BACKGROUND OF INVENTION
Field of the invention
[0001] The present invention relates to a novel combination of a silver halide photographic
material and radiographic intensifying screens, and the invention also relates to
a silver halide photographic material employable for the combination. Particularly,
the present invention relates to a novel combination of a silver halide photographic
material and radiographic intensifying screens showing excellent characteristics in
balance between the sensitivity and the image quality.
Description of prior art
[0002] In medical radiography, a radiographic image of the organ of patient is obtained
by recording a pattern of X-rays having passed through the patient on a photographic
material (silver halide photographic material) in which at least one photosensitive
silver halide emulsion layer is provided on a transparent support by coating. Although
the pattern of X-rays having passed through the patient can be obtained using a silver
halide photographic material alone, a radiographic intensifying screen is usually
employed in combination with the photographic material so as to avoid exposure of
the objective human body to a large dose of X-rays. In a radiographic intensifying
screen, provided on a support is a phosphor layer which absorbs X-rays and then converts
them into the visible light to which the photographic material is sensitive. Therefore,
the sensitivity of the system for X-ray photography can be remarkably improved by
the use of a radiographic intensifying screen.
[0003] As a method for further enhancing the sensitivity of the system for X-ray photography,
proposed was the method in which a photographic material having photographic emulsion
layers provided on both sides, namely, a silver halide photographic material having
silver halide photosensitive layers provided on both of the front and the back sides
of the support, is used, and radiographic intensifying screens (which are sometimes
referred to as "intensifying screens") are placed on both sides of said material to
obtain an X-ray photography in this arrangement. At present, this method is generally
used in most cases. This method has been proposed in view of the fact that sufficient
amount of X-rays is not absorbed by the use of only one radiographic intensifying
screen. In fact, even if content of the phosphor in one intensifying screen is increased
in order to increase absorption of X-rays, the photographic material placed in contact
with said intensifying screen receives very diffuse visible light emitted by said
screen because the visible light converted within the phosphor layer is scattered
and reflected in the phosphor layer having an increased thickness which is caused
by the increase of the phosphor. In addition to that, the visible light converted
within the deep area of the thick phosphor layer hardly comes out of the phosphor
layer. Therefore immoderate increase of the phosphor content does not further increase
the effective visible light emitted by the intensifying screen.
[0004] By the X-ray photographic system (i.e., radiography) using two intensifying screens
each of which has a phosphor layer of adequate thickness, the total absorption of
X-rays can be increased and the visible light converted in the intensifying screen
can be efficiently used.
[0005] Commercially available are a variety of radiographic intensifying screens having
different sensitivities in a wide range; for example, from the type of low sensitivity
such as a screen that emits weak luminescence and gives an image of high sharpness
(such screen has a relatively thin phosphor layer) to the type of high sensitivity
such as a screen that emits high luminescence and gives an image of low sharpness
(such screen has a relatively thick phosphor layer).
[0006] However, although various types of silver halide photographic materials having photographic
emulsion layers provided on both sides are commercially available, their sensitivities
vary within a narrow range. In fact, the sensitivities of the most photographic materials
are only twice or three times as much as that of the least one (sensitivity of the
lowest sensitive material is used as standard).
[0007] Employable combinations of silver halide photographic materials and intensifying
screens used for radiography are not particularly restricted. However, when highly
sensitive radiography is required (for example, in the case of radiography for lumbar
vertebra, angiography for head or enlargement radiography), a combination of an intensifying
screens of high emission and a silver halide photographic material of standard type
or of high sensitivity is generally employed. In contrast, when high image quality
is needed (for example, in the case of simple radiography of chest, gastric radiography
using contrast medium, or radiography of bones), a combination of intensifying screens
providing high sharpness and a silver halide photographic material of standard type
is generally employed. While a combination of intensifying screens of high sensitivity
and a silver halide photographic material gives an image of low sharpness (namely,
low image quality), a combination of intensifying screens providing high image quality
and a photographic material shows low sensitivity.
[0008] Previously, in order to establish an X-ray photographic system having excellent characteristics
in balance between sensitivity and image quality, various studies have been continuously
made. For instance, although a combination of intensifying screens having phosphor
layers of calcium tungstate (which emits blue luminescence) and a silver halide photographic
material which is not spectral sensitized (e.g., a combination of HIGH SCREEN STANDARD
and RX [each of which is a trade name of Fuji Photo Film Co., Ltd.]) has been formerly
used, a combination of intensifying screens having phosphor layers of terbium activated
rare earth oxysulfide phosphor (which emits green luminescence) and a silver halide
photographic material which is orthochromatically spectral sensitized (e.g., a combination
of GREENEX 4 and RXO [each of which is a trade name of Fuji Photo Film Co., Ltd.])
has been recently used. The latter combination gives an image improved in both sensitivity
and image quality.
[0009] A silver halide photographic material having photographic emulsion layers provided
on both sides has a defect that the image quality is likely deteriorated by "cross-over
light". The word "cross-over light" means the visible light which is emitted by each
intensifying screen placed on each side of the photographic material and then passes
through the support of the photographic material (thickness of the generally used
support is 170-180 µm) and finally reaches the photosensitive layer provided on the
opposite side to deteriorate the image quality (particularly, in sharpness).
[0010] In order to reduce the cross-over light, various methods have been proposed. For
example, U.S. Patent Nos. 4,425,425 and 4,425,426 disclose inventions in which a spectral
sensitized emulsion including tabular silver halide grains having a high aspect ratio
is used as a silver halide photographic emulsion. According to these patented inventions,
the cross-over light can be reduced to 15-22 % level. Besides that, U.S. Patent No.
4,803,150 discloses an invention in which a dye layer comprising fine crystalline
dye particles and being decolorizable by the developing process is provided between
the support and the photosensitive layers in the silver halide photographic material.
It is described that cross-over light can be reduced to 10 % level or less by the
invention.
[0011] On the other hand, various attempts to provide an X-ray photographic system showing
excellent characteristics in balance between the sensitivity and the image quality
have been made by setting a combination of intensifying screens and a silver halide
photographic material (which has photographic emulsion layers on both sides) under
particular conditions. For example, Japanese Patent Provisional Publication Nos. 2(1990)-266344
and 2(1990)-297544 and U.S. Patent No. 4,803,150 disclose an X-ray photographic system:
in which the light property (sensitivity) of the front side combination (consisting
of an intensifying screen placed on the side to be exposed [i.e., front screen] and
a photosensitive layer [i.e., front photosensitive layer]) is made to differ from
that of the back combination (consisting of an intensifying screen placed on the opposite
side [i.e., back screen] and a photosensitive layer [i.e., back photosensitive layer]),
and the contrast given by the former combination is made to differ from that given
by the latter. In addition to that,
Photographic Science and Engineering, vol.
26(1982), No. 1, pp. 40, describes experiments about the combinations of intensifying
screens and a silver halide photographic material each of which is available from
3M Co. The experiments show the result that a combination of Trimax 12 (trade name
of intensifying screen commercially available from 3M Co.) and XUD (trade name of
silver halide photographic material commercially available from 3M Co.) gives better
NEQ (signal/noise ratio of output) than the combination of Trimax 4 (trade name of
intensifying screen commercially available from 3M Co.) and XD (trade name of silver
halide photographic material commercially available from 3M Co.), while the former
is at the same level of the latter with respect to sensitivity and sharpness (MTF).
It further describes that the above result is caused by the facts that XUD exhibits
higher sharpness than XD and that Trimax 12 absorbs more amount of X-rays than Trimax
4.
[0012] As is described above, various methods have been proposed to establish X-ray photographic
system showing excellent characteristics in balance between the sensitivity and the
image quality. However, previously proposed radiographic image forming methods still
do not satisfy the sensitivity and the image quality required, for instance, for X-ray
photographic system to be used for diagnosis of stomach or chest. Actually, while
it is very important to observe veins in lung to the minutest details in diagnosis
for chest, satisfactory observation can not be made by the known X-ray photographic
systems. Since the known systems often give radiographic images having poor contrast
of the vein image, image qualities are deteriorated in respect of grains, or blur.
Further, in diagnosis for stomach, diagnostically satisfactory radiographic images
in well picturing the gastric wall cannot obtained.
[0013] Needless to say, if other conditions are neglected, a radiographic image of high
quality can be obtained by a combination of a silver halide photographic material
of low sensitivity and radiographic intensifying screens of low sensitivity. However,
if such low-sensitive combination is used, the exposure (dose) of X-rays applied to
human body should be naturally increased. Therefore, such combination is not practically
applicable, and particularly, in the case of group examination in which it is required
to reduce the dose of X-rays to be applied as much as possible.
SUMMARY OF THE INVENTION
[0014] An object of the present invention is to provide a novel X-ray photographic system,
that is, a combination of a silver halide photographic material and radiographic intensifying
screens, which exhibits excellent characteristics in balance between the sensitivity
and the image quality obtained by the combination.
[0015] Particularly, an object of the invention is to provide a novel combination of a silver
halide photographic material and radiographic intensifying screens which has practically
satisfactory sensitivity and gives radiographic images having practically satisfactory
image quality.
[0016] A still further object of the invention is to provide a novel silver halide photographic
material advantageously employable for the above novel X-ray photographic system.
[0017] The present invention resides in a combination for forming a radiographic image comprising
a silver halide photographic material and two radiographic intensifying screens, one
of which is placed on the front of said photographic material and the other of which
is on the back;
wherein
1) at least one of said intensifying screens absorbs X-rays of 80 KV
p in an amount of not less than 25 % and shows contrast transfer function values of
at least 0.79 and at least 0.36 at spatial frequencies of 1 lp/mm and of 3 lp/mm,
respectively; and
2) said photographic material has silver halide photosensitive layers one of which
is provided on the front of its support and another of which is on the back; and at
least one of said photosensitive layers has such a sensitivity that 0.010-0.035 lux·second
of exposure dose is required to obtain an image having a density of 0.5 more than
the minimum density thereon, said density being determined by the steps of: exposing
the photosensitive layer of the photographic material to monochromatic light of which
wavelength is the same as the main emission wavelength of the intensifying screen
defined in the above 1) and of which half width is 15±5 nm, developing at 35°C for
25 seconds in the developing solution comprising the following:
potassium hydroxide |
21 g |
potassium sulfite |
63 g |
boric acid |
10 g |
hydroquinone |
25 g |
triethylene glycol |
20 g |
5-nitroindazole |
0.2 g |
glacial acetic acid |
10 g |
1-phenyl-3-pyrazolidone |
1.2 g |
5-methylbenztriazole |
0.05 g |
glutaraldehyde |
5 g |
potassium bromide |
4 g |
water to adjust the volume to 1 liter, the pH value being adjusted to 10.02, |
removing the photosensitive layer on the side reverse to the exposed side and then
measuring the density of the remaining photosensitive layer.
[0018] The invention also resides in a combination for forming a radiographic image comprising
a silver halide photographic material and two radiographic intensifying screens, one
of which is placed on the front of said photographic material and the other of which
is on the back;
wherein
1) at least one of said intensifying screens absorbs X-rays of 80 KV
p in an amount of not less than 25 %;
2) said photographic material has silver halide photosensitive layers one of which
is provided on the front of its support and another of which is on the back; and at
least one of said photosensitive layers has such a sensitivity that 0.010-0.035 lux·second
of exposure dose is required to obtain an image having a density of 0.5 more than
the minimum density thereon, said density being determined by the steps of: exposing
the photosensitive layer of the photographic material to monochromatic light of which
wavelength is the same as the main emission wavelength of the intensifying screen
defined in the above 1) and of which half width is 15±5 nm, developing at 35°C for
25 seconds in the developing solution comprising the following:
potassium hydroxide |
21 g |
potassium sulfite |
63 g |
boric acid |
10 g |
hydroquinone |
25 g |
triethylene glycol |
20 g |
5-nitroindazole |
0.2 g |
glacial acetic acid |
10 g |
1-phenyl-3-pyrazolidone |
1.2 g |
5-methylbenztriazole |
0.05 g |
glutaraldehyde |
5 g |
potassium bromide |
4 g |
water to adjust the volume to 1 liter, the pH value being adjusted to 10.02, |
removing (peeling off) the photosensitive layer provided on the reverse side of the
exposed face and then measuring the density of the remaining photosensitive layer;
and
3) not more than 10 % of the light emitted by the intensifying screen placed on the
front side of the silver halide photographic material reaches the photosensitive layer
on the back of said silver halide photographic material as cross-over light.
[0019] The former combination of the invention (COMBINATION I) comprises an intensifying
screen having high sensitivity and showing contrast transfer function (CTF) in the
specific range and a photographic material having sensitivity in the specific range.
Owing to such a specific combination, the former combination of the invention provides
an X-ray photographic system which shows excellent characteristics in balance between
the sensitivity and the image quality.
[0020] The latter combination of the invention (COMBINATION II) comprises an intensifying
screen having high sensitivity and the photographic material having sensitivity in
the specific range and prominently decreased cross-over. Owing to such a specific
combination, the latter combination of the invention provides an X-ray photographic
system which shows excellent characteristics in balance between the sensitivity and
the image quality.
[0021] In the present invention, the sensitivity of each of the silver halide photographic
material and the radiographic intensifying screen of the combination is independently
defined.
[0022] If a high sensitive intensifying screen absorbing a large amount of X-rays and a
low-sensitive photographic material are employed in combination under the condition
that the total sensitivity of the combination only is defined, the obtained radiographic
image exhibits poor sharpness while their graininess is excellent. In this case, even
if the photographic material is replaced with a low sensitive photographic material
showing high sharpness (which can be accomplished by reducing the cross-over), the
obtained radiographic image still exhibits unsatisfactory sharpness, which is unfavorably
accepted in clinical diagnosis. On the other hand, a radiographic image obtainable
by a combination of a low sensitive intensifying screen absorbing a small amount of
X-rays and a medium sensitive (i.e., standard) or high sensitive photographic material
exhibit poor graininess while their sharpness is excellent.
[0023] According to the study of the inventors, the suitable sensitivity of each of the
silver halide photographic material and the radiographic intensifying screens of the
combination depends upon various conditions such as the sensitivity level of the combination
and the size of the object. The further study, however, has revealed that a radiographic
image of high quality can be obtained with high sensitivity using a combination of
a photograpic material of a specific sensitivity and a radiographic intensifying screen
which exhibits high contrast transfer function (CTF) and of which phosphor contents
are increased to enhance the absorption of X-rays, while maintaining the required
sharpness. Further, it has been revealed that a radiographic image of high quality
is also obtainable with high sensitivity using a combination of a photograpic material
having a high sensitivity and a reduced cross-over and a radiographic intensifying
screen of which phosphor contents are increased to enhance the absorption of X-rays,
while maintaining the required sharpness.
[0024] Preferred sharpness level depends on the size of the object. In clinical evaluation,
the values of modulation transfer function (MTF) at spatial frequencies of 0.5 lp/mm
to 3 lp/mm are important, and preferred values are not less than 0.65 and not less
than 0.22 at 1 lp/mm and 2 lp/mm, respectively. Besides that, the sensitivity of the
combination is restricted because a highly sensitive combination does not provide
high image quality for diagnosis for chest even if the combination has the best balance.
On the contrary, a low-sensitive combination is not preferable on account of increasing
the dose of X-rays.
BRIEF DESCRIPTION OF DRAWINGS
[0025]
Figure 1 shows the relation between spatial frequency (lp/mm) and contrast transfer
function (CTF) with respect to the radiographic intensifying screen applied for the
combination of the invention of silver halide photographic material and radiographic
intensifying screens.
Figure 2 shows the characteristic curve of the green filter used in combination with
tungsten light source for measuring the sensitivity of silver halide photographic
material.
Figure 3 shows the relations between the sensitivity and the image quality of the
radiographic image of chest, with respect to the combinations of the invention of
silver halide photographic material and radiographic intensifying screens, and a combination
of radiographic intensifying screens and silver halide photographic material generally
used for X-ray photography.
DETAILED DESCRIPTION OF INVENTION
[0026] The combination of the present invention of silver halide photographic material and
radiographic intensifying screens is very sensitive and gives an image having excellent
quality. Therefore, using the combination of the invention, a radiographic image having
high recognizability can be obtained without increasing the dose of X-rays to which
a human boy is exposed. Consequently, the combination of the invention of silver halide
photographic material and radiographic intensifying screens is very advantageous for
improving the precision of medical diagnosis.
[0027] The following is detailed explanation of the radiographic intensifying screen used
for the invention.
[0028] The radiographic intensifying screen consists essentially of a support and a phosphor
layer provided thereon. The phosphor layer comprises a binder and phosphor particles
dispersed therein. Further, a transparent film is generally provided on the free surface
(surface which is not in contact with the support) of the phosphor layer to keep the
phosphor layer from chemical deterioration and physical shock.
[0029] A preferred phosphor for the radiographic intensifying screen is a phosphor represented
by the following formula:
M
(w-n)M'
nO
wX
in which M is at least one metal selected from the group consisting of Y, La, Gd and
Lu; M' is at least one rare earth element, preferably one rare earth element being
selected from the group consisting of Dy, Er, Eu, Ho, Nd, Pr, Sm, Ce, Tb, Tm and Yb;
X is an intermediate chalcogen (i.e., S, Se or Te) or a halogen; "n" is a number satisfying
the condition of 0.0002 ≤ n ≤ 0.2; and "w" is 1 when "X" is a halogen, or is 2 when
"X" is a chalcogen.
[0030] The concrete examples of phosphor preferably used for the radiographic intensifying
screen are given below:
terbium activated rare earth oxysulfide phosphors such as Y2O2S:Tb, Gd2O2S:Tb, La2O2S:Tb, (Y,Gd)2O2S:Tb, and (Y,Gd)2O2S:Tb,Tm;
terbium activated rare earth oxyhalide phosphors such as LaOBr:Tb, LaOBr:Tb,Tm, LaOCl:Tb,
LaOCl:Tb,Tm, GdOBr:Tb, and GdOCl:Tb; and
thulium activated rare earth oxyhalide phosphors such as LaOBr:Tm and LaOCl:Tm.
[0031] A particularly preferred phosphor for the radiographic intensifying screen is the
terbium activated gadolinium oxysulfide phosphor. There are detailed descriptions
about terbium activated gadolinium oxysulfide phosphors in U.S. Patent No. 3,725,704.
[0032] The phosphor layer comprises a binder and phosphor particles dispersed therein. The
phosphor layer is generally provided on a support under an atmospheric pressure utilizing
the following coating procedure.
[0033] The phosphor particles and the binder are mixed in an appropriate solvent to prepare
a coating dispersion. The coating dispersion is directly applied onto a surface of
a support for radiographic intensifying screen under an atmospheric pressure using
a doctor blade, roll coater, knife coater or the like, and the solvent contained in
the coating dispersion is removed to form a phosphor layer. Alternatively, the phosphor
layer is placed on the support by the steps of applying the coating dispersion on
a false support under an atmospheric pressure to form a phosphor sheet, peeling off
the sheet from the false support, and then causing the sheet to adhere to a genuine
support.
[0034] Preferably used for the invention is a radiographic intensifying screen in which
the phosphor density is increased (that is, void volume of the phosphor layer is lowered)
by compressing the phosphor layer containing the below-described thermoplastic elastomer
as a binder.
[0035] The sensitivity of the radiographic intensifying screen is essentially determined
by the total amount of emission given by the phosphor contained therein, and the total
amount of emission varies depending upon not only the emission luminance of the phosphor
per se but also the content (i.e., amount) of the phosphor in the phosphor layer. The large
content of the phosphor also results in increase of absorption of a radiation such
as X-rays, so that the screen shows high sensitivity and provides an image of improved
quality, especially in graininess. On the other hand, assuming that the content of
the phosphor layer is kept at the same level, an intensifying screen utilizing such
a phosphor layer provides an image of high sharpness if the phosphor layer is densely
packed with the phosphor, because such phosphor layer can be made thinner to reduce
spread of stimulating rays which is caused by scattering within the phosphor layer.
[0036] The above-mentioned radiographic intensifying screen is preferably prepared by a
process comprising the steps of:
a) forming a phosphor sheet comprising a phosphor and a binder,
b) placing said phosphor sheet on a support, then compressing and affixing simultaneously
said phosphor sheet on said support at a temperature not lower than softening point
or melting point of said binder.
[0037] In the first place, Step a) is described below.
[0038] A phosphor sheet for a phosphor layer of the radiographic intensifying screen can
be prepared in the process which comprises applying the coating dispersion (i.e.,
binder solution in which the phosphor particles are uniformly dispersed) onto a false
support, drying the coated film and peeling off the film to obtain the phosphor sheet
(film).
[0039] Initially, the phosphor particles and the binder are mixed and stirred in an appropriate
solvent to prepare a coating dispersion comprising the phosphor particles homogeneously
dispersed in a binder solution.
[0040] As the binder, a thermoplastic elastomer of which softening point or melting point
is in the range of 30-150°C is used alone or in combination with other binder polymers.
The destruction of the phosphor particles in a compression treatment can be avoided
by the use of the thermoplastic elastomer, because it has elasticity at room temperature
and has fluidity when it is heated. Examples for the thermoplastic elastomers include;
polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene-vinyl
acetate, polyvinyl chloride, natural rubber, fluorocarbon rubber, polyisoprene, chlorinated
polyethylene, styrene-butadiene rubber and silicone rubber.
[0041] If the ratio of amount of the thermoplastic elastomer to the total binder is kept
within the range of 10-100 wt.%, the effect of the invention can be achieved. However,
the binder preferably includes the thermoplastic elastomer as much as possible, and
therefore it is most preferred that the binder comprises thermoplastic elastomer in
its 100 wt.% content.
[0042] Examples of the solvents employable in the preparation of the dispersion include
lower aliphatic alcohols such as methanol, ethanol, n-propanol and n-butanol; chlorinated
hydrocarbons such as methylene chloride and ethylene chloride; ketones such as acetone,
methyl ethyl ketone and methyl isobutyl ketone; esters of lower aliphatic alcohols
with lower aliphatic acids such as methyl acetate, ethyl acetate and butyl acetate;
ethers such as dioxane, ethylene glycol monoethyl ether and ethylene glycol monomethyl
ether; and mixtures of the above-mentioned solvents.
[0043] The ratio between the binder and the phosphor in the coating solution may be determined
according to the characteristics of the aimed radiographic intensifying screen and
the nature of the employed phosphor. Generally, the ratio therebetween is in the range
of 1:1 to 1:100 (binder: phosphor, by weight), preferably in the range of 1:8 to 1:40,
by weight.
[0044] The coating solution may contain various additives such as a dispersing agent to
improve dispersibility of the phosphor particles therein and a plasticiser to increase
the bonding between the binder and the phosphor particles in the resulting phosphor
layer. Examples of the dispersing agent include phthalic acid, stearic acid, caproic
acid and a hydrophobic surface active agent. Examples of the plasticizer include phosphates
such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalates
such as diethyl phthalate, and dimethoxyethyl phthalate; glycolates such as ethylphthalyl
ethyl glycolate and butylphthalyl butyl glycolate; and polyesters of polyethylene
glycols with aliphatic dicarboxylic acids such as polyester of triethylene glycol
with adipic acid and polyester of diethylene glycol with succinic acid.
[0045] The coating dispersion containing the phosphor and the binder prepared as above is
applied evenly onto a surface of a support to form a layer of the coating dispersion.
The coating procedure can be carried out by a conventional method such as a method
using a doctor blade, a roll coater or a knife coater.
[0046] A false support material employable in the invention can be selected from those employed
in the conventional radiographic intensifying screens such as glass plate and metal
plate. Examples of the support material include plastic films such as films of cellulose
acetate, polyester, polyethylene terephthalate, polyamide, polyimide, triacetate and
polycarbonate; metal sheets such as aluminum foil and aluminum alloy foil; ordinary
papers; baryta paper; resin-coated papers; pigment papers containing titanium dioxide
or the like; papers sized with polyvinyl alcohol or the like; and ceramic sheets such
as sheets of alumina, zirconia, magnesia and titania.
[0047] The process for preparation of the phosphor sheet comprises the steps of applying
the coating dispersion onto a false support, drying the coated film and peeling off
the film to obtain the phosphor sheet for the phosphor layer of the radiographic intensifying
screen. Therefore, the surface of the false support preferably is beforehand coated
with a release agent so that the film may be easily peeled off.
[0048] In the second place, Step b) is described below.
[0049] A support for a radiographic intensifying screen is prepared. The support can be
freely selected from the same materials as the material for the false support used
in preparation of the phosphor sheet.
[0050] In the preparation of a known radiographic intensifying screen, one or more additional
layers are occasionally provided between the support and the phosphor layer, so as
to enhance the adhesion between the support and the phosphor layer, or to improve
the sensitivity of the screen or the quality of an image (sharpness and graininess)
provide thereby. For example, a subbing layer or an adhesive layer may be provided
by coating a polymer material such as gelatin over the surface of the support on the
phosphor layer side. Otherwise, a light-reflecting layer or a light-absorbing layer
may be provided by forming a polymer material layer containing a light-reflecting
material such as titanium dioxide or a light-absorbing material such as carbon black.
In the invention, one or more of these additional layers may be provided on the support,
and the constitution thereof can be optionally selected depending upon the purpose
of the radiographic intensifying screen.
[0051] The phosphor sheet prepared in Step a) is placed on a support, and then compressed
and affixed simultaneously on the support at a temperature of not lower than softening
point or melting point of the binder.
[0052] In this process, the phosphor sheet is not beforehand fixed on a support but simultaneously
compressed and affixed on the support. Therefore, the pressure extends throughout
the sheet and the destruction of the phosphor particles can be avoided. Moreover,
assuming that the pressure applied to the sheet is kept at the same level, the sheet
simultaneously compressed and affixed on the support has higher packing ratio of the
phosphor than that of the sheet which is beforehand fixed on the support and subjected
to compression treatment.
[0053] Examples of the compressing apparatus for the compression treatment include known
apparatus such as a calender roll and a hot press. For instance, a compression treatment
using a calender roll involves moving the phosphor sheet prepared in Step a) on a
support to pass through between two rollers heated at a temperature not lower than
softening point or melting point of the thermoplastic elastomer of the binder. The
compressing apparatus employable in the invention is not restricted to them. Any other
apparatuses can be employed so long as they can compress a sheet such as the above-stated
one under heating.
[0054] The pressure for compression preferably is not less than 50 kgw/cm
2.
[0055] A radiographic intensifying screen generally has a transparent film on the free surface
of the phosphor layer to physically and chemically protect the phosphor layer. In
the intensifying screen of the present invention, it is preferred to provide a transparent
film for the same purpose.
[0056] The transparent protective film generally has a thickness within the range of approximately
0.1 to 20 µm.
[0057] The transparent protective film can be formed on the phosphor layer by the steps
of coating the surface of the phosphor layer with a solution of a transparent polymer
such as a cellulose derivative (e.g., cellulose acetate or nitrocellulose), or a synthetic
polymer (e.g. polymethyl methacrylate, polyvinyl butyral, polyvinyl formal, polycarbonate,
polyvinyl acetate, or vinyl chloride-vinyl acetate copolymer), and drying the coated
solution. Alternatively, the transparent film can be provided on the phosphor layer
by beforehand preparing a protective film from a plastic sheet of polyethylene terephthalate,
polyethylene naphthalate, polyethylene, polyvinylidene chloride or polyamide; or transparent
glass sheet, followed by placing and fixing it onto the phosphor layer with an appropriate
adhesive agent.
[0058] The protective film for the radiographic intensifying screen preferably is a film
formed from a solution containing fluoro-resin soluble in an organic solvent. The
fluoro-resin is a polymer of an olefin having fluorine (i.e., fluoroolefin) or a copolymer
using an olefin monomer having fluorine as a copolymer component. The film formed
from the fluoro-resin solution may be cross-linked. The protective film of fluoro-resin
is advantageous because stain (caused by, for instance, the plasticizer and the like
exuding from radiographic films or other materials in contact with the protective
film) hardly permeates the film and the stain can be easily removed by wiping.
[0059] In the case that fluoro-resin soluble in organic solvents is used as the material
for forming a protective film, the film can be easily formed by the steps of applying
a solution of the resin dissolved in a proper organic solvent and drying the coated
solution in the same manner described above. Actually, the protective film can be
formed by the steps of evenly coating the surface of the phosphor layer with a solution
for forming a protective film containing the fluoro-resin soluble in organic solvents
by a doctor blade or the like, and drying the coated solution. The protective film
and the phosphor layer can be formed at the same time by simultaneous superposing
coating method.
[0060] The fluoro-resin is a polymer of an olefin having fluorine (fluoroolefin) or a copolymer
of an olefin having fluorine as a copolymer component. Examples of the fluoro-resins
include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride,
polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer and fluoroolefin-vinyl
ether copolymer. The fluoro-resin is generally insoluble in organic solvents, but
the resin comprising a fluoroolefin as a copolymer component is soluble in organic
solvents provided that other copolymer components (other than fluoroolefin) are appropriately
selected. Therefore, by the steps of dissolving such resin into an appropriate solvent,
applying the obtained solution onto the phosphor layer and drying the applied solution,
the protective film can be easily formed. An example of such copolymer is fluoroolefin-vinyl
ether copolymer. Polytetrafluoroethylene and its modified compounds are also employable
for forming the protective film by application as well as the above-mentioned copolymer
comprising fluoroolefin as a copolymer component, because they are soluble in a proper
organic solvent of fluorine type such as a perfluoro-type solvent.
[0061] The protective film may contain a resin other than the fluoro-resin and may also
contain additives such as a cross linking agent, a hardner and an anti-yellowing agent.
However, in order to achieve the above-mentioned purpose, the amount of the fluoro-resin
contained in the protective film is preferred to be not less than 30 wt.%, more preferably
not less than 50 wt.%, and most preferably not less than 70 wt.%. Examples of the
resin employable in combination with the fluoro-resin include polyurethane resin,
polyacryl resin, cellulose derivatives, polymethyl methacrylate, polyester resin and
epoxy resin.
[0062] The protective film of the radiographic intensifying screen may comprise one or both
of an oligomer having polysiloxane structure and an oligomer having perfluoroalkyl
group. The oligomer having polysiloxane structure has, for example, dimethylpolysiloxane
structure, and it preferably has at least one functional group (e.g., hydroxyl group:
-OH). Besides that, the molecular weight (average weight) preferably is within the
range of 500-100,000, more preferably 1,000-100,000 and most preferably 3,000-100,000.
The oligomer having perfluoroalkyl group (e.g., tetrafluoroethylene group) preferably
has at least one functional group (e.g., hydroxyl group: -OH), and the molecular weight
(average weight) of the oligomer preferably is within a range of 500-100,000, more
preferably 1,000-100,000 and most preferably 10,000-100,000. The oligomer having a
functional group is very advantageous because of the following reason: namely, such
oligomer is fastened to the structure of the resin for forming the protective film
by cross-linking reaction between the oligomer and the resin during formtaion of the
protective film, and so the oligomer is hardly removed by iterative use of the screen
or by cleaning the film surface, and consequently the oligomer can effectively work
for a long time.
[0063] The amount of the oligomer contained in the film preferably is within the range of
0.01-10 wt.%, more preferably 0.1-2 wt.%.
[0064] The protective film also may contain a powder of perfluoroolefin resin or a powder
of silicone resin. The average size of the powder of perfluoroolefin resin or silicone
resin preferably is within the range of 0.1-10 µm, more preferably 0.3-5 µm. The amount
of the powder of perfluoroolefin resin or the powder of silicone resin contained in
the protective film preferably is within the range of 0.5-30 wt.%, more preferably
2-20 wt.% and most preferably 5-15 wt.%, based on the total weight of the protective
film.
[0065] The radiographic intensifying screen used in the invention preferably is highly sensitive
and shows contrast transfer function (CTF) values of at least 0.79 and at least 0.36
at the spatial frequencies of 1 line/mm and of 3 lines/mm, respectively.
[0066] Preferably, the radiographic intensifying screen used in the invention shows CTF
values higher, at any spatial frequency, than the following relation curve between
spatial frequency plotted on horizontal axis (1p/mm or line/mm) and CTF values plotted
on vertical axis.
1p/mm |
CTF |
0.00 |
1.00 |
0.25 |
0.950 |
0.50 |
0.905 |
0.75 |
0.840 |
1.00 |
0.790 |
1.25 |
0.720 |
1.50 |
0.655 |
1.75 |
0.595 |
2.00 |
0.535 |
2.50 |
0.430 |
3.00 |
0.360 |
3.50 |
0.300 |
4.00 |
0.255 |
5.00 |
0.180 |
6.00 |
0.130 |
[0067] The measurement and evaluation of the contrast transfer function from a radiographic
intensifying screen to a photographic material can be carried out using the MRE single
face material specimen (available from Eastman Kodak) on which a rectangular chart
is printed.
[0068] Figure 1 shows the above relation curve between spatial frequency (1p/mm) and CTF
values.
[0069] The preferred radiographic intensifying screen having the above-mentioned characteristics
can be easily prepared by the method in which the above-described thermoplastic elastomer
is used as a binder and the phosphor layer is compressed.
[0070] Preferably, the protective film of the radiographic intensifying screen is a transparent
synthetic resin layer having the thickness of not more than 5 µm. Such a thin protective
layer contributes to improving the sharpness of the obtained radiographic image, because
it shortens the distance between the silver halide photographic material and the phosphor
on the radiographic intensifying screen.
[0071] The detailed explanation with respect to the silver halide photographic material
for the invention is given below.
[0072] The silver halide photographic material for the invention has the constitution: in
which provided are silver halide photographic layers one of which is provided on the
front of a support and another of which is on the back of the support; and at least
one of said photosensitive layers has the sensitivity that 0.010-0.035 lux·second
(preferably, 0.012-0.030 lux·second) of exposure dose is required to obtain an image
having a density of 0.5 more than the minimum density thereon, said density being
obtained by the steps of: exposing the photographic material to monochromatic light
of which wavelength is the same as the main emission wavelength of the radiographic
intensifying screen defined in the aforementioned 1) and of which half width is 15±5
nm, developing at 35°C for 25 seconds in the developing solution (which is referred
to as "Standard developer" or "Developer A", hereinafter) comprising the following:
potassium hydroxide |
21 g |
potassium sulfite |
63 g |
boric acid |
10 g |
hydroquinone |
25 g |
triethylene glycol |
20 g |
5-nitroindazole |
0.2 g |
glacial acetic acid |
10 g |
1-phenyl-3-pyrazolidone |
1.2 g |
5-methylbenztriazole |
0.05 g |
glutaraldehyde |
5 g |
potassium bromide |
4 g |
water to adjust the volume to 1 liter, the pH value being adjusted to 10.2, |
removing another photosensitive layer provided on the reverse side of the exposed
face and then measuring the density of the remaining photosensitive layer.
[0073] The silver halide photographic material is so produced that more not than 15 %, more
preferably not more than 10 %, most preferably 10 to 2 %, of the light emitted by
the intensifying screen placed on the front of said photographic material, that is,
cross-over light, may not reach the photosensitive layer provided on the back of said
material.
[0074] In the measurement of the sensitivity of the silver halide photographic material,
the wavelength of exposing light should precisely or nearly correspond to the main
emission wavelength of the radiographic intensifying screen used in combination. For
instance, when terbium activated gadolinium oxysulfide phosphor is used as the phosphor
of the intensifying screen, the wavelength of the light used for measuring the sensitivity
of the photographic material should be around 545 nm because the main emission wavelength
of the phosphor is 545 nm.
[0075] The monochromatic light can be obtained by means of a filter system in which interference
filters are combined. Using such filters system, a monochromatic light which has sufficient
intensity to be used and of which half width is 15±5 nm can be easily obtained, though
the intensity of the light depends upon the combination of the interference filters.
Since the spectral sensitivity spectrum of photographic material is continuous independently
of spectral sensitization, the sensitivity is practically constant within the half
width of 15±5 nm.
[0076] An example of the exposure light source, in the case that terbium activated gadolinium
oxysulfide phosphor is used as the phosphor of the intensifying screen, is a system
comprising a tungsten light (color temperature: 2,856 K) and a filter having the characteristics
shown in Fig. 2.
[0077] The following are standard conditions of a development process using the above-described
Standard developer.
- Developing time:
- 25 seconds
(21 sec. in the solution + 4 sec. in air)
- Fixing time:
- 20 seconds
(16 sec. in the solution + 4 sec. in air;
The fixing solution has the below-described composition.)
- Washing:
- 12 seconds
- Squeege and drying:
- 26 seconds
- Developing Apparatus:
- a commercially available roller conveyor automatic developing machine (e.g., FPM-5000
automatic developing machine available from Fuji Photo Film Co., Ltd.);
(Developing tank 22 liter [vol.],35°C [temp.]);
(Fixing tank 15.5 liter [vol.], 25°C [temp.]);
Another example of the commercially available roller conveyor automatic developing
machine is M-6AW available from Eastman Kodak.
[0078] The composition of the fixing solution (hereinafter, referred to as Fixing Solution
F) is as follows:
ammonium thiosulfate (70 % wt./vol.) |
200 ml |
sodium sulfite |
20 g |
boric acid |
8 g |
sodium ethylenediaminetetraacetate (dihydrates) |
0.1 g |
aluminum sulfate |
15 g |
sulfuric acid |
2 g |
glacial acetic acid |
22 g |
and water to adjust the volume to 1 liter, and then, if required, the value of pH
is adjusted to 4.2 using sodium hydroxide or glacial acetic acid. |
[0079] The measurement of the amount of the cross-over light (hereinafter simply referred
to as "cross-over") is performed in the following manner: a photographic material
having photosensitive layers provided on both sides is placed on the radiographic
intensifying screen in contact with the front surface or the screen; and then a sheet
of black paper is placed on the photographic material in contact with the front surface
(i.e, the surface other than the surface contacting the screen) of said material;
in this arrangement, the material is exposed to X-rays with various doses, which are
adjusted by varying the distance between the intensifying screen and the focal spot
of the X-ray generator; thereafter, the exposed material is developed and then divided
into two sheets. From one sheet, the photosensitive layer having been in contact with
the intensifying screen (back side photosensitive layer) is peeled off, and from another
sheet, the photosensitive layer on the other side (front side photosensitive layer)
is peeled off. Then, with respect to each of the remaining photosensitive layers,
the optical density is measured and plotted against the corresponding dose to draw
a characteristic curve for each layer. The average difference of the sensitivity (Δlog
E) between the front and the back side layers is estimated from the straight line
portion of each characteristic curve; and the amount of cross-over is calculated based
on the estimated average difference of the sensitivity (Δlog E) in accordance with
the following formula:

[0080] A typical silver halide photographic material for the invention comprises, for example,
a subbing layer, a dye layer (which is provided to reduce the cross-over, if needed),
at least one photosensitive silver halide emulsion layer, and a protective layer,
superposed in this order on each side (i.e., on each of the front side and the back
side) of a blue-colored transparent support. Preferably, each layer provided on one
side is substantially the same as the corresponding layer provided on the other side.
[0081] The support is made of transparent material such as polyethylene terephthalate, and
is colored with a blue dye. Various blue dyes such as anthraquinone dye, which is
known as a dye for radiographic film, are employable. The thickness of the support
is within the range of 160-200 µm.
[0082] A subbing layer of water-soluble polymer such as gelatin can be provided on the support
in the same way as the conventional radiographic film.
[0083] If necessary, a dye layer is provided on the subbing layer to reduce cross-over.
The dye layer is usually prepared in the form of a colloidal layer containing a dye,
and the layer can be preferably decolorized in the developing process defined in the
above. It is also preferred that the dye be fixed in the bottom part of the layer
in order not to enter into the photosensitive silver halide emulsion layer or the
protective layer provided thereon.
[0084] Various methods for decolorizing or fixing the dye in the colloidal layer described
above are known. Examples of such methods include: method in which a combination of
an anionic dye and a cationic mordant (European Patent Publication No. 211273B1) is
used; method in which a combination of an anionic dye and a mordant of polymer dispersion
prepared by adding unsaturated ethylene monomer having an anionic function group into
a cationic mordant to be polymerized (Japanese Patent Provisional Publication No.
2(1990)-207242) is used; and method in which a solid fine crystalline dye (fine crystalline
dye particles) is used (U.S. Patent No. 4,803,150). Among the above methods, prefered
is the method in which a solid fine crystalline dye (fine crystalline dye particles)
is used.
[0085] The above-mentioned dye layer effectively reduces the cross-over to 15 % or less,
particularly 10 % or less.
[0088] A photosensitive silver halide emulsion layer is provided on the dye layer. The photosensitive
silver halide emulsion layer of the photographic material of the invention can be
prepared in the known manner. However, since the silver halide emulsion used for the
invention is relatively low-sensitive among the emulsions for known radiographic materials,
it is preferred to comprise silver halide particles of a small size. The preferred
size of the particles is 0.3-0.8 µm (more preferably, 0.5-0.7 µm) in terms of the
mean diameter of the circle corresponding to the projected area, when a non-tabular
particle (of which aspect ratio is nearly 1) is used for the invention. On the other
hand, when the silver halide particles of tabular type (of which aspect ratio is 5/1-10/1)
are used for the invention, the size of the particles preferably is within the range
of 0.4-1.4 µm (more preferably, 0.5-1.0 µm).
[0089] The sensitivity of the silver halide emulsion can be reduced by other methods such
as the method in which dyes are added to the emulsion, and the method in which the
degree of sensitization (spectral sensitization or chemical sensitization) is reduced.
[0090] The silver halide photographic material should be sensitive to the light emitted
by the radiographic intensifying screen used in combination. Since an ordinary silver
halide emulsion is sensitive to the light of which wavelength is within the range
of blue to ultraviolet, it can be used in combination with an intensifying screen
which emits the luminescence of which wavelength is within the range of blue to ultraviolet
(example of such screen is a radiographic intensifying screen using calcium tungstate
phosphor). However, the silver halide in the photographic material should be spectral
sensitized to green light if an intensifying screen using terbium activated gadolinium
oxysulfide phosphor, which emits luminescence having main wavelength of 545 nm, is
used.
[0091] Preferably, the silver halide emulsion for the silver halide photographic material
of the invention comprises tabular silver halide particles. In fact, the emulsion
comprising tabular silver halide particles exhibits excellent characteristics in balance
between the sensitivity and the image quality, and has excellent spectral-sensitizable
characteristics and high ability to reduce the cross-over. Therefore, such emulsion
is very advantageous.
[0092] With respect to the process for preparing the tabular silver halide particle emulsion,
various improved methods have been recently proposed. Such methods are employable
for preparing the tabular silver halide particle emulsion for the preparation of the
photographic material of the invention. Examples of such improved methods include:
the method in which reduction sensitization is performed in combination with addition
of a mercapto compound or a certain dye to improve the pressure characteristics; the
sensitization method using selenium compounds; the method in which the iodide content
of the particle surface is lowered to reduce the pressure mark possibly produced in
the transfer using rollers; and the method (which is applied for preparing two silver
halide emulsions used for the photographic material having double photosensitive layers)
in which the silver/gelatin ratio of each emulsion is optimized to improve the balance
between drying ability and reduction of the pressure mark produced in the transfer
using rollers. These methods are disclosed in Japanese Patent Applications No. 3(1991)-145164,
No. 3(1991)-228639, No. 2(1990)-89379, NO. 2(1990)-288898, No. 2(1990)-225637, and
No. 3(1991)-103639.
[0093] As is described above, the silver halide photographic material of the invention preferably
has a dye layer which can be decolorized in the developing process performed under
the aforementioned conditions. From this point of view, it is preferred to reduce
the amount of the binder used in the photosensitive layer superposed on the dye layer.
Actually, the amount of the binder in the photosensitive layer preferably is not more
than 5 g/cm
2, more preferably not more than 3 g/cm
2. On the other hand, the amount of the silver contained in the photosensitive layer
preferably is not more than 3 g/cm
2, more preferably not more than 2 g/cm
2.
[0094] The silver halide photographic material used in the invention is prepared to give
an exposure image having the following characteristic curve, after stepwise exposing
the photographic material to X-rays and developing the material under the conditions
described above: the characteristic curve having the mean gamma (γ) between the point
of the density higher than the minimum density by 0.1 (the point of D
min + 0.1) and the point of the the density higher than the minimum density by 0.5 (the
point of D
min + 0.5) within the range of 0.5-0.9, and the mean gamma (γ) between the point of D
min + 1.2 and the point of D
min + 1.6 within the range of 3.2-4.0; said characteristic curve being drawn on the rectangular
coordinate in which the unit length of the axis of optical density (D) is the same
as that of the axis of exposure (log E).
[0095] If the silver halide photographic material giving the above-described characteristic
curve is employed for the radiographic system of the invention, a radiographic image
having excellent characteristics can be obtained. In more detail, the characteristic
curve of such image shows an elongated toe and high gamma in the medium density region.
Therefore, by the use of the photographic material having the above-described characteristics,
radiographic images of a low density (such as a radiographic image of mediastinum
or shadow of heart, through which only a small amount of X-rays can pass) can be made
much clearer and the density of a radiographic image of the field of lung through
which a large amount of X-rays can pass, can be more clearly visualized. Besides that,
the contrast of the images are also improved.
[0096] The silver halide photographic material giving the above-described preferable characteristic
curve can be a photographic material having two or more silver halide emulsion layers,
provided on each side of which sensitivities differ from each other. With respect
to such photographic material, it is particularly preferred that the upper layer be
of high sensitive and the lower one be of low sensitivity and give high contrast.
When the photographic material has two emulsion layers on each side, the difference
of sensitivity between the two layers generally is set to not less than 1.5 times,
preferably not less than twice, as much as the sensitivity of the lower layer. The
ratio of the amounts of the emulsions used in each layer is determined according to
the differences of sensitivity and covering power between the adopted emulsions. Generally,
the amount of the high sensitive emulsion to be used is reduced, when the difference
of sensitivity is increased. For instance, if one emulsion is twice as sensitive as
the other and that covering powers of them are nearly the same, the ratio of the high
sensitive emulsion to the low-sensitive one is within the range of 1:20 to 1:5, in
terms of the amount of silver.
[0097] On the above-described composite comprising a subbing layer and photosensitive layers
provided on each side of the support in the above-described manner, a protective layer
comprising a water-soluble polymer such as gelatin is provided in the known manner
to finally prepare a silver halide photographic material of the invention.
[0098] With respect to methods for sensitizing the emulsion, various additives, constituting
materials and processes for developing, there are no particular restrictions in the
invention. Actually, various known technologies, for example, the arts described in
Japanese Patent Provisional Publication (J.P.P.P.) Nos. 2(1990)-68539, 2(1990)-103037
and 2(1990)-115837 can be employed. Some of the descriptions concerning such technologies
are set forth in the following table:
Item |
Description |
1. |
Chemical sensitization |
J.P.P.P. No. 2(1990)-68539, pp.10, col.Right-Top, l.13 - pp.10, col.Left-Bottom, l.16 |
2. |
Anti-fogging agent & stabilizer |
ibid., pp.10, col.L-B, l.17 - pp.11, col.L-T, l.7 |
3. |
Spectral sensitizing agent |
ibid., pp.4, col.R-B, l.4 -pp.8, col.R-B, l.8 |
4. |
Surface active agent & Antistatic agent |
ibid., pp.11, col.L-T, l.14 - pp.12, col.L-T, l.9 |
5. |
Matte agent, Slipping agent & Plasticizer |
ibid., pp.12, col.L-T, l.10 - pp.12, col.R-T, l.10; and ibid., pp.14, col.L-B, l.10 - pp.14, col.R-B, l.1 |
6. |
Hydrophilic colloid |
ibid., pp.12, col.R-T, l.11 - pp.12, col.L-B, l.16 |
7. |
Hardening agent |
ibid., pp.12, col.L-B, l.17 - pp.13, col.R-T, l.6 |
8. |
Support |
ibid., pp.13, col.R-T, l.7 - pp.13, col.R-T, l.20 |
9. |
Dye & Mordant |
ibid., pp.13, col.L-B, l.1 - pp.14, col.L-B, l.9 |
10. |
Developing process |
J.P.P.P. No. 2(1990)-103037, pp.16, col.R-T, l.7 - pp.19, col.L-B, l.15; and J.P.P.P.
No. 2(1990)-115837, pp.3, col.R-B, l.5 - pp.6, col.R-T, l.10 |
[0099] The following is a detailed explanation of the combination of the invention.
[0100] The combination of the invention can be constituted by a combination of a photographic
material having the specific sensitivity and one or two high sensitive radiographic
intensifying screens which absorb X-rays to give spatial frequencies in the specific
range. However, a preferred example of the combination comprises a radiographic intensifying
screen which absorbs X-rays of 80 KV
p in the ratio of 30 to 40 % and a photographic material whose sensitivity defined
hereinbefore corresponds to 0.012-0.015 lux·second. A further preferred example of
the combination comprises a pair of a radiographic intensifying screen which absorbs
X-rays of 80 KV
p in the ratio of 30 to 40 % and a photographic material of which sensitivity defined
above corresponds to 0.02-0.03 lux·second. The latter can give an image having excellent
image quality with a practical sensitivity (i.e., an acceptable dose of X-rays).
[0101] Preferably used for the combination of the invention is a silver halide photographic
material in which each of the front and the back photosensitive layers satisfies the
above-described conditions concerning the sensitivity, and the characteristics of
corresponding layers are substantially the same. On each side of such photographic
material, a radiographic intensifying screen having the same characteristics as those
of the intensifying screen on the other side is preferably provided. However, in order
to improve the balance between image sharpness and sensitivity, the amount of the
phosphor coated on the front intensifying screen can be made to be smaller than that
of the phosphor coated on the back side screen, as is described in U.S. Patent No.
4,710,637.
[0102] Preferably, the combination of the invention comprising a silver halide photographic
material and two radiographic intensifying screens is selected so that the combination
can have practically acceptable sensitivity and futher that excellent radiographic
image quality can be obtained. Actually, it is preferred that the total sensitivity
of the combination gives the density of 1.0, the density being obtained by the steps
of exposing the combination to X-rays of 80 KV
p with a exposure dose in the range of 0.5-1.5 mR generated by a three-phase X-ray
generator and developing in the above-defined developing solution under the aforementioned
conditions.
[0103] The following is the explanation of the measurement and the principle concerning
the measurement to evaluate the performance of the combination of the invention.
[0104] The measurement of Detective Quantum Efficiency (DQE) is generally utilized for measuring
image formation efficiency of a combination comprising a silver halide photographic
material and radiographic intensifying screens. Further, the measurement of Noise
Equivalent Quanta (NEQ) is also used for totally evaluating both sharpness and graininess.
The value of DQE is calculated by dividing (Signal/Noise)
2 value of the image finally formed on the photographic material of the combination
by (Signal/Noise)
2 value of the X-rays impinged onto the photographic material. If an ideal image is
formed, the value of DQE is 1. However, the value is usually less than 1. On the other
hand, the value of NEQ is defined by (Signal/Noise)
2 value of the finally obtained image. The relation between DQE and NEQ is represented
by the following formulas:

wherein γ represents the contrast, MTF(ν) is the modulation transfer function of
the image, NPS
0(ν) is the output noise power spectrum, ν represents spatial frequency, and
Q is the number of the impinged X-ray quanta.
[0105] The relation between sensitivity and image quality can be evaluated by DQE. A combination
of high DQE exhibits excellent balance between sensitivity and image quality. On the
other hand, the image quality of the finally obtained image can be evaluated by NEQ.
In other words, if the combination has a higher NEQ, it gives better image quality.
However, since NEQ gives physical evaluation of the image quality, it does not directly
indicate clinical recognizability of the image. In fact, if the graininess and the
sharpness of the image are extremely unbalanced, the image does not exhibit high visual
recognizability for diagnosis. Therefore, from a clinical point of view, the image
is preferably evaluated based on both NEQ and MTF.
[Examples for COMBINATION I]
Example 1
(1) Each of the following radiographic intensifying screens was prepared in a pair
(i.e, front screen and back screen).
[0106]
HR-3 (commercially available from Fuji Photo Film Co., Ltd.)
HR-4 (commercially available from Fuji Photo Film Co., Ltd.)
HR-8 (commercially available from Fuji Photo Film Co., Ltd.)
Radiographic intensifying screen A (Sample A)
Radiographic intensifying screen B (Sample B)
1) Preparation of Radiographic intensifying screen A
[0107] 200 g of a phosphor (Gd
2O
2S:Tb), 20 g of Binder A (polyurethane, Desmolac TPKL-5-2625 (trade name); available
from Sumitomo Bayer Urethane Co., Ltd. [solid content: 40 %]), and 2 g of Binder B
(nitrocellulose, nitration degree: 11.5 %) were added to methyl ethyl ketone. The
resulting mixture was stirred by a propeller agitator to prepare a coating dispersion
(for forming a phosphor sheet) having a viscosity of 30 PS (at 25°C) [binder/phosphor
= 1/20].
[0108] The obtained dispersion was coated on a polyethylene terephthalate film (false support,
thickness: 180 µm) which had been beforehand coated with a silicon release agent so
that the thickness of the obtained phosphor layer would be 160 µm (this thickness
was measured after the compression treatment described below was done). After being
dried, the coated film was peeled off to give a phosphor sheet.
[0109] Further, 90 g of soft acryl resin and 50 g of nitrocellulose were added to methyl
ethyl ketone. The resulting mixture was stirred to prepare a coating dispersion for
a subbing layer having a viscosity of 3 - 6 PS (at 25°C).
[0110] The obtained dispersion for a subbing layer was coated by a doctor blade on a polyethylene
terephthalate film containing titanium dioxide (support, thickness: 250 µm) which
was placed on a glass plate. The coated layers were heated at temperatures gradually
rising from 25°C to 100°C to prepare a subbing layer (thickness: 15 µm). The phosphor
sheet prepared above was superposed on the subbing layer, and then the prepared composite
was compressed at a pressure of 400 kgw/cm
2 and a temperature of 80°C using a calender roll.
[0111] Independently, 70 g of fluoro-resin (fluoroolefinvinyl ether co-polymer, Lumiflon
LF100 (trade name); available from Asahi Glass Co., Ltd.), 25 g of a crosslinking
agent (isocyanate, Desmodul Z4370 (trade name); available from Sumitomo Bayer Urethane
Co., Ltd.), 5 g of an epoxy resin of Bisphenol A type and 5 g of an alcohol modified
silicone oligomer (which had dimethylpolysiloxane structure and hydroxyl groups (carbinol
groups) at both terminals, X-22-2809 (trade name); available from Shin-Etsu Chemical
Co., Ltd.) were added to a solvent mixture of toluene and isopropyl alcohol (1:1,
in volume) to prepare a dispersion for a protective film.
[0112] The obtained dispersion for a protective film was coated by a doctor blade on the
phosphor layer having been compressed on the support. The coated film was heated to
120°C for 30 minutes to prepare a transparent protective film having a thickness of
3 µm.
[0113] Thus, a radiographic intensifying screen consisting of a support, a subbing layer,
a phosphor layer and a transparent protective film was prepared. The obtained screen
was named "Radiographic intensifying screen A".
2) Preparation of Radiographic intensifying screen B
[0114] The procedure of the above-described preparation of Radiographic intensifying screen
A was repeated except that the phosphor layer was prepared so that the thickness of
the obtained layer would be 230 µm (this thickness was measured after the compression
treatment was made) to prepare a radiographic intensifying screen consisting of a
support, a subbing layer, a phosphor layer and a transparent protective film. The
obtained screen was named "Radiographic intensifying screen B".
(2) Evaluation of characteristics of radiographic intensifying screens
1) Measurement of X-ray absorption
[0115] An X-ray generator of tungsten target tube (80 KV
p, three-phase) was set, and the sample screen was placed in front of the tungsten
anode of the target tube at a distance of 200 cm. Thereafter, the sample screen was
exposed to X-rays generated by the tube through an aluminium plate having the thickness
of 3 mm. The amount of X-rays passing through the screen was measured by an ionization
dosimeter placed behind the screen at a distance of 50 cm. Independently, as a blank
test, the measurement without the screen was carried out to obtain the amount of X-rays
directly reaching the dosimeter.
[0116] The obtained values are set forth in Table 1.
2) Measurement of contrast transfer function (CTF)
[0117] A photographic material (MRE single face type; available from Eastman Kodak) was
placed in close contact with the sample screen, and then a radiographic image of a
rectangular chart for measuring MTF (made of molybdenum, thickness: 80 µm, spatial
frequency: 0-10 lp/mm) was obtained in the following manner.
[0118] The chart was placed in front of an X-ray tube at a distance of 2 m. The photographic
material was placed behind the chart (i.e., material faced the tube through the chart)
and the sample intensifying screen was provided behind the photographic material in
close contact.
[0119] The X-ray tube was DRX-3724HD (Trade name) available from Toshiba Corporation, in
which X-rays were generated by tungsten target and a pulse generator (80 KV
p, three-phase), and then passed through 3 mm thick aluminium equivalent material including
aperture to make the focal spot size of 0.6 mm × 0.6 mm. The X-rays generated from
the tube were made to pass through a filter of water having a path of 7 cm (which
absorbed X-rays in nearly the same amount as a human body) to obtain a radiographic
image of the chart.
[0120] The exposed photographic material was developed by means of a roller conveyor automatic
developing machine (FPM-5000) available from Fuji Photo Film Co., Ltd. in the manner
described hereinbefore. In the development process, RD III developing solution available
from Fuji Photo Film Co., Ltd. (of which composition was the same as that of above-described
Developing Solution A) was used at 35°C, and Fixing Solution F (which was prepared
in the following manner: 200 ml of ammonium thiosulfate [70 % wt./vol.], 20 g of sodium
sulfite, 8 g of boric acid, 0.1 g of disodium ethylenediaminetetraacetate [dihydrates],
15 g of aluminum sulfate, 2 g of sulfuric acid, and 22 g of glacial acetic acid were
added to water so that the volume would be 1 liter, and then the value of pH was adjusted
to 4.2) was used at 25°C. Thus, the sample for the measurement was prepared. The dose
of X-rays in the exposure process described hereinbefore was determined so that the
average difference between the highest and the lowest density of the developed image
would be 1.
[0121] The density of the radiographic image of the developed sample was measured to obtain
a density profile by means of a microdensitometer under the condition that the aperture
was a slit of 30 µm × 500 µm (scanning direction × vertical direction) and the sampling
distance was 30 µm. This procedure was repeated twenty times and the obtained values
were averaged to obtain the density profile on which CTF was calculated. Thereafter,
the peak corresponding to the pulse of each spatial frequency in the density profile
was observed to calculate the density contrast of each frequency.
[0122] The obtained values concerning spatial frequencies of 1 lp/mm and 3 lp/mm are set
forth in Table 1.
3) Measurement of sensitivity
[0123] A green-sensitized photographic material (MRE single face type; available from Eastman
Kodak) was combined with the sample intensifying screen to give a combination, and
then the combination was stepwise exposed to X-rays varying the dose by the step width
of log E = 0.15. In this exposure process, the dose was adjusted by varying the distance
between the combination and the X-ray source, which was the same generator as used
in the above-described CTF measurement. The exposed material was developed in the
same manner as described in the CTF measurement. Thus, the sample for the measurement
was prepared.
[0124] The density of the prepared sample was measured using visible light to obtain a characteristic
curve. According to the obtained characteristic curve, the dose of X-rays required
to give a density of D
min + 1.0 was measured and the sensitivity was defined by the reciprocal number of said
required dose. The calculated sensitivity of each sample was reduced to a relative
value, based on the sensitivity of HR-4 (commercially available radiographic intensifying
screen) on the back side being set at the value of 100 as the standard. The results
are set forth in Table 1.
Table 1
screen |
X-ray absorption |
Sensitivity |
CTF (1 lp/mm) |
CTF (3 lp/mm) |
HR-3 (front) |
18.2 % |
48 |
0.890 |
0.660 |
HR-3 (back) |
18.2 % |
48 |
0.889 |
0.660 |
HR-4 (front) |
22.3 % |
89 |
0.850 |
0.510 |
HR-4 (back) |
23.1 % |
100 |
0.850 |
0.506 |
HR-8 (front) |
31.3 % |
155 |
0.775 |
0.340 |
HR-8 (back) |
32.2 % |
170 |
0.763 |
0.336 |
Screen A |
32.8 % |
200 |
0.869 |
0.494 |
Screen B |
43.2 % |
270 |
0.802 |
0.375 |
(3) Each of the following silver halide photographic materials was prepared.
[0125]
Super HR-S (commercially available from Fuji Photo Film Co., Ltd.)
Silver halide photographic material I (Sample I)
Silver halide photographic material II (Sample II)
Silver halide photographic material III (Sample III)
Silver halide photographic material IV (Sample IV)
1) Preparation of silver halide photographic material I
(Preparation of fine tabular particle-monodispersed emulsion)
[0126] 6.0 g of potassium bromide and 8.0 g of gelatin were added to 1 liter of water, and
the prepared mixture was stirred and kept at 55°C. At this temperature, 37 cc of aqueous
silver nitrate solution (containing 4.0 g of silver nitrate) and 38 cc of an aqueous
solution of 5.7 g of potassium bromide were added to the mixture by the double-jet
method for 37 seconds. After 18.6 g of gelatin was further added to the obtained solution,
the solution was heated to 70°C, and then 89 cc of aqueous silver nitrate solution
(containing 9.8 g of silver nitrate) was added for 22 minutes. To the resulting solution,
7 cc of 25 % aqueous ammonia was added. Then, the solution was settled for 10 minutes,
keeping the temperature for physical-ripening. Subsequently, 6.5 cc of 100 % acetic
acid was added. To the obtained solution, an aqueous solution of 153 g of silver nitrate
and an aqueous potassium bromide solution were added by the controlled double-jet
method for 35 minutes while the pAg value of the solution was kept at 8.5. To the
obtained emulsion, 15 cc of 2 N potassium thiocyanate was added. Then, the prepared
emulsion was settled for 5 minutes keeping the temperature for physical-ripening.
The emulsion was cooled to 35°C.
[0127] Thus, a silver halide emulsion (tabular silver bromide particle-monodispersed emulsion,
thickness: 0.165 µm, variation coefficient: 18.5 %, mean diameter of the circle corresponding
to the projected area: 1.10 µm) was obtained.
[0128] From the prepared emulsion, salts were removed by the precipitation method. After
the emulsion was heated to 40°C, 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8
g of sodium polystyrenesulfonate as a viscosity improver were added. The pH and pAg
values of the resulting emulsion were adjusted to 5.90 and 8.25, respectively, with
sodium hydroxide and aqueous silver nitrate solution.
[0129] After the above-described procedure was complete, the emulsion was chemically sensitized
under stirring at 56°C in the following manner.
[0130] Silver bromide was added to the emulsion at a ratio of 0.1 mol %, and then 0.043
mg of thiourea dioxide was added. Subsequently, the emulsion was settled for 22 minutes
for performing reduction sensitization. To the sensitized emulsion, 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
and 400 mg of the following sensitizing dye were added:

To the resulting emulsion, 0.83 g of calcium chloride was further added. Subsequently,
1.3 mg of sodium thiosulfate, 2.7 mg of the following selenium sensitizer:

2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added. The emulsion
was settled for 40 minutes and then cooled to 35°C. Thus, a fine tabular particle-monodispersed
emulsion was obtained.
(Preparation of coating dispersion)
a) coating dispersion for silver halide emulsion layer
[0131] To the above-prepared fine tabular particle-monodispersed emulsion, the following
components were added in the amounts described below per 1 mol of silver halide to
prepare a coating dispersion for the emulsion layer.

[0132] The hardening agent was added in such amount that the swelling ratio would be 230
%.
b) coating dispersion for surface protective layer
[0133] A coating dispersion containing the following components per 1 m
2 was prepared:

(Support)
[0134] The surface of a biaxially stretched polyethylene terephthalate film colored with
a blue dye having a thickness of 175 µm was subjected to corona discharge treatment.
Then, each surface was sequentially and superposingly coated with the coating dispersions
having the following composition in the amounts described below (amount of each component
was based on a dispersion for coating a single face) by a wire-bar coater to form
a subbing layer consisting of two sub-layers on each surface.
a) lower sub-layer of subbing layer
[0135]

b) upper sub-layer of subbing layer
[0136]

(Photographic material)
[0137] The above-described coating dispersions for silver halide emulsion layer and for
surface protective layer were simultaneously and superposingly applied on the support
having subbing layers each of which had been provided on each surface. Thus, Silver
halide photographic material I, which had a silver halide emulsion layer and a surface
protective layer both of which were provided on each side, was obtained. The amount
of the applied coating dispersion of silver halide emulsion was 1.8 g/m
2 (amount in terms of silver metal) per one surface.
2) Preparation of Silver halide photographic material II
[0138] The procedure of the preparation of Silver halide photographic material I was repeated
except that the amount of gelatin initially used was changed to 6 g to prepare a silver
halide emulsion (tabular silver bromide particle-monodispersed emulsion, thickness:
0.160 µm, variation coefficient: 17.5 %, mean diameter of the circle corresponding
to the projected area: 1.00 µm).
[0139] The obtained emulsion was sensitized to prepare a coating dispersion in the same
manner as described in the procedure for Silver halide photographic material I. From
the obtained dispersion, Silver halide photographic material II was prepared in the
same manner as described in the procedure for Silver halide photographic material
I. The amount of the applied coating dispersion of silver halide emulsion was 1.64
g/m
2 (amount in terms of silver metal) per one surface.
3) Preparation of Silver halide photographic material III
[0140] The procedure of the preparation of Silver halide photographic material I was repeated
except that the amount of gelatin initially used was changed to 6 g and that the temperature
was changed to 50°C to prepare a silver halide emulsion (tabular silver bromide particle-monodispersed
emulsion, thickness: 0.155 µm, variation coefficient: 19.0 %, mean diameter of the
circle corresponding to the projected area: 0.85 µm).
[0141] The obtained emulsion was sensitized to prepare a coating dispersion in the same
manner as described in the procedure for Silver halide photographic material I. From
the obtained dispersion, Silver halide photographic material III was prepared in the
same manner as described in the procedure for Silver halide photographic material
I. The amount of the applied coating dispersion of silver halide emulsion was 1.50
g/m
2 (amount in terms of silver metal) per one surface.
4) Preparation of Silver halide photographic material IV
[0142] The procedure of the preparation of Silver halide photographic material I was repeated
except that the amount of gelatin initially used was changed to 5 g and that the temperature
was changed to 40°C to prepare a silver halide emulsion (tabular silver bromide particle-monodispersed
emulsion, thickness: 0.155 µm, variation coefficient: 18.0 %, mean diameter of the
circle corresponding to the projected area: 0.65 µm).
[0143] The obtained emulsion was sensitized to prepare a coating dispersion in the same
manner as described in the procedure for Silver halide photographic material I. From
the obtained dispersion, Silver halide photographic material IV was prepared in the
same manner as described in the procedure for Silver halide photographic material
I. The amount of silver halide emulsion of the applied coating dispersion was 1.38
g/m
2 (amount in terms of silver metal) per one surface.
(4) Evaluation of characteristics of the silver halide photographic material
1) Measurement of sensitivity
[0144] The sensitivity of the sample material was measured using light emitted by a tungsten
light source (color temperature: 2856 K) and then passing through the optical filter
having the characteristic curve shown in Fig. 2 (by which the wavelength of the light
was set to around 545 nm - corresponding to the main wavelength of the luminescence
of the below-described radiographic intensifying screen used in combination). The
sample photographic material was exposed to the above light through a neutral step
wedge for 1/20 second.
[0145] The exposed photographic material was developed in RD III developing solution available
from Fuji Photo Film Co., Ltd. (of which composition was the same as those of the
above-described developing solution A) at 35°C for 25 seconds (total processing time:
90 seconds) by means of an automatic developing machine (FPM-5000) available from
Fuji Photo Film Co., Ltd. The photosensitive layer provided on the reverse side of
the exposed face was removed, and the density was measured on the remaining photosensitive
layer to obtain the characteristic curve.
[0146] According to the obtained characteristic curve, the exposure dose required to give
the density of D
min + 0.5 was calculated and the sensitivity was defined by the required exposure dose.
The results expressed by lux·second are set forth in Table 2. In order to calculate
the exposure dose, the illuminance of the light emitted by the tungsten light source
and then passing through the optical filter was measured by an compnsated illuminometer
of PI-3F type (compensated).
2) Measurement of cross-over
[0147] The sample silver halide photographic material was placed between a sheet of black
paper and Radiographic intensifying screen A (containing terbium activated gadolinium
oxysulfide phosphor, the main emission wavelength: 545 nm, green light). The black
paper on this combination was placed to face an X-ray generator, and then exposed
to X-rays. The X-ray generator used in this measurement was the same as used for the
evaluation of a radiographic intensifying screen. The photographic material was exposed
to X-rays in various doses, which were adjusted by varying the distance between the
intensifying screen and the X-ray generator. After the exposing process was complete,
the exposed material was developed in the same manner as stated in the measurement
of sensitivity. The developed photographic material was divided into two sheets. The
photosensitive layer on each sheet was independently peeled off. The density of the
photosensitive layer having been in contact with the intensifying screen was found
higher than that of the photosensitive layer in the other side (black paper side).
With respect to each of the remaining layers, the characteristic curve was obtained
and the average difference of the sensitivity (Δlog E) was obtained from the straight
line portion (density: 0.5 to 1.0) of each characteristic curve; and then the amount
of cross-over was calculated based on the estimated average difference of the sensitivity
(Δlog E) in accordance with the following formula:

[0148] The above-described procedure was repeated except that Radiographic intensifying
screen A was replaced with other intensifying screens. However, the obtained values
were nearly the same as obtained in the above measurement.
[0149] The calculated values of cross-over (%) are set forth in Table 2.
Table 2
Photosensitive material |
Sensitivity (Dmin+0.5) (lux·second) |
Cross-over (%) |
Super HRS |
0.0076 |
18 |
Material I |
0.0070 |
20 |
Material II |
0.0105 |
21 |
Material III |
0.0140 |
22 |
Material IV |
0.0250 |
24 |
(5) Evaluation of characteristics of the combinations of silver halide photographic
materials and radiographic intensifying screens
1) Measurement of sensitivity and gamma
[0150] A photographic material to be measured was sandwiched between two radiographic intensifying
screens to prepare a sample combination. With respect to the prepared combination,
the exposing and developing processes were carried out in the same manner as described
in the measurement of sensitivity of intensifying screens.
[0151] The dose of X-rays required to give the density of D
min + 0.5 was measured and the sensitivity was defined by the reciprocal number of said
required dose. The calculated sensitivity of each sample was converted to a relative
value, based on the sensitivity of the combination consisting of HR-4/Super HRS being
set at the value of 100 as the standard. The value of gamma was expressed by the average
gamma between density of 0.8 and 1.2.
2) Measurement of MTF
[0152] A sample photographic material was placed between two sample radiographic intensifying
screens, and then a radiographic image of the rectangular chart for measuring MTF
described above was formed. The chart was placed in front of the aforementioned X-ray
tube at a distance of 2 m. The photographic material was placed behind the chart (i.e.,
the material faced the tube through the chart) and the sample intensifying screen
was placed behind the photographic material in close contact.
[0153] The exposed photographic material was developed by means of a roller conveyor automatic
developing machine available from Fuji Photo Film Co., Ltd. (FPM-5000) in the manner
described above. The dose of X-rays in exposing process was the same as described
above.
[0154] The density of the radiographic image of the developed sample was measured by microdensitometer
to obtain a density profile. This procedure was twenty times repeated and the obtained
values were averaged to obtain the density profile on which CTF was calculated. Thereafter,
the peak corresponding to the pulse of each spatial frequency in the density profile
was detected to calculate the density contrast at each frequency.
[0155] The obtained density contrast was converted to the effective exposure rectangular
contrast based on the independently obtained characteristic curve.
[0156] In order to derive MTF, the model MTF was assumed in accordance with the following
formula:

The parameters were determined in the same manner as in the derivation of Coltman's
formula. In more detail, the effective exposure rectangular contrast was expressed
by MTF(ν) and its components at high frequencies such as MTF(3), MTF(5), · · · · ·,
MTF(111); and then the parameters were determined so that the calculated values might
correspond to the observed values. This procedure is described in detail in "HOSHASEN
GAZO JYOHO KOGAKU (I)" (published by Tsusho Kenkyu-sha, 1981) by Uchida et al., pp.171.
The obtained values of the parameters were applied to the above formula, and then
MTF(ν) was calculated.
3) Measurement of Noise power spectrum (NPS0(ν))
[0157] The measurement was carried out using the same X-ray generator as used in the measurement
of MTF (in which the X-rays of 80 KV
p were caused to pass through the 3 mm aluminum equivalent material and the filter
of water having the path of 7 cm). The combination was placed in front of the X-ray
tube at a distance of 2 m, and exposed to the X-rays. The dose of X-rays was so adjusted
that the density of the image of the developed material might be 1.0. Thus, the sample
for measuring NPS
0(ν) was prepared. The density of the image of the sample was measured by the microdensitometer
on condition that the aperture was a slit of 30 µm × 500 µm (scanning direction ×
vertical direction) and that the sampling distance was 20 µm. The number of sampling
points was 8192 points/line × 12 lines. The results were divided at every 256 points,
and FFT processing was performed. The FFT treatment was 1320 (average) times repeated
to obtain a noise power spectrum.
4) Calculation of NEQ
[0158] NEQ was calculated in accordance with the formula:

Each obtained value was converted to a relative value, based on the NEQ value of
the combination of HR-4/Super HRS being set at the value of 100 as standard. As representative
values, the resulting values concerning spatial frequencies of 1 lp/mm and 3 lp/mm
were set forth.
5) Calculation of DQE
[0159] DQE was calculated in accordance with the formula:

(
Q is the number of the impinged X-ray quanta.)
In the calculation, the above-obtained relative value was applied to NEQ(ν). Since
Q is inversely proportional to the sensitivity of the combination, the above formula
can be rewritten to give the following formula:

Each value obtained in accordance with the above formula was converted to a relative
value, based on the DEQ value of the combination of HR-4/Super HRS being set at the
value of 100 as standard. As representative values, the obtained values concerning
spatial frequencies of 1 lp/mm and 3 lp/mm are set forth.
6) Visual estimation
[0160] An image of the chest phantom (available from Kyoto Kagaku Co., Ltd.) was photographed
in the following manner. An X-ray generator (three-phase; 12 pulse; 100 KV
p) equipped with a 3 mm aluminum equivalent material to make the focal spot size of
the generated X-rays to be 0.6 mm × 0.6 mm was used. The phantom was placed in front
of the X-ray generator at a distance of 140 cm. Behind the phantom, a grid for inhibiting
scattering (grid ratio: 8:1) and the combination of photographic material and intensifying
screen were placed. In this arrangement, a radiographic image of the phantom was obtained.
[0161] The photographic material of the combination was developed in RD III developing solution
and the aforementioned Fixing Solution F at 35°C for 25 seconds (total processing
time: 90 seconds) by the automatic developing machine (FPM-5000) in the same manner
as in the measurement of photographic characteristics.
[0162] The dose of X-rays was adjusted by varying the exposure time so that the density
of the determined point on the image might be 1.6. The quality of the obtained image
of the chest phantom was visually estimated mainly from the viewpoint of clinical
recognizability of veins in lung. The results were expressed by the marks A, B, C
and D which mean "excellent", "good", "recognizable" and "not recognizable", respectively.
Further, more detailed estimation was expressed using small letters "a" and "z". For
instance, if two images each of which quality was assigned to the same mark A have
slightly different qualities, the better one was expressed by Aa and the worse was
by Az.
[0163] The results of the above measurements are set forth in Tables 3 and 4.
Table 3
No. |
Photosensitive Material/Screen |
Sens.of Photosensitive Material (lux·second) |
Cross-Over (%) |
X-ray abs. of Screen (front/back) (%) |
|
Combination of the invention |
1 |
P.M. II /Screen A |
0.0105 |
21 |
32.8/32.8 |
2 |
P.M. III /Screen A |
0.0140 |
22 |
32.8/32.8 |
3 |
P.M. IV /Screen A |
0.0250 |
24 |
32.8/32.8 |
4 |
P.M. III /Screen B |
0.0140 |
22 |
43.2/43.2 |
5 |
P.M. IV /Screen B |
0.0250 |
24 |
43.2/43.2 |
Combination for comparison |
6 |
P.M. I /Screen A |
0.0076 |
20 |
32.8/32.8 |
7 |
P.M. II /HR-8 |
0.0105 |
21 |
31.3/32.2 |
8 |
P.M. III /HR-8 |
0.0140 |
22 |
31.3/32.2 |
9 |
Super HRS/HR-3 |
0.0076 |
18 |
18.2/18.2 |
10 |
Super HRS/HR-4 |
0.0076 |
18 |
22.3/23.1 |
11 |
Super HRS/HR-8 |
0.0076 |
18 |
31.3/32.2 |
Table 4
No. |
Sens. (Dmin+1.0) |
γ (0.8-1.2) |
DQE |
NEQ |
MTF |
Visual Est. |
|
|
|
1 |
3 |
1 |
3 |
1 |
3 |
|
|
|
|
(lp/mm) |
|
|
Combination of the invention |
1 |
159 |
2.62 |
160 |
130 |
100 |
82 |
0.71 |
0.31 |
C |
2 |
119 |
2.80 |
155 |
128 |
130 |
107 |
0.70 |
0.31 |
B |
3 |
67 |
2.90 |
158 |
131 |
236 |
196 |
0.69 |
0.30 |
A |
4 |
155 |
2.80 |
182 |
105 |
117 |
68 |
0.67 |
0.25 |
C |
5 |
87 |
2.90 |
180 |
110 |
207 |
126 |
0.67 |
0.26 |
Ba |
Combination for comparison |
6 |
220 |
2.58 |
155 |
125 |
70 |
57 |
0.72 |
0.32 |
Cz |
7 |
138 |
2.62 |
150 |
95 |
109 |
69 |
0.64 |
0.22 |
Cz |
8 |
103 |
2.80 |
145 |
95 |
141 |
92 |
0.63 |
0.21 |
Cz |
9 |
55 |
2.55 |
72 |
89 |
131 |
162 |
0.82 |
0.51 |
Ca |
10 |
100 |
2.55 |
100 |
100 |
100 |
100 |
0.75 |
0.37 |
C |
11 |
180 |
2.55 |
148 |
93 |
82 |
52 |
0.65 |
0.23 |
D |
[0164] The above data inidcate the following facts:
1) The combinations (1) and (2) according to the invention, in which the sample radiographic
intensifying screen A is used give images having excellent characteristics in balance
between the sensitivity and the image quality, as compared with the combinations (7)
and (8) for comparison. In fact, the DQE values (3 lp/mm) of the images of (1) and
(2) are about 1.35 times as high as those of (7) and (8). Further, the MTF values
of the images of (7) and (8) are at the lowest level for diagnosis of chest and the
images of veins obtained by (7) and (8) are considerably dim.
2) The combinations (4) and (5) according to the invention, which are the same combinations
as (2) and (3) also according to the invention except that the intensifying screen
A was replaced with the sample radiographic intensifying screen B (which absorbs X-rays
more than the screen A does), give images of which DQE values (3 lp/mm) are superior
to those of (2) and (3) but of which DQE values (1 lp/mm) are inferior to those of
(2) and (3). Further, radiographic images given by the combinations (4) and (5) exhibit
excellent graininess.
3) The combination (2) of the invention is more sensitive than the combination (10)
for comparison by 19 %. Further, with respect to each of DQE (3 lp/mm) and DQE (1
lp/mm), the combination (2) is superior to the combination (10). Moreover, the radiographic
image obtained by the former has less "roughness" and better recognizability of veins
than that obtained by the latter.
4) The combination (2) of the invention is more than twice as sensitive as the combination
(10) for comparison. Further, the radiographic image obtained by the former has better
recognizability of veins than that obtained by the latter.
5) The combination (11) for comparison is very sensitive and gives high DQE, but on
the other hand it gives low NEQ. According to visual observation of the radiographic
image obtained, the image given by the combination (11) is too dim and too rough for
medical diagnosis.
6) The combination (3) of the invention gives very high DQE, and it is more sensitive
than the combination (9) for comparison by 21 %. Further, the chest radiographic image
given by the former exhibits excellent image quality.
7) The combination (1) of the invention gives higher DQE than the combination (10)
for comparison. While the image quality of the chest radiographic image given by the
former is comparable to that given by the latter, the former is about 1.5 times as
sensitive as the latter.
8) The combination (6) for comparison, which consists of a standard radiographic film
and highly sensitive intensifying screens, is very sensitive and gives high DQE, but
on the other hand it gives low NEQ. The chest radiographic image obtained by the combination
has roughness, and therefore the image does not have the quality enough for precise
diagnosis though it is usable.
9) The combination (9) for comparison gives very high MTF, but on the other hand low
DQE is given because the combination comprises an intensifying screen which absorbs
X-rays in a small amount. Besides that, the sensitivity of the combination is low.
The combination gives the chest radiographic image having roughness, and therefore
it is not suitable for precise diagnosis.
Example 2
[0165] The following shows a study of the case in which the cross-over level of the silver
halide photographic material used for the combination of the invention was varied.
(1) Preparation of silver halide photographic materials V, VI, VII and VIII
[0166] The procedure of the preparation of Silver halide photographic material I in Example
1 was repeated except that the upper sub-layer of the subbing layer of the support
was formed by coating the following dispersion of fine crystalline dye particles,
to prepare four Silver halide photographic materials V, VI, VII and VIII.
(Preparation of dispersion of fine crystalline dye particles)
[0167] A 2 liter ball mill was charged with 434 ml of water and 791 ml of 6.7 % aqueous
solution of surface active agent Triton-200 (TX-200), and then the following Magenta
dye A was added. After 400 ml of zirconium oxide (ZrO
2) beads (diameter: 2 mm) was added to the mixture, the resulting mixture was pulverized
for 4 days. Thereafter, 160 g of 12,5 % aqueous gelatin was added. The resulting mixture
was degassed, and then ZrO
2 beads were removed by filtration. The obtained dye dispersion was measured. According
to the measurement, the diameters of pulverized dye were found to have distribution
in the wide range of 0.05-1.15 µm, and the average diameter was found to be 0.37 µm.
[0168] The dye particles having the diameter of not less than 0.9 µm were removed by centrifugation
to obtain the aimed dye dispersion.

(2) Evaluation of characteristics of the silver halide photographic material
[0169] The sensitivity of the photosensitive layer on one side and the cross-over were measured
and calculated in the manner described in Example 1.
[0170] The measured sensitivities and the calculated values of cross-over (%) are set forth
in Table 5. In Table 5, the data of Photographic materials I-IV in Example 1 are also
set forth for reference.
Table 5
Photosensitive material |
Sensitivity (Dmin+0.5) (lux·second) |
Cross-over (%) |
Material I |
0.0070 |
20 |
Material II |
0.0105 |
21 |
Material III |
0.0140 |
22 |
Material IV |
0.0250 |
24 |
Material V |
0.0078 |
5.0 |
Material VI |
0.0118 |
5.2 |
Material VII |
0.0157 |
5.4 |
Material VIII |
0.0280 |
6.0 |
(3) Evaluation of characteristics of the combinations of silver halide photographic
materials exhibiting various cross-over values and radiographic intensifying screens
[0171] Various characteristics of the combinations, each comprising one of the above-described
silver halide photographic materials and Radiographic intensifying screen A, were
evaluated in the manner described in Example 1. The results are set forth in Table
6. In Table 6, the marks of visual estimation stand for the same meanings as used
in Table 4.
Table 6
P.S. Mat. |
Sens. (Dmin+1.0) |
γ (0.8-1.2) |
DQE |
NEQ |
MTF |
Visual Est. |
|
|
|
1 |
3 |
1 |
3 |
1 |
3 |
|
|
|
|
(lp/mm) |
|
II |
159 |
2.62 |
160 |
130 |
100 |
82 |
0.71 |
0.31 |
C |
III |
119 |
2.80 |
155 |
128 |
130 |
107 |
0.70 |
0.31 |
B |
IV |
67 |
2.90 |
158 |
131 |
236 |
196 |
0.69 |
0.30 |
A |
V |
180 |
2.60 |
173 |
135 |
96 |
75 |
0.78 |
0.38 |
Cz |
VI |
139 |
2.65 |
180 |
132 |
138 |
102 |
0.78 |
0.38 |
B |
VII |
100 |
2.80 |
175 |
140 |
175 |
140 |
0.77 |
0.37 |
A |
VIII |
55 |
2.90 |
175 |
135 |
318 |
245 |
0.77 |
0.37 |
Aa |
[0172] The above data indicate the following facts:
1) If the cross-over of the silver halide photographic material is made to be less
than 15 %, the obtained MTF and DQE are evidently improved while the sensitivity slightly
lowers. According to the above data, obtained was the relation shown in Fig. 3 between
the sensitivity of the combination and the image quality of the radiographic image
of chest. Further, with respect to the combinations generally used for radiography
shown in Tables 3 and 4 (i.e., the combination (9) for comparison: Super HR/HR-3,
and the combination (10) for comparison: Super HR/HR-4; commercially available from
Fuji Photo Film Co., Ltd.), the relations between the sensitivity and the image quality
are also shown in Fig. 3 for reference.
[0173] As is evident from Fig. 3, the combination of the invention of silver halide photographic
material and radiographic intensifying screen exhibits excellent characteristics in
balance between the sensitivity and the image quality, as compared with the known
combination of silver halide photographic material and radiographic intensifying screen
generally used for radiography. In other words, the combination of the invention gives
a radiographic image of better quality, under the condition that the sensitivity is
kept at the same level, and on the other hand, under the condition that the image
quality is kept at the same level, the radiography can be carried out at a smaller
dose of X-rays.
[0174] If a silver halide photographic material showing small cross-over is applied for
the combination of the invention of silver halide photographic material and radiographic
intensifying screens, the above-described advantage of the invention is particularly
enhanced.
[Examples for COMBINATION II]
Example 3
(1) Each of the following radiographic intensifying screens was prepared in a pair
(i.e, front screen and back screen).
[0175]
HR-3 (commercially available from Fuji Photo Film Co., Ltd.)
HR-4 (commercially available from Fuji Photo Film Co., Ltd.)
HR-8 (commercially available from Fuji Photo Film Co., Ltd.)
HR-12 (commercially available from Fuji Photo Film Co., Ltd.)
Trimax 12 (commercially available from 3M Co.)
Radiographic intensifying screen A (Sample A, which was the same as Radiographic intensifying
screen A prepared in Example 1)
Radiographic intensifying screen B (Sample B, which was the same as Radiographic intensifying
screen B prepared in Example 1)
(2) Evaluation of characteristics of radiographic intensifying screens
1) Measurement of X-ray absorption
[0176] The X-ray absorption was measured in the manner as described in Example 1.
[0177] The obtained values are set forth in Table 7.
2) Measurement of contrast transfer function (CTF)
[0178] The contrast tansfer function was measured in the manner as described in Example
1.
[0179] The obtained values concerning spatial frequencies of 1 line/mm and 3 lines/mm are
set forth in Table 7.
3) Measurement of sensitivity
[0180] The sensitivity was measured in the manner as described in Example 1. The results
are set forth in Table 7.
Table 7
screen |
X-ray absorption |
Sensitivity |
CTF (1 lp/mm) |
CTF (3 lp/mm) |
HR-3 (front) |
18.2 % |
48 |
0.890 |
0.660 |
HR-3 (back) |
18.2 % |
48 |
0.889 |
0.660 |
HR-4 (front) |
22.3 % |
89 |
0.850 |
0.510 |
HR-4 (back) |
23.1 % |
100 |
0.850 |
0.506 |
HR-8 (front) |
31.3 % |
155 |
0.775 |
0.340 |
HR-8 (back) |
32.2 % |
170 |
0.763 |
0.336 |
HR-12 (front) |
30.6 % |
181 |
0.773 |
0.294 |
HR-12 (back) |
42.7 % |
275 |
0.681 |
0.213 |
Trimax 12 (front) |
29.7 % |
151 |
0.782 |
0.226 |
Trimax 12 (back) |
47.3 % |
245 |
0.643 |
0.191 |
Screen A |
32.8 % |
200 |
0.869 |
0.494 |
Screen B |
43.2 % |
270 |
0.802 |
0.375 |
(3) Each of the following silver halide photographic materials was prepared.
[0181]
Super HR-S (commercially available from Fuji Photo Film Co., Ltd.)
T-Mat M2 (commercially available from Eastman Kodak)
GTU (commercially available from 3M Co.) Silver halide photographic material IX (Sample
IX)
Silver halide photographic material X (Sample X)
Silver halide photographic material XI (Sample XI)
Silver halide photographic material XII (Sample XII)
1) Preparation of silver halide photographic material IX
(Preparation of fine non-tabular particle-monodispersed emulsion A)
[0182] To 1 liter of aqueous gelatin solution (gelatin content: 2 wt.%) containing 5.3 g
of potassium bromide and 4 g of sodium p-toluenesulfonate were added 10 mg of sodium
thiosulfate 5 hydrates, 4 g of potassium thiocyanate, and 10 cc of glacial acetic
acid. To the resulting aqueous mixture were added under vigorous stirring 14 cc of
aqueous solution containing 5.2 g of silver nitate and 7 cc of aqueous solution containing
1.8 g of potassium bromide and 0.33 g potassium iodide for 30 sec. according to the
double jet method. To the obtained mixture was added 12 cc of aqueous solution containing
1.2 g of potassium iodide.
[0183] To the obtained solution were added 200 cc of aqueous solution containing 78 g of
silver nitrate and, after 1 min., 200 cc of aqueous solution containing 50.6 g of
potassium bromide and 3.65 g of potassium iodide for a total period of 15 min. To
the obtained mixture was added 22 cc of aqueous ammonia solution (ammonia content:
25 wt.%). After the mixture was ripened for 10 min., to the mixture were added simultaneously
an aqueous solution containing 117 g of silver nitrate and an aqueous solution containing
82.3 g of potassium bromide for the period of 14 min. These procedures were performed
under the conditions that the reaction mixtures were kept at 70°C.
[0184] The obtained reaction mixture was washed by the known flocculation method, and then
in the mixture were dispersed at 40°C, gelatin, a viscosity increasing agent and antiseptic.
The mixture was adjusted to pH 5.6 and pAg 8.9. To the mixture kept at 55°C were added
21 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 170 mg of the following sensitizing
dye:

The obtained mixture was ripened for 10 min. To the mixture were then added successively
9 g of sodium thiosulfate 5 hydrates, 77 mg of potassium thiocyanate, and 1.6 mg of
chloroauric acid. The mixture was ripened for 50 min. The ripened mixture was chilled
after addition of 70 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene emulsion, to
obtain a fine non-tabular particle-monodispersed emulsion A.
[0185] The silver halide particles of the obtained silver halide emulsion were in the form
of potatoes and had a mean diameter of the circle corresponding to the projected area
of 0.60 µm and variation coefficient of 18 %.
(Preparation of coating dispersion)
a) coating dispersion for silver halide emulsion layer
[0186] To the above-prepared fine non-tabular particle-mono-dispersed emulsion A, the following
components were added in the amounts described below per 1 mol of silver halide to
prepare a coating dispersion for the emulsion layer.
polymer latex (poly(ethyl acrylate/methacrylate), 97/3, weight ratio) |
20.0 g |
1,2-bis(vinylsulfonylacetamide)ethane [hardening agent] |
2.4 g |
2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine |
76 mg |
sodium polyacrylate (mean m.w.: 41,000) |
2.1 g |
sodium poly(styrenesulfonate) (mean m.w.: 600,000) |
1.0 g |
dextran (mean m.w.: 39,000) |
23.6 g |
trimethylolpropane |
9.8 g |
b) coating dispersion for surface protective layer
[0187] A coating dispersion containing the following components per 1 m
2 was prepared:

(Support)
[0188] The surface of a biaxially stretched polyethylene terephthalate film colored with
blue dye having a thickness of 175 µm was subjected to corona discharge treatment.
Then, each surface was sequentially and superposingly coated with the coating dispersions
having the following components in the amounts described below (amount of each component
was based on a dispersion for coating a single surface) by a wire-bar coater to form
a subbing layer consisting of two sub-layers on each surface.
a) lower sub-layer of subbing layer
[0189]

b) upper sub-layer of subbing layer (dye layer)
[0190]

Magenta dye A
[0191]

[0192] The above magenta dye was added to the gelatin solution after it was prepared in
the form of a dispersion of microcrystalline particles according to the following
method.
[0193] 20 g of the dye, 200 g of aqueous carboxymethyl cellulose solution (carboxymethyl
cellulose content: 1 wt.%) and 287 g of water were mixed and processed in an Aiger
Mill (Aiger Japan Co., Ltd.) for 8 hours at 5,000 r.p.m. using zirconium oxide (ZrO
2) beads. The obtained dye particles had a mean diameter of 0.37 µm.
(Photographic material)
[0194] The above-described coating dispersions for silver halide emulsion layer and for
surface protective layer were simultaneously and superposingly applied on the support
having subbing layers each of which had been provided on each surface. Thus, Silver
halide photographic material IX, which had a silver halide emulsion layer and a surface
protective layer both of which were provided on each side, was obtained. The amount
of silver halide emulsion of the applied coating dispersion was 2 g/m
2 (amount in terms of silver metal) per one surface. The amount of gelatin of the emulsion
of the surface protective layer was 1 g/m
2 per one surface.
2) Preparation of silver halide photographic material X
(Preparation of fine tabular particle-monodispersed emulsion B)
[0196] 6.0 g of potassium bromide and 5.0 g of gelatin were added to 1 liter of water, and
the prepared mixture was stirred and kept at 55°C. At this temperature, 30 cc of aqueous
silver nitrate solution (containing 5.5 g of silver nitrate) and 33 cc of an aqueous
solution of 9.4 g of potassium bromide were added to the mixture by the double-jet
method for 45 seconds. The solution was heated to 62°C, and then 60 cc of aqueous
silver nitrate solution (containing 11.1 g of silver nitrate) was added for 12 minutes.
To the resulting solution, 6 cc of 25 % aqueous ammonia was added. Then, the solution
was settled for 5 minutes, keeping the temperature for physical-ripening. Subsequently,
5.6 cc of 100 % acetic acid was added. To the obtained solution, an aqueous solution
of 150.0 g of silver nitrate and an aqueous potassium bromide solution were added
by the controlled double-jet method for 25 minutes while the pAg value of the solution
was kept at 8. To the obtained emulsion, 15 cc of 2 N potassium thiocyanate and silver
iodide particles (diameter: 0.07 µm) were added. In this procedure, the silver iodide
particles were added in the amount that the added silver was made to 0.1 mole % based
on the silver content of the emulsion to be added. Then, the prepared mixture was
settled for 5 min. keeping the temperature for physical-ripening. The emulsion was
cooled to 35°C.
[0197] Thus, a silver halide emulsion (tabular silver bromide monodispersed emulsion, silver
iodide content: 0.1 mole %, thickness: 0.12 µm, variation coefficient: 16.8 %, mean
diameter of the circle corresponding to the projected area: 0.70 µm) was obtained.
[0198] From the prepared emulsion, salts were removed by the precipitation method. After
the emulsion was heated to 40°C, 41 g of gelatin, 1.4 g of phenoxyethanol and 0.8
g of sodium polystyrenesulfonate as a viscosity improver were added. The pH and pAg
values of the resulting emulsion were adjusted to 5.90 and 7.90, respectively, with
sodium hydroxide and aqueous silver nitrate solution.
[0199] After the above-described procedure was complete, the emulsion was chemically sensitized
under stirring at 56°C in the following manner.
[0200] Silver bromide was added to the emulsion at a ratio of 0.05 mol %, and then 0.1 mg
of thiourea dioxide was added. Subsequently, the emulsion was settled for 10 minutes
for performing reduction sensitization. To the sensitized emulsion, 430 mg of the
aforementioned sensitizing dye A, sodium thiosulfate and the following selenium sensitizing
agent (sodium thiosulfate:selenium sensitizing agent=6:4, molar ratio) successively
were added:

[0201] To the emulsion were added chlroroauric acid and potassium thiocyanate. The emulsion
was cooled to 35°C, after 40 min. Thus, a fine tabular particle-monodispersed emulsion
B was obtained.
(Photographic material)
[0202] The procedure for the preparation of the coating dispersion was performed using the
above-obtained fine tabular particle-monodispersed emulsion B in place of the fine
non-tabular particle-monodispersed emulsion A used for the preparation of Silver halide
photographic material IX. The coating dispersions for silver halide emulsion layer
and for surface protective layer were then simultaneously and superposingly applied
on the support having subbing layers each of which had been provided on each surface.
Thus, Silver halide photographic material X, which had a silver halide emulsion layer
and a surface protective layer both of which were provided on each side, was obtained.
The amount of silver halide emulsion of the applied coating dispersion was 1.5 g/m
2 (amount in terms of silver metal) per one surface.
3) Preparation of Silver halide photographic material XI
(Preparation of tabular particle-monodispersed emulsion C)
[0203] 4.5 g of potassium bromide, 20.6 g of gelatin and 2.5 cc of aqueous thioether solution
(HO(CH
2)
2S(CH
2)
2S(CH
2)
2OH, content: 5%) were added to 1 liter of water, and the prepared mixture was stirred
at 65°C. At the temperature, an aqueous silver nitrate solution (containing 3.43 g
of silver nitrate) and an aqueous solution containing 2.97 g of potassium bromide
and 0.36 g of potassium iodide were added to the mixture by the double-jet method
for 7 seconds. To the resulting mixture was added 0.1 mg of thiourea having the following
formula:
(H
2N)(HN=)CSO
2H
[0204] The solution was heated to 70°C, and to the solution was added 18 cc of 25 % aqueous
ammonia. The mixture was neutralized by addition of 17 cc of 100 % acetic acid. To
the mixture was then added an aqueous silver nitrate solution (silver nitrate content:
133.4 g) by the controlled double-jet method for 35 min., keeping the potential at
pAg 8.2. The flow rate was adjusted to increase 2.6 times from the starting time to
the termination of the addition. After the addition was complete, to the mixture were
added 15 cc of 2 N aqueous potassium thiocyanate, and further 38.5 g of 1 % aqueous
potassium iodide solution for 30 min. Thereafter, the mixture was cooled to 35°C,
and soluble salts were removed by the precipitation method. The mixture was then heated
to 40°C, and gelatin and phenoxyethanol were added. The mixture was then adjusted
by addition of sodium hydroxide and potassium bromide to pH 6.50 and pAg 8.20. The
mixture was subsequently heated to 56°C, and 0.05 mg of thiourea dioxide. The mixture
was then stirred for 20 min., and 154 mg of 4-hydroxy-1,3,3a,7-tetraazaindene was
added. After 10 min., to the mixture were added 500 mg of the aforementioned sensitizing
dye A and after 5 min., 1.44 g of sodium chloride. After additional 10 min., 3.3 mg
of sodium thiosulfate 5 hydrates, 18 mg of potassium thiocyanate and 2 mg of chloroauric
acid were added. After lapse of additional 70 min., the mixture was rapidly chilled
to become a solid. Thus, a tabular particle-monodispersed emulsion C was obtained.
[0205] The obtained a silver halide emulsion C had the following characteristics: mean thickness:
0.200 µm, variation coefficient (standard deviation): 22.3 %, mean diameter of the
circle corresponding to the projected area: 1.35 µm, aspect ratio: 6.8.
(Photographic material)
[0206] The procedure for the preparation of the coating dispersion was performed using the
above-obtained tabular particle-monodispersed emulsion C in place of the fine non-tabular
particle-monodispersed emulsion A used for the preparation of Silver halide photographic
material IX. The coating dispersions for silver halide emulsion layer and for surface
protective layer were then simultaneously and superposingly applied on the support
having subbing layers each of which had been provided on each surface. Thus, Silver
halide photographic material XI, which had a silver halide emulsion layer and a surface
protective layer both of which were provided on each side, was obtained.
4) Preparation of Silver halide photographic material XII
[0207] The procedure of the preparation of Silver halide photographic material IV was repeated
except that the magenta dye was not incorporated into the upper sub-layer of the subbing
layer to obtain Silver halide photographic material XII. In the procedure for the
preparation of fine non-tabular particle-monodispersed emulsion, however, the following
magenta dye B was added to the emulsion to give a coating amount of 20 mg/m
2, so that increase of the cross-over (namely, increase of sensitivity) which would
be caused by the removal of the dye layer is suppressed to give the same sensitivity
as that of Silver halide photographic material IX.

(4) Evaluation of characteristics of the silver halide photographic materials
1) Measurement of sensitivity
[0208] The sensitivity of the sample material was measured in the manner as described in
Example 1.
2) Measurement of cross-over
[0209] The cross-over was measured in the manner as descirbed in Example 1.
[0210] The calculated values of cross-over (%) are set forth in Table 8.
Table 8
Photosensitive material |
Sensitivity (Dmin+0.5) (lux·second) |
Cross-over (%) |
Super HRS |
0.0076 |
18 |
T-Mat M2 |
0.0055 |
3.0 |
GTU |
0.0093 |
16 |
Material IX |
0.0135 |
5.3 |
Material X |
0.0240 |
5.0 |
Material XI |
0.0068 |
5.3 |
Material XII |
0.0175 |
28 |
(5) Evaluation of characteristics of the combinations of silver halide photographic
materials and radiographic intensifying screens
1) Measurement of sensitivity and gamma
[0211] The sensitivity and gamma were measured in the manner as described in Example 1.
2) Measurement of MTF
[0212] MTF was measured in the manner as described in Example 1.
3) Measurement of Noise power spectrum (NPS0(ν))
[0213] The noise power specturm was measured in the manner as described in Example 1.
4) Calculation of NEQ
[0214] NEQ was calculated in the manner as described in Example 1.
5) Calculation of DQE
[0215] DQE was calculated in the manner as described in Example 1.
6) Visual estimation
[0216] The visual estimation was performed in the manner as in described in Example 1.
[0217] The quality of the obtained image of the chest phantom was visually estimated mainly
from the viewpoint of clinical recognizability of veins in lung. The results were
expressed by the marks A, B, C and D which mean "excellent", "good", "recognizable"
and "not recognizable", respectively. Further, more detailed estimation was expressed
using small letters "a" and "z". For instance, if two images each of which quality
was assigned to the same mark A have slightly different qualities, the better one
was expressed by Aa and the worse was by Az.
[0218] The results of the above measurements are set forth in Tables 9 and 10.
Table 9
No. |
Photosensitive Material/Screen |
Sens.of Photosensitive Material (lux·second) |
Cross-Over (%) |
X-ray abs. of Screen (front/back) (%) |
|
Combination of the invention |
1 |
P.M. IX /HR-8 |
0.0135 |
3.6 |
31.3/32.2 |
2 |
P.M. X /HR-8 |
0.0240 |
3.0 |
31.3/32.2 |
3 |
P.M. IX /Screen A |
0.0135 |
3.6 |
32.8/32.8 |
4 |
P.M. X /Screen A |
0.0240 |
3.0 |
32.8/32.8 |
5 |
P.M. X /Screen B |
0.0240 |
3.0 |
43.2/43.2 |
6 |
P.M. X /HR-12 |
0.0240 |
3.0 |
30.6/42.7 |
Combination for comparison |
7 |
Super HRS/HR-3 |
0.0076 |
18 |
18.2/18.2 |
8 |
Super HRS/HR-4 |
0.0076 |
18 |
22.3/23.1 |
9 |
Super HRS/HR-8 |
0.0076 |
18 |
31.3/32.2 |
10 |
P.M. XI /HR-8 |
0.0068 |
3.6 |
31.3/32.2 |
11 |
P.M. XI /HR-4 |
0.0068 |
3.6 |
22.3/23.1 |
12 |
P.M. XII /HR-8 |
0.0175 |
28 |
31.3/32.2 |
13 |
T-Mat M2/HR-4 |
0.0055 |
3.0 |
22.3/23.1 |
14 |
T-Mat M2/HR-8 |
0.0055 |
3.0 |
31.3/32.2 |
15 |
GT /HR-8 |
0.0093 |
16 |
31.3/32.2 |
16 |
GT /Traimax 12 |
0.0093 |
16 |
29.7/47.3 |
Table 10
No. |
Sens. (Dmin+1.0) |
γ (0.8-1.2) |
DQE |
NEQ |
MTF |
Visual Est. |
|
|
|
1 |
3 |
1 |
3 |
1 |
3 |
|
|
|
|
(lp/mm) |
|
|
Combination of the invention |
1 |
87 |
2.90 |
158 |
105 |
181 |
121 |
0.70 |
0.27 |
B |
2 |
48 |
2.90 |
161 |
109 |
335 |
227 |
0.71 |
0.27 |
A |
3 |
100 |
2.90 |
173 |
132 |
173 |
132 |
0.77 |
0.37 |
A |
4 |
55 |
2.90 |
179 |
135 |
325 |
245 |
0.77 |
0.37 |
Aa |
5 |
66 |
2.90 |
186 |
115 |
281 |
174 |
0.72 |
0.28 |
A |
6 |
73 |
2.90 |
170 |
56 |
233 |
77 |
0.65 |
0.15 |
Ca |
Combination for comparison |
7 |
55 |
2.55 |
72 |
89 |
131 |
162 |
0.82 |
0.51 |
Ca |
8 |
100 |
2.55 |
100 |
100 |
100 |
100 |
0.75 |
0.37 |
C |
9 |
180 |
2.55 |
148 |
93 |
82 |
52 |
0.65 |
0.23 |
D |
10 |
180 |
2.70 |
155 |
100 |
86 |
56 |
0.70 |
0.27 |
C |
11 |
100 |
2.70 |
105 |
110 |
105 |
110 |
0.78 |
0.40 |
Cz |
12 |
88 |
2.90 |
125 |
60 |
142 |
68 |
0.67 |
0.21 |
C |
13 |
117 |
2.92 |
110 |
113 |
94 |
97 |
0.84 |
0.48 |
Cz |
14 |
219 |
2.90 |
147 |
95 |
67 |
43 |
0.70 |
0.28 |
D |
15 |
155 |
2.88 |
129 |
64 |
83 |
41 |
0.67 |
0.24 |
C |
16 |
204 |
2.90 |
197 |
56 |
97 |
28 |
0.61 |
0.16 |
D |
[0219] The above data inidcate the following facts:
1) The combinations (1) and (2) according to the present invention show DQE 1.5 to
2.1 times as high as the combinations (7) and (8) for comparison. Further, the combinations
(1) and (2) show well balanced image quality and sensitivity.
2) The combinations (3) and (4) utilizing the specifically prepared Radiographic intensifying
screen A, which embody the present invention, show slight increase of DQE (1 lp/mm)
and prominent increase of DQE (3 lp/mm), as compared with the combinations (3) and
(4) which also embody the invention. Further, the combinations (3) and (4) show improvement
of the sensitivity, NEQ and MTF, and further are superior in visual recognizability
of the obtained radiographic image, particulary in visual recognizability of the shadow
of veins to the combinations (1) and (2).
3) The combination (5) of the invention utilizing the specifically prepared Radiographic
intensifying screen B is further superior to the above-described combinations of the
invention, particularly in the visual recognizability of the obtained radiographic
image and gives less roughness in the image.
4) The combination (6) of the invention is extremely excellent in graininess of the
radiographic image. In the observation of the obtained radiographic image, some dim
is noted in the vein image. However, the dim observed in this case is low and gives
no disturbance to the practical clinical examination.
5) The combination (9) for comparison shows DQE which is similar to these shown by
the combinations of (1) and (2) according to the invention. However, it shows low
MTF. Further, the observation of the radiographic image indicates that unfavorable
dim and roughness are noticeably present. As a result, the obtained radiographic image
is not utilizable for clinical examination.
6) The combinations (10) and (14) for comparison utilizing a photographic material
showing high sensitivity and low cross-over and a radiographic intensifying screen
capable of absorbing a large amount of X-rays shows high MTF. However, there is shown
extreme roughness in the radiographic image, because the sensitivity given by the
combination is too high. As a result, the obtained radiographic image is not utilizable
for clinical examination.
7) The combinations (11) and (13) for comparison utilizing a photographic material
showing high sensitivity and low cross-over and a radiographic intensifying screen
absorbing a small amount of X-rays shows high MTF. However, DQE and NEQ are low. Further,
there is shown extreme roughness in the radiographic image. As a result, the obtained
radiographic image is not utilizable for clinical examination.
8) The combination (12) for comparison utilizing a photographic material showing cross-over
more than that shown by the combination of the invention gives low MTF because of
dim occurring due to cross-over. DQE and NEQ at 3 lp/mm are low. Further, the dim
appearing in the radiographic image disturbs the clinical examination.
9) The combinations (15) and (16) for comparison utilizing the photographic material
showing cross-over higher than the upper limit of the invention shows low MTF, while
the sensitivity is high. The obtained radiographic image shows poor image quality,
as compared with the radiographic image given by the combinations (1) and (2) according
to the invention, and is not satisfactory.
Example 4
(1) Preparation of silver halide photographic materials XIII, XIV, XV and XVI
[0220] The procedure of the preparation of Silver halide photographic material in Example
3 was repeated except that the upper sub-layer (i.e.., dye layer) of the subbing layer
of the support was formed by coating the dispersion of fine crystalline dye particles
in the combination of magenta dye B and mordant C set forth in the following Table
11, to prepare four Silver halide photographic materials XIII, XIV, XV and XVI.

(Mordant C was prepared by incorporating acrylic acid into a dispersion of the above-mentioned
mordant under the condition that the amount of the incorporated -COOH group was 1/2
of the total nitorgen amount of the mordant, and then performing polymerization reaction.)
(2) Measurement of characteristics of the silver halide photographic material
[0221] The sensitivity of one photosensitive layer and the cross-over of the sample material
were measured in the manner as described in Example 1.
[0222] The calculated values of cross-over (%) are set forth in Table 12.
Table 12
Photosensitive material |
Sensitivity (Dmin+0.5) (lux·second) |
Cross-over (%) |
Material IX |
0.0135 |
5.3 |
Material XIII |
0.0133 |
16 |
Material XIV |
0.0136 |
10 |
Material XV |
0.0135 |
5.5 |
Material XVI |
0.0134 |
4.2 |
[0223] It is confirmed that the photosensitive layers on one side of the photographic mateirals
IX, XIII, XIV, XV and XVI show almost the same sensitivity. Accordingly, the dyes
employed are well fixed in the dye layer (upper sublayer). The photographic material
XV shows cross-over at almost the same level as the photographic mateial IX. Accordingly,
the magenta dye B should be coated on one surface of the photographic material at
the coating amount of 160 mg/m
2 .
(3) Photographic material of XV showing the cross-over at almost the same level as
Photographic material IX was further examined with respect to the sensitivity and
obtainable image quality, utilizing Radiographic intensifying screen A ,according
to the methods stated in Example 1.
[0224] It has been revealed that the tested combination of Photographic material XV and
Radiographic intensifying screen A shows the almost same sensitivity, MTF, DQE and
NEQ as the combination of Photographic material IX and Radiographic intensifying screen
A. Accordingly, various dyes can be employed for reducing the cross-over without
[0225] imparting adverse effect to sensitivity and image quality.
(4) Residual colors in Photographic materials IX, XIII, XIV, XV and XVI were examined
in the following method.
[0226] The photographic material was cut to give a sheet of 24 cm x 30 cm. The photographic
material having been not exposed was developed in the following two develping apparata
of roller-conveyor type.
1) Automatic Developer FPM-5000 (available from Fuji Photo Film Co., Ltd.)
[0227]
Deveoping Solution RDIII (Developing solution A)
Development time 25 sec., Temperature 35°C
Fixing Solution F
Fixing time 20 sec., Temperature 25°C
Washing
Washing time 12 sec., Temperature 25°C
Drying
Drying time 26 sec., Temperature 55°C
(Total time for processing: 90 sec.)
2) Automatic Developer FPM-9000 (available from Fuji Photo Film Co., Ltd.)
[0228]
High active developing solution (Developing solution A in which the content of 1-phenyl-3-pyrazolone
was changed to 2.4 g/l.)
Development time 13.7 sec., Temperature 35°C
Fixing Solution F
Fixing time 10.6 sec., Temperature 25°C
Washing
Washing time 6.2 sec., Temperature 25°C
Drying
Drying time 14.1 sec., Temperature 55°C
(Total time for processing: 45 sec.)
The residual color on the developed photographic material was observed. The results
are set forth in Table 13.
Table 13
Photosensitive material |
FPM-5000 (90 sec.) |
FPM-9000 (45 sec.) |
Material IX |
A |
B |
Material XIII |
B |
E |
Material XIV |
Ca |
D |
Material XV |
C |
D |
Material XVI |
D |
D |
Remarks:
A means that no residual color was observed.
B means that slight but non-disturbing resiual color was observed.
C means that some but allowable residual color was observed. (Ca is less in the residual
color than C.)
D means that disturbing residual color was observed. |
[0229] The experimental data set forth in Table 13 indicate that Photogrpahic material IX
having the fine crystalline solid dye in the dye layer gives the most superior image.
Further, it is confirmed that Photographic material IX gives only slight residual
color (which is well acceptable in practice) in the rapid 45 sec. processing.
Example 5
(1) Preparation of Photographic materials XVII, XVIII and XIX
[0230] The procedures of Example 3 were repeated except that the photosensitive emulsion
A (fine non-tabular particle monodispersed emulsion A) and the photosensitive emulsion
C (tabular particle emulsion C) were employed in the combination set forth in Table
14 to form a double coated photosensitive layer, to give three photographic materials,
namely, Photographic materials XVII, XVIII and XIX.
Table 14
Photosensitive material |
Upper photo. layer (Emulsion C) |
Lower photo. layer (Emulsion A) |
Material IX |
-- |
2,000 mg/m2 |
Material XVII |
100 mg/m2 |
2,000 mg/m2 |
Material XVIII |
200 mg/m2 |
2,000 mg/m2 |
Material XIX |
400 mg/m2 |
2,000 mg/m2 |
Remark: The amount set forth in Table 14 indicates the amount of silver coated on
one surface. |
(2) Measurement of characteristics of silver halide photographic material
[0231]
1) In the manner as described in Example 1, the sample photographic material was sandwiched
with two radiographic intensifying screens A. The step exposure at log E = 0.15 was
carried out, and the photographic material was developed. The developed photographic
material was measured in its density to give a characteristic curve. From the obtained
characteristic curve, the sensivity at Dmin + 1.0, average gamma (γ1) obtained from the point at Dmin + 0.1 and the point at Dmin + 0.5, and average gamma (γ2) obtained from the point at Dmin + 1.2 and the point at Dmin + 1.6 were obtained. The results are set forth in Table 15.
2) In the same manner as in Example 1, the chest phantom was exposed to X-rays at
100 KVp, using the sample photographic materials and the radiographic intensifying
screen A. Because the combination gave different sensitivity, the exposure period
was changed to give a lung field image of the same density (approx. 1.6). The development
was performed in Automatic Developing Apparatus FPM-5000 under the same conditions
as in Example 1.
[0232] The obtained radiographic images were checked by observation. The visual recognizability
of the images on the shadow of veins and structure of mediastinum was marked in the
following manner:
A: prominently good (Az is relatively lower than A),
B: good
C: not good but can be used in clinical examination
D: bad and cannot be used in clinical examination
Table 15
Photosensitive material / Intensifying screen |
Sensitivity (Dmin+1.0) |
γ1 |
γ2 |
Images of |
|
|
|
|
Lung Field |
Mediastinum |
IX / A |
100 |
1.30 |
4.2 |
A |
C |
XVII / A |
102 |
1.00 |
3.8 |
A |
C |
XVIII / A |
110 |
0.75 |
3.6 |
A |
B |
XIX / A |
118 |
0.55 |
3.4 |
Az |
A |
[0233] From the results shown in Table 15, it is understood that the deposition of a small
amount of the tabular particle emulsion C over the photosensitive layer brings about
enlargement of latitude at the toe part and further gives an increased amount of information
on mediastinum without lowering discrimination of image of shadow of veins. The combination
of Photographic material XVIII and Intensifying screen A, as well as the combination
of Photographic material XIX and Intensifying screen A give less roughness, as compared
with the combination of Photographic material IX and Intensifying screen A. Accordingly,
it can be said that the last two combinations give radiographic image of the highest
quality.