Method Of Preventing Color Mixing In Multilayer-type Reversal Color Photographic Light-sensitive Materials

Nagae , et al. February 8, 1

Patent Grant 3640716

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.

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