Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
  • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/36—Couplers containing compounds with active methylene groups
  • G03C7/38—Couplers containing compounds with active methylene groups in rings
  • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

• 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.
• 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.
• One object of this invention is to provide a color photographic material forming a fast or stable magenta color 1ma e.
• 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 afore
• R represents an alkyl group having 1 to 19, preferably, 1 to 7 carbon
• 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 aceta
• 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 col
• At least one of R R and R has a ballast group which (I)CH3 2 makes the coupler non-diffusible.
• '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.
• 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;
• 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.
• 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.
• aldehyde examples 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 2,156,91
• 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.
• 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.
• a hydrophilic colloid constituting a photographic material according to a known manner.
• 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.
• a high boiling organic solvent such as dibutyl phthalate and tricresyl phosphate as described in U.S. Pat. 2,322,027, etc.
• a low boiling organic solvent such as ethyl acetate and tetrahydrofuran as described in US. Pats. 2,801,170
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• a stabilizer such as a mercury compound, mercaptotetrazole, thiazole, azaindene, etc.
• a plasticizer such as glycerin, a latex, etc.
• a coating aid such as saponin, polyethylene glycol monolauryl ether, etc.
• 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.
• 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.
• 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.
• a color developing agent all known aromatic primary amine dye-forming developing agents can be used.
• aromatic primary amine dye-forming developing agents can be used.
• 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.
• the color developer may contain ordinary additives such as an alkali metal sulfite, a carbonate, a bisulfite, a bromide, an iodide, benzyl alcohol, etc.
• 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,
• 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.
• 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.
• 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:
• 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.
• 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.
• 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.
• 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 10% aqueous gelatin soln., g 1, 000 1, 000 1, 000 1, 000
• 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.
• 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 (3) g Coupler (9) g-.. Coupler (15), g. Coupler (16), g-
• 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.
• 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).
• 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.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=13401764

Family Applications (1)

Country Status (4)

Cited By (9)

Families Citing this family (1)

• 1972
  • 1972-07-11 JP JP47069409A patent/JPS4929638A/ja active Pending
• 1973
  • 1973-07-10 US US00377991A patent/US3834908A/en not_active Expired - Lifetime
  • 1973-07-11 GB GB3316373A patent/GB1398828A/en not_active Expired
  • 1973-07-11 DE DE19732335279 patent/DE2335279A1/de active Pending

Also Published As

Similar Documents