U.S. patent number 3,640,716 [Application Number 04/826,283] was granted by the patent office on 1972-02-08 for method of preventing color mixing in multilayer-type reversal color photographic light-sensitive materials.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Jun Hayashi, Tadashi Nagae, Yasushi Oishi.
United States Patent |
3,640,716 |
Nagae , et al. |
February 8, 1972 |
METHOD OF PREVENTING COLOR MIXING IN MULTILAYER-TYPE REVERSAL COLOR
PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS
Abstract
The invention is directed to a method for preventing color
mixing in multilayer-type color photographic light-sensitive
materials developed by the coupler-in-developer process. The
multilayer light-sensitive materials used herein comprise a film
base coated with a red-sensitive emulsion layer, a green-sensitive
emulsion layer, and a blue-sensitive emulsion layer respectively.
Cyan and magenta dye formation is prevented in the blue emulsion
layer by addition thereto of a ballasted yellow coupler having the
general formula wherein R.sub.1 represents a tertiary alkyl group,
an unsubstituted cycloalkyl group, a substituted cycloalkyl group,
an unsubstituted dicycloalkyl group, a substituted dicycloalkyl
group, an unsubstituted aryl group or a substituted aryl group;
R.sub.2 represents an unsubstituted aryl group, a substituted aryl
group, an unsubstituted heterocyclic group, or a substituted
heterocyclic group; and X represents a hydrogen atom or a group
capable of being split off during the coupling reaction.
Inventors: |
Nagae; Tadashi (Kanagawa,
JA), Oishi; Yasushi (Kanagawa, JA),
Hayashi; Jun (Kanagawa, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Kanagawa, JA)
|
Family
ID: |
12398643 |
Appl.
No.: |
04/826,283 |
Filed: |
May 20, 1969 |
Foreign Application Priority Data
|
|
|
|
|
May 20, 1968 [JA] |
|
|
43/33874 |
|
Current U.S.
Class: |
430/372; 430/503;
430/551 |
Current CPC
Class: |
G03C
7/362 (20130101) |
Current International
Class: |
G03C
7/36 (20060101); G03c 007/00 () |
Field of
Search: |
;96/56,74,99 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3180734 |
April 1965 |
Willems et al. |
3265506 |
August 1966 |
Weissberger et al. |
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Goodrow; John L.
Claims
What is claimed is:
1. A process for the prevention of color mixing for a
multilayer-type reversal photographic light-sensitive material of
the type developed in color-forming developers, each containing a
coupler, which comprises developing said multilayer-type reversal
photographic light-sensitive material having on a support,
a. a red-sensitive emulsion layer,
b. a green-sensitive emulsion layer, and
c. a blue-sensitive emulsion layer,
said developing being carried out with color developers containing
a diffusable cyan, yellow and magenta couplers, respectively, said
blue emulsion layer containing a ballasted yellow coupler of the
formula
wherein R.sub.1 represents a member selected from the group
consisting of a tertiary alkyl group, an unsubstituted cycloalkyl
group, a substituted cycloalkyl group, an unsubstituted
dicycloalkyl group, a substituted dicycloalkyl group, an
unsubstituted aryl group and a substituted aryl group; R.sub.2
represents a member selected from the group consisting of an
unsubstituted aryl group, a substituted aryl group, an
unsubstituted heterocyclic group, and a substituted heterocyclic
group; and X represents a member selected from the group consisting
of a hydrogen atom and a group capable of being split off during
the coupling reaction.
2. A multilayer-type reversal color photographic material of the
type to be developed in color developers containing couplers, which
comprises a support having thereon,
a. a red-sensitive emulsion layer,
b. a green-sensitive emulsion layer, and
c. a blue-sensitive emulsion layer,
said blue-sensitive emulsion layer containing a ballasted yellow
coupler of the formula
wherein R.sub.1 represents a member selected from the group
consisting of a tertiary alkyl group, an unsubstituted cycloalkyl
group, a substituted cycloalkyl group, an unsubstituted
dicycloalkyl group, a substituted dicycloalkyl group, an
unsubstituted aryl group and a substituted aryl group; R.sub.2
represents a member selected from the group consisting of an
unsubstituted aryl group, a substituted aryl group, an
unsubstituted heterocyclic group, and a substituted heterocyclic
group; and X represents a member selected from the group consisting
of a hydrogen atom and a group capable of being split off during
the coupling reaction.
3. The color mixing preventing process as claimed in claim 1
wherein the proportion of the ballasted yellow coupler is
0.0005-0.5 mole per mole of said blue-sensitive silver halide
emulsion.
4. The color mixing preventing process as claimed in claim 1
wherein said blue-sensitive silver halide emulsion containing the
ballasted yellow coupler is a gelatino silver iodobromide
emulsion.
5. The multilayer-type reversal color photographic material of
claim 2, wherein the amount of said ballasted yellow coupler is
present in an amount of from 0.0005 to 0.5 mols per mol of said
blue-sensitive silver halide emulsion.
6. The multilayer-type reversal color photographic material of
claim 2, wherein said ballasted yellow coupler is a member selected
from the group consisting of ##SPC7## ##SPC8## ##SPC9##
##SPC10##
7. The process for the prevention of color mixing of claim 1,
wherein said color forming developing agent is a p-phenylenediamine
derivative.
8. The process for the prevention of color mixing of claim 7,
wherein said derivative is a member selected from the group
consisting of 4-amino-N,N-diethylaniline,
4-amino-3-methyl-N-methyl-N-(.beta.-methyl-sulfonamidoethyl)-aniline,
and 4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxy-ethyl)-aniline.
9. The process for the prevention of color mixing of claim 1,
wherein said diffusible cyan coupler is a phenolic coupler.
10. The process for the prevention of color mixing of claim 9,
wherein said coupler is a member selected from the group consisting
of 2-chloro-1-naphthol, 2,4-dichloro-1-naphthol,
1-hydroxy-N-butyl-2-naphthamide and
1-hydroxy-N-(2-acetamidophenethyl)-2-naphthamide.
11. The process for the prevention of color mixing of claim 1,
wherein said diffusable magenta coupler is a member selected from
the group consisting of open-chain methylene couplers and cyclic
methylene couplers.
12. The process for the prevention of color mixing of claim 11,
wherein said open-chain methylene coupler is a member selected from
the group consisting of acylacetonitriles, 2- cyanoethylbenzofuran,
and benzylacetonitrile and said cyclic methylene coupler being a
member selected from the group consisting of
1-phenyl-3-methyl-5-pyrazolone,
1-phenyl-3-(4-chlorobenzamido)-5-pyrazolone,
1-phenyl-3-(3-nitrobenzoyl-amino)-5-pyrazolone, and
1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone.
13. The process for the prevention of color mixing of claim 1,
wherein said yellow coupler is an acylacetamide type open-chain
methylene coupler.
14. The process for the prevention of color mixing of claim 13,
wherein said coupler is a member selected from the group consisting
of 2-acetanilide, 2-aceto-2',4'-dichloroacetanilide,
2-benzoylacetanilide, 2-benzoyl-2'-methoxyacetanilide, and
2-benzoyl(4'-p-toluene-sulfonamido) acetanilide.
15. A process for the prevention of color mixing for a
multilayer-type reversal photographic light-sensitive material of
the type developed in color forming developers, each containing a
coupler, which comprises developing said multilayer-type reversal
photographic light-sensitive material having on a support,
a. a red-sensitive emulsion layer,
b. a green-sensitive emulsion layer, and
c. a blue-sensitive emulsion layer,
said developing being carried out with color developers containing
a diffusable cyan, yellow and magenta couplers, respectively, said
blue emulsion layer containing a ballasted yellow coupler of the
formula
wherein R.sub.1 represents a member selected from the group
consisting of a tertiary alkyl group, an unsubstituted cycloalkyl
group, a substituted cycloalkyl group, an unsubstituted
dicycloalkyl group, a substituted dicycloalkyl group, an
unsubstituted aryl group and a substituted aryl group; R.sub.2
represents a member selected from the group consisting of an
unsubstituted aryl group, a substituted aryl group, an
unsubstituted heterocyclic group, and a substituted heterocyclic
group; and X represents a member selected from the group consisting
of a hydrogen atom and a group capable of being split off during
the coupling reaction, said ballasted yellow coupler being present
in an amount of from 0.0005 to 0.5 mols per mol of said
blue-sensitive silver halide emulsion.
16. A multilayer-type reversal color photographic material of the
type to be developed in color developers containing couplers, which
comprises a support having thereon,
a. a red-sensitive emulsion layer,
b. a green-sensitive emulsion layer, and
c. a blue-sensitive emulsion layer,
said blue-sensitive emulsion layer containing a ballasted yellow
coupler of the formula
wherein R.sub.1 represents a member selected from the group
consisting of a tertiary alkyl group, an unsubstituted cycloalkyl
group, a substituted cycloalkyl group, an unsubstituted
dicycloalkyl group, a substituted dicycloalkyl group, an
unsubstituted aryl group and a substituted aryl group; R.sub.2
represents a member selected from the group consisting of an
unsubstituted aryl group, a substituted aryl group, an
unsubstituted heterocyclic group, and a substituted heterocyclic
group; and X represents a member selected from the group consisting
of a hydrogen atom and a group capable of being split off during
the coupling reaction, said ballasted yellow coupler being present
in an amount of from 0.0005 to 0.5 mols per mol of blue-sensitive
silver halide emulsion.
17. The multilayer-type reversal color photographic material of
claim 2, wherein said blue-sensitive silver halide emulsion
containing a ballasted yellow coupler is a gelatino silver
iodobromide emulsion.
Description
The present invention relates to a method of preventing color
mixing in a multilayer-type color photographic light-sensitive
material.
As a multilayer-type color photographic light-sensitive material
having on a support a red-sensitive emulsion layer, a
green-sensitive emulsion layer, and a blue-sensitive emulsion
layer, there are a type in which the photographic emulsion layers
contain couplers capable of forming dyes by the reaction with the
oxidation product of a silver halide and an aromatic amino
developing agent and a type in which the photographic emulsion
layers do not contain such couplers therein.
Since the latter-type color photographic light-sensitive material
is, after exposure, processed in color-forming developers
containing the coupler, the latter type of light-sensitive material
is superior in image sharpness to the former type in which the
photographic emulsion layers contain the couplers. However, in
development, there is formed in the emulsion layer, besides a
desired dye, other undesirable dyes, which cause color mixing and
degrades the color reproduction of the color photographic
light-sensitive material thus developed. For example, when, after
light exposure, a reversal color photographic light-sensitive
material of the latter type having on a support a red-sensitive
emulsion layer, a green-sensitive emulsion layer, and a
blue-sensitive emulsion layer in this order is subjected to a black
and white development, a cyan color-forming development, a yellow
color-forming development and a magenta color-forming development
(hereinafter, these procedures are called
"coupler-in-developer-type reversal color process"), there is
formed in the blue-sensitive emulsion layer, besides a yellow dye,
a cyan dye or magenta dye, whereby the yellow image has a slight
tinge of green or orange and hence a yellow color having a high
color purity cannot be obtained.
There are various causes for the color mixing but the most
important cause is a development fog, i.e., when an emulsion layer
is subjected to a color-forming development, a silver halide grain
in the unexposed portions of another emulsion layer is developed to
produce an undesirable dye. Still another cause for the color
mixing is that exposed silver halide grains having a latent image
are not activated in a color-forming developer containing a coupler
capable of giving a dye image, that is, left undeveloped and
finally developed in a subsequent color-forming developer
containing a coupler capable of giving another dye. For example,
when the aforesaid reversal color photographic light-sensitive
material is developed in the aforesaid order, the blue-sensitive
layer to be developed in a yellow color-forming developer is
brought into contact with a cyan color-forming developer before it
is developed in the yellow color-forming developer, which tends to
cause the formation of cyan fog and then the formation of cyan
color mixing. Moreover, since the blue-sensitive emulsion layer is,
after the development in the yellow color-forming developer,
brought into contact with a magenta color-forming developer, the
silver halide grains in the blue-sensitive emulsion layer which
have not completely been developed in the yellow color-forming
developer are subjected to the magenta color-forming development in
the magenta color-forming developer, which tends to cause magenta
color mixing.
In order to overcome these drawbacks, various solutions have been
proposed. For example, to prevent the formation of cyan color
mixing, it has been proposed to incorporate an antifoggant into the
cyan color forming developer. However, according to the method, the
cyan color forming development is also suppressed to increase the
proportion of the undeveloped silver halide grains and these grains
are developed in the subsequent yellow or magenta color forming
developer to cause the yellow or magenta color mixing in the cyan
image.
Moreover, a development accelerator may be added to the yellow
color-forming developer for preventing the formation of magenta
color mixing but when the yellow color-forming developer is
activated by the addition of development accelerator, the grains to
be coupled into magenta in the green-sensitive emulsion layer tends
to be fog-developed, which tends to cause yellow color mixing in
the green-sensitive emulsion layer. Also, it is possible to
incorporate such a stabilizer or development accelerator in
emulsion layers, but since such additives generally give serious
influences on other important properties of the photographic
light-sensitive material, the use of such additives is
restricted.
Accordingly it is very difficult to prevent the formation of cyan
color mixing or magenta color mixing into the yellow color-forming
emulsion layer in the coupler-in-developer type reversal color
process without adversely influencing the photographic properties
thereof.
Therefore, an object of the present invention is to provide a
process for preventing the formation of cyan color mixing or
magenta color mixing in the yellow color-forming emulsion layer
after development by the coupler-in-developer-type reversal color
process and providing a yellow dye image having a high color
purity.
Another object of the present invention is to provide a multilayer
color photographic light-sensitive material capable of forming a
yellow dye image having a high color density after development by
the coupler-in-developer-type reversal color process.
These objects can be attained by incorporating a diffusion
resisting or ballasted yellow coupler in a blue-sensitive emulsion
layer of a reversal color photographic light-sensitive material of
a type to be developed in coupler-containing developer.
By the process of the present invention, even though fog
development occurs on the silver halide grains in the
blue-sensitive emulsion layer during cyan color-forming
development, the oxidation product of the developing agent is
surprisingly caused to react predominantly with the ballasted
yellow coupler present in the blue-sensitive emulsion layer rather
than with the cyan coupler supplied from the developer and hence
the cyan color mixing is remarkably reduced. Furthermore, by the
incorporation of the ballasted yellow coupler in the blue-sensitive
emulsion layer, the development in the yellow color-forming
developer is markedly accelerated and no undeveloped silver halide
grains are left, which results in reducing the formation of magenta
color mixing in yellow.
The inventors have at the same time found that by incorporating the
ballasted yellow coupler in the blue-sensitive emulsion layer, the
density of the yellow dye image formed after development is
increased. Therefore, by these effects, a desirable yellow image
having a high color density and less color mixing can be
obtained.
The ballasted yellow coupler used in the present invention can be
selected from yellow couplers having the general formula
where R.sub.1 is a tertiary alkyl group, an unsubstituted or
substituted cycloalkyl group, an unsubstituted or substituted
dicycloalkyl group, or an unsubstituted or substituted aryl group;
R.sub.2 is an unsubstituted or substituted aryl or heterocyclic
group; and X is a hydrogen atom or a group capable of being split
off at coupling.
Examples of a suitable R.sub.1 group in general formula (1) are a
tertiary alkyl group having from four to 32 carbon atoms such as an
.alpha.-pivalyl group, a 1,1-dimethylpropyl group, a
1,1-dibutylheptadecyl group, a 1,1-diisobutylheptadecyl group, a
1,1-di-tert-butylheptadecyl group and the like; an unsubstituted
cycloalkyl group or a cycloalkyl group substituted with an alkyl
group, an alkoxy group, an alkoxyalkyl group, or an aryl group, in
which the alkyl radical may have from one to 18 carbon atoms, such
as, a cyclohexyl group, a 1-methylcyclohexyl group, a
1-butylcyclohexyl group, a 1-oxadecylcyclohexyl group, a
2-ethylcyclohexyl group, a 3-ethylcyclohexyl group, a
1-ethoxycyclohexyl group, a 1-nonoxycyclohexyl group, a
2-butoxycyclohexyl group, a 1-methoxyethylcyclohexyl group, a
3-methoxymethylcyclohexyl group, a 1-phenylcyclohexyl group, a
1-toluylcyclohexyl group, and the like; an unsaturated dicycloalkyl
group or a dicycloalkyl group substituted with an alkyl group
having one to 18 carbon atoms, an alkoxyl group, an alkoxyalkyl
group, or an aryl group, such as, a 7,7-dimethylnorbornyl group, a
2-methyl-7,7-dimethylnorbornyl group, a
2-octadecyl-7,7-dimethylnorbornyl group, a
2-ethoxy-7,7-dimethylnorbornyl group, a
2-octadecoxy-7,7-dimethylnorbornyl group, a
2-octoxydecyl-7,7-dimethylnorbornyl group, a
2-phenyl-7,7-dimethylnorbornyl group, and the like; an
unsubstituted aryl group or an aryl group substituted with an alkyl
group, an alkoxyl group, an alkoxyalkyl group, in which the alkyl
radical may have from one to 18 carbon atoms, a halogen atom, an
amino group, a carboxylic acid amido group, a ureido group, a
sulfamyl group, a sulfone group, or a carboxyl group, such as, a
phenyl group, a 3-methylphenyl group, a 2-butylphenyl group, a
4-dodecylphenyl group, a 4-octadecylphenyl group, a
2-trifluoromethylphenyl group, a 2-methoxyphenyl group, a
2-butoxyphenyl group, a 2-octadecoxyphenyl group, a
4-methoxyethylphenyl group, a 2-chlorophenyl group, a
2,4-dichlorophenyl group, a 4-aminophenyl group, a
4-N-methyl-N-butylaminophenyl group, a 2-propylamidophenyl group, a
3-butylamidophenyl group, a 2-octadecylamidophenyl group, a
3-octadecylsuccinmonoamidophenyl group, a
4-octadecylsuccinmonoamidophenyl group, a
3-.alpha.(2,4-di-tert-amylphenoxy) butylamidophenyl group, a
.gamma. (4-N-butyl-N-pentadecyloxycarbonylamino) propionamidophenyl
group, a 4-phenylureido group, a 4-toluylsulfamylphenyl group, a
3-sulfophenyl group, a 3-carboxyphenyl group, and the like.
Examples of a suitable R.sub.2 group in formula (1) are an
unsubstituted aryl group or an aryl group substituted with a
halogen atom, an alkyl group, an alkoxyl group, an aryloxyl group,
an acyl group, an alkoxy-carbonyl group, in which the alkyl radical
may have from one to 18 carbon atoms, an amino group, a carbonamido
group, a sulfonamido group, a ureido group, a carbamyl group, a
sulfamyl group, a carboxyl group or a sulfone group, such as, a
phenyl group, a 2-chlorophenyl group, a 2,4-dichlorophenyl group, a
2,4,6-trichlorophenyl group, a 2-bromophenyl group, a
2-fluorophenyl group, a 4-methylphenyl group, a
4-trifluoromethylphenyl group, a 2-methoxyphenyl group, a
4-[N-(.gamma. -phenylpropyl)-N-(p-toluyl) carbamylmethoxy]-phenyl
group, a 2-phenoxyphenyl group, a 2-chloro-5-octanoylphenyl group,
a 2-methoxy-5-octadecanoylphenyl group, a
2-methoxy-5-tetradecyloxycarbonylphenyl group, a
3,5-dimethoxycarbonylphenyl group, a 3,5-didodecyloxycarbonylphenyl
group, a 2-chloro-5-[.alpha.-(2,4-di-tert-amylphenoxy) acetamido]
phenyl group, a
2-chloro-5-[.alpha.-(2,4-di-tert-amylphenoxy)butylamido] phenyl
group, a 2-methoxy-5-[.alpha.-(2,4-di-tert-amylphenoxy)acetamido]
phenyl group, a 2-chloro-5-[.gamma.-(N-butyl-N-hexadecanoylamino)
propionamido] phenyl group, a 3-octadecylsuccinmonoamidophenyl
group, a 2-chloro-5-(4-methylphenylsulfonamido) phenyl group, a
4-phenylureidophenyl group, a
2-(2,4-di-tert-amylphenoxy)-5-(3,5-dimethoxycarbonylphenylcarbamyl)-phenyl
group, a 3,5-dicarbamylphenyl group, a
4-[N-(phenylethyl)-N-(p-toluyl)sulfamyl] phenyl group, a
4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a
2-methoxy-5-carboxyphenyl group, a 2-chloro-5-carboxyphenyl group,
a 2-(N-methyl-N-octylamino)-5-carboxyphenyl group, a 2-sulfophenyl
group, a 2-methoxy-5-sulfophenyl group, a 2-chloro-5-sulfophenyl
group, and the like; or a heterocyclic group such as a 2-thiazole
group, a 2-benzothiazole group, and the like.
Examples of a suitable X-group are a hydrogen atom or a group
capable of being split off at coupling, such as, a halogen atom,
e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine
atom, an --SCN group, --OR.sub.3 group, --SR.sub.3 group,
--OCOR.sub.3 group, and --OSO.sub.2 R.sub.3 group (wherein R.sub.3
represents an alkyl group, an aryl group, or a heterocyclic group),
a phenoxy group, a 4-nitrophenoxy group, an acetyloxy group, a
4-nitrophenylthio group, a benzothiazolethio group, a
methylsulfonyloxy group, a 3-nitrophenylsulfonyloxy group, and the
like.
The typical examples of the ballasted yellow couplers used in the
present invention are as follows: ##SPC1## ##SPC2## ##SPC3##
##SPC4##
The ballasted yellow couplers shown above may be prepared by
well-known methods as disclosed in, for example, British Pat. Nos.
595,314; 800,108; 1,045,633 and 1.052,488; U.S. Pat. No. 3,265,506;
Belgian Pat. 692,947; and Japanese Pat. application No. 3985/'
66.
The ballasted coupler used in this invention may be added to a
photographic emulsion by such conventionally known methods. For
example, the yellow coupler may be added directly to the
photographic emulsion as an alkali solution thereof, or it may be
dissolved in an organic solvent such as dibutyl phthalate or
tricresyl phosphate and after dispersing the solution in an aqueous
medium such as an aqueous gelatin solution, the resulting
dispersion is added to a photographic emulsion (cf., e.g., C.E.K.
Mees and T. H. James, "The Theory of the Photographic Process," 3rd
Ed., Macmillan Co., p. 393 (1966)), or it may be first fused by
heating and the fused coupler directly added to a photographic
emulsion or an aqueous medium.
The ballasted yellow coupler may be incorporated in a photographic
emulsion in any step before coating but is desirably added at a
step between the end of post ripening and coating.
The amount of the yellow coupler depends on the properties of a
photographic silver halide emulsion to be used but in general is
suitably 0.0005-0.5 mole per mole of the silver halide emulsion in
the blue-sensitive emulsion layer. However, the amount of the
coupler is not limited to the above range. Furthermore, the
ballasted yellow couplers mentioned above may be used alone or in
combinations of two or more.
As the silver halide emulsion used for the blue-sensitive emulsion
layer in this invention, a silver iodobromide emulsion is desirable
but other silver halide emulsions such as a silver chloride
emulsion, a silver chlorobromide emulsion, and a silver bromide
emulsion can be employed.
The silver halide emulsion used in this invention may have been
sensitized by well-known methods, e.g., with a compound containing
an unstable sulfur such as ammonium thiosulfate or
allylthiocarbamide, a gold compound such as a complex salt of
monovalent gold and thiocyanic acid, a reducing agent such as
stannous chloride, a polyalkylene oxide derivative, or a
combination thereof. Also, the silver halide emulsion may contain a
stabilizer such as benzimidazole, 1-phenyl-5-mercaptotetrazole, and
the like; a hardening agent such as formaldehyde, much-bromic acid,
and the like; and a wetting agent such as saponine.
Between the blue-sensitive emulsion layer and the green-sensitive
emulsion layer there may be inserted a yellow filter layer. The
function of the yellow filter layer is to absorb remaining blue
light which the blue-sensitive layer does not absorb.
The blue-sensitive emulsion layer containing the ballasted yellow
coupler is desirably positioned at the uppermost position as silver
halide emulsion layer, that is, it is desirable that the
red-sensitive emulsion layer, the green-sensitive emulsion layer,
the yellow filter layer, and the blue-sensitive emulsion layer
containing the yellow coupler be formed on a support in that order.
Moreover, the red-sensitive emulsion layer and the green-sensitive
emulsion layer contain desirably no couplers in general but one of
them may contain a ballasted cyan coupler and a ballasted magenta
coupler respectively.
The multilayer color photographic light-sensitive material
containing the yellow coupler in this invention is desirably
processed by a usual coupler-in-developer-type reversal color
process.
Each of the cyan, magenta and yellow color-forming developers
contains at least a color-forming developing agent and a diffusible
coupler coupling into a cyan, magenta or yellow dye
respectively.
As the color-forming developing agent are employed well-known
p-phenylene diamine derivatives such as 4-amino-N,N-diethylaniline,
4-amino-3-methyl-N-methyl-N-(.beta.-methylsulfonamidoethyl)-aniline,
4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl) aniline, and the
like (cf., e.g., C.E.K. Mees and T. H. James, "The Theory of the
Photographic Process," 3rd Ed., page 387).
As the diffusible cyan couplers there are employed generally known
phenolic couplers such as 2-chloro-1-naphthol,
2,4-dichloro-1-naphthol, 1-hydroxy-N-butyl-2-naphthamide,
1-hydroxy-N-(2-acetamidophenethyl)-2-naphthamide, etc. (cf. ibid,
page 387). Also, as the diffusible magenta couplers, there are
open-chain methylene couplers such as acylaceto-nitriles,
2-cyanoethylbenzofuran, benzylacetonitrile, and the like, cyclic
methylene couplers such as 1-phenyl-3-methyl-5-pyrazolone,
1-phenyl-3-(4-chlorobenzamido)-5-pyrazolone,
1-phenyl-3-(3-nitrobenzoyl-amino)-5-pyrazolone,
1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone, and the
like. Moreover, as the diffusible yellow couplers, there are
acylacetamide-type open-chain methylene couplers such as
2-acetanilide, 2-aceto-2', 4'-dichloroacetanilide,
2-benzoylacetanilide, 2-benzoyl-2'-methoxyacetanilide,
2-benzoyl(4'-p-toluene-sulfonamido) acetanilide, and the like (cf.,
ibid, page 389 and G. H. Broun et al., "Journal of American
Chemical Society," 79, 2919-2927 (1957)).
The invention will be explained more in detail by the following
examples.
EXAMPLE 1
A highly sensitive gelatino silver iodobromide reversal color
photographic emulsion subjected to a sulfur sensitization and a
gold sensitization was melted by heating and divided into several
parts. Each emulsion was mixed with an aqueous alkaline solution of
the yellow coupler shown in table 1 and then the pH of the emulsion
was adjusted to 7.0 with the addition of citric acid. To a
cellulose triacetate film base were applied a red-sensitive
reversal color photographic emulsion containing no coupler, a
green-sensitive reversal color photographic emulsion containing no
coupler, and a yellow filter layer in this order and the
blue-sensitive reversal color photographic emulsion containing the
yellow coupler prepared above, and the thus-coated film was dried.
The proportion of the silver halide in the blue-sensitive layer was
16.5 mg./100 cm..sup.3. The dried sample was uniformly subjected to
yellow exposure by means of a NSG II-type sensitometer and then
subjected to the following reversal color processing at 27.degree.
C.:
1. prehardening 3 min. 2. Washing 4 min. 3. Negative development 7
min. 4. Washing 2 min. 5. Reversal red flash exposure 6. Cyan color
development 5 min. 7. Washing 2 min. 8. Reversal blue flash
exposure 9. Yellow color development 5 min. 10. Washing 2 min. 11.
Reversal white light exposure 12. Magenta color development 5 min.
13. Washing 2 min. 14. Silver bleaching 5 min. 15. Fixing 3 min.
16. Washing and drying
The compositions of the processing baths used in the above
processings were as follows:
Prehardening solution: Sodium pyrophosphate 20 g. Sodium sulfate 50
g. 37% Formaldehyde 17 ml. 10% Aqueous NaOH solution 1 ml. Water to
make 1 liter Negative developer: N-Methyl-p-amininophenol sulfate 1
g. Sodium sulfite (anhydrous) 60 g. Hydroquinone 10 g. Sodium
carbonate (mono-hydrate) 40 g. Potassium bromide 5 g. Potassium
thiocyanate 1.5 g. 0.1% Aq.soln. of potassium iodide 5 ml. Sodium
hydroxide 2 g. Water to make 1 liter Cyan color developer:
Potassium bromide 2.0 g. 0.1% Aq.soln. of potassium iodide 20 ml.
Potassium thiocyanate 3 g. Sodium sulfite (anhydrous) 10 g. Sodium
carbonate (mono-hydrate) 30 g. Sodium hydroxide 2 g.
5-Nitrobenzimidazole nitrate 0.5 g. 2,4-Dichloro-1-naphthol 2.0 g.
4-Amino-3-methyl-N,N- diethylaniline hydrochloride 3.0 g. Water to
make 1 liter
Yellow color developer: Sodium sulfite 5.0 g.
N,N-Diethyl-p-phenylenediamine hydrochloride 1.2 g. Sodium
carbonate (mono-hydrate) 20.0 g. 0.1% Aq.soln. of potassium iodide
2.0 ml. Potassium bromide 0.3 g. 2-Benzoyl-(4'-p-toluenesulfon-
amido) acetanilide 1.0 g. Sodium hydroxide 4.0 g. Water to make 1
liter Magenta color developer: Sodium sulfite 5.0 g.
4-Amino-3-methyl-N,N-diethyl aniline hydrochloride 2.0 g. Potassium
bromide 0.2 g. 1-Phenyl-3-(3-nitrobenzoylamino)- 5-pyrazolone 1.4
g. Sodium hydroxide 2.5 g. n-Butylamine 5 ml. Water to make 1 liter
Silver bleaching solution: Ferricyanide 60 g. Potassium bromide 20
g. Water to make 1 liter Fixing solution: Sodium thiosulfate 100 g.
Sodium sulfite 15 g. Water to make 1 liter
The density of the yellow dye image after development was measured
using blue, green and red filters each, the results of which are
shown in table 1.
As shown in table 1, the yellow density was increased and the cyan
density and the magenta density were remarkably reduced. This shows
that by the practice of the present invention, the formation of
cyan color mixing and magenta color mixing are markedly reduced and
the yellow density is increased.
TABLE 1
yellow amount mole/ yellow cyan magenta coupler Ag x 1 mole density
density density
__________________________________________________________________________
none (control -- -- -- 1.90 0.30 0.30 coupler (1) 0.0005 1.90 0.25
0.23 coupler (1) 0.005 1.92 0.18 0.19 coupler (1) 0.05 1.98 0.15
0.18 coupler (1) 0.5 2.21 0.15 0.18 coupler (2) 0.05 2.04 0.15 0.19
coupler (2) 0.1 2.13 0.14 0.18 coupler (3) 0.05 2.02 0.15 0.19
coupler (3) 0.1 2.21 0.15 0.17 coupler (4) 0.05 1.99 0.15 0.18
coupler (4) 0.1 2.12 0.14 0.18 coupler (5) 0.05 1.95 0.16 0.19
coupler (5) 0.1 2.18 0.14 0.18 coupler (6) 0.05 2.00 0.15 0.18
coupler (6) 0.1 2.17 0.15 0.17 coupler (7) 0.05 1.96 0.16 0.18
coupler (7) 0.1 2.12 0.15 0.18
EXAMPLE 2
The gelatino silver iodobromide reversal color photographic
emulsion same as in example 1 was melted by heating and divided
into several parts. Five grams of the coupler shown in table 2 was
dissolved in a mixed solution of 10 g. of dibutyl phthalate and 10
g. of ethyl acetate, the solution was dispersed in 50 g. of an
aqueous 10 percent gelatin solution together with a surface active
agent, the dispersion of the coupler thus obtained was added to the
aforesaid silver halide emulsion in an amount shown in table 2, and
the pH of the resulting emulsion was adjusted to 7.0.
As in example 1, the blue-sensitive reversal color photographic
emulsion containing the aforesaid coupler was applied to a
photographic film having on a cellulose triacetate film a
red-sensitive reversal color photographic emulsion layer, a
green-sensitive reversal color photographic emulsion layer, a
yellow filter layer, and a blue-sensitive emulsion layer such that
the amount of Ag was 16.5 g./100 cm..sup.3 in the blue-sensitive
layer and dried. The sample thus dried was exposed and processed as
in example 1 and the density was measured as in the example, the
results shown in table 2. The results show that the yellow density
was increased and the cyan density and the magenta density were
extremely reduced. ##SPC5##
EXAMPLE 3
The same highly sensitive gelatino silver iodobromide reversal
color photographic emulsion as in example 1 was melted by heating.
In a mixed solution of 10 g. of dibutyl phthalate and 10 g. of
ethyl acetate was dissolved 5 g. of coupler (13) and the solution
was dispersed in 50 g. of an aqueous 10 percent gelatin solution
together with a surface active agent. The coupler dispersion thus
obtained was added to the aforesaid silver halide emulsion in an
amount of 100 g. per mole of silver halide and the pH thereof was
adjusted to 7.0.
As in example 1, the thus prepared blue-sensitive reversal color
photographic emulsion containing the aforesaid yellow coupler was
applied to a photographic film having on a polyethylene
terephthalate base a red-sensitive reversal color photographic
emulsion layer containing no coupler, a green-sensitive reversal
color photographic emulsion layer containing no coupler, a yellow
filter layer and a blue-sensitive emulsion layer such that the
amount of silver became 16.5 mg./100 cm..sup.3 in the
blue-sensitive layer, followed by drying. The dried sample was
exposed and developed as in example 1 except that different kinds
of diffusible couplers were used in the cyan, yellow, and magenta
color developers respectively and the density of each dye image was
measured, the results of which are shown in table 3 together with
the diffusable couplers used. The values in table 3 are the
differences in yellow density, cyan density and magenta density
between the case of adding the diffusible yellow coupler to the
emulsion and the case of adding no such yellow coupler to the
emulsion. When the value was plus (+), it means that the density
was increased by the addition of the ballasted yellow coupler to
the emulsion layer, while minus (-) value means that the density
was reduced by the addition thereof. Thus, as shown in table 3, in
the case of practicing the process of this invention, when the
color photographic light-sensitive material of this invention is
developed in color-forming developers containing diffusible
couplers, the yellow density is increased and the cyan and magenta
densities are extremely reduced as compared with the case of adding
no ballasted yellow coupler to the silver halide emulsion layer.
##SPC6##
Almost the same results were obtained when other ballasted yellow
couplers were used. Also, in the case of employing other
coupler-in-developer-type reversal color processes than the color
process described in the examples, the same results were
obtained.
* * * * *