US3834908A - Color silver halide photographic materials containing bis-pyrazolone color couplers - Google Patents

Abstract

A SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CAPABLE OF PROVIDING STABLE MAGENTA IMAGES CONTAINING A BIS-3UREIDO-5- PYRAZOLONE PREPARED BY THE REACTION OF A 3UREIDO-5-PYRAZOLONE WITH A COMPOUND HAVING AN ALDEHYDE GROUP.

Description

3,834,908 COLOR SILVER HALIDE PHOTOGRAPHIC MATE- RIALS CONTAINING BIS-PYRAZOLONE COLOR COUPLERS Hiroshi Hara, Yukio Yokota, Hiroyuki Amano, and Tokio Nishimura, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan N Drawing. Filed July 10, 1973, Ser. No. 377,991 Claims priority, application Japan, July 11, 1972, 47/69,409 Int. Cl. G03c 1/40 US. Cl. 96-100 2 Claims ABSTRACT OF THE DISCLOSURE A silver halide color photographic material capable of providing stable magenta images containing a bis-3- ureido-S- pyrazolone prepared by the reaction of a 3- ureido-S-pyrazolone with a compound having an aldehyde group. 1

BACKGROUND OF THE INVENTION Field of the (Invention The present invention relates to a color photographic material, in particular, to a silver halide color photographic material containing a color coupler providing particularly stable magenta dye images.

DESCRIPTION OF THE PRIOR ART It is well known in color photography that cyan, magenta and yellow dye images are formed by the coupling reaction of the oxidation product of an aromatic primary amino developing agent and color forming couplers. Various kinds of pyrazolone derivatives are also known as couplers for forming magenta color images.

However, magenta color images formed from known pyrazolone derivatives are generally unstable to heat and humidity and when the images are exposed to heat and moisture or stored for a long period of time, the low density portions tend to fade.

This fading phenomenon is caused by unreacted couplers, and this tendency is particularly remarkable at low density portions containing a large proportion of unreacted couplers [see P.W. Vittum; Journal of American Chemical Society, Vol. 72, l533(1950)].

Various methods of preventing the occurence of such fading of magenta color images have been proposed. One is described in US. Pat. 3,140,177, wherein a color photographic material is treated by an acid processing solution containing formalin in the final processing step of the color photographic material. However, this method is undesirable since formalin gives oif a bad smell and is toxic, and hence there is a danger to humans during processing or from the waste solutions generated by such a processing. Another method is described in US. Pat. 3,468,666, wherein the bispyrazolone prepared by the condensation of 3-acylamino-5-pyrazolone with an aldehyde is used as the magenta coupler. However, this latter method has the faults that the bispyrazolones do not give sufiicient color density upon color development and the color images formed therefrom are not fast to heat and moisture.

SUMMARY OF THE INVENTION One object of this invention is to provide a color photographic material forming a fast or stable magenta color 1ma e.

If has now been discovered that the above object of this invention can be attained by using a bis-3-ureido-5- pyrazolone prepared by the reaction of a 3-ureido-5-pyrazolone with a compound having an aldehyde group.

United States Patent O ice That is, according to this invention there is provided a silver halide color photographic material containing a bispyrazolone coupler which is the reaction product of a 3-ureido-5-pyrazolone type magenta coupler and a compound having an aldehyde group.

DETAILED DESCRIPTION OF THE INVENTION According to one embodiment of this invention, the color photographic material comprises a support having coated thereon a silver halide emulsion layer containing a non-dilfusible bis-3-ureido-5-pyrazolone represented by general formula I wherein R represents an alkyl group having 1 to 19, preferably, 1 to 7 carbon atoms (e.g., a methyl, ethyl, isopropyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, pentadecyl, cyclohexyl, terpenyl or norbornyl group), a (mono)aralkyl group having 7 to 9 carbon atoms (e.g., a benzyl or cinnamyl group) or an aryl group (e.g., a phenyl or naphthyl group), where the aforesaid groups each may have one or more substituents such as a halogen atom, a nitro group, a hydroxyl group, a carboxy group, an amino group (e.g., amino, N-alkylamino, N,N- dialkylamino, anilino or N-alkylanilino group, the alkyl group having 1 to 8, preferably, 1 to 4 carbon atoms), a carboxyester group (e.g., an alkoxycarbonyl group having 1 to 8, preferably, 1 to 4 carbon atoms in the alkyl moiety or an aryloxycarbonyl group wherein the aryl moiety is a phenyl or naphthyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom), an amide group (e.g., an acetamide, butylamide, ethylsulfonamide or N-methylbenzamide group), a carbamyl group (e.g., a carbamyl or N,N-diethylcarbamyl group), a sulfamyl group (e.g., an N- propylsulfamyl, N,N-diethylsulfamyl or N-tolylsulfamyl group), an alkoxyl group having 1 to 12, preferably, -1 to 4 carbon atoms (e.g., a methoxy or dodecyloxy group), an aryloxy group (e.g., a phenoxy or tolyloxy gro p), a sulfo group, a sulfonyl group (e.g., an ethylsulfonyl, phenylsulfonyl or phenoxysulfonyl group), and the like.

R represents an alkyl group having 1 to 22 carbon atoms (e.g., a methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl or docosanyl groups) or an aryl group (e.g., a phenyl or naphthyl which may be substituted with halogen, cyano, nitro, alkyl having 1 to 18, preferably, 1 to 5 carbon atoms, alkoxy having 1 to 18, preferably 1 to 5 carbon atoms, aryl such as phenyl, tolyl and the like, aryloXy such as phenoxy and the like, carbamoyl, sulfamoyl, sulfonamido, acyl, acylamino such as acetamido, u-(2,4-di-tert-amylphenoxy)butylamido and the like or sulfo, for example, a phenyl, 2-cl1loropheny1, Z-methoxyphenyl, 2-ethoxyphenyl, 4-methylphenyl, 2,4,6-trichl0rophenyl, 2,5-dichlorophenyl, 2,4-dichloro-G-methylphenyl, 2,4-dimethyl-G-chlorophenyl, 2,6-dichl0r0-4-methylphenyl, 2,6-dichloro-4-methoxyphenyl, 3,5-dibromophenyl, 2,6-dichloro-4-acylaminophenyl, 2,6-diethyl-3-acylaminophenyl, 4-sulfophenyl, naphthyl or 2-chloronaphthyl group).

R represents an alkyl group having 1 to 32 (e.g., a methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, docosanyl, allyl, heptadecenyl, cyclohexyl, terpenyl or norbornyl group), an aralkyl group having 7 to 9' carbon atoms (e.g., a benzyl or cinnamyl group) or an aryl group (e.g., a phenyl or naphthyl group), where each of these groups may have the substituent as described for R The term non-diffusible is one usually applied to Coupler (3) color couplers in the field of color photography and means that the coupler does not substantially move in the colloid layer of a photographic material in the presence NHG ONH-CCH of an aqueous alkaline processing solution. 1

The bis-3-ureido-5-pyrazolone couplers represented by t-O5Hu- OCHCONH- general formula I in which R is a phenyl group having N a halogen atom or an alkoxyl group having 1 to 5 car- H113!) bon atoms as substituents at least one ortho position (t) 01 1 thereof are especially preferred.

It is preferred that in the coupler of general formula I at least one of R R and R has a ballast group which (I)CH3 2 makes the coupler non-diffusible. As is known in the art, 'ballast groups are hydrophobic groups usually containmg 8 to 32 carbon atoms. Various kinds of ballast groups are well known and may suitably be employed.

Examples of the ballast groups are described in US. Pats. 2,600,788; 2,865,751; 3,337,344 and 3,418,129 and cwPler (4) Japanese Patent Publications 27,563/64 and 19,035/70.

Typical examples are represented by the following for- NHCONH C CH -NHOO-CHO LII .Jn R1 (0) COR;

-NHCOCHCH2N a, COR CHCH=CH '--S OZN R" Coupler (5) -CO0Rn a) @NnooNH-o-e1er crr cm)mon, wherein R R R R R R and R each represents 11*]! :0 an alkyl group; R R and R each represents a hydrogen atom or an alkyl group; and n is an integer of 1 to 7 5. Generally, any alkyl group for the groups R; to R de- 91 scribed above contains from 1 to 18 carbon atoms.

Among the bis3-ureido-5-pyrazolone couplers represented by the general formula I, the couplers of the formula in which R represents a phenyl group having a 1 2 ballast group as described above are particularly pre- Coupler (6) ferred.

Specific examples of the bis-3-ureido-5-pyrazolone counn nC ONE Coupler 17) NH 0 o bnoQ-oumo Coupler l 8) Hum The bis-3-ureido-5-pyrazolone used in this invention can be prepared by condensing 3-ureido-5-pyrazolone with a compound having an aldehyde group. This condensation is preferably carried out using 2 to 2.2 moles of 3-ureido- 5-pyrazolone per 1 mole of the aldehyde in an inert organic solvent such as ethyl alcohol, ethyl acetate, etc. at a temperature in the range of from to 80 C., usually at atmospheric pressure, for a period of from 1 to 6 hours. In the above condensation, the concentration of the reactants in the solvent is generally not critical.

The compund having an aldehyde group used in the above condensation can be represented by the formula wherein R is as defined above for the compound of the formula (I). Preferred examples of the aldehydes are benzaldehyde or substituted benzaldehydes where the substituents are as previously defined. Representative examples of the aldehyde include acetaldehyde, propionaldehyde, butylaldehyde, iso-butylaldehyde, pivalylaldehyde, heptaldehyde, laurin aldehyde, stearinaldehyde, succindialdehyde, crotonaldehyde, benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyd,e o-tolualdehyde, cinnamaldehyde and anaphthaldehyde. The starting material, B-ureido-S-pyrazolone, can be prepared by the methods described in US. Pat. 3,558,319 and German OLS 2,156,913 and 2,160,166.

Specific examples of preparing the bis-3-ureido-5-pyrazolones used as a magenta coupler in this invention are illustrated below.

Production of 4,4'-p-nitrobenzylidene-bis-1-(2,6-dichlor0 4 methoxyphenyl) 3 [3-{a-(2,4-di-tert-amylphenoxy)butylamido} phenylureido] -5-pyrazolone (Coupler 142 g. of 1-(2,6-dichloro-4-methoxvphenyl)-3-[3-{u- (2,4 di-tert amylphenoxy)butylamido}phenylureid0]-5- pyrazolone and 15- g. of p-nitrobenzaldehyde were dissolved in 1500 ml. of ethyl acetate. After refluxing for 2 hours at atmospheric pressure, the product was allowed to stand at room temperature and the precipitates formed were recovered by filtration and reccrystallized from ethyl acetate to give 4,4'-p-nitrobenzylidene-bis-1-(2,6-dichloro- 4-methoxyphenyl) 3 [3 a- (2,4-di-tert-amylphenoxy) butylamido}phenylureido]-5-pyrazolone melting at 188- 190 C.

Production of 4,4-p-chlorobenzylidene-bis 1 (2,6-dichloro-4-methoxyphenyl)-3-[3-{a (2,4 di-tert-amylphenoxy)butylarnido}phenylureido] 5 pyrazolone (Coupler 142 g. of 1-(2,6-dichloro-4-methoxyphenyl) 3 [3-{a- (2,4 di-tert amylphenoxy)butylamido}phenylureido]-5- pyrazolone and 14 g. of p-chlorobenzaldehyde were dissolved in 1500 ml. of ethyl acetate. After refluxing for 3 hours at atmospheric pressure, the product was distilled to remove ethyl acetate and the residue was dissolved in 3 liters of acetonitrile. When the solution was allowed to stand at room temperature, crystals, precipitated. The crystals were recovered by filtration under reduced pressure and washed with acetonitrile to give 4,4-p-chlorobenzylidene-bis1-(2,6-dichloro 4 methoxyphenyl)-3-[3- {a (2,4 -di tert-amylphenoxy) butylamido}phenylureido]-5-pyrazolone melting at -172 C.

Production of 4,4-p-nitr0benZylidene-bis-1-(2,6-di-chlo-' ro-4-methoxyphenyl) 3 [3-(2,4-di-tert-amylphenoxyacetamido)phenylureido]-5-pyrazolone (Coupler (13)):

50 g. of 1-(2,6-dichloro-4-methoxyphenyl)-3[3-(2,4-ditert-amylphenoxyacetamido)phenylureido] 5 pyrazolone and 5.5 g. of p-nitrobenzaldehyde were dissolved in 1000 ml. of ethanol. After refluxing the system for 4 hours at atmospheric pressure, ethanol was distilled off and the,

solution was allowed to stand at room temperature, crystals precipitated. The crystals were recovered by filtration and washed with methanol to give 4,4-p-nitrobenzylidenebise1-(2,6-dichloro 4 methoxyphenyl)-3-[3-(2,4-di-tertamylphenoxyacetarnido)phenylureido]--pyrazolone.

According to this invention the bis-3-ureido-5-pyrazolone magenta couplers may be used individually or as a mixture of two or more of such couplers, or may be used together with other known 2-equivalent or 4-equivalent magenta couplers. These well-known couplers are sometimes called colorless couplers, colored couplers or DIR couplers, and specific examples thereof are described in U.S. Pats. 2,455,170; 2,600,788; 2,908,573; 3,062,653; 3,148,062; 3,227,551; 3,227,554; 3,418,129; 3,516,831; 3,519,429; 3,558,319 and 3,617,291. In a mixed coupler system, the use of more than about 5 mol percent of a bis-B-ureido-S-pyrazolone of this invention based on the total magenta couplers is effective.

The color coupler of this invention is incorporated in a hydrophilic colloid constituting a photographic material according to a known manner. For instance, it can be dispersed in the hydrophilic colloid as a solution thereof in a high boiling organic solvent such as dibutyl phthalate and tricresyl phosphate as described in U.S. Pat. 2,322,027, etc., and/or a low boiling organic solvent such as ethyl acetate and tetrahydrofuran as described in US. Pats. 2,801,170; 2,801,171 and 2,946,360.

Any known hydrophilic colloid can be used for the silver halide emulsion layers in this invention. Preferred examples of the hydrophilic colloid are gelatin, gelatin derivatives such as acylated gelatin as described in U.S. Pats. 2,523,753 and 2,691,582, and graft gelatin as described in U.S. Pat. 2,831,767 and British Patent 1,211,- 039, albumin, gum arabic, agar agar, cellulose derivatives (such as alkyl esters of carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose, etc.), and synthetic resins (such as polyvinyl alcohol, polyvinyl pyrrolidone, etc.). These hydrophilic colloids are further preferably used as binders for layers of the photosensitive materials other than the silver halide emulsion layers (for instance, protective layers, filter layers, intermediate layers, antihalation layers, subbing layers and backing layers).

The hydrophilic colloids used for the various layers of the photographic materials of this invention are preferably hardened by a hardening agent such as a 1,4-dioxane or aziridine type hardening agent, an iso-oxazole type hardening agent, an active halogen type hardening agent, an active vinyl type hardening agent, etc. Typical examples'of such hardening agents are described in U.S. Pats. 3,232,- 764; 3,288,775; 2,732,303; 3,635,718; 3,232,763; 2,732,- 316; 2,586,168; 3,103,437; 3,017,280; 2,983,611; 2,725,- 294; 2,725,295; 3,100,704; 3,091,537; 3,321,313 and 3,543,292 and British Pats. 974,723; 1,167,207 and 994,869. In the present invention, all silver halide emulsions as are used in the field of photography, such as a silver bromide emulsion, a silver iodide emulsion, a silver chloroiodobromide emulsion, a silver chlorobromide emulsion and a silver chloride emulsion can be used. Also, the socalled converted halide type silver halide grains as disclosed in U.S. Pat. 3,622,318 and British Pat. 635,841 may be profitably used in this invention. A preferred average grain size for the silver halide is from about 0.05 to about 1.5 microns. The weight ratio of silver halide to binder most suitably ranges from about 0.2 to about 20 (silver halide/binder), preferably about 0.3 to about 5 in the layer. Generally, the ratio of a silver halide/a couple of the present invention is from about 1 to 40, preferably 2 to 20. These values are not limitative, but provide a most superior element.

The silver halide emulsions of this invention can be chemically sensitized by active gelatin or a sulfur compound according to the process described in U.S. Pats.

1,574,944; 1,623,499 and 2,410,689. They can also be sensitized by a noble metal salt such as a palladium or a gold salt as described in U.S. Pats. 2,448,060; 2,399,083 and 2,642,361. Furthermore, they can be sensitized by a reducing agent such as a stannous salt as described in U.S. Pat. 2,487,850, or sensitized by a polyalkylene derivative. They can also be spectra'lly sensitized by a cyanine or merocyanine dye such as described in U.S. Pats. 2,519,001; 2,666,761; 2,734,900; 2,739,964 and 3,481,742. The silver halide emulsion may further contain a stabilizer such as a mercury compound, mercaptotetrazole, thiazole, azaindene, etc.; a plasticizer such as glycerin, a latex, etc.; and a coating aid such as saponin, polyethylene glycol monolauryl ether, etc. Furthermore, the silver halide emulsion may contain an antistatic agent, an ultraviolet absorbent, a fluorescent brightening agent, a dye, and the like.

The silver halide emulsion containing the bis-3-ureido- S-pyrazolone coupler of this invention is most profitably used as the green-sensitive photosensitive layer in a multicolor type color photographic material. In this case, the disposition order of the photosensitive emulsion layers may be, from the support side, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, or, alternatively a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer. The photographic material may also have, besides those photosensitive layers, an antihalation layer, intermediate layers, a filter layer, and a protective layer.

Preferred examples of the support on which the silver halide photosensitive emulsion layers are carried are cellulose ester films such as cellulose nitrate films, cellulose acetate films, etc.; polyester films such as polyethylene terephthalate films, etc.; polyvinyl chloride films; polystyrene films; polycarbonate films, baryta-coated papers; resin-coated papers; and the like.

The color photographic material of this invention is imagewise exposed according to an ordinary manner and then processed by standard color processing procedures. The main processing steps are color development, bleach and fix. A washing step may be applied, if desired, between these steps. After fixing, the color photographic material is washed and dried but it is desirable to process it in a fix bath before drying.

As is known to those skilled in the art, photographic processing temperatures typically range from about 20 C. or less to 60 C. or higher. Temperatures of about 30 C. or higher are suitable for high speed processing procedures.

A useful color developer is an alkaline aqueous solution containing a color developing agent. As the color developing agent all known aromatic primary amine dye-forming developing agents can be used. For instance, there are phenylenediamines such as N,N diethyl-p-phenylenediamine, N ethyl-N-hydroxyethyl-pphenylenediamine, N- ethyl N-hydroxyethyl-2-methyl-p-phenylenediamine, N- ethyl fl N-methanesulfonamidoe'thyl-3-methyl-4-aminoaniline, N,N-Z-methyl-p-phenylenediamine, sulfates thereof, hydrochlorides thereof and sulfites thereof. See C. E. K. Mees and T. H. James, The Theory of the Photographic Process, pages 294295 (The MacMillan Co., 1966), and U.S. Pats. 2,592,364 and 2,193,015. The color developer may contain ordinary additives such as an alkali metal sulfite, a carbonate, a bisulfite, a bromide, an iodide, benzyl alcohol, etc.

As the bleach solution, all known bleach solutions containing a ferricyanide, a bichromate, etc., can be used. Also, all known fix solutions containing sodium thiosulfate, potassium thiocyanide, etc., may be used as the fix solution. Furthermore, the bleaching step and the fixing step may be conducted in one bath. Such a blix bath is described in, e.g., U.S. Pat. 3,582,322. Typical bleach agents are discussed in detail in the Journal of the Society of Motion Picture and Television Engineers 61,.667-701 and U.S. Pat. 3,189,452; typical fix agents in Mason,

Photographic Processing Chemistry, pages 187-188, Focal Press (1966); and typical blix solutions in German Patents 866,605 and 966,410, in British Journal of Photography, pages 122-123 and 126 (1966) and in US. Pat. 3,582,322. These references also disclose generally used proportions.

The feature of this invention lies in the point that the magenta coupler is a bis-compound having a ureido bond at the 3-position of the pyrazolone. Even if the photographic material of this invention containing such a coupler is exposed to heat or moisture or is stored for a long period of time it provides a stable color image giving less fading. Also, the magenta coupler of this invention has the merit that it does not cause insufficient coloring, which usually happens in the case of using conventional bis-type magenta couplers. Furthermore, the magenta coupler of this invention has the effect of controlling the occurrence of development fog. Moreover, in the photosensitive emulsion layer containing the magenta coupler of this invention, changes in sensitivity during storage are suppressed. This surprising effect is also observed in the emulsion layer formed on or under the emulsion layer containing the magenta coupler of this invention.

The invention will now be illustrated more in detail by the following examples.

EXAMPLE 1 60 g. of a coupler dispersion prepared by dispersing a sensitizing dye having its sensitization maximum at about 545 m and the following components by means of a homogenizer was added to 100 g. of a silver chlorobromide emulsion (bromine content: 50 m1. percent) containing 0.05 mol of silver and the mixture was coated on a baryta-coated paper (amount of coated silver was 6 10- mol/m3). Samples A, B and C were thus produced.

A B C Coupler dispersion:

Coupler (3) g 100 Coupler (6) g 100 Comparison coupler A, g- 1000 Dibutyl phthalate, g- 100 100 100 Ethyl acetate, g 200 200 200 10% aqueous gelatin solution, g 1, 000 1, 000 1, 000 5% aqueous solution of sodium dodecylbenzenesulionate, g 50 50 50 Comparison coupler A:

N HC ONH- C-CH1 CzHi il E} N tert-C H -O HOONH- \N/ I O CH:

Each of the samples Was subjected to a staged exposure of 1000 lux for /2 seconds through a green filter transmitting light of 500-600 mg and a silver wedge and then subjected to the following processings.

The formulations of the processing solutions used in the above processings were as follows:

Color developer:

Sodium metaborate g 25 5 Sodium sulfite g 2 Hydroxylamine (sulfate) g 2 Potassium bromide g 0.5 6-Nitrobenzimidazole (nitrate) g 0.02 Sodium hydroxide g 4 l0 Benzyl alcohol ml 15.8 Diethylene glycol ml 20 N-Ethyl N ,8 (methanesulfonamidoethyl)- p phenylenediamine g 8 Water to make ml 1000 Blix solution:

Iron salt of ethylenediamine tetraacetic acid g 45 Ammonium thiocyanate g 10 Sodium sulfite g 10 Ammonium thiocyanate (60% aqueous solution) m1 100 Ethylenediamine tetraacetic acid tetrasodium salt g 5 Water to make ml 1000 Stabilization bath:

Tartaric acid g 10; Zinc sulfate g 10 Sodium metaborate g 20 Water to make ml 1000 After measuring the reflection density of the magenta dye image thus formed, each sample was stored for 14 days of 60 C. and 70% relative humidity to conduct a fading test, and then the reflection density of the color image was measured again. The dye remaining rate (percentage) of the portions of the sample having image densities of 0.5 and 1.5 before the fading test was calculated by the following equation, and the results are shown in Table 1.

Dye remaining rate (percent) X 100 wherein A=dye density after the fading test-fog density after the fading test; B=dye density before the fading test-fog density before the fading test.

Dye remaining rate (percent) Initial Initial Sample density 0.5 density 1.5 86 90 88 92 45 60 As is clear from the above results, samples A and B containing a bis-3-ureido-5-pyrazolone magenta coupler according to this invention have stable magenta dye images showing less fading and this tendency Was particularly remarkable at the low-density portion. On the other hand, in the case of using comparison coupler A (this coupler corresponds to a mono-type, i.e., mono-3- ureido-5-pyrazolone type, of Coupler (3) and Coupler (6)), the color image formed showed great fading.

EXAMPLE 2 coupler. A gelatin intermediate layer was coated on the blue-sensitive layer, and, further, a coating composition containing a silver chlorobromide emulsion containing 30 mol percent bromine and spectrally sensitized so that the silver halide emulsion had its sensitization maximum at about 685 m and a coupler dispersion prepared by dispersing a cyan coupler, 1-hydroxy-4-chloro-N-hexadecyl-'N-(2-cyanoethyl)-2-naphthamide, in a mixture of dibutyl phthalate and ethyl acetate was coated on the intermediate layer to give a red-sensitive emulsion layer containing 7.4 10 mol/m. of a silver halide and 1.7 10 mol/m. of the coupler. A gelatin intermediate layer was coated on the red-sensitive emulsion layer, and, further, a coating composition consisting of 100 g. of a silver chlorobromide emulsion (bromide content: 35 mol percent containing 0.06 mol of silver and spectrally sensitized so that the emulsion had the sensitization maximum at about 555 m and 250 g. of a coupler dispersion prepared by dispersing the following components by means of a homogenizer was coated on the intermediate layer to give a green-sensitive emulsion layer containing 2x10 mol/m? of a silver halide and 1.5 10 mol/m. of the coupler. Finally, a gelatin protective layer was coated on the green-sensitive layer. Thus, samples D, E, F and G were prepared.

D E F G Coupler dispersion:

Coupler (2), g 30 Coupler (6), g 30 Coupler (11), g 30 Known coupler E, g 70 70 70 100 Dubutyl phthalate, g. 50 50 50 50 Ethyl acetate, g 200 200 200 200 10% aqueous gelatin soln., g 1, 000 1, 000 1, 000 1, 000

% aqueous solution of sodium dodecylbenzene sulfonate, g 100 100 100 100 Each of the samples thus prepared was exposed as in Example 1 and subjected to the following processings.

Temperature, C. Time Processing:

Pre-processing bath.. 27 sec. Washing 27 15 sec. Color development. 27 5 min. sec. Washing 27 15 see. Blix 27 4 min. Washing 27 2 min. Stabilization 27 10 sec.

The formulations of the processing solutions used in the above processings were as follows: Pre-processing bath:

14 Blix solution:

Sodium iron (III) ethylenediamine tetraacetic After measuring the transmission density of the magenta dye images thus formed, each sample was stored for 30 days at 50 C. and 70% relative humidity to conduct a fading test, and then the transmission density of the dye images was measured again. The dye remaining rate (percentage) at portions having image densities of 0.5 and 20 before the fading test are shown in Table 2.

TABLE 2 Dye remain rate (percent) Initial Initial Fog density density density 0.5 20

From the above results, it was clear that the photographic material of this invention containing a bis-3- ureido-S-pyrazolone shows an effective fading prevention effect in the color image, even if the content thereof was about 15 mol percent of the total couplers, and also in the photographic materials the formation of magenta development fog Was suppressed.

EXAMPLE 3 On a paper support having coated on both surfaces polyethylene containing titanium dioxide, a coating composition containing a silver chlorobromide emulsion containing 85 mol percent bromine and a coupler dispersion prepared by dispersing a yellow coupler, oc(4-methoxybenzoyl) 3 [ot-(2,4-di-tert-amylphenoxybutylamido)]- 6-chloro-acetanilide, in a mixture of dibutyl phthalate and ethyl acetate was coated to give a blue-sensitive emulsion layer containing 9X10- mol/m. of silver and 7X 10- mol/m. of the coupler, and then an intermediate layer of gelatin was coated on the blue-sensitive layer. A coating composition consisting of g. of a silver chlorobromide emulsion containing 30 mol percent bromide and 0.07 mol of silver and 100 g. of a coupler dispersion prepared by dispersing a sensitizing dye having its sensitization maximum at about 545 m and the following components by means of a homogenizer Was coated on the intermediate layer (amount of coated silver was 1 10 mol/m Thus, samples H, I, J, K, and L were prepared.

Coupler dispersion:

Coupler (3), g Coupler (9) g-.. Coupler (15), g. Coupler (16), g-

1 5 Coupler C:

o ONH-C-CH: CzHs tort-05H" O HCONH- \N/ 'a protective layer of gelatin was coated on the emulsion layer. Thus, Samples H, I, J, K and L were prepared.

Directly after the production of the samples or after storing them for 3 days at 40 C. and 80% relative humidity, each of the samples was wedge exposed to the light of 1000 lux for 1 second through a filter transmitting light of 500-6001;. and a filter transmitting light having wave lengths longer than 600 1., and then processed as in Example 1.

The red sensitivity and the green sensitivity were measured for each sample and the change of sensitivity upon storage under the high-temperature and high-humidity conditions (for 3 days at 40 C. and 80% relative humidity) was measured, the results of which are shown in Table 3. In Table 3, -0.15 shows that the sensitivity of the stored sample was reduced as compared with that of the fresh sample by 0.15 (logarithmic units). Also, the fog density of the stored sample was measured and a fading test on the sample as in Example I was conducted, the results also being shown in Table 3.

As is clear from Table 3, by using the bis-type magenta coupler of this invention in an amount of about 15 mol percent of the total magenta couplers, the stability of the magenta color images was improved, the formation of magenta development fog when the photographic material was preserved under high-temperature and highhumidity conditions was suppressed, and, further the change in sensitivities in the green-sensitive layer and the red-sensitive layer was lessened.

From the specific examples described above, it will be understood that excellent characteristics were obtained using the bis-3-ureido-5-pyrazolones according to this invention.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A silver halide color photographic material comprising a support having thereon an emulsion layer containing the bis-3-ureido-5-pyrazolone represented by the general formula wherein R represents an alkyl group, an aralkyl group or an aryl group, R represents an alkyl group or an aryl group; and R represents an alkyl group, an aralkyl group, or an aryl group.

2. The silver halide color photographic material as set forth in Claim 1 in which at least one of said groups R R and R has a ballast group.

References Cited UNITED STATES PATENTS 2,294,909 9/ 1942 Jennings 96-100 2,618,641 11/1952 Weissberger et a1 96-100 3,393,071 7/1968 Monbaliu et al 96-100 3,468,666 9/1969 Shiba et a1 96-100 3,558,319 1/1971 Hamaoka et al 96-100 I. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R.