U.S. patent number 3,847,613 [Application Number 05/325,338] was granted by the patent office on 1974-11-12 for silver halide photosensitive materials for color photography.
This patent grant is currently assigned to Konishiroku Photo Industry Co. Ltd.. Invention is credited to Noboru Fujimori, Shigemasa Ito, Kiyomitsu Mine, Eiichi Sakamoto, Kaiichiro Sakazume.
United States Patent |
3,847,613 |
Sakazume , et al. |
November 12, 1974 |
SILVER HALIDE PHOTOSENSITIVE MATERIALS FOR COLOR PHOTOGRAPHY
Abstract
A silver halide photosensitive material for color photography
providing excellent color reproducibility is disclosed which
comprises a support and at least three emulsion layers supported
thereon; said layers being a red-sensitive emulsion layer, a
green-sensitive emulsion layer, and a blue-sensitive emulsion
layer; the blue-sensitive emulsion layer containing a sensitizing
dye represented by the following formula: ##SPC1## Wherein Y.sub.1
and Y.sub.2 each stand for a non-metallic atomic group necessary
for forming a nitrogen-containing heterocyclic ring nucleus
selected from the group consisting of pyrroline, thiazoline,
thiazole, benzothiazol, naphthothiazole, selenazole
benzoselenazole, naphthoselenazole, oxazole, benzoxazole,
naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline,
which heterocyclic ring nucleus may be substituted by a halogen
atom, a lower alkyl group, a lower alkoxy group, or an aryl group,
which group may be substituted by a halogen atom, a lower alkyl
group or a lower alkoxy group; R.sub.1 stands for a lower alkyl
group, a hydroxyalkyl group, or a sulfoalkyl group; R.sub.2 is a
hydrogen atom or a lower alkyl group; A designates an alkylene
group or a group --(CH.sub.2)2 --O --(CH.sub.2).sub.2 --or,
--(CH.sub.2).sub.2 --O --CH.sub.2 CH(OH) CH.sub.2 --; and n.sub.1
and n.sub.2 are each 0 or 1.
Inventors: |
Sakazume; Kaiichiro (Tokyo,
JA), Sakamoto; Eiichi (Hanno, JA), Mine;
Kiyomitsu (Tokyo, JA), Fujimori; Noboru (Tokyo,
JA), Ito; Shigemasa (Tokyo, JA) |
Assignee: |
Konishiroku Photo Industry Co.
Ltd. (Tokyo, JA)
|
Family
ID: |
11689290 |
Appl.
No.: |
05/325,338 |
Filed: |
January 22, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Jan 24, 1972 [JA] |
|
|
47-8300 |
|
Current U.S.
Class: |
430/505; 430/582;
430/583; 546/172; 548/121; 548/150; 548/156; 548/159; 548/179;
548/219 |
Current CPC
Class: |
G03C
1/16 (20130101) |
Current International
Class: |
G03C
1/14 (20060101); G03C 1/16 (20060101); G03c
007/32 (); G03c 001/16 () |
Field of
Search: |
;96/74,140,132,143
;260/240.7,240.65 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
2170803 |
August 1939 |
Brooker |
2231659 |
February 1941 |
Brooker et al. |
2921067 |
January 1960 |
Henrilarive et al. |
3149105 |
September 1964 |
Henrilarive et al. |
|
Primary Examiner: Klein; David
Assistant Examiner: Suvo Pico; Alfonso T.
Attorney, Agent or Firm: Bierman & Bierman
Claims
We claim:
1. A silver halide photosensitive material for color photography
comprising a support and at least three emulsion layers supported
thereon; said layers being a red-sensitive emulsion layer, a
green-sensitive emulsion layer, and a blue-sensitive emulsion
layer: the blue-sensitive emulsion layer containing a sensitizing
dye represented by the following formula: ##SPC8##
Wherein Y.sub.1 and Y.sub.2 each stand for a non-metallic atomic
group necessary to form a nitrogen-containing heterocyclic ring
nucleus selected from the group consisting of pyrroline,
thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole,
benzoselenazole, naphthoselenazole, oxazole, benzoxazole,
naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline,
which nucleus may be substituted by a halogen atom, a lower alkyl
group, a lower alkoxy group, or an aryl group, which group may in
turn be substituted by halogen, lower alkyl or lower alkoxy;
R.sub.1 stands for lower alkyl, hydroxyalkyl, or sulfoalkyl;
R.sub.2 is hydrogen or lower alkyl, A designates alkylene,
--(CH.sub.2).sub.2 --0--(CH.sub.2).sub.2 --or-- (CH.sub.2).sub.2
--0 CH.sub.2 CH(OH) CH.sub.2 --; and n.sub.1 and n.sub.2 are each 0
or 1.
2. A silver halide photosensitive material for color photography
according to claim 1, wherein each of said layers contains a
coupler.
3. A silver halide photosensitive material for color photography
according to claim 1, wherein said heterocyclic ring nucleus in
said general formula is selected from thiazole, benzothiazole,
selenazole, and benzoselenazole.
4. A silver halide photographic material for color photography
according to claim 1, wherein said blue-sensitive emulsion layer
contains a yellow coupler, said green-sensitive emulsion layer
contains a magenta coupler, and said red-sensitive emulsion layer
contains a cyan coupler.
5. A silver halide photosensitive material for color photography
according to claim 4, wherein said heterocyclic nuclei in said
sensitizing dye are each selected from thiazole, benzothiazole,
selenazole, and benzoselenazole.
Description
This invention relates to a silver halide photosensitive material
for color photography. More particularly, it relates to a
coupler-containing, silver halide, photosensitive material for
color photography which includes a blue sensitive emulsion layer
sensitized by a spectral sensitizer.
In silver halide photosensitive materials for color photography,
chemical sensitization using sulfur or noble metals can increase
the sensitivity of the blue sensitive emulsion layer. However, when
the sensitivity inherent in the silver halide is increased without
use of sensitizing dyes, the particle size becomes coarser,
resulting in loss of clarity and sharpness in the reproduced
images.
In some cases, the sensitivity region inherent to the silver halide
is utilized as the spectral sensitivity region of the blue
sensitive emulsion layer. Sometimes, these silver halide sensitive
materials do not have the desired spectral sensitivity in the blue
sensitive emulsion layer especially toward the longer wavelengths.
Attempts have been made to increase the sensitivity of the
blue-sensitive emulsion layer in the range of the longer
wavelengths by the use of a spectral sensitizer.
However, most dyes heretofore used for this purpose are too
effective and expand the photosensitive region of the blue
sensitive emulsion layer excessively toward the longer wavelength
region. This forms an image of an undesirable yellow color and
degrades the color reproducibility in the green image. Also, it
reduces the sensitivity inherent in the silver halide and leaves
color stains on the photosensitive material after development.
Because of these defects, such dyes are not completely satisfactory
as spectral sensitizers for the blue sensitive emulsion layer.
Moreover, when photosensitive materials prepared with such dyes are
stored under high temperature and humidity conditions, the
sensitivity of the blue sensitive emulsion layer is drastically
lowered, resulting in formation of fog or color stain. With the
recent demand for acceleration of the processing of photosensitive
materials, high temperatures are necessary. When photosensitive
materials comprising such sensitizing dyes are developed at such
high temperatures, the developing rates in the red sensitive
emulsion layer and, the green sensitive emulsion layer differ from
that of the blue sensitive emulsion layer. As a result, good
balance of the photographic characteristics of these three layers
is not obtained and the color reproducibility is greatly impaired.
Accordingly, sensitizing dyes suitable for the blue sensitive
emulsion layer, without such defects, has been long sought by those
skilled in the art.
It is, therefore, a primary object of this invention to provide a
coupler-containing, silver halide, photosensitive material for
color photography having excellent color reporducibility, which
comprises a blue sensitive emulsion layer sensitized by sensitizing
dyes free of the afore mentioned defects.
This object can be attained by using a silver halide photosensitive
material comprising a support and at least three emulsion layers
thereon; namely a red sensitive emulsion layer, a green sensitive
layer, and a blue sensitive layer, wherein a compound of the
following general formula is incorporated in the blue sensitive
emulsion layer: ##SPC2##
Wherein Y.sub.1 and Y.sub.2 each stand for a non-metallic atomic
group necessary for forming a nitrogen containing heterocylic ring
nucleus selected from the group consisting of pyrroline,
thiazoline, thiazole, benzothiazole, naphthothiazole, selenazole,
benzoselenazole, naphthoselenazole, oxazole, benzoxazole,
naphthoxazole, imidazole, benzimidazole, pyridine and quinoline;
which nucleus may be substituted by a halogen atom, a lower alkyl
group, a lower alkoxy group or an aryl group; which group may in
turn be substituted by halogen, lower alkyl or lower alkoxy;
R.sub.1 stands for lower alkyl, hydroxy alkyl, carboxyalkyl or
sulfoalkyl; R.sub.2 is hydrogen or lower alkyl; A designates
alkylene,--(CH.sub.2) .sub.2 O(CH.sub.2) .sub.2 --, or --
(CH.sub.2) .sub.2 OCH.sub.2 CH(OH)CH.sub.2 --; and n.sub.1 and
n.sub.2 are each 0 or 1.
Typical examples of compounds expressed by the above general
formula and useful in this invention are listed below. However, the
list is exemplary only and is not intended to limit the invention.
##SPC3##
The compounds of the above general formula useful in this invention
can readily be synthesized by methods disclosed in, for instance,
specification of British Pat. No. 660,408 and U.S. Pat. No.
3,149,105.
The compounds of the present invention are preferably added to the
emulsions in the form of solutions in a watermiscible organic
solvent such as methanol or ethanol. The addition of such compounds
may be effected at any desired point during the preparation of the
emulsions. In general, however, it is preferable that they be added
just after the chemical ripening or chemical sensitization. The
compounds are incorporated in an amount of 0.01 to 0.5 g per mole
of silver halide, although the preferred amount can vary depending
on the kind of additive and silver halide emulsion.
The couplers to be incorporated in the silver halide photosensitive
materials for color photography are not particularly critical in
this invention, and couplers customarily used in this field can be
used effectively. For instance, the blue sensitive layer may
contain a compound which can react with an oxide of a color
developer containing a primary amino group to form a yellow dye.
The amount of such coupler to be added in generally 1.0 to 200 g
per mole of the silver halide. The coupler is preferably
incorporated into the emulsion as an aqueous alkali solution or as
a solution in a high or low boiling point organic solvent.
It is also possible to incorporate other photographic additives
such as stabilizers, film-hardening agents, pH--adjusting agents,
viscosity--increasing agents, coating assistants and color stain
preventive agents in the photosensitive material. Synthetic and
natural high molecule compounds such as gelatin, casein and
polyvinyl alcohol can be used singly or in combination as a
binder.
The silver halide may, for example, be silver chloride, silver
bromide, silver iodide-bromide and silver chloride-iodide-bromide.
Various materials such as paper, cellulose acetate film, polyester
film, polycarbonate and polyolefineoated paper may be used as the
support.
The silver halide photosensitive material according to this
invention can achieve a good balance in photographic
characteristics between the red, green and blue sensitive layers
even in high-temperature, high-speed development. It is also one of
the advantages of this invention that the silver halide
photographic material is freer from spot-like fog than the
photographic material of the prior art. Spot-like fog often arises
during development according to prior art and is believed to result
from a small quantity of fine metal stuck to the surface of the
photosensitive material during its preparation, processing or
during actual photographing.
This discovery is further illustrated in more detail by the
following Examples, which illustrate but do not limit the
invention.
Example 1
A color negative emulsion of silver iodidebromide containing 5 mole
percent of silver iodide was chemically ripened and 0.15g per mole
of silver halide of anhydro-5,5' -dichloro- 3,3'
-disulfopropyl-9-ethyl-thiacarbocyanine hydroxide was added as a
sensitizing dye to the emulsion in the form of a methanol solution.
Then, 50g per mole of silver halide of 4-chloro-1-hydroxy-2-n-octyl
naphthamide as a cyan coupler was further added in the form of the
dispersion of the following composition:
Composition of Coupler Dispersion Coupler 100 g Dibutyl phthalate
100 ml Ethyl Acetate 300 ml 5% Aqueous solution of Alkanol B
(manufactured by Du Pont) 150 ml 6% Aqueous solution of gelatin 500
ml
Then, a stabilizer, a film-hardening agent, a coating assistant and
a pH-adjusting agent were added to the emulsion to form a red
sensitive emulsion.
Similarly, a green sensitive emulsion was prepared by using a
sensitizing dye, anhydro-5,5' -diphenyl-3,3' -disulfopropyl-9
-ethyl-oxacarbocyanine hydroxide in an amount of 0.15g per mole of
the silver halide and, as a coupler, 1-(2,4,6
-trichloro-phenyl)--[3-(2,4
-di-tertiary-amylphenoxyacetamide)benzamido] -5-pyrazolone in an
amount of 60g per mole of the silver halide.
A color negative emulsion of silver bromideiodide containing 4.5
mole percent of silver iodide was chemically ripened and divided
into seven portions. From these seven portions of the emulsion,
seven kinds of blue sensitive emulsions were prepared by adding
compounds (7), (9) or (14) of this invention individually in an
amount of 0.00g, 0.10g or 0.15g per mole of the silver halide.
After the resulting mixtures were sufficiantly agitated to
stabilize the absorption of the sensitizing dyes, 70g per mole of
silver halide of 4-dodecyl-benzoyl-2'-methoxyacetoanilide was
incorporated as a yellow coupler into each mixture in the form of a
coupler dispersion. The dispersion was prepared in the same manner
as the above described red and green sensitizing emulsions. Then a
stabilizer, a film-hardening agent, a coating assistant and a
pH-adjusting agent were incorporated into each of the resulting
compositions.
For each of the blue sensitive emulsions, a photographic film was
prepared by coating on a cellulose triacetate film base. An anti
halation layer, a red sensitive emulsion layer, a gelatin film
layer, a green sensitive layer, a colloidal silver-containing
yellow filter layer, a blue sensitive and a gelatin protective
layer were successively coated on the base in that order.
These seven samples were exposed to artificial daylight of 160
luxes (5,400.degree.K) by employing a sensitometer (model KS-1
manufactured by Konishiroku Photo Industry Co., Ltd.), and
subjected to the color development treatment according to the
following procedures:
Color Development Steps and Recipes (I) Color Development
(24.degree. C., 12 minutes) Benzyl alcohol 3.8 ml Anhydrous sodium
sulfite 2.0 g N-Ethyl-N-B-methanesulfonamide-
ethyl-3-methyl-4-aminoaniline sulfate 5.0 g Sodium carbonate
(monohydrate) 50.0 g Potassium bromide 1.0 g Water to make 1 liter
The p.sup.H was adjusted to 10.8 by addition of sodium hydroxide.
(2) First Fixation (24.degree. C., 5 minutes) 150 g of sodium
thiosulfate was added to enough water to make 1 liter of solution
(3) Water Washing (24.degree. C., 5 minutes) (4) Bleaching
(24.degree.C., 6 minutes) Formula: Potassium ferricyanide 100 g
Potassium bromide 50 g Water to make 1 liter (5) Water Washing
(24.degree. C., 5 minutes) (6) Second Fixation (24.degree.C., 5
minutes), the same recipe as that of the first fixation (7) Water
Washing (24.degree.C., 10 minutes) (8) Drying
With respect to each of the resulting color negative images, the
relative blue light sensitivity of the blue sensitive emulsion
layer and the degree of the residual coloration were measured and
the results are shown in Table 1. The relative sensitivity is
expressed as a relative value based on the blue light sensitivity
(100) of the sample (1) containing no sensitizing dyes, and the
degree of the residual coloration is expressed as a value of the
complementary color concentration at the non-image area.
Table I ______________________________________ Sample Sensitizing
Compound Relative Degree of Sensiti- Residual vity Coloration No.
Compound Amount (g per mole of silver No. halide
______________________________________ 1 -- -- 100 0.10 2 (7) 0.10
125 0.10 3 (7) 0.15 130 0.11 4 (9) 0.10 110 0.10 5 (9) 0.15 125
0.10 6 (14) 0.10 120 0.10 7 (14) 0.15 135 0.11
______________________________________
As is seen from the results shown in Table 1, it will readily be
understood that the samples containing the compounds of this
invention exhibit not only a low degree of the residual coloration
but also a high blue light sensitivity and are thus particularly
suitable as sensitizing dyes for blue sensitive emulsion.
Example 2
A color reversable emulsion of silver iodidebromide containing 5
mole % of silver iodide was chemically ripened and 0.15 g per mole
of silver halide of anhydro
5,5'-disulfopropyl-9-ethyl-thiacarbocyane hydroxide was added as a
sensitizing dye to the emulsion in the form of a methanol solution.
Then 50 g per mole of 4-chloro-1 -hydroxy-2-n-octylnaphthamide was
added as a cyan coupler in the form of a dispersion prepared in the
same manner as in Example 1, the resulting was well mixed and
dispersed. A stabilizer, a film-hardening agent, a coating
assistant and a pH-adjusting agent, were then added to form the red
sensitive emulsion.
According to the same procedures as set forth above with respect to
the preparation of the red sensitive emulsion, a green sensitive
emulsion was prepared by employing, as a sensitizing dye,
anhydro-5,5'-diphenyl-disulfopropyl-9-ethyl-oxacarbocyanine
hydroxide in an amount of 0.15 g per mole of the silver halide and,
as a magenta coupler, 1-(3-carboxyphenyl)-
3-(4-stearoylaminophenyl)-5-pyrazolone in an amount of 60g per mole
of the silver halide.
According to the same procedures as set forth above for the
preparation of the red sensitive emulsion, blue sensitive emulsions
were prepared by employing as a sensitizing dye 0.10 g or 0.20 g
per mole of the silver halide of compound (4) or (14) of this
invention or dye (A) or (B) below. As a yellow coupler,
4-dodecylbenzoyl-2'-methoxyacetoanilide (yellow coupler) in an
amount of 70 g per mole of the silver halide is used. Similarly, a
blue sensitive emulsion without sensitizing dye was also
prepared.
Comparative dye A (disclosed in the specification of Belgian Pat.
No. 738,921): ##SPC4##
Comparative dye B (disclosed in the specification of U.S. Pat. No.
3,480,434): ##SPC5##
With use of the so prepared red, green, and 9 blue sensitive
emulsions, layer structures were formed on cellulose triacetate
film bases having an antihalation layer, in the same manner as in
Example 1, thereby obtain 9 silver halide color reversal
photosensitive materials differing only in the blue sensitive
layer. These photosensitive materials were used as test
samples.
In the same manner as in Example 1, these samples exposed to light,
and the high-temperature, high-speed reversal color development was
carried out according to the following steps to obtain color
positive images:
Reversal Color Development Steps and Recipes (1) Film-Prehardening
(38.degree.C., 2 minutes and 30 seconds 50% Aqueous solution of
sulfuric acid 5 ml Sodium sulfate 154 g Sodium acetate 20 g 37%
Aqueous solution of formalin 27 ml Water to make 1 liter (2)
Neutralization (38.degree.C., 30 seconds) (3) First Development
(38.degree.C., 2 minutes and 30 minutes) Sodium polyphosphate 2 g
Sodium bisulfite 8 g Phenidone 0.4 g Hydroquinone 5 g Sodium
Carbonate (monohydrate) 30 g 10% Aqueous solution of potassium
thiocyanide 15 ml Potassium bromide 1.5 g 0,1 % Aqueous solution of
potassium iodide 10 ml Anhydrous sodium sulfite 40 g Water to make
1 liter (4) First Stopping (5) Water Washing (38.degree.C., 1
minute) (6) Reversal Light Explosure (7) Color Development
(38.degree.C., 3 minutes and 40 seconds) Sodium polyphosphate 5 g
Benzyl alcohol 5 g Anhydrous sodium sulfite 7 g Sodium phoshate 35
g Potassium bromide 1 g 0.1% Aqueous solution of potassium iodide
90 ml Sodium hydroxide 3 g 4-Amino-N-methyl-N-(B-methane-
sulfoamide-ethyl)-m-toluyl-B- phenyl-ethylamine hydrochloride 10 g
Water to make 1 liter (8) Second Stopping (38.degree.C., 30
seconds) (9) Water Washing (38.degree.C., 1 minute) (10) Bleaching
(38.degree.C., 1 minute and 30 seconds) Potassium ferricyanide 100
g Potassium bromide 50 g Water to make 1 liter (11) Water Washing
(38.degree.C., 20 seconds) (12) Fixation (38.degree.C., 1 minute
and 30 seconds) Sodium thiosulfate 150 g Water to make 1 liter (13)
Water Washing (38.degree.C., 1 minute) (14) Drying
With respect to each of the color positive images obtained, the
relative sensitivities of the blue sensitive layers and the blue
densities (D min) of the high light portions were determined. The
results are shown in table 2. In the Table, the "Immediate Test"
data were obtained when the freshly prepared samples were tested.
The "Test after Preservation" data were obtained when the samples
were tested after they had been maintained at high temperature
(50.degree.c) and high humidity relative humidity 80 percent for 2
days. The relative sensitivity is expressed as a relative value
based on the sensitivity (100) in the "Immediate Test" of the
sample containing no sensitizing dye in the blue sensitive
layer.
Table 2
__________________________________________________________________________
Sample dye Added and Its Amount Immediate Test Test after
Preservation (g per mole of silver Relative Relative No. halide)
Sensitivity Dmin Sensitivity Dmin
__________________________________________________________________________
Kind Amount 8 -- --100 0.06 93 0.07 9 comparative colorant (A) 0.10
115 0.07 94 0.08 10 comparative colorant (A) 0.20 110 0.08 100 0.09
11 comparative colorant (B) 0.10 120 0.08 93 0.09 12 comparative
colorant (B) 0.20 115 0.08 96 0.09 13 illustrated compound (4) 0.10
125 0.06 120 0.06 14 illustrated compound (A) 0.20 140 0.07 135
0.07 15 illustrated compound (12) 0.10 115 0.06 110 0.06 16
illustrated compound (12) 0.12 125 0.07 120 0.07
__________________________________________________________________________
With respect to each of samples subjected to the immediate test,
the values of the maximum density (D max), the minimum density (D
min) and gamma (r) of each of the sensitive layers were determined
to evaluate their photographic characteristics. The results shown
in Table 3 were obtained.
Table 3
__________________________________________________________________________
Sample Added dye and Its Photographic Characteristics of Three
Layers Amount (g per mole of Blue Sensitive Green Sensitive Red
Sensitive No. halide) Emulsion layer Emulsion Layer Emulsion Layer
Kind Amount Dmax Dmin r Dmax Dmin r Dmax Dmin r 8 -- -- 3.1 0.06
1.90 3.3 0.05 2,10 3.4 0.03 2.12 9 comparative colorant (A) 0.10
3.2 0.07 1.85 3.3 0.05 2.10 3.4 0.03 2.12 10 comparative colorant
(A) 0.20 3.1 0.08 1.91 3.3 0.05 2.10 3.4 0.03 2.12 11 comparative
colorant (B) 0.10 3.2 0.08 1.94 3.3 0.05 2.10 3.4 0.03 2.12 12
comparative colorant (B) 0.20 3.1 0.08 1.98 3.3 0.05 2.10 3.4 0.03
2.12 13 illustrated compound (4) 0.10 3.3 0.06 2.11 3.3 0.05 2.10
3,4 0.03 2.12 14 illustrated compound (4) 0.20 3.4 0.07 2.10 3.3
0.05 2.10 3.4 0.03 2.12 15 illustrated compound (12) 0.10 3.3 0.06
2.12 3.3 0.05 2.10 3.4 0.03 2.12 16 illustrated compound (12) 0.20
3.3 0.07 2.10 3.3 0.05 2.10 3.4 0.03 2.12
__________________________________________________________________________
From the results shown in Tables 2 and 3, it will readily be
understood that silver halide photosensitive materials prepared
with use of sensitizing dyes of this invention are far superior to
the silver halide photosensitive materials with no sensitizing dye
as well as those using "comparable" prior art dyes. The blue light
sensitivity is much higher and the sensitivity reduction after
storage under high temperature and high humidity conditions is very
low. Further, the Dmin value is lower and a clear image of no
residual coloration can be obtained. Moreover, even when
high-temperature, high-speed development is used a good balance is
attained among the three emulsion layers and thereby excellent
color reproducibility is obtained.
In order to test formation of spot-like fog, "immediate test"
samples (8) to (16) were subjected to the following test:
200mg of metallic zinc powder was added to 5l of water under a
agitation and the resultant mixture was filtered to remove the
larger zinc particles, thereby forming an aqueous suspension of
zinc. The sample was dipped for 30 seconds in this suspension and
dried. Without exposure to light, the treated sample was subjected
to high-temperature, high-speed reversal color development under
the same conditions as described above.
In the samples containing no sensitizing dye in the blue sensitive
layer (8) and containing the prior art "comparable" dyes in the
blue (9-12), 90 to 120 fog spots were formed per 100 cm.sup.2.
However, according to the present invention (13-16), only 20 to 40
of fog spots were formed per 100cm.sup.2. As is apparent from the
foregoing results, the dyes of this invention control the formation
of fog spots resulting from the presence of fine metallic
powder.
Example 3
According to the procedures of Example 1, various silver halide
color negative photosensitive materials were prepared as
follows:
One silver halide color negative photosensitive material containing
no sensitizing dye in the blue sensitive layer;
four silver halide color negative photosensitive materials
containing 0.10 or 0.15g per mole of silver halide of compounds (3)
or (4) of this invention in the blue sensitive layer, and;
four silver halide color positive photosensitive materials
containing comparative dyes (C) or (D) in an amount of 0.10 or
0.15g per mole of silver halide in the blue sensitive layer.
##SPC6## ##SPC7##
These samples were exposed to light under the same conditions as in
Example 1, and color negative images were obtained by color
development treatment according to the same procedures as in
Example 1 except that the treatment temperature
and treatment time were changed as indicated below.
Color Development Treatment
1. Color Development (31.degree.C., 5 minutes)
2. First Fixation (31.degree.C., 2 minutes and 30 seconds)
3. Water Washing (31.degree.C., 2 minutes and 30 seconds)
4. Bleaching (31.degree.C., 3 minutes)
5. Water Washing (31.degree.C., 2 minutes and 30 seconds)
6. Second Fixation (31.degree.C., 2 minutes and 30 seconds)
7. Water Washing (31.degree.C., 5 minutes)
8. Drying
In order to determine the stability of the foregoing samples they
were maintained at a temperature of 50.degree.C., and a relative
humidity of 80 percent for 2 days. They were then exposed to light
and subjected to the color development in the same manner as
described above to obtain the color negative image.
With respect to each of the resulting color negative images, the
blue light sensitivity of the blue sensitive layer and the residual
coloration were determined and the results are shown in Table 4. In
the Table, the "Immediate Test" data were obtained from the fresh
samples and the "Test after Preservation" data were obtained from
samples which had been stored under the high temperature and high
humidity conditions as described above. The relative sensitivity is
a relative value based on the value (100) of the sensitivity in the
"Immediate Test" of the sample containing no sensitizing dye in the
blue sensitive layer, and the residual coloration is expressed in
terms of the value of the complementary color concentration of the
non-image area.
Table 4
__________________________________________________________________________
Sample dye Added and Its Amount (g per mole Immediate Test Test
after Preservation No. of silver halide)
__________________________________________________________________________
Kind Amount Relative Residual Relative Residual Sensitivity
Sensitivity Sensitivity Coloration
__________________________________________________________________________
17 -- -- 100 0.11 93 0.13 18 comparative colorant (C) 0.10 94 0.12
88 0.14 19 comparative colorant (C) 0.15 90 0.12 86 0.14 20
comparative colorant (D) 0.10 92 0.12 89 0.14 21 comparative
colorant (D) 0.15 95 0.12 90 0.14 22 illustrated compound (3) 0.10
125 0.11 125 0.11 23 illustrated compound (3) 0.15 140 0.11 135
0.11 24 illustrated cp,.degree.pimd (14) 0.10 130 0.11 120 0.11 25
illustrated compound (14) 0.15 135 0.12 130 0.12
__________________________________________________________________________
From the results shown in Table 4, it will easily be understood
that silver halide photosensitive material prepared in accordance
with this invention is far superior to silver halide photosensitive
materials without any sensitizing dye as well as those materials
using prior art "comparable" dyes. When the high-temperature
development treatment is applied, a higher blue light sensitivity
is attained, and, even after storage under high temperature and
high humidity conditions, the reduction in sensitivity is extremely
slight and a sufficient sensitivity is retained. Moreover, the
degree of the residual coloration is low, resulting in a very clear
image.
The spectrophotography was conducted on the same samples as
described above to examine the spectral sensitivity curves of blue
sensitive emulsion layers. The results are shown in FIGS. 1 and
2.
In FIG. 1, broken line (1) is the spectral sensitivity curve of the
blue sensitive emulsion layer of sample (23) having compound (3) of
this invention therein in an amount of 0.15g per mole of silver
halide. Solid line (2) is the spectral sensitivity curve of the
blue sensitive emulsion layer of sample (17) containing no
sensitizing dye.
In FIG. 2, broken line (3) is the spectral sensitivity curve of
sample (25) having compound (14) of this invention therein in an
amount of 0.15g per mole of the silver halide. Solid line (4) is
the spectral sensitivity curve of the blue sensitive layer of
sample (19) having comparative dye (C) therein in an amount of
0.15g per mole of silver halide. As is apparent from these Figures,
the blue sensitive emulsion layer having the compounds of this
invention therein has a desirable spectral sensitivity distribution
with low residual coloration.
* * * * *