U.S. patent number 3,738,837 [Application Number 05/256,011] was granted by the patent office on 1973-06-12 for light-sensitive color photographic material.
This patent grant is currently assigned to Konishiroku Photo Industry Co., Ltd.. Invention is credited to Hidehiko Ishikawa, Yoshimi Kuwabara, Shunji Matsuo, Mikio Sato.
United States Patent |
3,738,837 |
Kuwabara , et al. |
June 12, 1973 |
LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL
Abstract
A light-sensitive silver halide color photographic material
comprising one or more layers. At least one layer constituting the
photographic material contains a dispersion in a difficulty
water-soluble high boiling organic solvent, either singly or in
admixture with a low boiling organic solvent, of two or more
compounds represented by the general formula ##SPC1## Wherein
R.sub.1, R.sub.2 and R.sub.3 are individually a hydrogen or halogen
atom or a cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfone
group having one to six carbon atoms and at least one of the groups
R.sub.1, R.sub.2 and R.sub.3 is not hydrogen; R.sub.4 and R.sub.5
are individually a hydrogen or halogen atom or an alkyl,
cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfone group having
one to six carbon atoms; and the sum of the carbon atoms of
R.sub.1, R.sub.2 and R.sub.3 is 8 or less, provided that in case
the sum of the carbon atoms of R.sub.1 R.sub.2 and R.sub.3 is 8,
each of R.sub.1, R.sub.2 and R.sub.3 has less than four carbon
atoms.
Inventors: |
Kuwabara; Yoshimi (Koganei-shi,
Tokyo, JA), Matsuo; Shunji (Nishitama-gun, Tokyo,
JA), Ishikawa; Hidehiko (Odawara-shi, Kanagawa-ken,
JA), Sato; Mikio (Odawara-shi, Kanagawa-ken,
JA) |
Assignee: |
Konishiroku Photo Industry Co.,
Ltd. (Tokyo, JA)
|
Family
ID: |
25758292 |
Appl.
No.: |
05/256,011 |
Filed: |
May 23, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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889298 |
Dec 30, 1969 |
|
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|
Current U.S.
Class: |
430/517; 548/259;
252/589 |
Current CPC
Class: |
C07D
249/20 (20130101); G03C 1/815 (20130101); G03C
1/8155 (20130101) |
Current International
Class: |
C07D
249/00 (20060101); C07D 249/20 (20060101); G03C
1/815 (20060101); G03c 001/84 () |
Field of
Search: |
;96/84UV ;252/300 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Smith; Ronald H.
Parent Case Text
CROSS RELATED APPLICATION
This application is a continuation of application Ser. No. 889,298
filed Dec. 30, 1969 and now abandoned.
Claims
What we claim is:
1. A light-sensitive silver halide color photographic material
comprising one or more layers wherein at least one layer
constituting the photographic material contains a dispersion in a
difficultly water-soluble high boiling organic solvent, either
singly or in admixture with a low boiling organic solvent, of 2 or
more compounds represented by the general formula ##SPC3##
wherein R.sub.1, R.sub.2 and R.sub.3 are individually a hydrogen or
halogen atom or a cycloalkyl, alkoxy, aryl, carbalkoxy or
alkylsulfone group having one to six carbon atoms and at least one
of the groups R.sub.1, R.sub.2 and R.sub.3 is not hydrogen; R.sub.4
and R.sub.5 are individually a hydrogen or halogen atom or an
alkyl, cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfone group
having one to six carbon atoms; and the sum of the carbon atoms of
R.sub.1, R.sub.2 and R.sub.3 is 8 or less, provided that in case
the sum of the carbon atoms of R.sub.1, R.sub.2 and R.sub.3 is 8,
each of R.sub.1, R.sub.2 and R.sub.3 has less than four carbon
atoms.
2. A photographic material as in claim 1 whereein R.sub.1 is
methoxy, ethoxy, n-butoxy, t-butoxy, phenyl, cyclohexyl or chloro,
R.sub.2, R.sub.3 and R.sub.5 are hydrogen or chloro and R.sub.4 is
hydrogen, methyl, ethyl sulfonyl, chloro, methoxy, or carbo-t
-butoxy.
3. A photographic material as claimed in claim 1 wherein said
material comprises equal amounts of
2(2'-hydroxy-5-cyclohexoxyphenyl) benzotriazole and 2(2'-hydroxy-5'
tert-butoxyphenyl) benzotriazole.
4. A photographic material as claimed in claim 1 wherein said
material comprises equal amounts of 2-(2'-hydroxy-3',5' -
dichlorophenyl)-5-methoxy-benzotriazole and
2-(2'-hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole.
5. A photographic material as claimed in claim 1 wherein said
material comprises equal amounts of 2-(2'-hydroxy-5' -
cyclohexoxyphenyl)-benzotriazole, 2(2'-hydroxy-5'
tert-butoxyphenyl) benzotriazole,
2-(2'hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole and
2-(2'-hydroxy-5'-cyclohexoxyphenyl)-benzotriazole.
Description
The present invention relates to light-sensitive color photographic
materials containing ultraviolet ray absorbers. More particularly,
the invention pertains to light-sensitive color photographic
materials having incorporated in at least one of the layers
constituting the photographic materials a solvent dispersion
containing two or more compounds represented by the general formula
##SPC2##
Wherein R.sub.1, R.sub.2 and R.sub.3 are individually a hydrogen or
halogen atom or cycloalkyl, alkoxy, aryl, carbalkoxy or
alkylsulfone group having one to six carbon atoms, and at least one
of said R.sub.1, R.sub.2 and R.sub.3 is not hydrogen; R.sub.4 and
R.sub.5 are individually a hydrogen or halogen atom or an alkyl,
cycloakyl, alkoxy, aryl, carbalkoxy or alkylsulfone group having
one to six carbon atoms; and the sum of the carbon atoms of
R.sub.1, R.sub.2 and R.sub.3 is 8 or less, provided that in case
the sum of the carbon atoms of R.sub.1, R.sub.2 and R.sub.3 is 8,
each of R.sub.1, R.sub.2 and R.sub.3 has less than four carbon
atoms.
It is well known that ultraviolet rays have detrimental effects on
photographic images. Particularly in the case of a light-sensitive
color photographic material which forms, by color development, a
dye image on its light-sensitive emulsion layer, the said dye image
is unstable to ultraviolet rays and hence is liable to be decolored
or discolored when subjected to the action of ultraviolet rays.
Further, there is the fear that after formation of said dye image,
a coupler remaining in the light-sensitive emulsion layer of the
color photographic material brings about, due to the action of
ultraviolet rays, a cause for contamination of the dye image.
In order to protect photographic images from such action of
ultraviolet rays, various processes have been proposed heretofore.
Among these, the most common porcess is such that a ultraviolet ray
absorber is incorporated into a layer constituting a
light-sensitive photographic material, e.g. silver halide emulsion
layer, protective layer, inter layer or the like. However,
light-sensitive photographic materials according to the prior art
processes are not satisfactory in protection of photographic images
from ultraviolet rays, and have such drawbacks that they are
inferior in photographic properties or become unstable in
properties when stored for a long period of time.
In view of such circumstances as mentioned above, the present
inventors made various studies for years to find that a
light-sensitive color photographic material, which is obtained by
incorporating an organic solvent dispersion containing two or more
compounds represented by the aforesaid general formula into at
least one of the layers constituting the light-sensitive
phogographic material, is markedly excellent in protection of the
photographic image from ultraviolet rays and is storage stable for
a long period of time without being deteriorated in photographic
properties.
The compounds represented by the aforesaid general formula are
excellent ultraviolet ray-absorbing agents when effectively absorb
ultraviolet rays without absorbing visible rays, are substantially
colorless, and are so stable to ultraviolet rays that they are not
injured in photographic properties or contaminated even when
irradiated with ultraviolet rays. However, such excellent
characteristics are not exhibited if said compounds are
incorporated into layers constituting a light-sensitive
photographic material by the Fischer's method (a method carried out
by introducing a soluble group such as carboxyl or sulfone group
into a ultraviolet ray-absorbing agent, which has been made
non-diffusible, to form a water-soluble alkali metal salt thereof
and then incorporating said alkali metal salt in a hydrophilic
colloid layer). Further, if only one compound represented by the
aforesaid general formula is applied to a light-sensitive
photographic material by adoption of the solvent dispersion method
(a method carried out in such a manner that a non-diffusible
ultraviolet ray-absorbing agent having an oleophilic group is
dissolved in an organic solvent and is immediately dispersed in an
aqueous gelatine solution), crystals of said compound deposit to
greatly injure the photographic properties of the material, because
the compounds of the aforesaid general formula are extremely low in
solubility in organic solvents. If, in the above case, the amount
of the solvent is so increased as not to deposit the crystals of
the compound, a large amount of the organic solvent is necessarily
incorporated into the layers constituting the photographic
material, whereby the penetration of other treating liquids into
said layers is inhibited or physical properties of said layers are
undesirably deteriorated.
In contrast thereto, when two or more of the compounds represented
by the aforesaid general formula are subjected, according to the
present invention, to the solvent dispersion method, the compounds
show markedly excellent solubility for the organic solvent employed
in said method, as is clear from the test Example set forth later.
This has not been anticipatable heretofore.
Typical examples of the compounds represented by the aforesaid
general formula, which are used in the present invention, are set
forth below together with the absorption maximum wave lengths
thereof in methanol (.lambda..sub.max.sup.MeOH), but it is needless
to say that compounds usable in the present invention are not
limited thereto.
1. 2-(2'-Hydroxyphenyl-5'-t-butoxyphenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 335 m.mu.
2. 2-(2'-Hydroxy-5'-ethoxyphenyl)-benzotriazole
.lambda..sub.max.sup. MeOH 338 m.mu.
3. 2-(2'-Hydroxy-5'-methoxyphenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 350 m.mu.
4. 2-(2'-Hydroxy-5'-cyclohexoxyphenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 340 m.mu.
5. 2-(2'-Hydroxy-5'-phenylphenyl)-methoxybenzotriazole
.lambda..sub.max.sup.MeOH 340 m.mu.
6. 2-(2'-Hydroxy-5'-cyclohexylphenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 338 m.mu.
7. 2-(2'-Hydroxy-5'-phenylphenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 340 m.mu.
8. 2-(2'-Hydroxy-5' -methoxyphenyl)-5,6-dimethylbenzotriazole
.lambda..sub.max.sup.MeOH 342 m.mu.
9. 2-(2'-Hydroxy-5'-methoxyphenyl)-5-methylbenzotriazole
.lambda..sub.max.sup.MeOH 350 m.mu.
10. 2-(2'-Hydroxy-5'-phenylphenyl)-5-butoxybenzotriazole
.lambda..sub.max.sup.MeOH 345 m.mu.
11.
2-(2'-Hydroxy-5'-methyoxyphenyl)-benzotriazole-5-ethylsulfone
.lambda..sub. max.sup.MeOH 350 m.mu.
12.
t-Butyl-2-(2'-hydroxy-5'-methoxyphenyl)-benzotriazole-5-carboxylate
.lambda..sub.max.sup.MeOH 340 m.mu.
13. 2-(2'-Hydroxy-5'-chlorophenyl)-5-chlorobenzotriazole
.lambda..sub.max.sup.MeOH 335 m.mu.
14. 2-(2'-Hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole
.lambda..sub.max.sup.MeOH 342 m.mu.
15. 2-(2'-Hydroxy-5'-cyclohexylphenyl)-5-chlorobenzotriazole
.lambda..sub.max.sup.MeOH 342 m.mu.
16. 2-(2'-Hydroxy-4', 5'-dichlorophenyl)-benzotriazole
.lambda..sub.max.sup.MeOH 334 m.mu.
17. t-Butyl
2-(2'-hydroxy-5'-ethoxyphenyl)-benzotriazole-5-carboxylate
.lambda..sub.max.sup.MeOH 342 m.mu.
18. 2-(2'-Hydroxy-3',5'-dichlorophenyl)-5-methoxybenzotriazole
.lambda..sub.max.sup.MeOH 350 m.mu.
19. 2-(2'-Hydroxy-4',5'-dichlorophenyl)-5-methylbenzotriazole
.lambda..sub.max.sup.MeOH 348 m.mu.
20.
t-Butyl-2-(2'-hydroxy-4'-methoxyphenyl)-benzotriazole-5-carboxylate
.lambda..sub.max.sup.MeOH 347 m.mu.
21. 2-(2'-Hydroxy-4'-butoxyphenyl)-benzotriazole-5-ethylsulfone
.lambda..sub.max.sup.MeOH 351 m.mu.
The following test example shows the fact that when two or more of
the above-mentioned compounds are used in combination, they
interact each other to exhibit markedly excellent solubility in
organic solvents.
TEST EXAMPLE
Two or more of the compounds represented by the aforesaid general
formula were mixed with each other in the proportions as shown in
Table 1, and the mixture was dissolved at 65.degree.C. in a mixed
solvent comprising 1 ml. of tri-o-cresyl phosphate and 2 ml. of
ethyl acetate and was dispersed in 10 ml. of a 5 percent gelatine
solution containing 0.1 g. of saponin. Thereafter, the dispersion
was added to 100 ml. of a silver chlorobromide emulsion, was coated
onto a photographic baryta paper, and was then dried to prepare a
sample. Each sample prepared in the above manner was
microscopically observed in dispersed state of the ultraviolet
ray-absorbing agent to obtain the results as set forth in the right
hand column of Table 1.
The amounts of the tri-O-cresyl phosphate necessary for individual
disperson of the exemplified compounds (2), (9), (18) and (19) were
7 ml., 6.5 ml., 5 ml. and 4 ml., respectively. Further, the amount
of ethyl acetate employed in the above case was 2 ml., and no
influence on dispersibility was observed even when said amount was
varied.
TABLE 1
Exemplified compound Depo- Run No. (2) (9) (18) (19) sition 1 1.0
Great 2 1.0 g Great 3 1.0 g 4 1.0 g Great 5 0.5 0.5 None 6 0.5 0.5
None 7 0.5 0.5 None 8 0.5 0.5 None 9 0.5 0.5 None 10 0.5 0.5 None
11 0.33 0.33 0.33 None 12 0.33 0.33 0.33 None 13 0.33 0.33 0.33
None 14 0.33 0.33 0.33 None 15 0.25 0.25 0.25 0.25 None
From the above test example, it is clear that when used in
combination of two or more in accordance with the present
invention, the compounds represented by the aforesaid general
formula, which have substituents less in molecular weight in view
of the fundamental structure for ultraviolet ray-absorbing
characteristics, are greatly increased in solubility in organic
solvents employed in the solvent dispersion method to make it
possible to attain successfully far higher ultraviolet
ray-absorbing efficiencies than those of the conventional
ultraviolet ray-absorbing agents. Accordingly, the light-sensitive
color photograhpic materials in accordance with the present
invention have such advantages that the dye images obtained are
greatly inhibited from decoloration, discoloration or contamination
due to irradiation of ultraviolet rays, and are not colored or
contaminated by the ultraviolet ray-absorbing agents themselves.
Further, they are free from the fear that the photographic
properties thereof would be injured, because of the decrease in
amount of organic solvents dispersed in layers of the photographic
materials, and stably maintain excellent photographic
properties.
When specifically used in combination, the ultraviolet
ray-absorbing agents employed in the present invention become
soluble in a markedly small amount of organic solvent, as mentioned
above. Accordingly, the incorporation of said agents into layers of
light-sensitive photographic materials may be effected according to
the conventional solvent dispersion method, whereby they can be
dispersed uniformly and stably in a finely-divided non-crystalline
form into any one of the layers constituting light-sensitive
photographic materials. For example, there may be adopted such
procedures that a mixture of two or more members selected from the
above-mentioned ultraviolet ray-absorbing agents is dissolved in an
organic solvent employed in the solvent dispersion method and is
then dispersed in an aqueous gelatine solution by use of a suitable
mixing means, and the resulting dispersion, when desired to be
added to a silver halide emulsion, is added thereto after
completion of the second ripening, and when desired to be
incorporated into an auxiliary layer, e.g. a protective layer or an
inter layer, is added to a coating liquid which is the component of
said layer. As the coating liquids which are the components of the
silver halide emulsion layer and auxiliary layers constituting
light-sensitive photographic materials, there may be used those
which have been employed heretofore, and the ultraviolet
ray-absorbing agents used in the present invention do not show any
detrimental interactions with with various photographic additives
present in said coating liquids. Further, the organic solvent
solutions of the above-mentioned ultraviolet ray-absorbing agents
may be incorporated with couplers, contamination-preventing agents,
fluorescent whitening agents, etc. Ordinarily; the total amount of
the ultraviolet-ray-absorbing agents is preferably 1-10 mg per 100
cm.sup.2 of the area to be coated. In the above case, the mixing
proportions of the ultraviolet ray-absorbing agents used in
combination are equal proportions. However, the mixing proportions
are, of course, not limited thereto and are variable according to
the object of application.
The amount of organic solvent necessary for dispersing 1 g. of a
mixture of the ultraviolet ray-absorbing agents is adequately about
0.5 ml. to 3 ml., though the amount varies depending on the
combination and mixing proportions of the ultraviolet ray-absorbing
agents employed and on the kind of the organic solvent. The organic
solvent employed in the above case may be any of those which have
heretofore been used in the solvent dispersion method. For example,
there is used a difficulty water-miscible high boiling solvent
having a boiling point of more than 150.degree.C. such as
di-n-butyl phthalate, triphenyl phosphate, tri-o-cresyl phosphate
or the like, either singly or in combination with a low boiling
solvent such as methyl acetate, ethyl acetate, propyl acetate,
n-butyl acetate, ethyl propionate, carbon tetrachloride,
chloroform, methanol, ethanol, dimethylformamide, dioxane, methyl
cellosolve acetate or the like.
The light-sensitive color photographic materials of the present
invention, which are produced in the above-mentioned manner, have
such advantages that the ultraviolet ray-absorbing agents contained
therein do not crystallize and deposit during the production and
storage of the photographic materials and photographic properties
can be stably maintained even when they are irradiated with
ultraviolet rays.
The present invention is illustated in detail below with reference
to examples.
EXAMPLE 1
Onto a photographic baryta paper was applied a red color-sensitive
silver chlorobromide gelatine emulsion containing a cyan coupler.
Thereafter, a gelatine protective layer containing one or more of
the exemplified compounds (2), (9), (18) and (19) in such
proportions as set forth in Table 2 was applied so that the amount
of the ultraviolet ray-absorbing agent became 2.8 mg/100 cm.sup.2,
followed by drying. In the above manner, there were prepared
samples 1-9 of which sample 1 was a so-called blank sample
containing no ultraviolet ray-absorbing agent.
In the application of the above-mentioned gelatine protective
layer, there was used a liquid formed by dissolving at 65.degree.C.
3 parts of the ultraviolet ray-absorbing agent(s) in a mixed
solvent comprising 6 parts of ethyl acetate and 3 parts of
tri-o-cresyl phosphate, adding the resulting solution to 60 parts
of a 10 percent aqueous gelatine solution containing saponin,
dispersing the mixed solution by means of a colloid mill and then
adding 40 parts of water to the resulting dispersion.
The above-mentioned samples were exposed to light, were subjected
to color development, stopping, film hardening-fixing,
bleaching-fixing and water-washing treatments, and were then dried.
The red color densities of cyan images of these samples and the
contamination densities (measured on the basis of blue color
densities) of non-image portions thereof were measured before and
after exposure to direct sunlight for 50 hours to calculate the red
color density lowering ratios and contamination densities of the
samples. The results were as set forth in Table 3.
TABLE 2
Exemplified compound Sample Total No. (2) (9) (18) (19) amount 1 0
g 2 3 3 3 3 3 4 3 3 5 3 3 6 1.5 1.5 3 7 1.5 1.5 3 8 1 1 1 3 9 1 1 1
3
TABLE 3
Red color density Sample lowering ratio Contamination density No.
(%) Before test After test 1 60 0.04 0.18 2 58 0.04 0.18 3 55 0.04
0.17 4 57 0.04 0.16 5 51 0.04 0.15 6 13 0.04 0.06 7 10 0.04 0.05 8
11 0.04 0.04 9 10 0.04 0.05
From Table 3, it is understood that in the case of samples 2-5
prepared by independent use of the exemplified compounds (2), (9),
(18) and (19), the ultraviolet ray-absorbing agents had
crystallized and deposited, and hence were lowered in ultraviolet
ray-absorbing ability to inhibit only slightly the discoloration of
color images and the generation of contamination. On the other
hand, in the case of the samples 6-9 in accordance with the present
invention, the discoloration of cyan dyes and increase of
contamination were greatly inhibited.
EXAMPLE 2
Onto a photographic baryta paper was applied a samples
color-sensitive silver chlorobromide gelatine emulsion layer
containing a magenta coupler, which layer had been incorporated
according to the same procedure as in Example 1 with a liquid
containing one or more of the exemplified compounds (1), (8), (11)
and (20) in such proportions as set forth in Table 4, so that the
amount of the ultraviolet ray-absorbing agent(s) became 8.2 mg/100
cm.sup.2, followed by drying. In the above manner, there were
prepared samples 1-8, of which sample 1 was a blank sample.
The green color densities of image portions of these samples and
the contamination densities (measured on the basis of blue color
densities) of white grounds thereof were measured before and after
exposure to Fade-Ometer to calculate green color density lowering
ratios and contamination densities of the samples. The results were
as set forth in Table 5.
TABLE 4
Exemplified compound 1 Total No. (1) (8) (11) (20) amount 1 0 g 2 1
1 3 1 1 4 1 1 5 1 1 6 0.25 0.25 0.25 0.25 1 7 0.33 0.33 0.33 1 8
0.5 0.5 1
TABLE 5
Green color density Sample lowering ration Contamination density
No. (%) Before test After test 1 19 0.04 0.11 2 17 0.04 0.10 3 17
0.04 0.11 4 15 0.04 0.09 5 16 0.04 0.10 6 4 0.04 0.05 7 4 0.04 0.05
8 5 0.04 0.06
From Table 5, it is understood that in the case of the samples 6-8
in accordance with the present invention, the discoloration of
magenta dye and the increase of contamination were greatly
inhibited.
EXAMPLE 3
Onto a photographic baryta paper were applied a red color-sensitive
silver chlorobromide emulsion layer containing a cyan coupler, and
a green color-sensitive silver chlorobromide emulsion layer
containing a magenta coupler. Further, a gelatine inter layer
containing one or more of the exemplified compounds (2), (7), (15)
and (21) in such proportions as shown in Table 6 was applied
thereon so that the amount of the ultraviolet ray-absorbing
agent(s) became 0.4 mg/100 cm.sup.2. In addition, a blue
color-sensitive silver chlorobromide emulsion layer containing a
yellow coupler, which layer had been incorporated with one or more
of the exemplified compounds (2), (7), (15) and (21) in the
proportions as shown in Table 6, was applied so that the amount of
the ultraviolet ray-absorbing agent(s) became 1.0 mg/100 cm.sup.2,
and then a gelatine protective layer was applied, followed by
drying. In the above manner, there were prepared samples 1-9, of
which sample 1 was a blank sample.
The gelatine layer and the blue color-sensitive silver
chlorobromide emulsion layer containing the exemplified compounds
(2), (7), (15) and (21) in such proportions as shown in Table 6
were prepared individually by dissolving at 65.degree.C. 4 parts of
one or more of the ultraviolet ray-absorbing agents in a mixed
solvent comprising 3 parts of triphenyl phosphate and 10 parts of
butyl acetate, adding the resulting solution to 100 parts of a 10
percent solution containing saponin, dispersing the mixed solution
by means of an ultrasonic emulsifier, and then adding the
dispersion to 40 parts of water or to 200 parts of a blue
color-sensitive silver chlorobromide emulsion.
The above-mentioned samples 1-9 were exposed, were subjected to
color development, stopping, film hardening, fixing, bleaching
fixing and water-washing treatments, and were then dried. The blue,
green and red color densities of image portions of these samples
and the contamination densities (measured on the basis of blue
color densities) of white grounds thereof were measured before and
after exposure to direct sunlight for 6 hours to calculate
individual color density lowering ratios and contamination
densities. The results were as set forth in Table 7.
TABLE 6
Exemplified compound Sample Total No. (2) (7) (15) (21) amount 1 0
g 2 4 4 3 4 4 4 4 4 5 4 4 6 2 2 4 7 2 2 4 8 2 2 4 9 1 1 1 1 4
TABLE 7
Density lowering ratio (%) Sample Blue Green Red Contamination
density No. color color color Before After test test 1 41 50 63
0.09 0.23 2 40 50 60 0.09 0.23 3 38 49 60 0.09 0.23 4 38 47 58 0.09
0.21 5 35 47 56 0.09 0.19 6 3 5 8 0.09 0.10 7 3 6 7 0.09 0.10 8 2 4
5 0.09 0.11 9 1 4 8 0.09 0.09
As is clear from Table 7, the samples 6-9 in accordance with the
present invention are markedly less in discoloration of individual
color densities and in increase of contamination.
* * * * *