each represent a hydrogen atom, an alkyl group
having 1 to 20 carbon atoms e.g. methyl, ethyl, n-propyl, n-butyl,
n-pentyl, n-hexyl, n-heptyl, n-nonyl, i-propyl, i-butyl, i-pentyl, and
t-butyl; and the alkyl group further includes those substituted with a
substituent, examples of which substituents are a halogen atom (e.g.
chlorine, bromine, iodine, fluorine), a nitro group, an alkoxy group (e.g.
methoxy, ethoxy), an aryl group (e.g. phenyl), an aryloxy group (e.g.
phenoxy), an amido group, a carbamoyl group, a sulfo group, a hydroxyl
group, a carboxyl group, an alkylthio group (e.g. methylthio), and a cyano
group; hereinafter these groups are referred to as a substituent group X!,
an aryl group having 6 to 20 carbon atoms (e.g. phenyl, 1-naphthyl, and
2-naphthyl; and the aryl group further includes those substituted with
such a substituent as the above-described substituent group X), an alkoxy
group having 1 to 20 carbon atoms (e.g. methoxy, ethoxy; and the alkoxy
group further includes those substituted with such a substituent as the
above-described substituent group X), or an aryloxy group having 6 to 20
carbon atoms (e.g. phenoxy; and the aryloxy group further includes those
substituted with such a substituent as the above-described substituent
group X); Y4, Y5, Y6, and Y7 each represent a hydrogen atom, an alkyl
group having 1 to 20 carbon atoms (e.g. methyl, ethyl, n-propyl, n-butyl,
n-pentyl, n-hexyl, n-heptyl, n-nonyl, i-propyl, i-butyl, i-pentyl, and
t-butyl; and the alkyl group further includes those substituted with such
a substituent as the above-described substituent group X), or an aryl
group having 6 to 20 carbon atoms (e.g. phenyl, 1-naphthyl, and
2-naphthyl; and the aryl group further includes those substituted with
such a substituent as the above-described substituent group X); and n3
represents an integer of not less than 0.
Specific examples of the streptocyanine dyes include Dye Nos. 61021 to
61074 described by M. Okawara, T. Kitao, T. Hirashima, M. Matuoka, in
Organic Colorants, A Handbook of Data of Selected Dye for Electro-optical
Applications, Elsvir, New York (1988), pp. 306 to 308.
Al and A3 may be connected to each other to form a streptocyanine dye,
forming a ring structure.
L1, L2, L3, L4, L5, L6, L7, and L8 each represent a divalent linking group.
Examples of the divalent linking group include an alkylene group having 1
to 20 carbon atoms e.g. ethylene, propylene, butylene, 1-methylethylene,
and 2-methylpropylene; and the alkylene group further includes those
substituted with such a substituent as the above-described substituent
group X; and the alkylene group may contain, in its main chain, a hetero
atom (e.g. oxygen, sulfur, nitrogen), an arylene group (e.g.
1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene), a
heterocyclic group (e.g. 2,3-pyridylene) and the like!, an alkenylene
group having 1 to 20 carbon atoms (e.g. 1,2-ethenylene,
1-methyl-1,2-ethenylene, 1,2-dimethyl-1,2-ethenylene, 1,3-(1-propenylene),
and 1,4-(2-butenylene); and the alkenylene group further includes those
substituted with such a substituent as the above-described substituent
group X), and an alkinylene group having 1 to 20 carbon atoms (e.g.
ethinylene, and propinylene; and the alkinylene group further includes
those substituted with such a substituent as the above-described
substituent group X).
A preferable example of each of L1, L2, L3, L4, L5, L6, L7, and L8 is an
alkylene group. An ethylene group is particularly preferred.
R1, R2, R3, and R4 each represent an alkyl group having 1 to 20 carbon
atoms e.g. methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
n-nonyl, i-propyl, i-butyl, i-pentyl, and t-butyl; and the alkyl group
further includes those substituted with such a substituent as the
above-described substituent group X; and R1 and R2, and R3 and R4, may be
combined together to form such a ring as 4-, 5-, 6- or 7-membered ring, in
which ring a hetero atom (e.g. oxygen, sulfur, and nitrogen), an arylene
group (e.g. 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene),
and a heterocyclic ring (e.g. 2,3-pyridylene) may exist!, or an aryl group
having 6 to 20 carbon atoms (e.g. phenyl, 1-naphthyl, and 2-naphthyl; and
the aryl group further includes those substituted with such a substituent
as the above-described substituent group X).
Preferably examples of each of R1, R2, R3, and R4 include an unsubstituted
alkyl group, a cyclic alkyl group, and an aryl group. A methyl group, an
ethyl group, and a piperazine ring are especially preferred.
E1, E2, E3, E4, E5, E6, E7, E8, and E9 each represent a methine group
having 1 to 20 carbon atoms, which group may be substituted with such a
substituent as the above-described substituent group X. Preferred examples
of the substituent include a methyl group, an ethyl group, a phenyl group,
a chlorine atom, a bromine atom, and a methoxy group. Preferably, each of
El, E2, E3, E4, E5, E6, E7, E8, and E9 is an unsubstituted methine group.
n1 and n2 each represent an integer of not less than 0. Preferably, each of
them is not more than 1,000, although there is no particular upper
limitation. When the dye is a polymer dye, each of nl and n2 is preferably
in the range of from 10 to 100, and especially preferably from10 to 20.
When the dye is an oligomer, each of n1 and n2 is preferably in the range
of from 0 to 10, and especially preferably 0, 1, 2, or 3.
n3, ml, m2, and m3 each are preferably 0, 1, 2, 3, 4, or 5, and more
preferably 1, 2, or 3.
M represents an ion for charge neutralization. Whether a specific compound
is cationic or anionic, or whether the compound has a net ionic charge,
depends on the compound's substituent. Typical examples of a cation are an
ammonium ion and an alkali metal ion. On the other hand, an anion may be
an inorganic ion or an organic ion.
Examples of the cation include a sodium ion, a potassium ion, a
triethylammonium ion, a pyridinium ion, and a 1-ethylpyridinium ion.
Examples of the anion include a halogen anion (e.g. chloride, bromide,
fluoride, and iodide ion), a substituted arylsulfonic acid ion (e.g. a
peratoluene sulfonic acid ion), an alkylsulfuric acid ion (e.g. a methyl
sulfuric acid ion), a sulfuric acid ion, a perchioric acid ion, a
tetrafluoroboric acid ion, and an acetic acid ion.
Preferable combinations of streptocyanine dyes and linking groups are
explained below.
When the dye is represented by general formula (1), preferable combinations
are as follows:
a combination in which Al to A3 each represent a trimethinestreptocyanine
dye, and L1 to L4 each represent an alkylene group (n1 represents an
integer of not less than 0); a combination in which A1 to A3 each
represent a pentamethinestreptocyanine dye, L1 to L4 each represent an
alkylene group, and n1 is 0 or 1; a combination in which A1 to A3 each
represent a pentamethinestreptocyanine dye, L1 to L4 each represent an
alkylene group, and n1 is an integer of not less than 2; and a combination
in which A1 to A3 each represent a heptamethinestreptocyanine dye, and L1
to L4 each represent an alkylene group (n1 is an integer of not less than
0).
When the dye is represented by general formula (2), a combination in which
R1 to R4 each represent an alkyl group, L5 to L8 each represent an
alkylene group, E1 to E9 each represent an unsubstituted methine group, ml
to m3 each represent 1, 2, or 3, and n2 is an integer of from 0 to 10 is
preferred.
Specific examples of the compound represented by general formulas (1) and
(2) for use in the present invention are illustrated below, but the
present invention is not limited to those shown.
__________________________________________________________________________
##STR5##
Compound No.
m n R1 R2 M
__________________________________________________________________________
1 0 0 Me Me ClO.sub.4 .sup.-
2 0 1 Me Me Cl.sup.-
3 1 0 Me Me ClO.sub.4 .sup.-
4 1 1 Me Me Cl.sup.-
5 1 1 Me Me BF.sub.4 .sup.-
6 1 2 Me Me Cl.sup.-
7 2 0 Me Me ClO.sub.4 .sup.-
8 2 1
##STR6## Cl.sup.-
9 2 2
##STR7## Cl.sup.-
10 2 0
##STR8## Cl.sup.-
11 2 5
##STR9## Cl.sup.-
12 2 0
##STR10## Cl.sup.-
13 3 0 Me Me ClO.sub.4 .sup.-
14 4 0 Me Me ClO.sub.4 .sup.-
__________________________________________________________________________
##STR11##
Compound No.
m n R1 R2 R3 M
__________________________________________________________________________
15 2 1 Me Me H ClO.sub.4 .sup.-
16 2 2 Me Me H ClO.sub.4 .sup.-
17 2 3 Me Me H ClO.sub.4 .sup.-
18 2 4 Me Me H Cl.sup.-
19 2 10 Me Me H Cl.sup.-
20 2 0 Me Me Me BF.sub.6 .sup.-
21 1 0 Me Me CH.sub.3
ClSO.sub.3 .sup.-
22 I 0 Me Me CH.sub.2 Ph
ClSO.sub.3 .sup.-
23 2 0
##STR12## H ClO.sub.4 .sup.-
24 2 0
##STR13## H ClO.sub.4 .sup.-
25 2 0 Ph Ph H ClO.sub.4 .sup.-
26 2 0 CH.sub.2 CH.sub.2 OCH.sub.3
Me H ClO.sub.4 .sup.-
27 2 0 CH.sub.2 CH.sub.2 SCH.sub.3
Me H ClO.sub.4 .sup.-
28 3 0 Me Me Me ClO.sub.4 .sup.-
__________________________________________________________________________
##STR14##
Compound No. m n M
__________________________________________________________________________
29 1 4 Cl.sup.-
30 1 6 ClO.sub.4 .sup.-
31 2 4 Cl.sup.-
32 2 5 Cl.sup.-
33 2 6 Cl.sup.-
34 3 4 Cl.sup.-
35 3 6 Cl.sup.-
__________________________________________________________________________
##STR15##
Compound No. 36 m = 0 M = Cl.sup.-
n = 10.about.20
37 m = 1 M = ClSO.sub.3 .sup.-
n = 10.about.20
38 m = 2 M = Cl.sup.-
n = 10.about.20
39 m = 3 M = Cl.sup.-
n = 10.about.20
__________________________________________________________________________
(BOC = tBuO.sub.2 C)
Compound Nos. 36 to 39 have a ring structure.
__________________________________________________________________________
##STR16##
Compound No.
R1 R2 L1 L2 M
__________________________________________________________________________
40 Me Me CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2
ClO.sub.4 .sup.-
41 Me Me
##STR17## CH.sub.2 CH.sub.2
ClO.sub.4 .sup.-
42 Me Me
##STR18##
##STR19## ClO.sub.4 .sup.-
43 CH.sub.2 CHCH.sub.2
CH.sub.2 CHCH.sub.2
(CH.sub.2).sub.3
(CH.sub.2).sub.3
ClO.sub.4 .sup.-
44 Me Me (CH.sub.2).sub.4
(CH.sub.2).sub.4
Cl.sup.-
45
##STR20##
##STR21##
##STR22## ClO.sub.4 .sup.-
46
##STR23##
##STR24##
##STR25## Cl.sup.-
47 Me Me
##STR26## Cl.sup.-
No. 48
##STR27##
__________________________________________________________________________
##STR28##
The compound for use in the present invention can be synthesized according
to a method described in, for example, the following literature:
S. S. Malhotra and M. C. Whiting, J. Chem. Soc. (1960), page 3812.
Synthetic examples are shown below.
Synthetic Example 1
(Synthesis of Compound 7)
##STR29##
A perchloric acid aqueous solution was added to an ethanol solution of
Compound (C-1) and Compound (C-2), and the resultant mixture was stirred
for 15 minutes, with heating at 50.degree. C. After cooling, the mixture
was filtered. The thus obtained crude crystals were crystallized from a
mixed solvent of DMSO, ethyl acetate ester, and hexane. Further, this
crystallization was repeated, to obtain the objective Compound 7. Yellow
crystal.
.lambda.max=439 nm (MeOH)
Synthetic Example 2
(Synthesis of Compound 15)
Compound 15 was synthesized according to the scheme shown below. Yellow
crystal. .lambda.max=457 nm (MEOH)
##STR30##
Synthetic Example 3
(Synthesis of Compound 37)
##STR31##
To a DMF solution containing 1.64 g of Compound (C-3) and 0.86 g of
Compound (C-2), was added 1.16 g of chlorosulfonic acid, and then
refluxing was conducted for 2 hours, with heating. After cooling,
crystallization from acetone was performed, to obtain the objective
Compound 37. Yield: 1.20 g. .lambda.max=350 nm (MeOH)
Synthetic Example 4
(Synthesis of Compound 38)
##STR32##
An ethanol solution containing 2.72 g of Compound (C-4) and 0.86 g of
Compound (C-2) was refluxed for 15 minutes, with heating. After cooling,
the thus obtained crystals were separated by filtration, and then they
were crystallized from a mixed solvent of methanol, acetone, and hexane,
to obtain an objective Compound 38. Yield: 0.40 g. .lambda.max=484 nm
(MeOH).
The timing for adding the methine compound for use in the present
invention, as well as other sensitizing dyes, to a silver halide emulsion
for use in the present invention, may be at any step of the preparation of
the emulsion that has been recognized as being useful. That is, the
compound may be added at any timing and steps, as long as it is added
before a photographic emulsion is coated. For example, it may be added at
the step of the formation of silver halide grains or/and at the timing
before desalting, or at the step of desalting and/or at the timing of
after the desalting, but before the start of chemical ripening, as
disclosed in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, and
4,225,666, and JP-A ("JP-A" means unexamined published Japanese patent
application) Nos. 184142/1983 and 196749/1985. Alternatively, the compound
may be added just before or at the step of the chemical ripening, or at
the timing of after the chemical ripening, but before coating, as
disclosed in JP-A No. 113920/1983. Further, the methine compound may be
partially added alone, or in a combination with compound(s) having a
different structure, at different steps of, for example, during the
formation of silver halide grains, and at the step of chemical ripening or
after the completion of the chemical ripening; or alternatively before or
during chemical ripening, and after completion of the same, as disclosed
in, for example, U.S. Pat. No. 4,225,666 and JP-A No. 7629/1983. Further,
different kinds of compounds, or different kinds of combinations of
compounds, may be added partially at any step prior to coating of the
emulsion.
The addition amount of the dye for use in the present invention depends on
the form and the size of silver halide grains. Generally, the dye may be
used in an amount of 1.times.10.sup.-6 to 8.times.10.sup.-3 mole, per mole
of silver halide. For example, when the size of the silver halide grains
is in the range of from 0.2 to 1.3 .mu.m, the addition amount is
preferably from 2.times.10.sup.-6 to 3.5.times.10.sup.-3 mol, and more
preferably from 7.5.times.10.sup.-6 to 1.5.times.10.sup.-3 mole, per mole
of silver halide, respectively.
The dyes for use in the present invention may be dispersed directly in an
emulsion. Alternatively, they may be added to an emulsion in the form of a
solution of the dye dissolved in a suitable solvent, such as methyl
alcohol, ethyl alcohol, methyl cellosolve, acetone, water, and pyridine,
or a mixed solvent thereof. At this time, such additives as a base, an
acid, and a surfactant may exist together with the dye. Further,
ultrasonic wave may be used to prepare the solution. Further, with respect
to a method for adding the dye, use can be made of the method in which the
said compound is dissolved in a volatile organic solvent, and the
resultant solution is dispersed in a hydrophilic colloid, and then the
thus obtained dispersion is added to an emulsion, as described in, for
example, U.S. Pat. No. 3,469,987; the method in which the said compound is
dispersed in an water-soluble solvent, and then the thus obtained
dispersion is added to an emulsion, as described in, for example, JP-B
("JP-B" means examined Japanese patent publication) No. 24185/1971; the
method in which the methine compound is dissolved in a surfactant, and
then the resultant solution is added to an emulsion, as described in, for
example, U.S. Pat. No. 3,822,135; the method in which the methine compound
is dissolved by virtue of a compound that is able to cause a red shift of
the absorption of the methine compound, and then the resultant solution is
added to an emulsion, as described, for example, in JP-A No. 74624/1976;
and the method in which the methine compound is dissolved in an acid that
contains substantially no water, and then the resultant solution is added
to an emulsion, as described, for example, in JP-A No. 80826/1975.
Further, with respect to other methods for adding a dye to an emulsion,
use can be made of the methods described in, for example, U.S. Pat. Nos.
2,912,343, 3,342,605, 2,996,287, and 3,429,835.
The dye according to the present invention can be used as various kinds of
filter dyes, irradiation- preventing dyes, or antihalation dyes, for the
purpose of improving image sharpness, color separation, and the like.
The dye may be incorporated in a coating solution for a silver halide
photographic light-sensitive layer, a filter layer, and/or an antihalation
layer, according to a conventional method. The amount of the dye to be
used is enough to color a photographic layer. One skilled in the art can
easily determine an optimum amount, in accordance with the purpose of the
dye to be used. Generally, the dye is preferably used in an amount that
will obtain an optical density in the range of from 0.05 to 3.0.
The timing for adding the dye may be at any step prior to coating.
Further, the dye can be localized in a specific layer, by incorporating the
dye in a layer together with a polymer (mordant) that has a charge
opposite to the ion that the dye has, so that an interaction between the
polymer and the dye molecule can be used.
Examples of the polymer mordant include those described in U.S. Pat. Nos.
2,548,564, 4,124,386, 3,625,694, 3,958,995, 4,168,976, and 3,445,231.
Examples of a supersensitizing agent that is useful for the spectral
sensitization according to the present invention include pyrimidylamino
compounds, triazinylamino compounds, and azorium compounds, as described,
for example, in U.S. Pat. Nos. 3,511,664, 3,615,613, 3,615,632, 3,615,641,
4,596,767, 4,945,038, 4,965,182, and 4,965,182. The supersensitizing agent
is also preferably used according to such methods as described in the
above-described patents.
The silver halide that can be used in the silver halide light-sensitive
material of the present invention may be silver bromide, silver
iodobromide, silver iodochlorobromide, silver chlorobromide, or silver
chloride. Preferred, of these silver halides, are silver bromide, silver
chlorobromide, silver iodochlorobromide, and a high silver chloride
described in JP-A No. 42/1990.
Structures of the light-sensitive material and processings for it are
described below. The structures and the processings described in JP-A No.
42/1990 are preferably used particularly when the halide of the
light-sensitive material is a high silver chloride. On the other hand, the
structures and the processings described in JP-A No. 264743/1988 are
preferably used particularly when the halide is silver chlorobromide.
The shape of silver halide grains incorporated in the a photographic
light-sensitive material may be regular crystals, such as cubic,
teteradecahedral, or rhombic dodecahedral crystals; or irregular crystals,
such as spherical or tabular crystals; or a mixture of regular and
irregular crystals. Further, the grains may be composed of a mixture of
grains having various crystal shapes.
The silver halide grains may have phases that are different between the
inside and the surface of the grain, or they may be composed of a uniform
phase. Further, the silver halide grains may be ones that form latent
images predominantly on the surfaces of the grains (e.g. a negative-type
light-sensitive material), or ones that form latent images predominantly
on the inside of the grains (e.g. an internal latent image-type
light-sensitive material), or previously fogged ones (e.g. a direct
positive-type light-sensitive material).
Silver halide grains having various kinds of halogen compositions, crystal
habits, internal structures, shapes, and distribution, as mentioned above,
are used in photographic light-sensitive materials (elements) that are
designed for various purposes.
The dyes according to the present invention may be used in light-sensitive
materials that are designed for the purposes described below, as a
sensitizer, a sensitizing dye, a filter, a halation- or
irradiation-preventing agent, and the like. These dyes may be added not
only to a light-sensitive emulsion layer but also to any other layers,
such as an interlayer, a protective layer, and a backing layer.
The dyes according to the present invention may be used in a variety of
silver halide color or black/white photographic light-sensitive materials.
More specifically, they may be used in, for example, a color positive
light-sensitive material, a light-sensitive material for color printing
paper, a color negative light-sensitive material, a color reversal
light-sensitive material that may or may not contain a coupler, a direct
positive silver halide photographic light-sensitive material, a
photographic light-sensitive material for reprophotography (e.g. a lith
film, and a lith duplicate film), a light-sensitive material for a cathode
ray tube display, an X-ray recording light-sensitive material (especially,
direct radiographic materials and photofluorographic materials employing a
screen), a light-sensitive material for a silver salt diffusion transfer
process, a light-sensitive material for a color diffusion transfer
process, a light-sensitive material for an inhibition process, a
light-sensitive material for a silver dye bleaching process, and a heat-
development light-sensitive material.
The silver halide photographic emulsion for use in the present invention
can be prepared with the method described by, for example, P. Glafkides,
in "Chemie et Phisique Photograhique," Paul Montel, 1967; G. F. Duffin, in
"Photographic Emulsion Chemistry," The Focal Press, 1966; and V. L.
Zelikman et al., in "Making and Coating Photographic Emulsion," The Focal
Press, 1964.
Further, at the time of the formation of silver halide grains, a silver
halide solvent may be used in order to control the growth of the grains.
Examples of the silver halide solvent include ammonia, potassium
thiocyanate, ammonium thiocyanate, thioether compounds (e.g. those
described in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439,
and 4,276,374), thione compounds (e.g. those described in JP-A Nos.
144319/1978, 82408/1978, and 77737/1980), and amine compounds (e.g. those
described in JP-A No. 100717/1979).
At the stage of the formation of silver halide grains, or physical
ripening, simple salts or complex salts of a metal different from silver,
such as a cadmium salt, a zinc salt, a thallium salt, an irridium salt, or
a complex salt thereof; a rhodium salt or complex salt thereof; an iron
salt or complex salt thereof, may exist together with a silver halide.
Examples of the internal latent image-type silver halide emulsion for use
in the present invention include a conversion-type silver halide emulsion,
a core/shell-type silver halide emulsion, and a silver halide emulsion in
which a metal different from silver is doped into silver halide grains, as
described, for example, in U.S. Pat. Nos. 2,592,250, 3,206,313, 3,447,927,
3,761,276, and 3,935,014.
The silver halide emulsion is generally subjected to chemical
sensitization. For the chemical sensitization, use can be made of the
method described in, for example, "Die Grundlagen der Photographischen
Prozesse mit Silberhalogeniden," edited by H. Frieser, Academische
Verlagsgesellschaft (1968), pp 675 to 734.
That is, examples of the chemical sensitization include, for example,
sulfur sensitization, using a sulfur-containing compound that is able to
react with an active gelatin or silver (e.g. thiosulfates, thioureas,
mercapto compounds, and rhodanines); selenium sensitization; reduction
sensitization, using a reducing substance (e.g. stannous salts, amines,
hydrazine derivatives, formamidine sulfinic acids, and silane compounds);
and noble metal sensitization, using a noble metal compound (e.g. gold
complex salts, and other complex salts of metal belonging to Group VIII of
the Periodic Table, such as Pt, Ir and Pd), which may be employed singly
or in combination.
The photographic light-sensitive material for use in the present invention
may contain various compounds, for the purpose of preventing the
photographic material from being fogged during preparation, storage, or
photographic processing of the material, and for stabilizing the
photographic properties of the material. That is, many compounds that are
known as antifoggants or stabilizers may be used. Examples of such
compounds include thiazoles (e.g. benzothiazolium salts described in, for
example, U.S. Pat. Nos. 3,954,478 and 4,942,721, and JP-A No. 191032/1984,
and their open-ring compounds described in JP-B No. 26731/1984);
nitro-indazoles, triazoles, benzotriazoles, and benzimidazoles (nitro- or
halogen-substituted compounds in particular); heterocyclic mercapto
compounds, such as mercapto thiazoles, mercapto benzothiazoles,
mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles
(especially 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines; the
above-described heterocyclic mercapto compounds having a water-soluble
group, such as a carboxyl group and a sulfo group; thioketones (e.g.
oxazoline thione); azaindenes, such as tetraazaindenes (especially
4-hydroxy-substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic
acids; benzenesulfinic acids; and acetylene compounds described in JP-A
No. 87957/1987.
The silver halide photographic light-sensitive material of the present
invention may contain color couplers, such as a cyan coupler, a magenta
coupler, and a yellow coupler, and a compound that is used for dispersion
of the coupler.
That is, the photographic light-sensitive material may contain a compound
that is capable of coloring upon an oxidation coupling reaction with an
aromatic primary amine developing agent (e.g. phenylenediamine derivatives
and aminophenol derivatives) in the color development processing. Examples
of the magenta coupler include 5-pyrazolone couplers,
pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, and
open-chain acylacetonitrile couplers. Examples of the yellow coupler
include acylacetoamide couplers (e.g. benzoylacetanilides and
pyraroylacetanilides). Examples of the cyan coupler include naphthol
couplers and phenol couplers. Preferably, the couplers have in their
molecule a hydrophobic group, which is called a ballasting group, so that
they are nondiffusing. The coupler may be 4-equivalent or 2-equivalent to
the silver ion. Further, the coupler may be a colored coupler that effects
color correction, or a coupler that releases a development inhibitor upon
development (a so-called DIR coupler).
Further, in addition to or in place of the DIR coupler, the photographic
light-sensitive material may contain a non-coloring DIR coupling compound
that forms a colorless product, and that releases a development inhibitor,
upon a coupling reaction.
The photographic light-sensitive material of the present invention may
contain polyalkylene oxides, and derivatives thereof, such as ethers,
esters, and amines; thioether compounds, thiomorpholines, quarternary
ammonium chloride, urethane derivatives, urea derivatives, imidazole
derivatives, 3-pyrazolidones, and the like, in order to increase
sensitivity and contrast, or to accelerate development.
The silver halide light-sensitive material of the present invention may
contain various kinds of dyes in addition to the methine compound for use
in the present invention, as a filter dye, or for prevention of
irradiation, or for other various purposes.
Examples of such dyes include oxonol dyes having a pyrazolone nucleus or a
barbituric acid nucleus, as described in, for example, British Patent Nos.
506,385, 1,177,429, 1,311,884, 1,338,799, 1,385,371, 1,476,214, 1,433,102,
and 1,553,516, JP-A Nos. 85130/1973, 114420/1974, 117123/1977,
161233/1980, and 111640/1984, JP-B Nos. 22069/1964, 13168/1968, and
273527/1987, and U.S. Pat. Nos. 3,247,127, 3,469,985, and 4,078,933; other
oxonol dyes described in, for example, U.S. Pat. Nos. 2,533,472 and
3,379,533, British Patent No. 1,278,621, and JP-A Nos. 134447/1989 and
183652/1989; azo dyes described in, for example, British Patent Nos.
575,691, 680,631, 599,623, 786,907, 907,125, and 1,045,609, U.S. Pat. No.
4,255,326, and JP-A No. 211043/1984; azomethin dyes described in, for
example, JP-A Nos. 100116/1975 and 118247/1979, and British Patent Nos.
2,014,598 and 750,031; anthraquinone dyes described in U.S. Pat. No.
2,865,752; arylidene dyes described in, for example, U.S. Pat. Nos.
2,533,009, 2,688,541, and 2,538,008, British Patent Nos. 584,609 and
1,210,252, JP-A Nos. 40625/1975, 3623/1976, 10927/1976, and 118247/1979,
and JP-B Nos. 3286/1973 and 37303/1984; styryl dyes described in, for
example, JP-B Nos. 3082/1953, 16594/1969, and 28898/1984; triarylmethane
dyes described in, for example, British Patent Nos. 446,583 and 1,335,422,
and JP-A No. 228250/1984; merocyanine dye described in, for example,
British Patent Nos. 1,075,653, 1,153,341, 1,284,730, 1,475,228, and
1,542,807; and cyanine dyes described in, for example, U.S. Pat. Nos.
2,843,486 and 3,294,539, and JP-A No. 291247/1989.
In order to prevent such dyes from diffusion, use can be made of the
methods described below.
For example, a method in which a dissociated anionic dye is incorporated in
the same layer, together with a hydrophilic polymer that has a charge
opposite to the dye therein, and that acts as a mordant, so that the dye
is localized in the particular layer by an interaction between the dye
molecule and the polymer, is disclosed in, for example, U.S. Pat. Nos.
2,548,564, 4,124,386, and 3,625,694.
Further, a method for dyeing a particular layer by the use of a
water-insoluble solid dye, is disclosed in, for example, JP-A Nos.
12639/1981, 155350/1980, 155351/1980, 27838/1988, and 197943/1988, and
European Patent No. 15,601.
Further, a method for dyeing a particular layer by the use of metal salt
fine particles having dyes adsorbed thereon, is disclosed in, for example,
U.S. Pat. Nos. 2,719,088, 2,496,841, and 2,496,843, and JP-A No.
45237/1985.
The photographic light-sensitive material of the present invention may
contain various kinds of surfactants for various purposes, such as coating
aid, antistatic, improvement of sliding (slip), emulsification and
dispersion, prevention of adhesion, and improvement of photographic
properties (e.g. development acceleration, high contrast, and
sensitization).
When the present invention is practically used, other additives may be used
with a silver halide emulsion, or with other hydrophilic colloids.
Examples of such additives include an anti-fading agent, an inorganic or
organic hardener, an anti-fogging agent, an ultraviolet ray-absorbing
agent, a mordant, a plasticizer, a latex polymer, and a matting agent.
Specific examples of these additives are described in, for example,
Research Disclosure, Vol.176 (1978, XI), D-17643.
Further, in the photographic light-sensitive material for use in the
present invention, a hydrophilic polymer, such as gelatin, may be used as
a protective colloid.
A finished silver halide emulsion and the like are coated on a suitable
support, examples of which include a baryta paper, a resin-coated paper, a
synthetic paper, a triacetate film, a polyethyleneterephthalate film, and
other plastic bases; and a glass plate.
In order to obtain a photographic image, exposure to light can be performed
according to a conventional method. In other words, for this purpose, use
can be made of any of various known light sources, such as natural light
(sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon
arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube
flying spot. With respect to an exposure time, not only an exposure time
of from 1/1000 sec. to 1 sec., as is usually applied for a camera, but
also an exposure time of less than 1/1000 sec., for example from
1/10.sup.4 to 1/10.sup.6 sec. by means of a xenon flash lamp or a cathode
ray tube, can be employed. Further, an exposure time of not less than 1
sec can also be applied. Optionally, the spectral composition of light
that is used for exposure may be controlled by the use of a color filter.
A laser light may be used for exposure to light. Further, exposure may be
performed using a light that is emitted from a fluorescent substance that
is excited by electronic rays, X rays, .gamma. rays, .alpha. rays, or the
like.
For the photographic processings of the light-sensitive material of the
present invention, any of known methods and known processing solutions, as
described, for example, in Research Disclosure, Vol. 176, pages 28-30,
(RD-17643), may be employed. The photographic processings may be a
photographic processing for forming a silver image (i.e. a black/white
photographic processing), or a photographic processing for forming a color
image (i.e. a color photographic processing), according to the purpose.
The processing temperature is usually set in a range of from 18.degree. C.
to 50.degree. C. However, the processing may be performed at a temperature
lower than 18.degree. C., or alternatively at a temperature over
50.degree. C.
The present invention may be applied to a silver halide photographic
light-sensitive material having a transparent magnetic recording layer. A
silver halide photographic light-sensitive material carrying magnetic
records, that may be used in the present invention, can be prepared by a
method in which ferromagnetic particles described in JP-A Nos. 23505/1984,
195726/1992, and 59357/1994 are coated on the following support.
Preferably, the support can be produced by a method in which a
pre-heat-treated thin- layer polyester support, as described in detail in
JP-A Nos. 35118/1994 and 17528/1994, and KOKAIGIHO 94-6023 (HATSUMEI
KYOKAI), an example of which is a polyethylene-aromatic
dicarboxylate-series polyester support of generally from 50 .mu.m to 300
.mu.m, preferably from 50 .mu.m to 200 .mu.m, more preferably from 80 to
115 .mu.m, and particularly preferably from 85 .mu.m to 105 .mu.m
thickness, is subjected to heat treatment (annealing), at a temperature of
from 40.degree. C. to the glass transition temperature, for 1 to 1500
hours, and then such an annealed support is further subjected to a surface
treatment, such as ultraviolet ray irradiation, as described in JP-B Nos.
2603/1968, 2604/1968, and 3828/1970, corona discharge, as described in
JP-B No. 5043/1973 and JP-A No. 131576/1976, and glow discharge, as
described in JP-B Nos. 7578/1960 and 43480/1971, followed by a coating of
a subbing layer, as described in U.S. Pat. No. 5,326,689, and if necessary
a coating of an underlayer, as described in U.S. Pat. No 2,761,791.
The above-mentioned magnetic layer may be a striped form, as described in
JP-A Nos. 124642/1992 and 124645/1992.
Further, if necessary, the above-described support is subjected to an
antistatic treatment as described in JP-A No. 62543/1992, and finally at
least one silver halide emulsion is coated thereon. Examples of the
above-described silver halide emulsion to be used are those described in
JP-A Nos. 166932/1992, 41436/1991, and 41437/1991.
Preferably, the thus-produced light-sensitive material is manufactured
according to the method of production management described in JP-B No.
86817/1992, and production data are recorded according to the method
described in JP-B No. 87146/1994. After that, or before that, in
accordance with the method described in JP-A No. 125560/1992, the material
is cut into a film whose width is narrower than the conventional 135 size,
and for the perforation, two holes are made at one side of the film, per
picture of small format, so that the perforation goes well with a picture
of smaller format than the conventional one.
The thus-manufactured film can be encased to be used in a cartridge
(magazine) package described in JP-A No. 157459/1992, a cartridge
illustrated in FIG. 9 shown in Example of JP-A No. 210202/1993, a film
patrone described in U.S. Pat. No. 4,221,479, or a cartridge described in
U.S. Pat. Nos. 4,834,306, 4,834,366, 5,226,613, and 4,846,418.
Preferred of these film cartridges and film patrones for use in the present
invention, from the viewpoint of light shielding, are those in which the
tongue is contained (encased), as described in U.S. Pat. Nos. 4,848,693,
and 5,317,355.
Further, a cartridge having a lock machinery, as described in U.S. Pat. No.
5,296,886; a cartridge in which the state of use of a film is indicated,
as described in U.S. Pat. No. 5,347,334; and a cartridge having a double
exposure-preventing function, are preferred.
Further, use can be made of a cartridge in which a film is easily encased
by simply inserting the film in the cartridge, as described in JP-A No.
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