Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ ~ 2 L~ ~3 7 ~
A SILVER HALIDE LIGHT-SENSITIVE
COLOR PHOTOGRAPHIC MATERIAL
FIELD OF THE INVENTION
The present invention relates to a silver halide
light-sensitive color photographic material, specifically to
a silver halide light-sensitive photographic material having
high sensitivity, excellent graininess and improved storage
stability.
BACKGROUND OF THE INVENTION
Recently, there has been increasing demand for higher
sensitivity and more improved image quality.
One of the key factors affecting the sensitivity of a
silver halide light-sensitive material and the quality of an
image is silver halide grains. Efforts have been made in
the art to develop silver halide grains for higher
sensitivity and image quality.
It is generally known that image quality can be
2~,~'.q~9
improved by employing silver halide grains with smaller
grain sizes. However, such smaller grain sizes inevitably
lower the sensitivity of a light-sensitive material and
therefore, it is difficult to balance the sensitivity with
the image quality.
There have been studied the methods of improving both
sensitivity and image quality by controlling a
sensitivity/size ratio of the silver halide grains. The
examples therecf are the use of tabular silver halide
grains, which are disclosed in Japanese Patent Publication
Open to Public Inspection (hereinafter referred to as
Japanese Patent O.P.I. Publication) Nos. 111935/1983,
111936/1983, 111937/1983, 113927/1983 and 99433/1984. These
tabular grains have a larger surface area than those of
regular octahedral, tetradecahedral and dodecahedral silver
halide grains each having the same volume. Such larger
surface area permits the silver halide grains to adsorb a
larger amount of a sensitizing dye on the surface thereof
and therefore to have an improved sensitivity.
Japanese Patent O.P.I. Publication No. 92942/1988
discloses tabular silver halide grains having therein a core
of high AgI; Japanese Patent O.P.I. Publication No. 163451
discloses tabular hexagonal grains; and Japanese Patent
O.P.I. Publication No. 163451/1988 discloses tabular silver
halide grains having an aspect ratio of not less than 5.
h ~ 7 9
-- 3
These methods can improve sensitivity and graininess to some
extent, however, are insufficient for balancing a
sensitivity with an image quality.
SUMMARY OF THE INVENTION
The object of the invention is to provide a silver
halide light-sensitive color photographic material having an
improved sensitivity, graininess and storage stability.
The above object can be attained by a silver halide
light-sensitive color photographic material comprising a
support and provided thereon at least one silver halide
emulsion layer, wherein at least one of the emulsion layers
contains core/shell type tabular silver halide grains
comprising: a) a ratio of monodispersed grains of not less
than 70~ in terms of the number of the grains; b) an average
aspect ratio (diameter/thickness) of not less than 1 and
less than 5; and the portion having a silver iodide content
of not less than 15.3 mol% in the core.
In a preferred embodiment, most of the tabular silver
halide grains are hexagonal and the degree of monodispersion
of the grains is less than 20%.
DETAILED DESCRIPTION OF THE INVENTION
In the invention, the tabular grain is defined by the
grain having two major faces parallel to each other.
2~2~79
Tabular silver halide grains of the invention have an
average diameter/thickness ratio (aspect ratio) of not less
than 1 and smaller than 5, preferably not less than 1 and
smaller than 4, more preferably not less than 1 and smaller
than 3. The average aspect ratio is obtained by averaging
the aspect ratios of all silver halide grains.
The diameter of a tabular silver halide grain, which is
represented by the diameter of a circle having the same area
as that of the projected major face of the grain, is
preferably 0.1 to 5.0 ym, more preferably 0.2 to 4.0 ~m,
most preferably 0.3 to 3.0 ~m.
The silver halide emulsion according to the invention
is monodispersed. The monodispersed silver halide emulsion
is defined by the silver halide emulsion containing 60% by
weight or more of the silver halide grains with the sizes
falling within the range of 80 to 120% of the average grain
size d. The above weight percentage is preferably not less
than 65%, more preferably not less than 70% of all silver
halide grains.
The average grain size d is defined by a dia~eter di
in which the product of di3 and the number thereof ni is
maximized.
The significant figure is calculated down to the third
decimal place and the fourth digit is rounded to the nearest
whole number.
7 9
The grain diameters can be calculated by taking an
electron microphotograph of a grain (x 10,000 to 50,000) and
measuring the projected area oE more than 1,000 grains
selected arbitrarily on this photograph.
The silver halide emulsion used in the invention
preferably has a degree of monodispersion of lower than 20%,
more preferably lower than 18%, most preferably lower than
15%, wherein the degree of monodispersion is defined by the
following formula:
Standard deviation of
grain diameter
Degree of monodispersion ~ - X 100
Average diameter
The numerical ratio of the tabular silver halide grains
to all silver halide grains contained in the silver halide
emulsion of the invention can be calculated by counting the
number of grains on an electron microphotograph of the
emulsion. The number of the tabular grains accounts for not
less than 70%, preferably not less than 75~, more preferably
not less than 80% of the total silver halide grains.
It is preferred that the tabular silver halide grains
have mainly the hexagonal major faces.
The ratio of the major length to the minor one in the
hexagonal major face is preferably not more than 2, more
preferably not more than 1.8, most preferably not more than
1.5. This ratio can be calculated also by using an electron
2~ 67l3
microphotograph of the silver halide emulsion. The tabular
grains of 50% or more have preferably the hexagonal major
faces.
The tabular silver halide grains of the invention is of
a core/shell type in which high content silver iodide is
localized in the core of the grain.
High content silver iodide localized in the core is
identified by the average silver iodide contents Jl and
J3 satisfying the following relationship:
Jl J3
wherein Jl represents an average silver iodide content
measured by a fluorescent X-ray spectroscopy and J3
represents the average value of silver iodide contents
measured by an X-ray microanalysis in which the contents
concerned are measured at the portions far away by 80% or
more of a grain radius from the center thereof.
The high iodidcportion in the grain has a silver iodide
content of higher than 15.3 mol%, preferably 18 to 45 mol~,
more preferably 20 to 45 mol%, most preferably 25 to 45 mol%.
The silver halide emulsion used in the invention can be
prepared by growing monodispersed spherical seed grains
prepared by the method described in Japanese Patent O.P.I.
Publication No. 6643/1986 under stirring with a stirrer
disclosed in Japanese Patent O.P.I. Publication
No. 92523/1982, at 500 to 1200 r.p.m. The seed grains can
2~2~7~
be grown by any of the acid method, the neutral method and
the ammonia method, or by utilizing the known methods
described in Japanese Patent Publication Nos. 6643~1986,
14630/1986, 112142/1986, 157024/1987, 18556/1987,
92942/1988, 151618/1988, 1613451/1988, 220238/1988 and
311244/1988. Water-soluble salts may be removed by a
flocculation method or a noodle washing method.
Silver halides used in the invention are silver
iodochloride and silver iodobromochloride and may be a
surface latent image type or an inner latent image type.
The silver halide grains may be chemically sensitized
by conventional methods, and spectrally sensitized to a
prescribed wavelength with sensitizing dyes.
The silver halide emulsion may contain various
additives such as an anti-foggant and a stabilizer. Gelatin
is used preferably as the binder.
Emulsion layers and other hydrophilic colloid layers
may be hardened and contain a plasticizer and a latex.
A coupler is contained in a silver halide
light-sensitive emulsion layer.
There may be added a color coupler, a competitive
coupler, and a compound capable of releasing by a coupling
reaction with an oxidation product of a developing agent,
various photographically useful fragments such as a
development accelerator, a bleaching accelerator, a
2~2~673
developing agent, a solvent for silver halide, a toning
agent, a hardener, a fogging agent, an anti-foggant, a
chemical sensitizer, a spectral sensitizer and a
desensitizer.
There may be provided various auxiliary layers such as
a filter layer, an anti-halation layer and an
anti-irradiation layer. These layers and the silver halide
emulsion layers may contain a dye which can be removed or
bleached during development.
The light-sensitive materiai may contain conventional
additives such as a formalin scavenger, a fluorescent
bleaching agent, a matting agent, a lubricant, an image
stabilizer, a surfactant, an anti-foggant, a development
accelerator, a development retarder and a bleaching
accelerator.
The support is polyethylene-coated paper, a
polyethylene terephthalate film, baryta paper or a cellulose
triacetate film.
The light-sensitive material of the invention is
subjected to conventional processing after exposure.
EXAMPLES
The present invention will be described in more detail
by referring to the following examples.
.,
2~2~73
g
Example 1
Preparation of Em-l
A comparative core/shell type emulsions was peepared
according to the method described in Japanese Patent O.P.I.
Publication No. 138538/1985, wherein the emulsion comprised
octahedral silver iodobromide grains (average grain size:
1.3 ~m, silver iodide content: 5 mol%).
Comparative emulsions, Em-2, Em-3 and Em-4 each
consisting of core/shell type tabular silver halide grains
were prepared by the following methods:
Preparation of Em-2
To 5Q of an aqueous 1.5% gelatin solution containing
44.9 g of potassium bromide, 119 mO of an aqueous solution
containing 9.76 g of potassium bromide and 119 mQ of an
aqueous solution containing 13.96 g of silver nitrate were
added with stirring at 70C and pH 5.8 at the equal flow
rate by the double-jet method while maintaining pBr at 0.9.
Subsequently, 2.0Q of an aqueous solution containing 337 g
of silver nitrate and 2.0Q of an aqueous solution containing
200.3 g of potassium bromide and 49.3 g of potassium iodide
were added at the equal flow rate by the double-jet method
while maintaining pBr at 1.2. Next, 4.0Q of an aqueous
solution containing 1685 g of silver nitrate and 4.0Q of an
aqueous solution containing 1157 g of potassium bromide and
32.9 g of potassium iodide were added at the equal flow rate
2~2~
- 10 -
by the double-jet method while maintaining pBr at 1.2, to
thereby prepare tabular silver halide grains. After
desalting at 40C, gelatin was added to the grains for
redispersion. The dispersion was then cooled to 20C for
coagulation, whereby 1.5 kg of a comparative silver halide
emulsion were prepared.
Preparation of Em-3
To 5Q of an aqueous 1.5% gelatin solution containing
44.9 g of potassium bromide, 119 mQ of an aqueous solution
containing 9.76 g of potassium bromide and 119 m of an
aqueous solution containing 13.96 g of silver nitrate were
added with stirring at 65C and pH 5.8 at the equal flow
rate by the double-jet method while maintaining psr at 0.9.
Subsequently, 2.2Q of an aqueous solution containing 337 g
of silver nitrate and 2.2Q of an aqueous solution containing
207.4 g of potassium bromide and 39.44 g of potassium iodide
were added at the equal flow rate by the double-jet method
while maintaining pBr at 1.2. Next, 4.2Q of an aqueous
solution containing 1685 g of silver nitrate and 4.2Q of an
aqueous solution containing 1157 g of potassium bromide and
32.9 g of potassium iodide were added at the same flow rate
by the double-jet method while maintaining pBr at 1.2, to
thereby prepare tabular silver halide grains. Then,
desalting, redispersion and coagulation were performed in
the same manner as in Em-2, whereby 1.5 kg of a comparative
2~2~
silver halide emulsion where prepared.
Preparation of Em-4
To SQ of an aqueous 1.5~ gelatin solution containing
44.g g of potassium bromide, 119 mQ of an aqueous solution
containing 9.76 g of potassium bromide and 119 mQ of an
aqueous solution containing 13.96 g of silver nitrate were
added with stirring at 70C and pH 5.8 at the equal flow
rate by the double-jet method while maintaining pBr at 0.9.
Subsequently, 2.8Q of an aqueous solution containing 337 g
of silver nitrate and 2.8Q of an aqueous solution containing
2.8Q of an aqueous solution containing 193.2 g of potassium
bromide and 59.2 g of potassium iodide were added at the
equal flow rate by the double-jet method while maintaining
pBr at 1.3. Next, 3.5Q of an aqueous solution containing
1685 g of silver nitrate and 3.5Q of an aqueous solution
containing 1157 g of potassium bromide and 32.9 g of
potassium iodide were added at the same flow rate by the
double-jet method while maintaining pBr at 1.2, to thereby
prepare tabular silver halide grains. Desalting,
redispersion and coagulation were performed in the same
manner as in Em-2, whereby 1.5 kg of a comparative emulsion
were prepared.
Inventive emulsions Em-5 to 8 were prepared by the
following procedures:
2 ~ 2 l~r ~ ~ ~
Preparation of Em-5
To 5Q of an aqueous 1.5% gelatin solution, there were
added 300 g of a seed emulsion consisting of monodispersed
spherical grains (0.082 mol silver halide), followed by
stirring at 70C and pH 5.8. To the mixture, 2.5Q of an
aqueous solution containing 337 g of silver nitrate and 2.5Q
of an aqueous solution containing 193.2 g of potassium
bromide and 59.2 g of potassium iodide were added at the
equal flow rate by the double-jet method while maintaining
pBr at 1.5. Next, 4.0Q of an aqueous solution containing
1685 g of silver nitrate and 4.0Q of an aqueous solution
containing 1157 g of potassium bromide and 32.9 g of
potassium iodide were added at the equal flow rate by the
double-jet method while maintaining pBr at 1.5, to thereby
prepare tabular silver halide grains. After desalting at
40C, gelatin was added to the grains for redispersion,
followed by cooling to 20C for coagulation, whereby, 1.5 kg
of an inventive emulsion were prepared.
Stirring was made at 700 r.p.m. with a stirrer
disclosed in Japanese Patent O.P.I. Publication
No. 92523/1982.
Preparation of Em-6
The same seed emulsion 300 g as in Em-5 was added to 5Q
of an aqueous 2.0% gelatin solution, followed by stirring at
75C and pH 5.8. To the mixture, 2.8Q of an aqueous
~ ~ 2 '~
solution containing 337 g of silver nitrate and 2.8Q of an
aqueous solution containing 188.5 g of potassium bromide and
65.8 g of potassium iodide were added at the equal flow rate
by the double-jet method while maintaining pBr at 1.5.
Next, 3.5~ of an aqueous solution containing 16a5 g of
silver nitrate and 3.5Q of an aqueous solution containing
1157 g of potassium bromide and 32.9 g of potassium iodide
were added at the equal flow rate by the double-jet method
while maintaining pBr at 1.5, to thereby prepare tabular
silver halide grains. Desalting, redispersion and
coagulation were performed in the same manner as in Em-5,
whereby 1.5 kg of an inventive emulsion were prepared.
Stirring was made at 800 r.p.m. with the same stirrer
as in Em-5.
Preparation of Em-7
The same seed emulsion 300 g as in Em-5 was added to
4.5~ of an aqueous 1.5% gelatin solution, followed by
stirring at 75C and pH 5.8. To the mixture, 2.4~ of an
aqueous solution containing 337 g of silver nitrate and 2.4
of an aqueous solution containing 183.8 g of potassium
bromide and 72.4 g of potassium iodide were added at the
equal flow rate by the double-jet method while maintaining
pBr at 1.8.
Next, 4.0Q of an aqueous solution containing 1685 g of
silver nitrate and 4.0~ of an aqueous solution containing
232~7~
- 14 -
1157 g of potassium bromide and 32.9 g of potassium iodide
were added at the equal flow rate by the double-jet method
while maintaining pBr at 1.8, to thereby prepare tabular
silver halide grains. Desalting, redispersion and
coagulation were performed in the same manner as in Em-5,
whereby 1.5 kg of an inventive emulsion were prepared.
Stirring was made in the same manner as in Em-6.
Preparation of Em-8
To 5Q of an aqueous 1.5% gelatin solution, there were
added 300 g of the same seed emulsion as in Em-5, followed
by stirring at 75C and pH 5.8. To the mixture, 2.2Q of an
aqueous solution containing 337 g of silver nitrate and 2.2Q
of an aqueous solution containing 189.7 g of potassium
bromide and 64.2 9 of potassium iodide were added at the
equal flow rate by the double-jet method while maintaining
pBr at 1.5. Next, 4.0~ of an aqueous solution containing
1685 g of silver nitrate and 4.0~ of an aqueous solution
containing 1157 g of pctassium bromide and 32.9 g of
potassium iodide were added at the equal flow rate by the
double-jet method while maintaining pBr at 1.3, to thereby
prepare tabular silver halide grains. Desalting,
redispersion and coagulation were performed in the same
manner as in Em-5, whereby 1.5 kg of an inventive emulsion
were prepared.
Stirring was made in the same manner as in Em-5.
The properties of Em-l to 8 are shown in Table 1.
2~2~7~
- 15 -
3~ 3~ 3 3~ 3~ 3 3~ 3 .
co ~I a~ ul ~P w ~) 1_ 3
_ ~ ~ ~ ~ ~ ~_
H )--I H ~_1 ~ ~ ~ ~ 1--
~ ~ ~ ~ O O O O Ul
C ~ ~: ': 3 g ~ ~ O
:~ 3 ~ ::~ ~ Dl QJ D~
,_. ,.. t~- t~- ~ Y- ,.. ~ Z
O O O O U~ U~ U~ U~ O
::) :~ ~ ~ O O O O
-- ~3 _ ~ ~3 __ O ~ cn
D~ ~ D~ 9~ D~ ~ rt
~J ~J ~ :r ~ ~ ~r
c c c c c c c ~ ~a
~) D~ ~ ~ P D~ D ~D
r~ _. ~ r~ rt ~ n D~
w ~ w .P ~ ~ a~ ~ u~
o o o o o l O-Q
-- D)~ z
1~ 3
0:~ ~ C~~I C~ _~ _1 l dP ~ O' '
o o 1~ _ o o ~ A ~3
I_ j_ I_ I_ NI_ I_ ~_ ^ D) Dl fD ~U
. . O 3 a~
~ ~D ~-
_ _
~ ~n ~ ~ ,P ~ ~ V~ D~ F ~ ,o
. . . . . . . I~ O ~ ~ ~
o ~ o ~ a- o~ 1_ ~ a ~
,..
O ~ 3 Q.
l_ I~ ~o ,_ ~_ ~_ ~_ o ~ O O ~
~. ~ oP~
_ _ ~0'1:
I_ ~_ I_ ~ ~ W W I_ ~ ~D
OD ~ CD 10 ~_ O ~n ~n `'0~
O
~r 1~0
~J~ O
CO _~ ~I ~ ~ ~ ~ ~ C ~
~' ~ 1~ o .P o~ u- ~ l ~ ~-xr
~-0 ..
U~ ~
_ _
, ' ' -
2~2'~6~
- 16 -
Five g of the magenta coupler M-l, 0.95 g of the
colored magenta coupler CM-l and 0.10 g of the DIR compound
D-l were dissolved in 5 mQ of dibutyl phthalate. The
solution was then mixed with 8 mQ of an aqueous 1.0
solution of Alkanol B (alkylnapthalene sulfonate
manufactured by Dupon Ltd.) and 70 mQ of an aqueous 5%
gelatin solution, followed by dispersing with of a colloid
mill.
M-l
~ NHCO ~ NHCOCH20 ~ C5HIl(t)
C2 ~ (CQ
C~
CM-l
C~
N=N ~ 1I NH ~ ~ CldH~s
N N N
C~ ~ CQ
C~
2 ~ 7 ~
D-l
C~ aH~ 7
N
~,~r S ~ 11
O N-N
The above dispersion and 350 g (containing 40 g of
silver) of Em-l to 8 subjected to optimum sulfur
sensitization, gold sensitization and green-sensitization
were mixed and coated on a subbed cellulose triacetate film
in a silver amount of 16 mg/dm2.
Further, a protective layer containing 2.3 g/m of
gelatin was coated on the emulsion layer, whereby silver
halide light-sensitive material Samples No. 1 to 8 were
prepared.
Each sample was exposed to white light for
sensitometry, and processed according to the following
processing procedures. Then, sensitivity and RMS
granularity were evaluated.
Processing procedures (38C)
Color developing 3 min 15 sec
Bleaching 6 min 30 sec
2 ~ 2 '~
- 18 -
Rinsing 3 min 15 sec
Fixing 6 min 30 sec
Rinsing 3 min 15 sec
Stabilizing 1 min 30 sec
.~rying
The composition of each processing liquid is as follows:
Color developer
4-Amino-3-methyl-N-ethyl-N-
(~-hydro~yethyl)aniline sulfate4.75 g
Sodium sulfite anhydrous 4.25 g
Hydroxylamine 1/2 sulfate 2.0 g
Potassium carbonate anhydrous37.S g
Sodium bromide 1.3 g
Trisodium nitrilotriacetate
(monohydride) 2.5 g
Potassium hydroxide 1.0 g
Water was added to make total quantity 1 liter, and pH
was adjusted to 10Ø
Bleacher
Ferric a~monium ethylenediaminetetraacetate 100 g
Ferric diammonium ethylenediaminetetraacetate 10 g
Ammonium bromide 150.0 g
Glacial acetic acid 10.0 g
Water was added to make total quantity 1 liter, and pH
was adjusted to 6.0 with aqueous ammonia.
2~2~7t3
-- 19 --
Fixer
Ammonium thiosulfate 175.0 g
Ammonium sulfite anhydrous 8.5 g
Sodium metasulfite 2.3 g
Water was added to make total quantity 1 liter, and pH
was adjusted to 6.0 with acetic acid.
Stabilizer
Formalin (an aqueous 37% solution) 1.5 m
Konidax (manufactured by Konica Corp) 7.5 m~
Water was added to make total quantity 1 liter.
Relative sensitivity is defined by a reciprocal of the
exposure required to provide a density of a fog + 0.1 and is
a value relative to the green sensitivity of Sample No. 1,
which is set at 100.
RMS is a value obtained by multiplying by 1000 times a
standard deviation for the variation of a density in
scanning a density of the minimum density + 0.1 with a
microdensitometer having a 250 ~m2 opening for scanning,
and shown by a value relative to that of Sample No. 1, which
is set at 100.
The evaluation results are shown in Table 2.
The results reveal that the samples of the invention
are superior to the comparative samples in both sensitivity
and granularity.
( ~
2 ~ 9
- 20 -
Table 2
Sample No Emulsion No. Relative sensitivity RMS
1 (Comparison) Em-l 100 100
2 (Comparison) Em-2 104 108
3 (Comparison) Em-3 102 103
4 (Comparison) Em-4 102 106
5 (Invention) Em-5 119 86
6 (Invention) Em-6 121 82
7 (Invention) Em-7 128 ` 78
8 (Invention) Em-8 127 82
Example 2
The layers of the following compositions were provided
on a subbed triacetyl cellulose in sequence from the
SUppGrt~ to thereby prepare multilayered light-sensitive
color photographic material Samples No. 9 to 16.
1st layer: anti-halation layer containing gelatin and
black colloidal silver
2nd layer: interlayer containing gelatin and
2,5-di-t-octylhydroquinone
3rd layer: low speed red-sensitive silver halide
emulsion layer
Monodispersed emulsion containing core/shell type AgBrI
202'~7~
- 21 -
grains with an average diameter of 0.45 ~m and an AgI
content of 7 mol%; the amount of silver coated: 1.8 g/m2;
Sensitizing dye I ... 5.0 x 10 4 mol per mol silver
Sensitizing dye II ... 0.7 x 10 mol per mol silver
Cyan coupler C-l ... OolO mol per mol silver
Colored cyan coupler CC-l ... 0.002 mol per mol silver
DIR compound D-2 ... 0.0005 mol per mol silver
DIR compound D-3 . . 0.003 mol per mol silver
HBS-lA ... 1.0 g/m
4th layer: interlayer same as the 2nd layer
5th layer: high speed red-sensitive silver halide
emulsion layer
Emulsion shown in Table 3; the amount of silver coated:
2.2 g/m ;
Sensitizing dye I ... 2.6 x 10 4 mol per mol silver
Sensitizing dye II ... 0.7 x 10 mol per mol silver
Cyan coupler C-l ... 0.004 mol per mol silver
Cyan coupler C-2 ... 0.014 mol per mol silver
Colored Cyan coupler CC-l ... 0.0005 mol per mol silver
DIR compound D-3 ... 0.0005 mol per mol silver
HBS-lA ... 0.37 g/m2
6th layer: interlayer same as the 2nd layer
7th layer: low speed green-sensitive silver halide
emulsion
Emulsion same as in the 3rd layer; the amount of silver
2 ~ 2 '~
- 22 -
coated: 1.0 g/m ;
Sensitizing dye III ... 2.0 x 10 mol per mol silver
Sensitizing dye IV ... 1.0 x 10 mol per mol silver
Magenta coupler M-l ... 0.090 mol per mol silver
Colored magenta coupler CM-l ... 0.007 mol per mol silver
DIR compound D-4 ... 0.002 mol per mol silver
DIR compound D-5 ... 0.003 mol per mol silver
HBS-2A ... 0.90 g/m
8th layer: interlayer same as the 2nd layer
9th layer: high speed green-sensitive silver halide
emulsion
Emulsion shown in Table 3; the amount of coated silver:
2.5 g/m .
Sensitizing dye III ... 1.2 x 10 mol per mol silver
Sensitizing dye IV ... 0.8 x 10 mol per mol silver
Magenta coupler M-l ... 0.01 mol per mol silver
Colored magenta coupler CM-l ... 0.005 mol per mol silver
DIR compound D-4 .. 0. 0002 mol per mol silver
HBS-2A ... 0. 22 g/m
10th layer: yellow filter layer containing gelatin,
yellow colloidal silver and
2, 5-di-t-octylhydroquinone
11th layer: low speed blue-sensitive silver halide
emulsion
Emulsion same as in the 3rd layer; the amount of silver
2~2~67~
- 23 -
coated: 0.5 g/m2;
Sensitizing dye V ... 1.3 x 10 mol per mol silver
Yellow coupler Y-l ... 0.35 mol per mol silver
HBS-2A ... 0.25g/m
12th layer: high speed blue-sensitive silver halide
emulsion
Emulsion shown in Table 3; the amount of silver coated:
1.2 g/m ;
Sensitizing dye V ... 1.8 x 10 4 mol per mol silver
Yellow coupler Y-l ... 0.04 mol per mol silver
HBS-2A ... 0.25 g/m
13th layer: 1st protective layer containing silver
iodobromide (AgI content: 1 mol%, average
diameter: 0.07 ~m) in the amount of silver
coated: 0.4 g/m and UV absorbers UV-l
and UV-2.
14th layer: 2nd protective layer containing polymethyl
methacrylate (diameter: 1.5 ~m) and
formalin scavenger (HS-l)
In addition to the above components, gelatin
hardeners(H-l) and (H-2), and a surfactant were added to
each layer.
The compounds contained in each layer:
ensitizing dye I : anhydro-5,5'~dichloro-9-ethyl-3,3'-di-(3-
sulfopropyl)thiacarbocyanine hydroxide
~2~579
- 24 -
Sensitizing dye II : anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-
4,5,4',5'-dibenzothiacaebocyanine
hydroxide
ensitizing dye III: anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-(3-
sulfopropyl) oxycarbocyanine hydroxide
ensitizing dye IV : anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)-
5,6,5',6'-dibenzoxacarbocyanine
hydroxide
ensitizing dye V : anhydro-3,3'-di-(3-sulfopropyl)-4,5-benzo
-5'-methoxythiacyanine hydroxide
C-l
OH ~ C~
(t)CsHI I~OCHOCNH
C~Hg
C-2
~CONH(CH~)~O~CsHI ,~t)
O~ NHCOCH zCH 2 COOH
2~2~79
/CONH(CH,),O ~ CsHll~t~
CsHI l(t)
¢~ OH NHCOCH 3
N = N X~ ,
NaO3S SO3Na
D -- 2
~ OC,, H 2 J
~ I ~C H 2 S ~ ¦¦
D -- 3 ~CONH$~
~ 2 ~
~3 ~\CH~
2a2'~67~
-- 26 --
D -- 4
OH
~CONHCH z CH 2
. O N--N
NO,~;~N~ fN
D -- 5 OH
CONHCH z CH 2 COOCH,
O N--N
,~
OH
Y-- 1 CQ
CH ~ O--~--COCHCONH ~
O~ O COOC I z H 2 5
CH2~;~
202~7~
- 27 -
M - 1
CQ H
N - N~ -CH2CHzSO2CH2CH/
C~H, 7
U V - 1 N OH
\ N ~ C~Hg(t)
C~lg~t)
U V - 2
CH ~N ~ CH-CH ~ CONHC H
C2Hs
H S - 1 I r
HN ~ NH
o
H - 1 ONa
N ~ N
CQ ~ C~
2 ~ 2 i~
- 28 -
H-2
~(CH2=CHSO2CH2)3CCH2SO2CH2CH2~2NCH2CH2SO3
HBS-lA
Dioctyl phthalate (DOP)
HBS-2A
Tricresyl phosphate (TCP)
Sample Nos. 9 to 16 were exposed to white light through
an optical wedge, and processed in the same manner as in
Example 1.
Sensitivity and RMS granularity were evaluated ~or the
high speed green-sensitive layers of the processed samples.
The results are shown in Table 3. Sensitivity and
granularity are the values relative to those of Sample
No. 9, which are set at 100, respectively.
The results reveal that the samples of the invention
are superior to the comparative samples in both sensitivity
and RMS.
2~2~9
- 29 -
Table 3
.
Sample No Emulsion No. Relative sensitivity RMS
_
9 (Comparison) Em-l 100 100
..... . ... _
10 (Comparison)Em-2 106 108
11 (Comparison)Em-3 103 106
12 (Comparison)Em-4 104 105
13 (Invention) Em-5 115 83
14 (Invention) Em-6 128 78
.
15 ~Invention) Em-7 128 74
_
16 (Invention) Em-8 121 80
Example 3
Light-sensitive material samples prepared in Example 2
were stored under the following two different conditions.
The stored samples were processed and evaluated in the same
manner as in Example 2.
Conditions:
A: 65C, 30%RH for 4 days
B: 50C, 80%RH for 4 days
The results are shown in Table 4. Under either
condition, the samples of the invention were superior to the
comparative samples in both sensitivity and RMS granularity.
2~2~9
- 30 -
Table 4
.
Condition A Condition B
Sample No Emulsion Relative Relative
sensi- RMS sensi.- RMS
tiVlty tivity
17 (Comparison) Em-l 100 100 100 100
18 (Comparison) Em-2 102 110 ~ 104 107
19 (Comparison) Em-3 94 109 95 104
20 (Comparison) Em-4 98 105 101 110
21 (Invention) Em-5 116 88 119 90
22 (Invention) Em-6 128 82 127 84
_
23 (Invention) Em-7 124 75 122 77
24 (Invention) Em-8 119 80 118 81
