Note: Descriptions are shown in the official language in which they were submitted.
2~2~73~
SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL
WITH HIGH-SENSITIVITY AND IMPROVED FOG AND GRANULARIT~
AND METHOD OF ITS PRODUCTION
FIELD OF THE INVENTION
The present invention relates to a silver halide
photographic light-sensitive material and a method of its
production, more specifically to a light-sensitive material
with high sensitivity, reduced and excellent granularity and
a production method thereof.
BACKGROUND OF THE INVENTION
In recent years, there have been increasing demands for
improvements in the sensitivity and image quality of silver
halide photographic light-sensitive materials.
In response to these demands, there have been proposed
various methods for controlling a shape, a size distribution
and a composition of a silver halide grain.
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-- 2 --
Japanese Patent Publication Open to Public Inspection
No. 113934/1983 discloses a method of improving color
photographic light-sensitive materials wherein a tabular
silver halide emulsion having a diameter/thickness ratio of
a grain (aspect ratio) exceeding 8 is applied to a green or
red-sensitive layer.
However, the emulsions having high aspect ratios
exceeding 8 does not have satisfactory improvement in
sensitivity or granularity since its latent image-forming
efficiency is not necessarily high while having an
excellent photoreceptive efficiency.
Further, investigations have been made to prepare
core/shell type tabular grains having a high silver iodide
content phase in the core as ~ell as to increase a
monodispersion degree thereof.
Japanese Patent Publication Open to Public Inspection
(hereinafter referred to as Japanese Patent O.P.I.
Publication) Nos. 14636/1986, 112142/1986 and 163451/1988
disclose monodispersed twinned tabular grains having a
core-shell structure.
In the above disclosures, the grains having the aspect
ratios of 3 to 8 show good performance but have insufficient
improvement in sensitivity and granularity.
,,
2 ~ 2 ~ rj~ 3 ;~
SUMMARY OF THE INVENTION
The object of the present invention is to provide a
silver halide photographic light sensitive material
(hereinafter referred to as a light-sensitive material) with
high sensitivity, improved fog and excellent granularity and
a production method thereof, more specifically to a
light-sensitive material containing an improved core/shell
type twinned silver halide grains and a production method
thereof.
The above object of the invention is accomplished by a
light-sensitive material containing a monodispersed silver
halide emulsion comprising mainly twinned grains, wherein a
high silver iodide content phase is present in the center of
the grain; an average aspect ratio is less than 3; the
grains consist mainly of {111} planes; and not less than 50%
by number are twinned grains having the parallel twinned
planes of an even number, and by a method of producing a
light-sensitive material containing silver halide grains
wherein pH is maintained at 1.5 to 5.8 during the formation
of any portion of at least 30% by volume in the grain.
BRIEF DESCRIPTION OF THE DRAWINGS
Figs. 1 and 2 are X ray diffraction patterns at (420)
of emulsion Em-l and emulsion Em-2 prepared in Examples 2
and 4, respectively, both having two peaks corresponding to
2~$~3~
-- 4
high and low silver iodide contents.
Fig. 3 is a schematic diagram of the twinned silver
halide grain of the present invention, in which a-a', b-b'
and c-c' each represent parallel twinned planes. (A) and
(B) show twinned crystals comprising {111} planes alone, and
(C) shows a twinned crystal comprising about 95% {111}
planes and about 5% {100} planes.
DETAILED DESCRIPTION OF THE INVENTION
It has been found that improvements in sensitivity and
image quality can be accomplished with an emulsion having
such a low aspect ratio as described above, while emulsions
having higher aspect ratios are popular.
In the present invention, a monodispersion of a silver
halide emulsion is defined by that the silver halide grains
falling within the range of 80 to 120% of an average grain
diameter d accounts for not less than 70~, preferably not
less than 80~, more preferably not less than 90% by weight
of the total silver halide grains.
The average grain size d is defined by the grain size
di in which the product of ni x di3 is maximized, wherein
ni is the number of the grains having the size di (the
significant figure is calculated down to the third decimal
place and the forth digit is rounded to the nearest whole
number).
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A diameter of a twinned grain is deined by a diameter
of the circle having the same area as that of the projected
grain.
Grain size can be determined by taking an electron
micrograph of the grain at a magnifying rate of 10000 to
50000 and measuring the diameters of the printed grain
images or the area of the projected images of more than
1000 grains selected arbitrarily.
The silver halide emulsion used in the invention has a
monodispersion degree of not more than 20%, preferably not
more than 15%, wherein the monodispersion degree is defined
by the following equation:
(standard deviation of grain size/average grain size) x 100
= monodispersion degree (%)
The grain size is determined by the method described
above, and the average grain size is a simple average value
calculated by the following equation:
average grain size = ~dini/~ni
In the invention, the silver halide emulsion is
prepared preferably by precipitating a high iodide content
phase on a monodispersed seed grain, more preferably by the
method described in Japanese Patent O.P.I. Publication
No. 6643/1986, in which monodispersed, twinned spherical
seed grains are grown. The silver halide emulsion of the
invention has mainly an even number of parallel twinned
:
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planes, preferably two twinned planes.
The silver halide emulsion of the invention comprises a
silver iodobromide having an average silver iodide content
of 4 to 20 mol%, preferably 5 to 15 mol%.
The concentration of an aqueous solution of silver
nitrate used to grow the high silver iodide content phase
present in the center of a grain is not more than 1 N,
preferably 0.3 to 0.8 N.
The twinned silver halide grains of the invention
comprise mainly {111} planes in a ratio of not less than
60%, preferably 70 to 100%, more preferably 75 to 98% based
on the whole grain.
The average ratio of a diameter of a circle having the
same area as that of the projected major plain to a distance
(thickness) between two grain surfaces parallel to the
twinned planes (aspect ratio) is less than 3, preferably not
less ~han 1.0 and less than 2.5, more preferably not less
than 1.3 and less than 2Ø
The method of producing a silver halide emulsion of the
invention by adding an aqueous silver salt solution and an
aqueous halide solution in the presence of protective
colloid is characterized by taking the following steps:
(a) forming nuclear grains having a silver iodide content of
0 to 5 mol% while pBr of the mother liquid is maintained at
2.0 to -0.7 during at least the first half of the time
202S73~
necessary for forming the nuclear grains;
(b) forming monodispersed seed grains of a spherical twinned
crystal by ripening the nuclear grains in the presence of a
silver halide solvent of 10 5 to 2.0 mol per mol silver
halide; and
(c) growing the seed grains by adding the water-soluble
silver salt and halide solutions and/or fine silver halide
grains.
The two or more twinned planes may be or may not be
parallel to each other. The grains may comprise {111}
planes, {100} planes or combination thereof.
In the formation of the nuclear grains, pBr is
maintained at -0.7 to 2.0, preferably -0.7 to 1.5 during at
least a half of the time necessary for forming the grains.
The nuclear grains may be monodispersed or
polydispersed. Polydispersion is defined by the
monodispersion degree of not less than 25%. The nuclear
grains contain twinned grains in a ratio of not less than
50%, preferably not less than 70%, and more preferably not
less than 90% based on the total grains.
Substantially monodispersed spherical grains are
prepared by adding the silver salt and halide solutions to
the nuclear grains in the presence of a silver halide
solvent of 10 5 to 2.0 mol per mol silver halide.
Substantially monodispersed grains are defined by the grains
having the monodispersion degree of less than 25%.
2 ~ 2 ri~ ~ ~
Substantially spherical grains are defined by the
grains which are round to such extent that {111} and {100}
planes are not clearly recognizable via electron
micrographic observation and have a L/~ ratio of 1.0 to 2.0,
preferably 1.0 to 1.5, wherein L and ~epresent the maximum
and minimum grain diameters, respectively.
The spherical grains account for not less than 60%,
preferably not less than 80%, and more preferably almost all
of the total seed grains.
Examples of the silver halide solvent used in the seed
grain formation are (a) organic thioethers described in US
Patent Nos. 3,271,157, 3,531,289 and 3,574,628, Japanese
Patent O.P.I. Publication Nos.,1019/1979 and 158917/1979 and
Japanese Patent Examined Publication No. 30571/1983; (b)
thiourea derivatives described in Japanese Patent O.P.I.
Publication Nos. 82408/1978, 29829/1980 and 77737/1980;
(c) AgX solvents having a thiocarbonyl group located between
an oxygen or sulfur atom and a nitrogen atom described in
Japanese Patent O.P.I. Publication Nos. 144319/1978;
(d) imidazoles described in Japanese Patent Publication
No. 100717/1979; (e) sulfites; (f) thiocyanates,
(g) ammonia (h) hydroxylalkyl-substituted ethylenediamines
described in Japanese Patent O.P.I. Publication
No. 196228/1982; (i) substituted mercaptotetrazoles
described in Japanese Patent O.P.I. Publication
202~73~
g
No. 202531/1982; (j) water-soluble bromides; and
(k) benzimidazole derivatives described in Japanese Patent
O.P.I. Publication No. 54333/1983.
Examples of these silver halide solvents (a) to (k) are
given below.
( a ) ~ CH.CH20CH3CHzOCH2CH2 ~
S S
CHzCH:OCHzCHzOCH2CH2 /
CH2CH20CHzCHz ~
~ CHzCH20CH2CH2 i
HOCH2CH2SCHzCH2SCH2CHzOH
fH NHCOCH CH2COOH
CH25CHzCHzSCzHs
CH 7 NHCOC,H 7
CH:SCH~CH2SCHzCH~COOH
CHzNHCOC~H7
1H2S
COOH
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- 10 -
{ b )
(CH ~ ) 2 N- C - N(CH~)z- S
(CH,)-N - C -N N- CH,
( C )
CH, ~ S CH,
CH2CH2SO,K CH,
( d )
N/ ~ N~ H,
H I H
CH,
N~ ~ ~
CH20CH, CH~CH = CH.
K2S0, Na2S0
NH~SCN , KSCN
2026732
11 -
( g ) NH,
( h ) ~HocH7cH7):NcH2cH:N~cHzcH:oH)2
~CH3CHCH2)2NCH2CH2N(CH2CHCH~)2
OH OH
(CzHs)2NCHzCH2N(CH2CHzOH)7
(C2HsCHCH2)2NCH2CH2N(CH2CHC2Hs)2
OH OH
( i )
N N N N
IN ~ SH N ~ ~ SH
CHzCH2NHCOCH~ CH2CH2N(C.Hs)z
N N N - N N N
ll ~ SH ll ~ SH ll ~S9
N N N~ N - 1~
e3
CHzCHzN(CH~)z CHzCHzNHz CH2CHzN(CH~)~
( i ) NaBr NH~Br KBr
( k )
~ ~ ~ ~ CH~
2 0 2 ~ r~ 3 2
- 12 -
These solvents may be used in combination. Preferred
solvents are thioethers, thiocyanates, thioureas, ammonia
and bromides, more preferably a combination of ammonia and
bromide.
pH is 3 to 13, preferably 6 to 12, and the temperature
is 30 to 70C, preferably 35 to 50.
In one mode of preferred embodiment of the p~esent
invention, the seed grains are prepared by ripening for
30 seconds to 10 minutes using 0.4 to 1.0 mol/Q ammonia and
0.03 to 0.5 mol/Q potassium bromide in combination at pH of
10.8 to 11.2 and a temperature of 35 to 45C.
A water-soluble silver salt may be added for adjustment
of ripening during the seed grain formation.
The seed grains are grown by adding the silver salt and
halide solutions by the double jet method with the addition
speed varied gradually so that the new grains are not formed
and Ostwald ripening does not occur, as described in
Japanese Patent O.P.I. Publication Nos. 39027/1976,
142329/1980, 113928/1983, 48521/1979 and 49938/1983. The
seed grains can be grown by another method described in the
proceeding of the 1983 annual meeting of the Society of
Photographic Science and Technology of Japan, p. 88, in
which fine silver halide grains coexist in the emulsion for
recrystallization on the nuclear grains.
In the preparation of the high silver iodide content
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- 13 -
silver halide emulsion of the present invention, pAg is
maintained at 5 to 11, preferably 6.0 to 9.5; the
temperature is 40 to 85C, preferably 60 to 80C; and pH is
1.5 to 5.8, preferably 1.8 to 3Ø
In the present invention, a stirring condition is an
important factor. The stirring apparatus disclosed in
Japanese Patent O.P.I. Publication No. 160128/1988 is
preferably used, in which a nozzle for adding a solution is
placed near the mother liquid inlet so that the nozzle is
dipped in the liquid. It is preferable that the rotating
rate of the stirrer be 400 to 1200 rpm.
The silver halide emulsion used in the present
invention may be subjected to chemical sensitization by an
ordinary method and to spectral sensitization to the
prescribed wavelength regions with sensitizing dyes.
The silver halide emulsion may contain an antifogging
agent~ a stabilizer and other additives. Gelatin is
preferably used as a binder.
The emulsion layers and other hydrophilic colloid
layers may be hardened and contain a plasticizer and a latex.
The present invention is applied preferably to color
photographic light-sensitive materials such as color
negative films and color reversal films.
The emulsion layers of the color photographic
light-sensitive materials contain couplers.
20~,i3~
- 14 -
There may be added a colored coupler having a
corrective effect, a competitive coupler and a compound that
releases photographically useful fragments such as a
development accelerator, a bleaching accelerator, a
developer, a silver halide solvent, a toning agent, a
hardener, a fogging agent, an antifogging agent, a chemical
sensitizer, a spectral sensitizer and a desensitizer by
coupling with the oxidation product of a developing agent.
The light-sensitive material may be provided with
supplementary layers such as a filter layer, an antihalation
layer and an anti-irradiation layer. These layers and/or
emulsion layers may contain a dye that elutes from the
light-sensitive material or is bleached during development.
The light-sensitive material may contain a formalin
scavenger, a fluorescent brightening agent, a matting agent,
a lub.icant, an image stabilizer, a surfactant, an
anti-fogging agent, a development accelerator, a development
retarder and a bleaching accelerator.
Examples of the supports are polyethylene-laminated
paper, polyethylene terephthalate film, baryta paper and
cellulose triacetate film.
The light-sensitive material is subjected to
conventional processing after exposure.
2~2~3~
- 15 -
EXAMPLE
The present invention is hereinafter described in more
detail by means of the following examples.
Example 1
Preparation of spherical seed emulsion
A monodispersed spherical seed emulsion was prepared by
the method described in Japanese Patent O.P.I. Publication
No. 6643/1986.
Solution Al
Ossein gelatin 150 g
Potassium bromide 53.1 g
Potassium iodide 24 g
Water was added to the total quantity of 7.2 Q.
Solution B1
Silver nitrate 1.5 kg
Water was added to the total quantity of 6.
Solution Cl
Potassium bromide 1327 g
l-phenyl-5-mercaptotetrazole
in methanol solution 0.3 g
Water was added to the total quantity of 3Q.
Solution Dl
Aqueous ammonia (28%) 705 mQ
'
2Q2~3.~
- 16 -
To solution Al stirred vigorously at 40C, solutions
Bl and Cl were added by the double jet method at pBr of
1.09 to 1.15 in 30 seconds to prepare nuclear grains.
One minute and 30 seconds later, solution Cl was
added in 20 seconds, followed by ripening for 5 minutes,
wherein the KBr and ammonia concentrations were 0.071 mol/~
and 0.63 mol/Q, respectively.
Then, pH was adjusted to 6.0, and the emulsion was
immediately desalted and washed with water. Observation via
an electron microscope revealed that this seed emulsion
contained the monodispersed spherical grains having an
average grain size of 0.36 ~m and a monodispersion degree of
18~.
Example 2
Preparation of emulsion of the present invention
An emulsion of the present invention having an average
silver iodide conten~ of 6.0% was prepared as follows:
Solution A2
Ossein gelatin 76.8 g
Seed emulsion of Example 1 0.191 mol eq.
Water was added to the total quantity of 4~.
solution B2_1
Silver nitrate 206.4 g
Water was added to the total quantity of 2209 mQ.
2~s~73~
Solution C2_1
Ossein gelatin 88.4 g
Potassium bromide 101.2 g
Potassium iodide 60.5 g
water was added to the total quantity of 2209 m~.
Solution B2_2
Silver nitrate 961.2 g
Water was added to the total quantity of 5143 mQ.
solution C2_2
Ossein gelatin 179 g
Potassium bromide 667 g
Potassium iodide 9.4 g
Water was added to the total quantity of 3800 m~.
Each six nozzles for supplying the B2 and C2
solutions were disposed under a stirring propeller of the
mixing apparatus disclosed in ~apanese Patent O.P.I.
Publication No. 160128/1988.
Solutions B2_1 and C2_1 were added to solution A2
stirred at a high speed of 1000 rpm at 75C by the double
jet method with an addition rate increased gradually from
8.57 m~/min at the beginning to 24.16 m~/min at the final
stage over a period of 135 minutes, during which pAg and pH
were maintained at 8.0 and 2.0, respectively.
Subsequently, solutions B2_2 and C2 2 were added by
the double jet method over a period of 73.5 minutes. The
'~2$~73~
initial and final addition rates of solution B2 2 were
43.1 mQ/min and 97.0 mQ/min, respectively, and the initial
and final addition rates of solution C2 2 were 31.8 mQ/min
and 71.6 mQ/min, respectively.
pAg and pH were maintained at 9.0 and 2.0 during the
addition.
After completion of the addition, pH was adjusted to
6.0, and the emulsion was desalted by a conventional method.
Observation via an electron microscope revealed that
the grains were monodispersed and 100% twinned and that the
monodispersion degree was 13% and the ratio of the grains
having twinned planes of an even number was 85~.
Measurement by X ray diffraction revealed that the grains
had two peaks and that there existed a clear border between
a high silver iodide content phase (core) and a low silver
iodide content phase.
The grains were found to comprise mainly {lll} planes.
The average aspect ratio of the grains having an even
number of twinned planes was l.9. This emulsion is
designated as Em-l.
Example 3
Preparation of spherical seed emulsion
A monodispersed spherical seed emulsion having an
average grain size of 0.34 ~m and a monodispersion degree of
~ ~ 2 ~ ~ ~ r;~
-- 19 -
21% was prepared in the same manner as in Example 1 except
that ripening time was changed from 5 minutes to 1 minute.
Example 4
An emulsion o~ the present invention having an average
silver iodide content of 6.0 mol% was prepared as ~ollows:
Solution A4
Ossein gelatin 74.1 g
Seed emulsion of Example 3 0.306 mol eq~
Water was added to the total quantity of 4000 m~.
sOlution B4_1
Silver nitrate 206.4 g
Nitric acid (1.38) 5.5 mQ
Water was added to the total quantity of 1105 mQ.
solution C4_1
Ossein gelatin 44.2 g
Potassium bromide 101 g
Potassium iodide 60.8 g
Water was added to the total quantity of 1105 m~.
Solution B4_2
Silver nitrate 941 g
Nitric acid (1.3~) 6.6 m~
Water was added to the total quantity of 1582 m.
sOlUtiOn C4_2
Ossein gelatin 63.3 g
2~2~ 73 ~
- 20 -
Potassium bromide 652 g
Potassium iodide 9.2 g
Water was added to the total quantity of 1582 m~.
Using the same apparatus as in Example 2, an emulsion
was prepared.
To solution A4 stirred at a high speed of 1000 rpm at
75C, solutions B4 1 and C4 1 were added by the double
jet method. The initial and final addition rates were
12.21 mQ/min and 26.03 mQ/min, respectively, and the
addition time was 58 minutes. pAg and pH were maintained at
8.0 and 2.0, respectively, during the addition.
Then, solutions B4 2 and C4 2 were added by the
double jet method. The initial and final addition rates
were 19.44 mQ/min and 44.0 mQ/min, respectively, and the
addition time was 50 minutes. pAg and pH were maintained at
8.0 and 2.0, respectively during the addition. After
completion of addition, pH was adjusted to 6.0, followed by
desalting and washing.
Observation via an electron microscope revealed that
the grains were monodispersed and 100% twinned and that a
monodispersion degree was 14% and the ratio of the grains
having twinned planes of an even number was 82%. The grains
having an even number of twinned planes consisted of 95%
{111} planes and 5% {100} planes. The average aspect ratio
of the grains having an even number of twinned planes was
1.7.
2~ 132
- 21 -
Measuremen~ by X ray diffraction revealed that the
grains had two peaks corresponding to a high silver iodide
content phase (core) and a low silver iodide content phase
and that there existed a clear border between the two phases.
This emulsion is designated as Em-2.
Example 5
Silver ioidobromide emulsion Em-3 having an average
silver iodide content of 9.0% was prepared in the same
manner as in Example 4 except that the volume of the high
iodide content phase was increased.
Em-3 consisted of 100% twinned grains having a
monodispersion degree of 14% and the ratio of the grains
having twinned planes of an even number was 80%. The grains
having an even number of twinned planes had an average
aspect ratio of 1.9 and consisted of 93% {111} planes and i%
{100} planes.
Example 6
The layers having the following compositions were
formed on a triacetyl cellulose film support in the order
from the support to prepare comparative light-sensitive
material sample No. 1.
In the examples below, the addition amounts are
expressed in grams per m2 unless otherwise stated. The
;.,, ~
2~2~73;~
amounts of silver halide and colloid silver are converted to
silver, and those of sensitizing dyes are expressed in mole
per mol of silver.
Layer 1: Antihalation layer
Black colloidal silver 0.2
Gelatin 0.4
UV absorber UV-l 0.3
High boiling organic solvent Oil-l 0.3
Layer 2: Interlayer
Gelatin 1.0
Layer 3: First red-sensitive emulsion layer
Silver iodobromide emulsion (AgI 7 mol%,
octahedron, 0.3 ~m) 0.6
Gelatin 1.2
Sensitizing dye S-l 8 x 10 4
Sensitizing dye S-2 5 x 10 4
Sensitizing dye S-3 3 x 10 5
Coupler C-l 0.10
Coupler C-3 0.25
Colored coupler CC-l 0.04
DIR coupler D-2 . 0.05
High boiling organic solvent Oil-l 0.45
Layer 4: Second red-sensitive emulsion layer
Silver iodobromide emulsion (AgI 8 mol~,
octahedron, 0.7 ~m) 1.0
2~2673~
- 23 -
Gelatin 1.3
Sensitizing dye S-l 3 x 10 4
Sensitizing dye S-2 2 x 10 4
Sensitizing dye S-3 2 x 10
Coupler C-l 0.10
Coupler C-3 0.30
Colored coupler CC-l 0.03
DIR coupler D-2 0.07
High boiling organic solvent Oil-l 0.50
Layer 5: Third red-sensitive emulsion layer
Em-A shown below 1.6
Gelatln 1.6
Sensitizing dye S-1 1 x 10
Sensitizing dye S-2 1 x 10
Sensitizing dye S-3 1 x 10 S
Coupler C-1 0.20
Coupler C-2 0.10
Colored coupler CC-1 0.02
DIR coupler D-2 0.05
High boiling organic solvent Oil-l 0.40
Layer 6: Interlayer
Gelatin 0.80
Additive SC-l 0.03
Additive SC-2 0.02
High boiling organic solvent Oil-2 0.05
2~2~ 2
- 24 -
Layer 7: First green-sensitive emulsion layer
5ilver iodobromide emulsion (AgI 7 mol%,
octahedron, 0.3 ~m) 0.4
Gelatin 0.8
Sensitizing dye S-4 6 x 10 4
Sensitizing dye S-5 1 x 10 4
Sensitizing dye S-6 1 x 10 4
Coupler M-l 0-05
Coupler M-3 0.25
Colored coupler CM-l 0.04
; DIR coupler D-l 0.06
High boiling organic solvent Oil-2 0.40
Layer 8: Second green-sensitive emulsion layer
Silver iodobromide emulsion (AgI 8 mol%,
octahedron, 0.7 ~m) 0.8
Gelatin 1.1
Sensitizing dye S-4 3 x 10 4
Sensitizing dye S-5 5 x 10 5
Sensitizina dye S-6 5 x 10 5
Coupler M-l 0.05
Coupler M-3 0.20
Colored coupler CM-l 0.03
DIR coupler D-l 0.05
High boiling organic solvent Oil-2 0.30
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- 25 -
Layer 9: Third green-sensitive emulsion layer
Em-A 1.2
Gelatin 1.1
Sensitizing dye S-4 2 x 10 4
Sensitizing dye S-5 5 x 10 4
Sensitizing dye S-6 5 x 10 4
Coupler M-2 0.05
Coupler M-3 0.10
Colored coupler CM-l 0.02
DIR coupler D-l 0~02
High boiling organic solvent Oil-2 0.30
Layer 10: Yellow filter layer
Yellow colloidal silver 0.05
Gelatin 1.0
Additive SC-l 0.03
Additive SC-2 0.02
High boiling organic solvent Oil-2 0.05
Layer 11: First blue-sensitive emulsion layer
Silver iodobromide emulsion (AgI 7 mol%,
octahedron 0.7 ~m) 0.20
Gelatin 1.30
Sensitizing dye S-7 1 x 10 3
Coupler Y-1 0.80
DIR coupler D-2 0.10
High boiling organic solvent Oil-2 0.28
~2~'737
- 26 -
Layer 12: Second blue-sensitive emulsion layer
Silver iodobromide emulsion (AgI 8 mol%,
octahedron, 0.7 ~m) 0.50
Gelatin 0~50
Sensitizing dye S-7 5 x 10
Coupler Y-l 0.60
DIR coupler D-2 0.08
High boiling organic solvent Oil-2 0.25
Layer 13: Third blue-sensitive emulsion layer
Em-B shown below 0.70
Gelatin 0.70
Sensitizing dye S-7 2 x 10 4Coupler Y-l 0.20
DIR coupler D-2 0.01
High boiling organic solvent Oil-2 0.07
Layer 14: First protective layer
Silver iodobromide (AgI 1 mol%, 0.08 ~m) 0.3
Gelatin 1.0
UV absorber UV-l 0.1
UV absorber UV-2 0.1
Formalin scavenger HS-l 0.5
Formalin scavenger HS-2 0.2
High boiling organic solvent Oil-l 0.1
High boiling organic solvent Oil-3 0.1
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- 27 -
Layer 15: Second protective layer
Gelatin 0.7
Alkali-soluble matting agent
(average grain size: 2 ~m) 0.12
Polymethyl methacrylate
(average grain size: 3 ~m) 0.02
Lubricant WAX-l 0.04
Antistatic agent Su-l 0.004
In addition to these compositions, each layer contained
coating aid Su-2, dispersion aids Su-2 and Su-3, hardeners
H-l and H-2, stabilizer Stab-l, antifogging agents AF-l and
AF-2 and preservative DI-l.
Em-A:
A monodispersed octahedral silver iodobromide emulsion
having an average AgI content of 6 mol%, a high silver
iodide content phase in the core, a monodispersion
degree of 13% and an average grain size of l.0 ~m.
Em-B:
A monodispersed octahedral silver iodobromide emulsion
having an average AgI content of 9 mol%, a high silver
iodide content phase in the core, a monodispersion
degree of 14% and an average grain size of 1.0 ~m.
~ O 2 ~ r~ 3 ~s
- 28 -
Em-C:
A tabular silver iodobromide emulsion having an average
AgI content of 6 mol%, a high silver iodide content
phase in the core, a monodispersion degree of 21%, an
average aspect ratio of 6 and an average grain size of
1.8 ~m.
Em-D:
A tabular silver iodobromide emulsion having an average
AgI content of 9 mol~, a high silver iodide content
phase in the core, a monodispersion degree of 19%, an
average aspect ratio of 5 and an average grain size of
1.6 ~m.
~02673~
~ 29 -
H= C - CH =
(CH2)~SO~e C.Hs
S - 2
H = C - CH ~ ~
(CH2),So,3 ~CH )3SO~H
H= T CH
(CH )~SO~9 (CH.)~SO~H
S - 4
~H = C - CH~
~CH2),SO,~ (CH2)~50~H N(C2Hs)~
2 ~ 3 ~
- 30 -
S - 5
H = C - CH
(CH2)~SO~e (CHz)lSO~H N(CzHs)~
S - 6
_ ~ C2Hs ~
(CHz)~SO~e (CH2)~SO~H N(C2Hs)3
S - 7
OCH~
(CH2)~SO~e (CH2)~SO~H N(CzHs)~
OH
C - 1 CsH~ ) ~ NHCONH ~ Ce
(~)CsH~I ~ OCHCONH ~ ~ CN
C~Hs
COCH(CHz)~O~CsH, I(~)
CsHIl(~)
O- ~ NHCOCH 7 CH2COOH
2~2~3~
- 31 -
C - 3 . OH
(t)C5HIl ~ NHCONH ~ CQ
~t)CsHIl ~ OCHCONH ~ ~ CN
- C~Hg OCH~COOCH,
Y-- 1 C~
CH,O ~ COfHCONN ~
N ~ COOCI~H s
~ N- CH~
M - 1
NHCO ~ CsHIl(t)
O ~ ~ \ = < NHCOCHz ~ sHll~t)
CQ
~l - 2
CQ
~ NH ~ ~
CQ ~ CQ C~sHIs
CQ
202~7~2
-- 32 --
M -- 3
~NHCO~
O N NHSO~OCI2Hz5
CQ~ CQ
CQ
C ~
CH ~ O~N = ~NHCo~9
C~ ~ C~ Nacoca,O~Sa,~
C~
C C-- 1
~COCH(CH.)~O~CsHI 1(~)
C s H
CH~
NaO, S SO, Na
202~73~
- 33 --
D -- 1 .
OH
~CONHCH 2 CH 2 COOH
~4CH2S ~ 3 OH
NO Z ~ N
H
I 1 2~
D - 2
~CONH ~ ~ OC 1 ~ H 2 9
~H ~ S~H,
U V - 1 OH
N ~D
C~Hg(~)
U V - 2
CH, r CN
CH,~N~CH CH~<CoNHCl 2H2 s
C7Hs
~02~73~
H S - 1 H S - 2
O H
H ~ H 2 NOCHNf ~
N ~ o ~ NH
o
H - 1 H - 2
ONa
N ~ N (CH.= CHSO 2 CH 2 ) 20
CQ N CQ
-S u --, 1
NaO,S - ICHCOOCH2(CF2CF ),H
CH:COOCH~(CF2CF2)3H
S u - 2
NaO,5 - ICHCOOC~H,~
CH2COOC~H, 7
S u - 3
C~2H2s ~ SO,Na
S C - 1 S C - 2
OH OH
CI~H " ~ C,~H, 7
OH OH
2~2~7~
- 35 -
W A-X -- 1
CH, ~ CH, 1 CH,
CH,--Si--OrSI--Ol--Si--CH,
CH, CH, n CH, MW: 30 000
O i I - 1 O i I - 3
~COOC~HI 7 ~COOC~Hg
COOC~ H, 7COOC~ H g
O i I - 3
~_ ~CH,
S ~ a b-- 1 CH,~
OH
A F -- 1 A F -- 2
H
D I -- 1
7~' ~C
2 0 2 ~ ~ 3 ~
- 36 -
The comparative llght-sensitive material sample No. 2
was prepared in the same manner as in sample No. 1 except
tha~ Em-A and Em-B used in Layers 5, 9 and 13 were replaced
with Em-C and Em-D as shown in Table 1.
The inventive light-sensitive material samples No. 3 to
5 were prepared in the same manner as in comparative sample
No. 1 except that the emulsions in Layers 5, 9 and 13 were
replaced with Em-l, Em-2 and Em-3 of the invention each
chemically sensitized with sodium thiosulfate, chloroauric
acid and ammonium thiocyanate, as shown in Table 1.
2 0 2 ~ 7 3 ~
-- 37 --
V
,, : ,
~ : .~ .~
c ~ Q ~1 ~ ~ s~
0 E E E E F. e E
ta w u~
E ~ C ~, .
~ ------ C-O So
C ~:
,~ 6 E E E E O _I O
_~ C ~ E~ 1:~ L'~ L~ E
,~ E n~
_ a ~ ~ V
. V~ SVC)
C ~ C~ ,-1 ~ ~7 Q {1~
c h E E E E la ~ ~ v
_1 Q.O 3~
E Q' ~ C
_ ~ 3 ~ 3 ~v
o o o ô O O m ~
Z ~J . v v VE c E
~ ~ ~ C C C ~ C
,1 ~ O. ~ ~ ~~ ~ ~ ,1
(a u 8 ~ c cc ~ ~
U~ _ _ _ _ _ ¢ I I U
. m E O E ~
~ 'I W ~D
202~'~ 3.~
- 38 -
Sample Nos. 1 to 5 were each subjected to wedge
exposure with white light and then to following processing:
Processes (38C)
Color development 3 minutes 15 seconds
Bleachiny 6 minutes 30 seconds
Washing 3 minutes 15 seconds
Fixation 6 minutes 30 seconds
Stabilization 1 minute 30 seconds
Drying
The compositions of the processing solutions used in
the respective processes are as follows:
Color developer
4-amino-3-methyl-N-ethyl-N-~-
hydroxyethylaniline sulfate 4.75 g
Sodium sulfite anhydrous 4.25 g
Hydroxylamine 1/2 sulfate 2.0 g
Potassium carbonate anhydrous 37.5 g
Sodium bromide 1.3 g
Trisodium nitrilotriacetate (monohydrate) 2.5 g
Potassium hydroxide 1.0 g
Water was added to the total quantity of 1~ (pH = 10.1).
Bleacher
Ferric ammonium ethylenediaminetetraacetate 100.0 g
Diammonium ethylenediaminetetraacetate 10.0 g
Ammonium bromide 150.0 g
20~73~
- 39 -
Glacial acetic acid 10.0 g
Water was added to the total quantity of lQ, and pH was
adjusted to 6.0 with aqueous ammonia.
Fixer
Ammonium thiosulfate 175.0 g
Ammonium sulfite anhydrous 8.5 g
Sodium metabisulfite 2.3 g
Water was added to the total quantity of 1~, and pH was
adjusted to 6.0 with acetic acid.
Stabilizer
Formalin (37% aqueous solution) 1.5 m~
Konidax produced by Konica Corporation 7.5 mQ
Water was added to the total quantity of lQ.
Fog and relative sensitivity of each sample were
measured with blue, green and red light. Granularity (RMS)
was determined by scanning an area having the density of fog
+ 0.3 with a microdensitometer having an opening scanning
area of 250 ~m2 and measuring a density variation.
The results are shown in Table 2.
2026732
-- 40 --
.. T I _ ~ ~.
o o ~ o~ a~ t~
I
o .,~, o o Ul U7 o o'
= o ,1 ~ ~ ~ ll
,~ ~ ~r ,~,: ~
1~ o o o o o r
V~ _ ____ :~
V ~ _l _~ ~ o~ a~ Z
C ~ _ ~
C ~. ~ O
L~ ,_~ O U~ O U7 O a)
~ V o~ ~ ~ ~ _~ ~0
O ,~ ~ ~ ~ ~ a~
~ o o o ,Va
~'7, o _ _ o _
_~ ~ ~ o~ ~
~: ~ _
~ ~ .
1~ .,1 O In O U~ U~ V
V o ~ ~ ~ ~ .~
= _ _1 ~o o ~
~ o o o o o
. O O ~ C C ,v~
Z 0 0 'v 'v 'v
~ ~ ~ C C C .~
O _ _ H H H
2~ 73~
As is evident from Table 2, the inventive
light-sensitive materials showed remarkable improvements in
fog, sensitivity and granularity in comparison with the
comparative light-sensitive materials.
Of the inventive light-sensitive materials, the
light-sensitive materials containing the AgX grains having
{100} planes had better performance.
