US3706556A - Method for preventing color mixing in multiple layer-type reversal color photographic light-sensitive materials - Google Patents

Abstract

A METHOD FOR PREVENTING COLOR MIXING IN A COUPLER-INDEVELOPER TYPE MULTIPLE LAYER REVERSAL COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL HAVING COATED ON A SUPPORT A REDSENSITIVE EMULSION LAYER, A GREEN-SENSITIVE EMULSION LAYER, AND A BLUE-SENSITIVE EMULSION LAYER, COMPRISING INCORPORATING AT LEAST ONE DIFFUSION RESISTANT MAGENTA COUPLER IN A GREEN-SENSITIVE EMULSION LAYER OF THE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL AND DEVELOPING SAID COLOR PHOTOGRAPHIC MATERIAL WITH THREE COLOR DEVELOPING SOLUTIONS CONTAINING DIFFUSING COUPLERS FOR THE RED-SENSITIVE EMULSION LAYER, THE GREEN-SENSITIVE EMULSION LAYER AND THE BLUESENSITIVE EMULSION LAYER, RESPECTIVELY, IS DISCLOSED.

Description

United States Patent Office Patented Dec. 19, 1972 3,706,556 METHOD FOR PREVENTING COLOR MIXING IN MULTIPLE LAYER-TYPE REVERSAL COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS Tadashi Nagae, Yasushi Oishi, and Jun Hayashi, Kauagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed July 17, 1970, Ser. No. 56,006 Claims priority, applicjlgignifiipan, July 17, 1969,

Int. Cl. G03c 7/10 US. Cl. 96-22 6 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a method for preventing color mixing in multiple layer-type reversal color photographic light-sensitive materials developed using the coupler-indeveloper process.

(2) Description of the prior art ;As a multiple layer-type color photographic light-sensitive material having a red-sensitive emulsion layer, a greensensitive emulsion layer, and a blue-sensitive emulsion layer on a support, a photographic light-sensitive material in which the photographic emulsion layers contain couplers capable of forming dyes by reaction with the oxidation product of the silver halide and an aromatic aminotype photographic primary developing agent and a lightsensitive material in which the photographic emulsion layers contain no such couplers are known.

TIWith the latter type of color photographic light-sensitive material, after exposure and development in colorforming developing solutions containing couplers, the sharpness of the color image is better than that of the former type of color photographic light-sensitive material. However, in the ordinary process, not only one type of dye but also other dyes which are not present in the emulsion layers are formed in the emulsion layers during developing causing color mixing. This results in degrading the color reproduction of the color photographic light-sensitive material formed by the development. For instance, when the latter type of reversal color photographic lightsensitive material, having a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support in this order, is, after exposure, subjected to black and white development, cyan color forming development, yellow color forming development, and magenta color forming development hereinafter, this development is called coupler-in-developer type reversal color photographic processing), a cyan color image or a yellow color image is formed in the greensensitive emulsion layer in addition to a magenta dye. Hence the magenta color image is to some extent purplish or reddish and a magenta color of high color purity cannot be obtained.

Such color mixing is caused by development fog. This phenomenon occurs in that at the color forming development of an emulsion layer, the silver halide grains in the unexposed portions of the emulsion layer are developed to produce an undesirable dye. For example, when the above-mentioned type of reversal color photographic lightsensitive material is developed in the above described order, the green-sensitive emulsion layer to be developed by a magenta color developing solution is subjected to cyan color development before it is subjected to the magenta color development. Thus, cyan fog development tends to occur resulting in cyan color mixing. When the emulsion layer is subsequently subjected to yellow color development, yellow fog development tends to occur to cause yellow color mixing.

Various approaches have been used for removing these difiiculties. For instance, a method is proposed in which an antifoggant is incorporated into the cyan developing solution to prevent the occurrence of cyan color mixing, but, with such an approach, the cyan color forming development is also suppressed, increasing the undeveloped grains. When they are then developed in the subsequent yellow or magenta developing solution, color mixing of yellow and magenta in the cyan image occurs.

Also, a method is known in which an antifoggant is incorporated in a yellow developing solution to prevent the occurrence of yellow mixing. However, with such a method the yellow color forming development is also suppressed to cause magenta color mixing in the yellow image.

Still further, it is possible to prevent a green-sensitive emulsion layer from being fogged on development with cyan color forming development or yellow color forming development by incorporating an antifoggant in the green-sensitive emulsion layer. Since such additive generally gives rise to adverse elfects on other important properties of the photographic light-sensitive material, selection of the additive is limited. Accordingly, it is extremely diflicult to prevent the occurrence of cyan color mixing and yellow color mixing in a magenta color forming emulsion layer using coupler-in-developer type reversal color photographic processing without also obtaining other adverse effects.

Therefore, an object of this invention is to provide a coupler-in-developer type reversal color photographic light-sensitive material capable of providing a magenta color image having a high color purity unaccompanied with the occurrence of cyan color mixing and yellow color mixing after development in the coupler-in-developer type reversal color photographic processing.

Another object of this invention is to provide a multiple layer type color photographic light-sensitive material having high color density after development in the coupler-in-developer type color photographic processing.

SUMMARY OF THE INVENTION The inventors have discovered that the objects of this invention can be attained by incorporating a diifusion resistant or ballasted magenta coupler in the green-sensitive emulsion layer of a coupler-in-developer type reversal color photographic light-sensitive material.

DETAILED DESCRIPTION OF THE INVENTION With the present invention, even if fog development occurs on the silver halide grains in the green-sensitive emulsion layer during cyan development, the oxidation product of the primary developing agent astonishingly reacts predominantly with the dilfusion-resistant magenta coupler present in the green-sensitive emulsion layer rather than with the cyan coupler supplied from the developing solution. This results in reducing markedly the occurrence of cyan color mixing. Also, in this case, even if fog de velopment occurs on the silver halide grains in the greensensitive emulsion layer in a yellow color forming developing solution, the oxidation product of the primary eveloping agent predominantly reacts with the diffusion resistant magenta coupler present in the green-sensitive emulsion layer rather than with the yellow coupler supplied from the developing solution to give a magenta image. This results in also reducing markedly the occurrence of yellow color mixing.

Therefore, with this invention, adesirable magenta coupler having a high color density and less color mixing is obtained.

The diffusion resistant magenta coupler used in this invention can be selected from the generally known magenta couplers (see: W. Pelz, Mitteilungen ans de Forschungs- Laboratorien der Agfa Leverkusen-Munchen, III, 126-156 1961) In particular, the compounds represented by the following general Formulae I and II are preferred:

Rz-COHX and R2-C-CHLIJHC--CR2 N o= l N N I l: I l:

wherein R represents an aryl group, a heterocyclic ring group, a carbamyl group, or a thiocarbamyl group; R represents a hydrogen atom, an alkyl group, an aryl group, an amino group, an ureido group, a carbonamide group, a sulfonamide group, or a sulfamyl group; R represents a lower alkyl group or an aryl group; and X represents a hydrogen atom or a group capable of being displaced on coupling; at least one of the R and R groups having at least one hydrophobic residual group having from 8 to 30 carbon atoms necessary to provide diffusion resistance to the coupler.

More specifically, R in the general Formulae I and II above can be an aryl group or an aryl group, substituted by an alkyl group having from 1 to 18 carbon atoms, an alkoxy group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group, or a halogen atom. Suitable examples of R as an aryl or substituted aryl group are a phenyl group, a 4-methoxyphenyl group, a Z-octadecoxyphenyl group, a 4-phenoxyphenyl group, a 2-chlorophenyl group, a 2,4- dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2-chloro-4,fi-dimethylphenyl gr0up, a 4 bromophenyl group, a 4 methoxy-2,6-dichlorophenyl group, a 4-fiuorophenyl group, a 2-chloro-5tetra-decoxycarbonylphenyl group, a Z-ChlOI'O-S-[a (2,4 ditert-amylphenoxy)acetamido] phenyl group, a 2-chloro-5-(4-methylphenylsulfonamido) phenyl group, a 3,5-dicar bamylphenyl group, a 4-N-(phenylethyl)-N-(p-tolyl)sulfamyl phenyl group, a 4-su1fophenyl group, a 4-phenoxy-3 sulfophenyl group, a 4 methoxysulfonylphenyl group, a 4 hydroxyphenyl group, or a 3-carboxyphenyl group.

R can also be a 5- or 6-membered heterocyclic ring group or a 5- or 6-membered heterocyclic ring group substituted with substituents such as those described above for the substituted aryl group. Suitable heterocyclic ring groups are a furanyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a quinolinyl group, and the like.

R, can also be a group in the carbamyl series, such as carbamyl group, and the like; a group in the thiocarbamyl series, such as a thiocarbamyl group, an ethylthiocarbamyl group, a phenylthiocar'bamyl group.

R is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and which may optionally contain a substituent or be unsaturated (for example, an alkoxyl group, an aryl group, an aryloxyl group, a halogen atom, a hydroxyl group, and the like), such as a methyl group, a 2-propenyl group, a pentadecyl group, a Z-methoxyethyl group, a benzyl group, a 2-phenoxyethyl group, a hydroxyethyl group, and the like; an aryl group or an aryl group substituted by substituents as described above for R R can" also be a group in the amino series such as a primary amino group, a benzylamino group, a 3,5-dicarboxyanilino group, a 4-nitroanilino group, a 2,4-dichloroanilino group, a 2-chloro-4-[a-(2,4-di-tert-amylphenoxy) butylamide] auilino group, a 5-[u-(2,4 di tert amylphenoxy) acetamido]2-methoxyanilino group, and the like.

R can also be a group of the ureido series, such as an N (0a,,B dicarboxyethyl)ureido group, an octylureido group, a 3-[a-(2,4-di-tert-amylphenoxy) acetamido]-phenyluredio group, and the like.

R can also be a group in the carbonamide series such as an octadecylamido group, an octadecylsuccinmonoamido group, a 3-(octadecylsuccinmonoamido) benzamido group, a 3-[a-(2,4-di-tert-amylphenoxy)acetamido] benzamido group, an a-(4-tert-butylphenoxy) propionamido group, a 3-[a-(3pentadecyl-4-sulfophenoxy) acetamido]benzamido group, a 'y-(4-N-butyl-N-pentadecoxycarbonylamino)propionamido group, and the like; a group in the sulfonamido series, such as a 4-methylphenylsulfonamido group, and the like: or a sulfamyl group such as a sulfamyl group an N-ethylsulfoamyl group, an N- a, carbamyl group, a methyl carbamyl group, a phenylphenylsulfamyl group, and the like.

R is an alkyl group having from 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and the like; or an aryl group such as a phenyl group, and the like.

Furthermore, X is a hydrogen atom; or a group capable of being liberated or displaced on coupling, such as a halogen atom, a SCN group, an OR group, a 4R, group, an OCOR, group, or an 0SO R group (in which R represents an alkyl group, an aryl group or a heterocyclic group), for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a SCN group, a phenoxy group, a 4-nitrophenoxy group, an acetyloxy group, a 4-nitrophenylthio group, a benzthiazolethio group, a methyl sulfonyloxy group, a 3-nitro-phenylsulfonyloxy group, and the like.

Specific examples of the diffusion resistant magenta couplers used in this invention are shown below. Other magenta couplers can also be used.

The diffusion resisting magenta couplers illustrated above can be prepared using well known methods. For example, they can be produced by the methods described in Fiat Final Report 943 and in U.S. Pat. Nos. 2,369,489 and 2,600,788; Japanese patent publication No. 32/ 7,039; UK. Pat. Nos. 1,018,810 and 1,142,553; and U.S. Pat. No. 2,618,641.

The magenta coupler described above can be incorporated in the photographic emulsion using conventional methods. For example, one method comprises adding directly thereto as an alkaline solution thereof, in a second method, the magenta coupler is dissolved in an organic solvent, such as dibutyl phthalate or tricresyl phthalate, the solution is dispersed in an aqueous medium such as an aqueous gelatin solution, and then the dispersion is added to the photographic emulsion (see, for example, C. E. K. Mees and T. H. James; The Theory of the Photographic Process, 3rd Edition, Macmillan Co., 1966), in a third method the magenta coupler is melted by heating and the molten coupler is dispersed directly in the photographic emulsion or an aqueous medium.

The magenta coupler can be added to the photographic emulsion at any step before coating the photographic emulsion but it is preferable to add the coupler in a step after ripening and before coating.

The amount of the magenta coupler to be added to the photographic emulsion depends upon the nature of the silver halide photographic emulsion to be used but suitably ranges from 0.0005 to 0.25 mol per mol of the silver halide in the green-sensitive emulsion layer. In the cou pler-in-developer type color photographic processing, a hardening treatment using a prehardening bath containing formaldehyde is generally practiced. In this case, a compound having an active methine group such as magenta coupler tends to form yellow stains by reacting with the formaldehyde. Hence, the amount of the magenta coupler is limited in such cases. The density of the yellow stain depends upon the type of magenta coupler used, the manner of incorporating the magenta coupler in the photographic emulsion, the composition of the hardening bath, and the like, but the amount of the magenta coupler defined above gives rise to no dilficulties with yellow staining. Of course, the amount can be increased further under the conditions that such yellow stain is less formed.

Moreover, the magenta couplers shown above can be used alone or as a combination of two or more couplers.

As the silver halide emulsion to be used is the greensensitive emulsion layer, a silver halide iodobromide emulsion is most preferred but other silver halide emulsions, such as a silver chloride emulsion, a silver chlorobromide emulsion or a silver bromide emulsion, can be used.

The silver halide photographic emulsion used in this invention can be chemically sensitized using methods well known in the art, for example, 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 derivative or a combination of them. The photographic emulsion can contain also a stabilizer, such as 4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, benzimidazole, or l-phenyl- S-mercaptotetrazole, and a hardening agent, such as formaldehyde or mucobrornic acid. Moreover, the emulsion can contain a wetting agent, such as saponin or sodium alkylbenzene sulfonate.

Sensitizing dyes giving green sensitivity to the photographic emulsion are cyanine dyes capable of sensitizing the wave length region ranging from 500 to 600 my, such as 1,1'-diethyl-2,2'-cyanine iodide, anhydro-5,5'-diphenyl- 9-ethyl-3,3'-di(2-sulfoethyl) benzoxazolocarbocyanine hydroxide, anhydro-S,5',6,6-tetrachloro-1,l'-diethyl-3,3'- di(3-sulfobutyl)benzimidazolocarbocyanine hydroxide, and the like. These dyes can be used alone or in combination.

It is preferred that the green-sensitive emulsion layer containing the above-described magenta coupler be between a red-sensitive layer and a blue-sensitive layer. That is, it is preferred that the order of the emulsion layers coated on the support be a red-sensitive emulsion layer, the green-sensitive emulsion layer containing the magenta coupler, a yellow filter layer, and a blue-sensitive emulsion layer.

Furthermore, it is preferred that the red-sensitive emulsion layer and the blue-sensitive emulsion layer generally contain no couplers. The red-sensitive emulsion layer can contain a diffusion resistant cyan coupler and the blue-sensitive emulsion layer can contain a difiusion resistant yellow coupler.

The multiple layer type color photographic light-sensitive material of this invention having the green-sensitive. emulsion layer containing the magenta coupler is desirably processed by the coupler-in-developer type color photographic processing.

The cyan, magenta and yellow color developing solutions contain at least a color forming primary develop ing agent and doiffusing couplers to be coupled into cyan, magenta and yellow dyes respectively.

Suitable color forming primary developing agents are the well-known p-phenylenediamine derivatives, such as 4-amino-N,N diethylaniline, 4-amino-N,N diethyl-3- methylaniline, 4-amino-3-methyl-N ethyl-N-(B-methylsulfonamidoethyl)aniline, 4-amino-3-methyl-N-ethyl-N- (B-hydroxyethyUaniline (see, e.g., C. E. K. Mees & T. H. James, The Theory of the Photographic Process, 3rd edition, 387, Macmillan Co. (1966)).

The diffusing cyan couplers which can be added to the cyan-forming developing solution are the well-known phenolic couplers, such as 2-chloro-l-naphthol, 2,4-dichloro-l-naphthol, 1-hydroxy-N butyl-2-naphthamide, 1- hydroxy-N-(Z-acetamidophenethyl) Z-naphthamide and the like (Mees et al., supra, page 387).

The diffusing magenta coupler which can be added to the magenta-forming developing solution are the ringclosed methylenic couplers, such as acylacetonitrile, 2- cyanoethyl-benzofuran, benzyl-acetonitrile or the cyclic methylene couplers such as l-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-(4-chlorobenzamido) 5-pyrazolone, 1-phenyl-3-(3-nitrobenzoylamino) S-pyrazolone, 1-(2,4, 6-trichlorophenyl)-3 (4-nitroanilino)-5-pyrazolone, and the like.

The diffusing yellow coupler which can be added to the yellow forming developing solution are the wellknown acylacetamide type open chain methylenic couplers, such as 2-acetoanilide, 2-aceto-2',4'-dichloroacetoanilide, 2-benzoylacetoanilide, 2-benzoyl-2-methoxyacetoanilide, 2-benzoyl(4'-p-toluenesulfonamido)acetoanilide, and the like (see, for example, Mees, supra, page 389 and G. H. Broun et al., Journal of American Chemical Society, 79, 2919-2927 (1957)).

The invention is illustrated further in greater detail by the following examples.

EXAMPLE 1 After melting by heating a gelatino silver iodobromide emulsion for a high speed reversal color photographic light-sensitive material, which had been sulfur-sensitized and gold-sensitized, the emulsion was green-sensitized using anhydro-5,5-diphenyl-9-ethyl-3,3'-di(2-sulfoethyl)- benzoxazolocarbocyanine hydroxide and anhydro-5,5',6,

'-tetrachloro-1,1-diethyl 3,3'-di(3-sulfobutyl)-benzimidazolocarbocyanine hydroxide. The green-sensitive emulsion, thus prepared, was divided into several parts. To each of the green-sensitive emulsions were added an aqueous alkaline solution of the magenta coupler shown in Table 1 below and citric acid, and, then the pH of the emulsion was adjusted to 7.0. The green-sensitive emulsion was applied to a red-sensitive silver halide emulsion layer containing no coupler for reversal color photograpic material formed on a cellulose triacetate film base so that the proportion of silver in the green-sensitive layer was 15 mg./ cm.*. The yelow filter layer and a bluesensitive emulsion containing no yellow coupler, for reversal color photographic material were further applied to the green-sensitive layer in this order and they were dried.

The sample thus dried was subjected uniformly to magenta exposure and then subjected to the following coupler-in-developer type color photographic processing:

C. Minutes 1. Pro-hardening 27 1 2. Water washing 27 1 3. Negative development 27 4 4. Water washing 27 3 5. Reversal red flash exposure 6. Cyan color development.-. 27 7. Water washing 27 2 8. Reversal blue flash exposure 9. Yellow color development 27 5 10. Water washing 27 5 11. Reversal white exposure- 12. Magenta color development. 27 2 13. Water washing 27 2 14. Silver bleaching 27 5 15. Fixing 27 3 16. Water washing and drying The compositions of the processing baths used in the above processing were as follows:

Pre-hardening solution:

Concentrated sulfuric acid cc 1.7 Borax (H O) g Potassium bromide g 2.3 Sodium sulfate g 200 Formaldehyde (37%) cc 10 Sodium bisulfite g 1 Water to make 1000 cc.

Negative developing solution:

S-nitrobenzimidole nitrate g 0.5 2,4-dichloro-l-naphthol g 2. 4-amino-3-methyl-N,N-diethylaniline hydrochloride g 3.0 Water to make 1000 cc.

Yellow color developing solution:

Sodium sulfite g 5.0 N,N-diethyl p phenylenediamine hydrochloride g 1.2 Sodium carbonate (H O) g 20.0 Potassium bromide g 0.3 Potassium iodide (0.1%) cc 2.0 2-benzoyl-(4' p tolnenesulfonamido)-acetoanilide g 1.0 4.0

Sodium hydroxide g Water to make 1000 cc.

Magenta color developing solution:

Water to make 1000 cc.

The density of the magenta dye image after development was measured using blue, green and red filters. The results obtained are shown in Table 1.

As can be seen from the results obtained, the density of magenta was increased but the densities of cyan and yellow were greatly decreased. This shows that by the application of the present invention the cyan color mixing and yellow color mixing were greatly reduced and the density of the magenta dye was increased.

TABLE 1 Amount (mol/mol- Yellow Cyan Magenta Magenta coupler Ag) density density density Ionei 0. 0. 50 2. 12

cup er EXAMPLE 2 After melting by heating the green-sensitive gelatino silver iodobromide emulsion for high speed reversal color photographic material as described in Example 1, the emulsion was divided into several parts. 5 g. of each of the couplers shown in Table 2 were dissolved in a mixed solution of 10 g. of tricresyl phosphate and 20 g. of ethyl acetate and the solution was dispersed by emulsification in 50 g. of a 10% aqueous gelatin solution together with a dispersing agent. The dispersion of the coupler thus obtained was added to the green-sensitive emulsion prepared above in the amount shown in Table 2 and the pH of the mixture was adjusted to 7.0.

The green-sensitive emulsion containing the magenta coupler was applied to a red-sensitive emulsion layer containing no coupler for reversal color photographic material and formed on a cellulose triacetate film so that the amount of the silver in the green-sensitive layer was 15 mg./ cm. On the green-sensitive emulsion layer were applied a yellow filter layer and a blue-sensitive emulsion layer containing no yellow coupler for reversal color photographic material and they were dried.

The sample thus dried was exposed, developed and the density measured according to the method describe in Example 1. The results obtained are shown in Table 2. These results show that the density of magenta was increased but the densities of cyan and yellow were extremely reduced.

TABLE 2 Amount of dispersion Yellow Cyan Magenta Magenta coupler (g./mol Ag) density density density None 0. 80 0. 50 2. 12

EXAMPLE 3 The same procedure as used in Example 1 was followed except that the couplers shown in Table 3 were used. The sample was subjected uniformly to a magenta exposure as in Example 1 and then processed in the same manner as in Example 1, except that the pre-hardening treatment was conducted for 3 minutes at 27 C. using a pre-hardening bath having the following composition:

Pro-hardening solution:

12 emulsion was mixed with an aqueous alkaline solution of Coupler 2 in an amount of 0.01 mol per mol of AgX and then the pH was adjusted to 7.0.

The green-sensitive emulsion layer containing the magenta coupler Was applied on a red-sensitive emulsion layer containing no coupler for reversal color photographic material and formed on a polyethylene terephthalate film so that the content of silver in the greensensitive layer was 15 mg./100 cm. and on the emulsion layer were applied a yellow filter layer and a blue-sensitive emulsion containing no yellow coupler for reversal color photographic material and they were dried. The sample thus obtained was exposed, developed and the density measured in the same manner as in Example 1 except that the diffusing couplers for the cyan, yellow and magenta color developing solutions as shown in Table 4 were employed.

The combinations of the diifusing couplers used in the example and results obtained by conducting the coupler-in-developer type color photographic processing are shown in Table 4.

The numerical values in Table 4 show the dilferences in yellow density, cyan densities and magenta between the results obtained by adding the dilfusion resisting magenta coupler to the green-sensitive emulsion layer and by adding no such magenta coupler.

The mark shows that the density was increased by the addition of the diffusion resistant magenta coupler, while the mark shows that the density was reduced 30 by the addition of the diffusion resistant magenta coupler. Water cc 800 Thus, in practicing the process of the present inven- Dimethoxytetrahydrofuran cc 4.3 tion, the magenta density was increased and the cyan and 0.8 NH SQ, cc 5.41 yellow densities were markedly reduced when the color Sodium p-toluenesulfonate g 0.5 photographic light-sensitive material of this invention was Sodium sulfate g 153 5 developed in the color developing solutions containing Potassium bromide g 2.3 any diffusing coupler in comparison with the case of Sodium acetate ..g 20 adding no diffusion resisting magenta coupler of this Formalin (37%) cc 27 invention to the green-sensitive emulsion layer.

TABLE 4 Density difierences of magenta images Difiusible coupler used in the color developer Yellow Cyan Magenta Test number Cyan coupler Yellow coupler Magenta coupler density density density 1 24-dich1oro-1-naphthoL2 g.ll-. 2-benzoylacetoanilide, 1.8 g.ll 1-phenyl-3-(4-chlorobenz- -0,o -.0. g 13 zlar rlndfiydpyrazolone,

. g. 2 1-hydroxy-N-butyl-2-naphth- Z-aceto-2,4'-dichloroacedo -0.05 0.03 +0. 19

ami e, g. toanilide, 1.8 g./l. 3 1-hydroxy-N-(2-acetamido- 2-benzoyl-2-methoxyacetanl- 1-(2,4,6-tnchlorophenyly3- 0.07 -0. 10 +0. 22

phenfithyDQ-naphthamide, lide, 1.5 g./l. 1( tarntrioarulino)-5-py-razolone, 1.8 g. 4 (1% 2-acetanllide, 1.3 g.ll Z-cgagpacetyl)-benzofuran, 0. 05 0. 07 +0. 20

After processing, the density was measured according to the method used as in Example 1. The results obtained are shown in Table 3.

These results show that the magenta density was high After melting by heating the green-sensitive gelatino silver iodobromide emulsion for high speed reversal color photographic materials as in Example 1, the silver halide When other diffusion resistant magenta couplers than those shown in Examples 1, 2, 3 and 4 were used, similar improved results were obtained. Also, when the procedure similar to the above was repeated using developing solutions for coupler-in-developer type color photo graphic processing having difierent compositions than those used in the above examples, similar improved results were obtained.

What is claimed is:

1. A method for the prevention of color mixing for a multi-layer-type reversal photographic light-sensitive silver halide material forming developer, which comprises: developing said multi-layer-type reversal photographic light-sensitive silver halide material having on a support thereof (a) a red-sensitive emulsion layer containing no couplers,

(b) a green-sensitive emulsion layer, and

(c) a blue-sensitive emulsion layer containing no couplers,

13 said developing being carried out with a color developer containing a difiusible cyan, yellow and magenta coupler, respectively, said green emulsion layer containing a ballasted magenta coupler of the general Formula I wherein R is a member selected from the group consisting of an aryl group, a heterocyclic ring, a carbamyl group, and a thiocarbamyl group; R is a member selected from the group consisting of a hydrogen atom, an alkyl group, and aryl group and amino group, a ureido group, a carbonamide group, a sulfonamide group, and a sulfamyl group; R is a member selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms and an aryl group; and X is a member selected from the group consisting of a hydrogen atom and a group capable of being displaced during coupling; at least one of R and R containing at least one hydrophobic residual group having from 8 to 30 carbon atoms, said group providing diffusion resistance to the coupler.

2. The method of claim 1, wherein R is selected from the group consisting of (1) an aryl group;

(2) a furanyl group;

(3) a benzthiazolyl group;

(4) an oxazolyl group;

(5) an imidazolyl group;

(6) a quinolinyl group;

(7) the substituted derivatives of (1), (2), (3), (4), (5) and (6) above, said substituents being selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, an alkoxyl group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfamyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group and a halogen atom;

(8) a carbamyl group;

(9) a methylcarbamyl group;

(10) a phenylcarbamyl group;

(11) a thiocarbamyl group;

(12) an ethylthiocarbamyl group; and

(13) a phenylthiocarbamyl group.

3. The method of claim 1, wherein R is selected from the group consisting of a hydrogen atom; an alkyl group having from 1 to 30 carbon atoms; a substituted alkyl group having from 1 to 30 carbon atoms, said substituent being selected from the group consisting of an alkoxyl group, an aryl group, an aryloxyl group, a halogen atom and a hydroxyl group; an aryl group; a substituted aryl group, said substituents being selected from the group consisting of an alkyl group having from 1 to 18 carbon atoms, an alkoxyl group, an aryloxyl group, an alkoxycarbonyl group, an amino group, a carbonamide group, a sulfonamide group, a carbamyl group, a sulfarnyl group, a sulfone group, a sulfonyl group, a hydroxyl group, a carboxyl group and a halogen atom; a primary amino group; a benzylamino group; 3,5-dicarboxyanilino group; a 4-nitroanilino group; a 2,4'dichloroanilino group; a 2 chloro 4 [a-(2,4-di-tert-amylphenoxy) butylamido1anilino group; a 5 [a (2,4 di-tert-amylphenoxy)acetamido 2 methoxyanilino group; an N'- (a,fl-dicarboxyethyl)ureido group; an octylureido group; a 3 a (2,4 di-tert-amylphenoxy)acetamido]-phenylureido group; an octadecylamido group; an octadecylsuccinmonoamido group; a 3 (octadecylsuccinmonoamido) benzamido group; a 3 [oz (2,4-di-tert-amylphenoxy) acetamidoJbenzamido group; an a-(4-tert-butylphenoxy) 14 propionamido group; a 3 [or (3-pentadecyl-4-sulfophenoxy)acetamido]benzamido group; a 'y (4 N-butyl- N-pentadecoxycarbonylamino)propionamido group; a 4- methylphenylsulfonamido group; a sulfamyl group, an N-ethylsulfamyl group; and a N-phenylsulfamyl group.

4. The method of claim 1, wherein X is selected from the group consisting of a hydrogen atom, a halogen atom, a SON group, an -OR., group, a -SR group, an -OC0R group, and an --0S0 R group, in which R, is selected from the group consisting of an alkyl group, an aryl group and a hetero cyclic group.

5. The method of claim 1 wherein the difl'usion resistant magenta coupler is a compound selected from the group consisting of compounds having the structural formulae:

C- Hr Coupler 5 C1 C-CH:

HrCOOH Coupler 6 Coupler 7 /N=CCnH:s

Coupler 8 /N=C 00 H @a fill-CH2 O Coupler 9 COCmHn N=CNHCOCH2CH2N Cl -N\ C4110 Coupler 10 CHa 6 CH N\ 2H5 H 3,706,556 15 16 Coupler 11 Q N=CNHC 3 I 1 CH2 NHCOCHzO-C5Hll(580) Coupler 12 Cl N=C-NH C O- CH3 N l NH C O C H O C-CHa (I;

II 7 A Coupler 13 /N=CNHC ONHCmHar in C-CH:

Coupler 14 C1 N=CNHC ONH Coupler 15 6 (U J n OCHzCONH 6H1|(t) 0NHf|JCH CHCH;

1 J2 and Coupler 16 6. The method of claim 1, wherein the amount of 3,383,214 5/1968 Anderson 9656.5 the diffusion resistant magenta coupler in the photo- 3,199,983 8/1965 Koepke et al. 96-565 graphic emulsion ranges from 0.0005 to 0.25 mol per 3,212,894 10/1965 Menzel et al. 9656.5 mol of silver halide in the green-sensitive emulsion layer. 2,369,489 2/ 1945 Porter et a1. 9656.5

2,600,788 6/1952 Loria et a1. 9656.5

J. TRAVIS BROWN, Primary Examiner UNITED STATES PATENTS E.C.KIMLIN,A '1 1 3,462,270 8/1969 Eynde et a1. 96-565 an Exammer 3,419,391 12/l968 Young 96--56.5 us. 01. X.R. 3,393,071 7/1968 Monbaliu et a1. 9656.5 as 9655, 56.5, 74

References Cited