U.S. patent number 3,840,377 [Application Number 05/237,041] was granted by the patent office on 1974-10-08 for supersensitized silver halide photographic emulsions.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Nobuaki Miyasaka, Akira Ogawa, Akira Sato, Keisuke Shiba, Minoru Sonoda, Haruo Takei.
United States Patent |
3,840,377 |
Shiba , et al. |
October 8, 1974 |
SUPERSENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSIONS
Abstract
A silver halide photographic emulsion containing a
supersensitizing amount of the combination comprising at least one
of the sensitizing -naphthoxazole represented by the following
General Formula (I). ##SPC1## wherein Z.sub.1 represents a
non-metallic atomic group necessary for forming a benzthiazole
nucleus or a benzselenazole nucleus; Z.sub.2 represents a
non-metallic atomic group necessary for forming a benzene nucleus;
R.sub.1 and R.sub.2 each represents an alkyl group having from one
to about six carbon atoms, a substituted lower alkyl group
conventionally used in cyanine dyes, or an aliphatic hydrocarbon
group having an unsaturated bond; X.sub.1 .sup.- represents an
anion and m is 1 or 2, said m being 1 when the dye forms an
intramolecular salt; and at least one of the sensitizing dyes
represented by the General Formula (II) ##SPC2## wherein Z.sub.3
represents a non-metallic atomic group necessary for forming a
benzoxazole nucleus, a .beta., .beta.naphthoxazole nucleus, or a
.beta.-naphthoxazole nucleus; Z.sub.4 represents a non-metallic
atomic group necessary for forming a benzene nucleus; R.sub.3 and
R.sub.4, each represents an alkyl group having from one to six
carbon atoms, a substituted alkyl group conventionally used in
cyanine dyes, or an aliphatic hydrocarbon group having an
unsaturated bond; at least one of said R.sub.3 and R.sub.4 being an
alkyl group having at least one of a sulfo group, a carboxyl group
or a hydroxyl group; R.sub.5 represents an alkyl group having from
one to about six carbon atoms, a substituted alkyl group
conventionally used in cyanine dye, an aryl group, or an
unsaturated aliphatic hydrocarbon group; X.sub.2 .sup.- represents
an anion; and n is 1 or 2, said n being 1 when the dye forms an
intramolecular salt is disclosed.
Inventors: |
Shiba; Keisuke (Kanagawa,
JA), Takei; Haruo (Kanagawa, JA), Sonoda;
Minoru (Kanagawa, JA), Miyasaka; Nobuaki
(Kanagawa, JA), Sato; Akira (Kanagawa, JA),
Ogawa; Akira (Kanagawa, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
11915841 |
Appl.
No.: |
05/237,041 |
Filed: |
March 22, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Mar 23, 1971 [JA] |
|
|
46-16424 |
|
Current U.S.
Class: |
430/574 |
Current CPC
Class: |
G03C
1/29 (20130101) |
Current International
Class: |
G03C
1/29 (20060101); G03C 1/08 (20060101); G03c
001/14 () |
Field of
Search: |
;96/124,132,137 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Brown; J. Travis
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A silver halide photographic emulsion containing a
supersensitizing amount of the combination comprising at least one
of the sensitizing dyes represented by the following General
Formula (I) ##SPC10##
wherein Z.sub.1 represents a non-metallic atomic group necessary
for forming a benzothiazole nucleus or a benzoselenazole nucleus;
Z.sub.2 represents a non-metallic atomic group necessary for
forming a benzene nucleus; R.sub.1 and R.sub.2 each represent an
alkyl group having from one to about six carbon atoms, a
substituted lower alkyl group conventionally used in cyanine dyes
selected from the group consisting of a sulfoalkyl group, a hydroxy
sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoarylalkyl group,
a sulfoalkyl amino alkyl group, a sulfoalkylamido alkyl group, and
a sulfoalkylthioalkyl group, or an aliphatic hydrocarbon group
having an unsaturated bond; X.sub.1.sup.- represents an anion and m
is 1 or 2, said m being 1 when the dye forms an intramolecular
salt; and at least one of the sensitizing dyes represented by the
General Formula (II) ##SPC11##
wherein Z.sub.3 represents a benzoxazole nucleus, Z.sub.4
represents a non-metallic atomic group necessary for forming a
benzene nucleus; R.sub.3 and R.sub.4 each represents an alkyl group
having from one to about six carbon atoms, a substituted alkyl
group conventionally used in cyanine dyes selected from the group
consisting of an alkoxyalkyl group, an alkallyl group, an aralkyl
group, an acetoxyalkyl group, a carboalkoxyalkyl group, an
arylmercaptoalkyl group, an aryloxyalkyl group, a
hydroxysulfoalkoxyalkyl group and a carbamylalkyl group, an aralkyl
group for an aliphatic hydrocarbon group having an unsaturated
bond; at least one of said R.sub.3 and R.sub.4 being an alkyl group
having at least one of a sulfo group, a carboxyl group or a
hydroxyl group; R.sub.5 represents an alkyl group having from one
to about six carbon atoms, a substituted alkyl group conventionally
used in cyanine dyes, selected from the group consisting of an
aralkyl group, a hydroxyalkyl group, and an acetoxyalkyl group, an
aryl group, or an unsaturated aliphatic hydrocarbon group;
X.sub.2.sup.- represents an anion; and n is 1 or 2; said n being 1
when the dye forms an intramolecular salt, and said emulsion having
a high sensitivity to the radiation emitted from a green
fluorescent substance and having a high stability to a safety
light.
2. An photographic light-sensitive material comprising a support
having thereon at least one layer of the silver halide photographic
emulsion as set forth in claim 1.
3. A silver halide photographic emulsion containing at least one of
the sensitizing dyes represented by the General Formula (I)
##SPC12##
wherein Z.sub.1 represents an atomic group necessary for forming a
benzothiazole nucleus or a benzoselenazole nucleus, in which the
benzene ring moiety of said nucleus may be unsubstituted or
substituted by a lower alkyl group having from one to about six
carbon atoms, an alkoxyl group, a hydroxyl group, a halogen atom,
an aryl group, a sulfoaryl group, an N-alkyl substituted amino
group, a carboxyaryl group or an alkoxycarbonyl group; wherein
Z.sub.2 represents a non-metallic atomic group necessary for
forming a benzene nucleus, which may be unsubstituted or
substituted by a lower alkyl group having from one to about six
carbon atoms, a halogen atom, or an alkoxy group; wherein R.sub.1
and R.sub.2 each represents an alkyl group having from one to about
six carbon atoms, an aralkyl group, an alkyl group having a sulfo
group, an allyl group, or an alkyl group having a carboxyl group;
wherein X.sub.1.sup.- represents an anion and m is 1 or 2, in which
when m is 1 an intramolecular salt is formed, and at least one of
the sensitizing dyes represented by the General Formula (II)
##SPC13##
wherein Z.sub.3 represents a benzoxazole nucleus, which may be
unsubstituted or substituted with a lower alkyl group having from
one to about six carbon atoms, a halogen atom, an alkoxyl group, a
hydroxyalkyl group, an alkoxycarbonyl group, an aryl group, a
carboxyaryl group or a sulfoaryl group; wherein Z.sub.4 represents
a non-metallic atomic group necessary for forming a benzene
nucleus, in which said nucleus may be unsubstituted or substituted
with a halogen atom, a cyano group, an alkoxycarbonyl group, a
trifluoromethyl group, a carbamoyl group, an alkyl-substituted
carbamoyl group, a sulfamoyl group, or an alkyl-substituted
sulfamoyl group; wherein R.sub.3 and R.sub.4 each represents an
alkyl group having from one to about six carbon atoms, an allyl
group, a hydroxyalkyl group, an alkyl group having a sulfo group,
an alkyl group having a carboxyl group, or an aralkyl group, and
wherein at least one of R.sub.3 and R.sub.4 is an alkyl group
having at least one of a sulfo group, a carboxy group or a hydroxy
group, R.sub.5 is a lower alkyl group having from one to about six
carbon atoms, an allyl group, a hydroxy-alkyl group, an aralkyl
group, an acetoxyalkyl group, or a aryl group wherein X.sub.2.sup.-
represents an anion and n is 1 or 2, in which when n is 1, an
intramolecular salt is formed, and said emulsion having a high
sensitivity to the radiation emitted from a green fluorescent
substance and having a high stability to a safety light.
4. The silver halide photographic emulsion of claim 3, wherein said
alkyl group having a sulfo group is selected from the group
consisting of a sulfo alkyl group, a hydroxy(sulfo) alkyl group, a
sulfo alkoxy alkyl group, a sulfo phenyl alkyl group, a sulfo-alkyl
amino alkyl group, a sulfo-alkyl amino alkyl group and a
sulfo-alkyl thio-alkyl group.
5. An photographic light-sensitive material comprising a support
having thereon at least one layer of the silver halide photographic
emulsion as set forth in claim 4.
6. A silver halide photographic emulsion containing a
supersensitizing amount of the combination comprising at least one
of the sensitizing dyes represented by the following General
Formula (I') ##SPC14##
wherein R.sub.1 and R.sub.2 each represents a methyl group, an
ethyl group, or an allyl group; X.sub.1 .sup.-represents an anion;
and R represents a hydrogen atom, a methyl group, or an ethyl
group; and at least one of the sensitizing dyes represented by the
following General Formula (II') ##SPC15## wherein W.sub.1 and
W.sub.2 each represents a hydrogen atom, a chlorine atom, or a
methoxycarbonyl group and R.sub.3 and R.sub.4 each represents a
sulfoalkyl group or an alkyl group; at least one of R.sub.3 and
R.sub.4 being a sulfoalkyl group.
7. The silver halide photographic emulsion of claim 1 wherein the
molar ratio of the sensitizing dye of the General Forumula (I) to
the sensitizing dye of the General Formula (II) ranges from 9:1 to
1:10 and wherein the amount of each of said dyes to the silver
halide ranges from 1.times.10.sup.-.sup.4 to 1 .times.
10.sup.-.sup.3 mole per mole of silver.
8. The emulsion of claim 1 wherein R.sub.3 and R.sub.4 if
substituted alkyl are selected from the group consisting of a
.beta.-methoxyethyl group, a .beta.-ethoxyethyl group, a
.beta.-methallyl group, a benzyl group, a .beta.-phenylethyl group,
a .beta.-acetoxyethyl group, a .beta.-acetoxypropyl group, a
carbomethoxymethyl group, a .beta.-carbomethoxyethyl group, a
carbethoxymethyl group, a .beta.-carbethoxyethyl group, a
phenylmercaptomethyl group, a phenoxymethyl group, a
.beta.-phenylmercaptoethyl group, a .beta.-phenoxyethyl group, and
a 2-(2-hydroxy-3-sulfopropxy) ethyl group and a carbamylmethyl
group.
9. A silver halide photographic emulsion as set forth in claim 1
wherein Z.sub.1 represents a non-metallic atomic group necessary
for forming a benzthiazole nucleus.
10. A silver halide photographic emulsion as set forth in claim 9
wherein R.sub.1 and R.sub.2 each represents an alkyl group having
from one to about six carbon atoms, and wherein both of R.sub.3 and
R.sub.4 have at least one sulfo group.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a gelatino silver halide
photographic emulsion which is spectrally sensitized by at least
two sensitizing dyes exhibiting a super sensitizing effect on each
other and in particular, it relates to a silver halide photographic
emulsion having an increased spectral sensitivity in the green wave
length region. 2. Description of the Prior Art
In the production of light-sensitive materials, it is well known to
expand the light-sensitive wave length region, of a silver halide
photographic emulsion, that is to say, to apply a spectral
sensitization to the silver halide photographic emulsion. In
particular, the sensitization in the green wave length region among
the spectral sensitization techniques is important since the
maximum sensitivity of the human eye is near 545 nm. and the human
eye is quite sensitive to the light in the green wave length
region.
It is known, in natural color sensitive materials, that even slight
differences in the light sensitivity and the spectral sensitivity
distribution of the green-sensitive emulsion layers influence to a
great extent the color reproducibility of color images and as a
result much activity exists in this area. If the maximum sensitive
wave length in the green wave length region of from 500 nm. to 600
nm. is shifted too much to a longer wave length, the yellow tones
become too strong, which reduces the color reproducibility for
green, whereas if the sensitivity in the shorter wave length region
of from 500 nm. to 540 nm. is low, a clear green color reproduction
is difficult to obtain. Therefore, the approach in spectral
sensitization techniques for the green-sensitive silver halide
emulsion for a natural color sensitive material is to locate the
maximum sensitive wave length in the wave length region of from 560
nm. to 570 nm. and to increase the sensitivity at the shorter wave
length side of from 520 nm. to 530 nm.
In X-ray recording materials, intensifying screens or fluorescent
screens are frequently used together with silver halide
photographic films for increasing the recording sensitivity to
X-rays. Because excessive exposure to X-ray radiation is hazardous
to humans various attempts have been made for increasing the
recoding sensitivity to X-rays to improve the reproducibility of
details by using X-rays in an amount as low as possible and by
expanding the X-ray recording range. For example, not only
techniques for highly sensitizing silver halide photographic
emulsions but also systems for using an X-ray image intensifier and
for using a solid-state light amplifier have been developed. In any
of these cases, however, the X-ray image is recorded finally on a
gelatino silver halide light-sensitive material as a fluorescent
image. As the fluorescent substances used for this purpose, there
are illustrated blue fluorescent substances such as calcium
tungstate, zinc sulfide activated by silver, and barium sulfate
activated by silver and green fluorescent substances such as zinc
sulfide cadmium activated by silver. The maximum emission energy of
the latter fluorescent substance is about 540 nm. and the intensity
distribution of the emission energy is as shown in FIG. 7 of the
accompanying drawings. Also, as is clear from the above
explanation, the human eye is particularly sensitive to light
emitted from the latter type of fluorescent substance. Therefore,
such a fluorescent substance is suitable as a fluorescent substance
which is used for observing X-rays directly with the naked eye.
That is to say, it is advantageous to use a fluorescent screen in
which the fluorescent substance for reproducing an X-ray image on a
fluorescent screen and observing the reproduced image with the
naked eye or taking X-ray photograph of the image.
In fact, a fluorescent screen employing a green fluorescent
substance is used in such an X-ray photographic method. On the
other hand, it is desirable that an X-ray light-sensitive material,
which is usually a so-called indirect X-ray photographic material,
be treated easily in processings such as development and fixing and
in particular it is desirable that such a lightsensitive material
be handled in a room in which the level of light is as high as
possible. Such an X-ray photographic material is, in fact, handled
under a safety light by using, for instance, Filter No. 7 made by
the Fuji Photo Film Co., Ltd. The spectral transmittance curve of
Filter No. 7 is illustrated in FIG. 8 of the accompanying drawings.
In other words, it is desirable that an X-ray photographic material
having a silver halide photographic emulsion layer be highly
sensitive to the radiation emitted from a green fluorescent
substance excited by X-rays and not very sensitive to ordinary
light.
In this information conscious age, the development of faster
information communicating systems has become necessary and various
systems have been developed. For instance, there are the press
facsimile system, the high speed photo-typesetting system, the
cathode ray tube display system, the high speed photographic
recording system employing high speed photography, in particular,
photography, and the printing method of photo-masks using in an IC
plate producing step conducted at a high speed.
For the cathode ray tube display system, the emissions on the order
of micro-seconds from various kinds of fluorescent substances are
used. The fluorescent substance, P-2 has at least one maximum
emission energy at about 545 nm., P-4 at about 560 nm., P-22D at
about 525 nm., P-31 at about 520 nm., and P-20 at about 560 nm.
The developing and fixing steps of light-sensitive materials using
silver halide photographic emulsions are shortened to 60 to 120
seconds each. Thus, the sensitizing dyes contained in the
photographic emulsion layers of the light-sensitive materials are
hardly washed out and then the photographs obtained by the
processings are apt to be stained by the remaining dyes, which is
one factor by which the photographic images are degraded.
The spectral sensitization in the green wave length region is also
conducted by a merocyanine dye, a hemicyanine dye, or a trinuclear
cyanine dye. However, such a technique is unsuitable for
sensitization in a narrow and specific wave length region and the
spectral sensitivity distribution obtained by such a sensitizing
means is too broad. Also, with such a technique, it is difficult to
obtain a high sensitivity and in particular, such a technique is
disadvantageous in the spectral sensitization of high-sensitive
silver iodo-bromide photographic emulsions due to its low
sensitizing power. Furthermore, the aforesaid spectral
sensitization has the disadvantage that it is not easy to find a
super-sensitizer for the sensitizing dye.
For this purpose the application of a J-aggregate type cyanine dye
is profitable and many such cyanine dyes are known. For instance,
using imidazolocarbocyanine dyes as disclosed in the specifications
of U.S. Pat. Nos. 2,701,198; 2,945,763; 2,973,264; 3,173,791;
3,364,031; 3,397,060; and 3,506,443, the specification of Japanese
Patent Publication No. 4936/1968, the specifications of German
Offenelgungsschriften Nos. 1,944,751; 2,011,879; 2,018,687; and
2,030,326 using oxacarbocyanine dyes as disclosed in the
specification of Japanese Patent Publication No. 32753/1969 and the
specification of German Offenlegungsschriften No. 1,928,295, and
using pseudocyanine dyes as disclosed in the specification of
German Offenlegungsschriften No. 1,936,262 and the specification of
French Pat. No. 1,488,057 are known techniques.
However, although such prior art techniques may give high
sensitivity, many of them are useless for practical purposes since
the wave length to which such prior art techniques sensitize
extends to the longer wave length side and color stains are formed
to too great an extent.
Techniques of using styryl type dyes as the super-sensitizer are
known by, for instance, as disclosed in the specification of
British Pat. No. 498,031, the specification of German Pat. No.
1,051,116, and the specifications of U.S. Pat. Nos. 2,313,922;
2,316,268; 2,533,426; and 2,852,385. However, when such a technique
is applied to the case in which the exposure period of time is on
the order of a microsecond which is far shorter than an ordinary
exposure period of time, only a low sensitivity is obtained. In
other words, the above-mentioned sensitization techniques are
accompanied by the difficulty in obtaining high sensitivity when
the exposure period of time is short.
An object of this invention is, therefore, to provide a silver
halide photographic emulsion which is spectrally sensitized, which
has a high green sensitivity and which gives rise to less color
stains.
A second object of this invention is to provide a silver halide
photographic emulsion which is suitable for making medical X-ray
photographic light-sensitive materials having a high sensitivity to
the radiation emitted from a green fluorescent substance and having
a high stability to a safety light.
A third object of this invention is to provide a silver halide
photographic emulsion having a high sensitivity in, particularly,
in the wave length region of 520 - 540 nm. and giving less color
stains.
A fourth object of this invention is to provide a silver halide
photographic emulsion having a spectral sensitivity which is
suitable for recording in a cathode ray tube type display
system.
A fifth object of this invention is to provide a spectrally
sensitized silver halide photographic emulsion which is suitable
for use in a rapid processing system yet which is resistant to the
formation of color stains as well as the harmful actions of
antifoggants and a developing promotors.
The above objects and additional objects of this invention will
become apparent from the descriptions contained in this
specification in detail.
SUMMARY OF THE INVENTION
The above-described objects of this invention can be attained by
incorporating in a silver halide emulsion a supersensitizing amount
of the combination comprising at least one of the sensitizing dyes
represented by the General Formula (I). ##SPC3##
wherein Z.sub.1 represents a non-metallic atomic group necessary
for forming a benzthiazole nucleus or a benzselenazole nucleus;
Z.sub.2 represents a non-metallic atomic group necessary for
forming a benzene nucleus; R.sub.1 and R.sub.2 each represents an
alkyl group having from one to about six carbon atoms, a
substituted lower alkyl group conventionally used in cyanine dyes,
or an aliphatic hydrocarbon group having an unsaturated bond;
X.sub.1 .sup.- represents an anion and m is 1 or 2, m being 1 when
the dye forms an intramolecular salt; and at least one of the
sensitizing dyes represented by the General Formula (II)
##SPC4##
wherein Z.sub.3 represents a non-metallic atomic group necessary
for forming a benzoxazole nucleus, a .beta., .beta.-naphthoxazole
nucleus, or a .beta.-naphthoxazole nucleus; Z.sub.4 represents a
non-metallic atomic group necessary for forming a benzene nucleus;
R.sub.3 and R.sub.4 each represents an alkyl group having from one
to about six carbon atoms, a substituted alkyl group conventionally
used in cyanine dyes, or an aliphatic hydrocarbon group having an
unsaturated bond; at least one of said R.sub.3 and R.sub.4 being an
alkyl group having at least one of a sulfo group, a carboxyl group
or a hydroxyl group; R.sub.5 represents an alkyl group having from
one to about six carbon atoms, a substituted alkyl group
conventionally used in cyanine dyes, an aryl group, or an
unsaturated aliphatic hydrocarbon group; X.sub.2 .sup.- represents
an anion; and n is 1 or 2, n being 1 when the dye forms an
intramolecular salt.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIGS. 1 to 4 show the spectrograms obtained using the combination
of the sensitizing dyes of the invention.
FIGS. 5 to 6 show spectrograms for comparison sensitizing dyes.
FIG. 7 is a graph showing the spectral energy distribution emitted
upon excitation by X-rays of a fluorescent screen usually used in
X-ray photography.
FIG. 8 is a graph showing the spectral penetration coefficient
curve of a dark room safty light filter used for developing X-ray
photographic films.
DETAILED DESCRIPTION OF THE INVENTION
As described above, in the General Formula (I) Z.sub.1 represents
an atomic group necessary for forming a benzthiazole nucleus or a
benzselenazole nucleus, the benzene nucleus of Z.sub.1 may be
unsubstituted or may be substituted by a lower alkyl group having
from one to about six, preferably from one to four, carbon atoms
(such as a 5-methyl group, a 6-methyl group, a 5-ethyl group, a
6-propyl group, etc.,), an alkoxyl group (such as a 6-methoxy
group, a 4-ethoxy group, etc.,), a hydroxyl group (such as a
5-hydroxyl group, a 4-hydroxyl group, etc.,), a halogen atom (such
as a 5-chloro substituent, a 6-bromo substituent, etc.,), an aryl
group (such as a 5-phenyl group etc., a sulfoaryl group (such as a
5-sulfophenyl group, etc.,), a carboxy aryl group, a N-alkyl
substituted amino group (such as a N, N-dimethylamino group,
etc.,), or an alkoxycarbonyl group (such as a 5-methoxy carbonyl
group, etc.,).
Z.sub.2 represents a non-metallic atomic group necessary for
forming a benzene nucleus; the benzene nucleus may be unsubstituted
or may be substituted by lower alkyl group having from one to about
six, preferably from one to four, carbon atoms (such as a 5-methyl
group, a 4-ethyl group, etc.,), a halogen atom (such as a chlorine
atom, a bromine atom, an iodine atom, etc.,), or an alkoxyl group
(such as a 5-methoxy group, etc.,).
R.sub.1 and R.sub.2 each represents a lower alkyl group having from
one to about six, preferably from one to four, carbon atoms (such
as an ethyl group, a propyl group, a butyl group, etc.,) or such a
substituted alkyl group as is conventionally used in cyanine dyes
such as an aralkyl group (e.g., a benzyl group), an alkyl group
having a sulfo group (e.g., a sulfoalkyl group such as a sulfobutyl
group, a hydroxy sulfo alkyl group such as a
.beta.-hydroxysulfoethyl group, a sulfoalkoxyalkyl group such as a
sulfopropoxyethyl group, a sulfoarylalkyl group such as a
p-sulfophenylethyl group, a sulfoalkyl aminoalkyl group such as a
sulfopropylaminoethyl group, a sulfoalkylamidoalkyl group such as a
sulfobutylamidoethyl group. a sulfoalkylthioalkyl group such as a
--C.sub.2 H.sub.4 --S--C.sub.3 H.sub.6 SO.sub.3 H group, etc.,) and
an alkyl group having a carboxyl group, and an alophatic
hydrocarbon group having an unsaturated bond (e.g., allyl).
X.sub.1 represents an anion conventionally used for forming a
cyanine dye such as a bromide ion, an iodide ion, a
p-toluene-sulfonic acid ion, a perchlorate ion, a methyl sulfate
ion, an ethyl sulfate ion, or a benzenesulfonate ion. m is 1 or 2;
and where m is 1 the sensitizing dye of the General Formula (I)
forms a intramolecular salt (betaine like structure), i.e., in such
a case no extra anion need be present.
As described above, in the General Formula (II) Z.sub.3 represents
an atomic group necessary for forming a .beta.
,.beta.-naphthoxazole nucleus, a .beta.-naphthoxazole nucleus, or a
benzoxazole nucleus, in which the nucleus may be unsubstituted or
may be substituted with a lower alkyl group having from one to six,
preferably from one to four, carbon atoms (such as a 6-methyl
group, a 5-ethyl group, etc.,) a halogen atom (such as a 5-chloro
substituent, a 5-bromo substituent, etc., ) an alkyl group (such as
a 6-methyl group, etc.,), an alkoxyl group (such as a 5-methoxy
group, 7-ethoxy group, etc.,), a hydroxyalkyl group (such as a
5-hydroxymethyl group, etc.,), an alkoxycarbonyl group (such as a
5-methoxycarbonyl group, etc.,), an aryl group (such as a 5-phenyl
group etc.,), a sulfoaryl group (such as a 5-sulfophenyl group, or
a carboxyaryl group etc.,).
Z.sub.4 represents a non-metallic atomic group necessary for
forming a benzene nucleus, in which the benzene nucleus may be
unsubstituted or may be substituted by a substituent conventionally
known as a substituent of the benzimidazole nucleus in a cyanine
dye nucleus. For example, the substituent can be a halogen atom
such as a chlorine atom, a bromine atom, an iodine atom; a cyano
group; an alkoxycarbonyl group; a trifluoromethyl group; a
carbamoyl group, an alkyl substituted carbamoyl group, such as a
methylcarbamoyl group or a dimethylcarbamoyl group; a sulfamoyl
group, an alkyl substituted sulfamoyl group, such as methyl
sulfamoyl and dimethyl sulfamoyl, etc.
R.sub.3 and R.sub.4 each represents a lower alkyl group having from
one to six, preferably from one to four carbon atoms e.g., a methyl
group, an ethyl group, a propyl group, a butyl group, an isobutyl
group, an unsaturated aliphatic hydrocarbon group for instance, an
allyl group, or a substituted alkyl group conventionally used as a
substituent on a nitrogen atom in the cyanine nucleus. Such nucleus
N-substituted groups can be groups such as a hydroxyalkyl group, an
alkyl group having a sulfo group (such as a .gamma.-sulfobutyl
group, a .gamma.-sulfobutyl group, a sulfopropoxy ethoxy ethoxy
ethyl group etc.,), an alkyl group having a carboxy group (such as
a .beta.-carboxyethyl group, a 2-(2-carboxyethoxy) ethyl group
etc.,), or an aralkyl group (such as a benzyl group etc.,). In
addition, R.sub.3 and R.sub.4 may further represent a
.beta.-methoxyethyl group, a .beta.-ethoxyelthyl group, a
.beta.-methallyl group, a benzyl group, a .beta.-phenylethyl group,
a .beta.-acetoxyethyl group, a .gamma.-acetoxypropyl group, a
carbomethoxymethyl group, a .beta.-carbomethoxyethyl group, a
carbethoxymethyl group, a .beta.-carbethoxyethyl group, a
phenylmercaptomethyl group, a phenoxymethyl group, a
.beta.-phenylmercaptoethyl group, a .beta.-phenoxyethyl group, and
a 2-(2-hydroxy-3-sulfopropxy) ethyl group and a carbamylmethyl
group. Groups R.sub.3 and R.sub.4 may be substituted by the
substituents described in the specifications of, e.g., German Pat.
No. 929,080; U.S. Pat. Nos. 2,537,880 and 2,776,280; British Pat.
No. 1,001,480; and Japanese Patent Publication No. 4843/1965;
Japanese Patent Publication No. 5829/1960; Japanese Patent
Publication No. 14112/1965; Japanese Patent Publication No.
23,467/1965; Japanese Patent Publication No. 27,164/1967; Japanese
Patent Publication No. 27,165/1967; Japanese Patent Publication No.
27,166/1967; Japanese Patent Publication No. 27,167/1967; Japanese
Patent Publication No. 2607/1968; Japanese Patent Publication No.
15,894/1970; Japanese Patent Publication No. 27,672/1970; Japanese
Patent Publication No. 27,673/1970; and Japanese Patent Publication
No. 32,740/1970; at least one of R.sub.3 or R.sub.4 is alkyl group
having at least one of sulfo group, carboxyl group and hydroxyl
group.
R.sub.5 represents a lower alkyl group having from one to about
six, preferably from one to four, (such as a methyl group, an ethyl
group, a propyl group, etc.,), an unsaturated aliphatic hydrocarbon
group (such as an allyl group, etc.,), a substituted alkyl group
and an aryl group (such as a phenyl group). The substituted alkyl
group can be a group such as an aralkyl group (such as a benzyl
group, etc.,), a hydroxyalkyl group (such as a .beta.-hydroxylethyl
group, etc.,), or an acetoxyalkyl group (such as a
.beta.-acetoxyethyl group, a .gamma.-acetoxypropyl group,
etc.,).
X.sub.2 .sup.- is an anion and has the same significance as X.sub.1
.sup.- in the General Formula (I); and n is 1 or 2, where n is 1
the sensitizing dye forms an intramolecular salt.
Preferred embodiments of combinations of the sensitizing dyes of
the above general Formulas are as follows: the combination of at
least one of the sensitizing dyes represented by the General
Formula (I') ##SPC5##
wherein R.sub.1 and R.sub.2 each represents a methyl group, an
ethyl group, or an allyl group; X.sub.1 .sup.- represents an anion;
and R represents a hydrogen atom, a methyl group, or an ethyl
group; and at least one of the sensitizing dyes represented by the
following General Formula (II') ##SPC6##
wherein W.sub.1 and W.sub.2 each represents a hydrogen atom, a
chlorine atom, or a methoxycarbonyl group and R.sub.3 and R.sub.4
each represents a sulfoalkyl group or an alkyl group; at least one
of R.sub.3 and R.sub.4 being a sulfoalkyl group.
An important feature of this invention is the discovery of the
imidaoxacarbocyanine dye of a so-called asymmetric nucleus
represented by the General Formula (II) and the pseudocyanine dye
represented by the General Formula (I).
By the discovery of the super-sensitizing action of these
sensitizing dyes, the difficulties caused by the use of the
sensitizing dyes individually can be overcome and the advantages of
these dyes can be utilized effectively. That is to say, when the
pseudocyanine dye of the General Formula (I) is used individually,
it gives rise to a low sensitivity only. However, it is known that
pseudocyanine dye described in the specification of some German
Offenlegungsschrift gives an exceptionally high sensitivity but in
order to obtain such a high sensitivity using the sensitizing dye
of the German Patent application, the dye must be used at 4 to 8
times on a molar basis the amount usually employed in this art.
Thus, the use of such a large amount of the dye gives rise to
disadvantages in that the formation of color stains increases, the
spectrally sensitized region extends to the longer wave length
side, and the light-sensitive material containing the sensitizing
dye tends to be fogged even under a safety light.
On the other hand, when the pseudocyanine dye of the General
Formula (I) is used together with the carbocyanine dye of the
General Formula (II), the maximum sensitivity can be obtained by
employing the pseudocyanine dye of the General Formula (I) at a
level of only a few percent of the amount required where the
pseudocyanine dye is used alone. Consequently, the aforesaid
difficulties are overcome by the present invention.
The sensitizing dye of the General Formula (II) sensitizes
essentially in the wave length region substantially corresponding
to the objects of this invention in giving a strong and sharp
J-aggregate, i.e., a J-band. When the sensitizing dye of the
General Formula (II) is used together with the pseudocyanine dye of
the General Formula (I), the J-aggregate is properly partitioned
and the spectral absorption region is shifted toward the blue to
give a spectral sensitivity distribution corresponding better the
emission energy distribution shown in FIG. 7 of the accompanying
drawings. Moreover, in the present invention, the maximum
sensitivity is obtained in a small range of the amount of the dye
and the formation of color stains is less. In general, the
formation of color stains tends to increase rapidly when the amount
of the same dye added is increased and the stronger aggregates are
formed. Accordingly, the fundamental features of this invention
will be understood on consideration of these circumstances.
Specific examples of the sensitizing dyes used in this invention
are illustrated herein below although the sensitizing dyes of this
invention are not to be interpreted as limited to these specific
dyes. Examples of the sensitizing dyes represented by the General
Formula (I) are as follows: ##SPC7##
Also, the specific examples of the sensitizing dyes represented by
the General Formula (II) are illustrated below: ##SPC8##
The spectral sensitizing method of the present invention is
particularly advantageous for the spectral sensitization of
gelatino silver halide photographic emulsions. However, the
spectral sensitizing method of this invention is also usefully
applied to a photographic emulsion containing other hydrophilic
polymers than gelatin, such as agar-agar, collodion, water-soluble
cellulose derivatives, polyvinyl alcohols, copolymers of polyvinyl
pyrrolidone, synthetic hydrophilic resins, natural hydrophilic
polymers, and gelatin derivatives.
As the photographic emulsion used in this invention, a mixed silver
halide emulsion containing silver chloride, silver bromide, or
silver iodide or a mixed silver halide thereof such as silver
bromoiodide and silver iodochlorobromide is suitable. Furthermore,
conventional methods of sensitization may be employed on a silver
halide photographic emulsion which is spectrally sensitized by the
sensitizing method of this invention, for instance, chemical
sensitization such as sulfur sensitization, reduction
sensitization, gold sensitization, sensitization by a metal
belonging to the Group VIII of the periodic table and Noble metals.
Combinations of these methods may also be used.
The photographic emulsion spectrally sensitized by the present
invention may be prepared by incorporating the sensitizing dyes
represented by the General Formula (I) and the General Formula (II)
in the photographic emulsion using conventional techniques.
Each of the sensitizing dyes of the general formulae is generally
added to a photographic emulsion as a solution thereof in a
water-miscible solvent such as methanol, ethanol, water,
cellosolve, or a water-miscible ketone such as methylethyl ketone,
methyl ketone and ethyl ketone. Also, the sensitizing dye may be
added to a photographic emulsion as a dispersion of a solution in a
weakly soluble oil in water or a hydrophilic colloid.
The addition ratio of the sensitizing dye of the General Formula
(I) to the sensitizing dye of the General Formula (II) to be
incorporated in the photographic emulsion may be varied over a wide
range, for example, from 9:1 to 1:10 on a molar basis, in
accordance with the effects or advantages desired. Also, it is
preferred that the amount of each of the sensitizing dyes employed
in this invention range from 1 .times. 10.sup.-.sup.6 mol to 1
.times. 10.sup.-.sup.3 mol per mol of silver depending upon the
characteristics of the photographic emulsion.
The photographic emulsion of this invention may further be
subjected to conventional supersensitization techniques. Moreover,
the spectrally sensitized photographic emulsion of this invention
may further contain additives conventionally employed in the art,
such as sensitizers, stabilizers, color toning agents, hardening
agents, surface active agents, antifoggants, plasticizers,
developing promotors, color couplers, and fluorescent brightening
agents.
The photographic emulsion of this invention may be applied to an
appropriate support such as a glass sheet, a cellulose ester
derivative film, a polyethylene terephthalate film, a synthetic
resin film, a barayta-coated paper, a resin-coated paper, or a
synthetic paper using conventional techniques.
Furthermore, as described before, the silver halide photographic
emulsion of this invention may be used as a light-sensitive
material suitable for cathode ray tube display.
This invention will now be explained in greater detail by reference
to the examples given below.
EXAMPLES 1 - 29
A silver halide photographic emulsion was prepared by incorporating
the sensitizing dyes represented by the General Formula (I) and the
General Formula (II) shown in the tables below in the amounts set
forth in a gelatino silver iodo-bromide emulsion (AgI: AgBr = 7
mol%: 93 mol%, gelatin (g)AgNO.sub.3 = 1.3: 0.26 mol silver salt/kg
emulsion). Also, for comparison, a silver halide photographic
emulsion was prepared by using individually each of the sensitizing
dyes of the General Formula (I) and the General Formula (II) and
also a comparison silver halide photographic emulsion was prepared
by using each of the comparison sensitizing dyes represented by the
Formula (T) and Formula (U) shown below.
Each of the silver halide photographic emulsions thus prepared was
applied to a triacetyl cellulose film base. The light-sensitive
photographic films thus prepared were each exposed to day light
radiation of 64 lux (corresponding to 5,400 K.degree.) through a
yellow filter (made by the Fuji Photo Film Co., a filter passing
light of wave lengths longer than 460 nm.), a green filter (made by
the Fuji Photo Film Co., a filter passing light of wave lengths of
480-620 nm. and having a maximum penetration coefficient at a wave
length of 530 nm.), or a blue filter (made by the Fuji Photo Film
Co., a filter passing light of wave lengths of 400-490 nm. and
having a maximum penetration coefficient at a wave length of 450
nm.). They were then developed for 2 minutes at 24.degree.C in a
developing solution haveing the following composition: Metol 2.2 g
Sodium Sulfite 96 g Hydroquinone 8.8 g Sodium Carbonate
(mono-hydrate) 56 g Potassium Bromide 5 g
Water added to make the total volume 1 liter. In the following
table, the yellow sensitivities and the green sensitivities
obtained by adding the sensitizing dyes illustrated above
individually and the comparison sensitizing dyes shown below and
the yellow sensitivities and the green sensitivities obtained by
adding the sensitizing dyes as combinations thereof are shown
together with the intrinsic sensitivities of the silver halide
photographic emulsion containing the sensitizing dye or dyes
relative to the intrinsic sensitivity of the original silver halide
photographic emulsion which did not contain a sensitizing dye.
In the following table, the yellow sensitivity and the green
sensitivity are the relative values when the sensitivities of the
silver halide photographic emulsion containing 4 .times.
10.sup.-.sup.5 mol/kg emulsion of the sensitizing dye (A) shown
above exposed to the above-mentioned day light radiation through
the yellow filter or the green filter respectively were defined as
100 each.
The relative sensitivity is shown relatively when the sensitivity
of the original silver halide photographic emulsion exposed to the
day light radiation through the blue filter is defined as 100.
The comparison sensitizing dyes used for the comparison tests have
the following structures; ##SPC9##
Table
__________________________________________________________________________
Ex. Sens.Dye Sens.Dye Max. Rel. Rel. Intrinsic Spectro- (amount*)
(amount*) sens. yellow green sens. gram (nm) sens. sens.
__________________________________________________________________________
A (1) 550 57 69 100 A (2) 550 88 88 100 A (4) 550 100 100 100 A (8)
550 125 120 100 7 (2) 540 100 115 100 7 (4) 540 120 120 100 7 (6)
540 120 125 94
__________________________________________________________________________
A (1) 7 (6) 544 125 140 100 1 A (2) 7 (6) 548 140 165 90 A (4) 7
(6) 550 155 170 90
__________________________________________________________________________
C (1) 546 52 48 104 C (2) 546 66 66 94 C (4) 550 70 70 94 C (8) 550
78 78 90
__________________________________________________________________________
C (1) 7 (6) 548 120 135 100 2 C (2) 7 (6) 548 150 170 100
__________________________________________________________________________
8 (2) 540 80 80 94 8 (4) 540 88 90 90 8 (6) 540 90 92 76
__________________________________________________________________________
A (1) 8 (6) 540 96 115 78 3 A (2) 8 (6) 540 112 115 78 A (4) 8 (6)
548 125 135 85
__________________________________________________________________________
L (4) 532 30 25 96 FIG.1(1) L (8) 532 38 30 94 6 (1) 556 71 62 94 6
(2) 556 80 72 94 6 (4) 560 92 90 90 FIG.1(2) 6 (8) 560 104 112 85
__________________________________________________________________________
L (8) 6 (1) 532/ 140 164 94 556 4 L (8 6 (2) 535/ 152 178 94 556 L
(4) 6 (4) 535/ 185 194 94 FIG.1(3) 560
__________________________________________________________________________
M (4) 540 70 82 88 M (8) 540 76 85 83
__________________________________________________________________________
M (8) 6 (1) 540/ 130 152 85 550 5 M (8) 6 (2) 540/ 140 172 85 560 M
(6) 6 (4) 560 135 158 85
__________________________________________________________________________
1 (1) 560 100 90 94 1 (2) 560 130 136 90 1 (4) 560 158 168 87 1 (8)
560 193 200 83
__________________________________________________________________________
L (8) 1 (1) 535/ 170 192 98 558 6 L (8) 1 (2) 535/ 200 208 96 560 L
(4) 1 (4) 540/ 216 225 96 560
__________________________________________________________________________
E (4) 544 148 156 100 E (8) 544 164 170 103 14 (4) 552 130 140 98
14 (8) 540- 146 185 98 556 14 )12) 540- 170 205 96 560
__________________________________________________________________________
E (8) 14 (4) 545 200 210 104 E (4) 14 (4) 550 200 208 104
__________________________________________________________________________
F (4) 538 82 90 100 F (8) 538 90 96 100
__________________________________________________________________________
F (4) 14 (4) 540- 180 180 100 8 550 F (8) 14 (4) 540- 185 180 100
550
__________________________________________________________________________
C (4) 515- 46 30 100 520 C (8) 515- 48 35 104 520
__________________________________________________________________________
C (8) 1 (1) 550 135 125 104 C (8) 1 (2) 550 146 160 104
__________________________________________________________________________
D (4) 530 46 34 96 D (8) 530 52 37 94
__________________________________________________________________________
D (4) (1) 525- 180 185 104 10 555 D (8) 1 (2) 525- 200 208 104 555
__________________________________________________________________________
G (4) 540 25 18 104 G (8) 540 31 21 104 21 (1) 560 102 90 96 21 (2)
560 134 140 94 FIG.4(11) 21 (4) 560 158 172 94 21 (8) 560 196 205
90
__________________________________________________________________________
G (8) 21 (1) 555 102 110 104 11 G (8) 21 (2) 555 152 150 104
__________________________________________________________________________
P (4) 538 30 22 104 P (8) 538 38 28 104 FIG.4(10)
__________________________________________________________________________
P (8) 21 (1) 540- 178 194 104 12 560 P (8) 21 (2) 540- 210 216 96
FIG.4(12) 560
__________________________________________________________________________
J (2) 556 107 100 98 J (4) 558 135 135 98 J (8) 558 158 164 98 4
(2) 548 92 55 100 4 (4) 548 100 60 100 4 (6) 548 107 66 100
__________________________________________________________________________
J (2) 4 (6) 550 170 170 100 13 J (4) 4 (6) 550 224 215 104
__________________________________________________________________________
K (2) 560 135 135 100 K (4) 560 170 170 100 K (8) 560 178 185 96
__________________________________________________________________________
K (2) 4 (6) 550 164 164 104 14 K (4) 4 (6) 550 208 208 104
__________________________________________________________________________
H (2) 540 42 28 100 H (4) 540 50 46 100 H (8) 540 66 60 100 3 (1)
562 76 64 96 3 (2) 562 107 85 96
__________________________________________________________________________
15 H (2) 3 (1) 560 76 78 96 H (2) 3 (2) 562 110 96 94
__________________________________________________________________________
I (2) 540 65 62 96 I (4) 540 76 73 96 I (6) 540 69 66 94 2 (1) 550
73 70 100 2 (2) 552 85 85 100
__________________________________________________________________________
I (6) 2 (1) 552 94 104 90 16 I (6) 2 (2) 552 112 116 88
__________________________________________________________________________
N (4) 560 158 152 96 N (8) 560 200 200 96 FIG. 2 (4) N (12) 560 224
208 96 16 (4) 520- 103 110 110 545 16 (8) 550 152 170 110 16 (12)
550 193 200 110
__________________________________________________________________________
N (1) 16 (8) 552 193 208 110 17 N (2) 16 (8) 552 210 240 110 N (4)
16 (8) 554 234 260 110
__________________________________________________________________________
5 (4) 540- 130 156 110 545 5 (8) 540- 158 178 110 FIG. 2 (5) 545 5
(12) 545 192 200 115
__________________________________________________________________________
N (2) 5 (8) 560 240 233 120 18 N (4) 5 (8) 560 260 280 120 FIG. 2
(6)
__________________________________________________________________________
Q (2) 520 30 19 100 Q (4) 520 38 25 100 Q (6) 520 42 29 98 17 (2)
550 88 85 94 17 (4) 550 110 110 90
__________________________________________________________________________
Q (6) 17 (2) 520- 140 152 100 19 550 Q (6) 17 (4) 520- 170 194 100
550
__________________________________________________________________________
R (4) 522 32 20 100 R (6) 522 37 27 100
__________________________________________________________________________
R (6) 17 (2) 540 152 152 104 20 R (6) 17 (4) 540 172 185 104
__________________________________________________________________________
18 (2) 530 69 56 90 18 (4) 542 83 73 88
__________________________________________________________________________
R (6) 18 (2) 530 90 83 100 21 R (5) 18 (4) 530 110 100 100
__________________________________________________________________________
B (4) 536 42 30 104 B (8) 536 45 40 104 FIG. 3 (7) 11 (4) 550 85 83
94 11 (8) 550 96 94 94 11 (12) 550 103 100 88
__________________________________________________________________________
B (4) 11 (4) 548 103 110 100 22 B (4) 11 (8) 548 110 110 100
__________________________________________________________________________
20 (0.5) 560 76 69 94 20 (1) 560 99 96 90 20 (2) 560 110 128 85
FIG. 3 (8) 20 (4) 560 130 152 80
__________________________________________________________________________
B (8) 20 (1) 540/ 152 88 108 23 558 B (8) 20 (2) 530/ 185 215 108
FIG. 3 558 (9) B (8) 20 (4) 558 194 224 100
__________________________________________________________________________
19 (2) 555 85 100 94 19 (4) 555 106 125 88 19 (8) 555 130 146 88
__________________________________________________________________________
B (8) 19 (1) 540 103 110 108 B (8) 19 (2) 530/ 130 152 108 552 B
(4) 19 (4) 554 136 152 100
__________________________________________________________________________
9 (2) 548 88 90 100 9 (4) 548 125 120 98
9 (8) 548 125 135 98
__________________________________________________________________________
N (1) 9 (4) 546/ 130 135 100 548 25 N (2) 9 (4) 550/ 135 152 96 560
N (4) 9 (4) 550/ 176 176 96 560
__________________________________________________________________________
10 (4) 562 90 80 76 10 (8) 562 90 80 76 10 (12) 564 85 76 70
__________________________________________________________________________
B (2) 10 (4) 560 96 96 76 26 B (4) 10 (4) 560 100 96 76
__________________________________________________________________________
12 (4) 566 116 100 76 12 (8) 566 116 107 71 12 (12) 568 100 96 48
__________________________________________________________________________
B (4) 12 (4) 564 178 185 94 27 B (2) 12 (8) 564 158 158 85
__________________________________________________________________________
15 (2) 540 70 78 92 15 (4) 540 86 90 88 15 (8) 540 90 96 83
__________________________________________________________________________
L (2) 15 (8) 540 128 130 90 28 L (4) 15 (8) 540 135 152 90
__________________________________________________________________________
13 (4) 540 120 140 104 13 (8) 540 145 158 104
__________________________________________________________________________
N (2) 13 (8) 560 228 216 100 29 N (4) 13 (8) 560 246 250 100
__________________________________________________________________________
T (4) 582 180 110 85 T (8) 584 185 120 76 FIG. 5 (13) T (12) 584
185 110 72
__________________________________________________________________________
U (4) 574 178 106 90 U (8) 574 182 114 66 FIG. 6 (14) U (12) 574
180 110 62
__________________________________________________________________________
* amount = 10.sup.-.sup.5 mol/kg emulsion
EXAMPLE 30
Two kinds of spectrally sensitized silver halide photographic
emulsions were prepared by adding the dye (2) show above alone and
the dye (B) and the dye (20) in the combination according to this
invention to a silver iodo-bromide emulsion (AgI : AgBr= 1.5 mol :
98.5 mol%, gelatin (g)/AgNo.sub.3 (g) = 0.4, 0.75 mol silver
salt/kg emulsion). Each of the photographic emulsions was applied
to a polyethylene terephthalate film base and after drying,
sensitometery was conducted on the light-sensitive films thus
obtained.
The light-sensitive films was exposed to a day light source
(corresponding to 5,400.degree.K) through a blue filter (made by
the Fuji Photo Film Co., a filter passing light of wave lengths of
400-500 nm. and having a maximum penetration coefficient at a wave
length of 450 nm.) or a green filter (made by the Fuji Photo Film
Co., a filter passing light of wave lengths of 480-650 nm., having
a maximum penetration coefficient at a wave length of 530 nm.) and
then developed for 4 minutes at 20.degree.C in the same developing
solution as used in the above Examples 1 - 29. The results obtained
are shown in the following table.
In the following table, the sensitivity is shown by the relative
sensitivity when the sensitivity of the silver halide photographic
emulsion containing the dye (20) shown above in an amount of 4
.times. 10.sup.-.sup.5 mol per kg of the emulsion is defined as
100.
Table 3
__________________________________________________________________________
Example Sens. Dye Sens. Dye Maximum Relative Relative (amount)*
(amount)* Sensitization Green Sens. Blue Sens.
__________________________________________________________________________
20 (4) 560 nm 100 100 20 (8) 560 125 100 20 (10) 560 130 90 B (1.7)
20 (4) 560 150 95 30 B (3.4) 20 (8) 560 191 95 B (4.0) 20 (10) 560
238 95
__________________________________________________________________________
* = 10.sup.-.sup.5 mol/kg emulsion
From the results shown in the tables, it can be seen that the green
sensitivity is super-additively increased, which is one of the
objects of this invention, by using at least one of the sensitizing
dyes of the General Formula (I) and at least one of the sensitizing
dyes of the General Formula (II).
The results obtained by the above examples are also shown in the
accompanying drawings. That is to say, FIG. 1, FIG. 2, FIG. 3 and
FIG. 4 are spectrograms obtained by using the combinations of the
sensitizing dyes of the General Formula (I) and the General Formula
(II) according to the present invention. FIG. 5 and FIG. 6 are the
spectrograms obtained by using the comparison sensitizing dyes of
the Formula (T) and the Formula (U) respectively. In addition, the
numbers in the parentheses the examples shown in the above table to
which the curves correspond.
FIG. 7 is a graph showing the spectral energy distribution of light
emitted by exciting by X-rays the fluoresecnt substance of a
fluorescent screen usually used for X-ray photography.
FIG. 8 is a graph showing the spectral penetration coefficient
curve of a safety light filter usually used in a dark room for
obtaining safety light in the case of developing direct X-ray
photographic films.
Now, as clear from the results of Example 18, when the dye (N),
which is one of the sensitizing dyes represented by the General
Formula (I) is added in such a large amount so as to give the
maximum green sensitivity, the sensitized region of the
light-sensitive film extends to 596 nm. as shown by the curve (4)
of FIG. 2 but when the dye (N) is used together with the
sensitizing dye (5) of the General Formula (II), the sensitized
wave length end of the light-sensitive film shifts to the shorter
wave length side and also the sensitivity reduction in the longer
wave length side is sharp as is shown by the curve (6) of FIG. 2.
Besides the above-described advantages the green sensitivity of the
light-sensitive film prepared by using the combination of the
sensitizing dyes according to the present invention is about 1.6
times higher than that of the light-sensitive film obtained by
using the sensitizing dye individually.
From the results shown above, it will aslo be understood that the
photographic emulsion of this invention is less fogged by exposure
to a safety light and also the spectral sensitivity distribution of
the photographic emulsion fits the energy distribution of the light
emitted from the green fluorescent substance of the X-ray
fluorescent screen as shown in FIG. 7.
Furthermore, on investigating the results of the table obtained in
the Examples 1 - 29 and the results shown in FIG. 1 to FIG. 6 of
the accompanying drawings, it will be understood that the objects
of this invention are well attained by using the sensitizing dye of
the General Formula (I) together with the sensitizing dye of the
General Formula (II).
Also, from the results of the examples, it will be understood that
the present invention can be applied effectively to various fields
in a practical manner.
* * * * *