Classifications

• • 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
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39232—Organic compounds with an oxygen-containing function

Definitions

• the present invention relates to color photography, more particularly, it relates to a color photographic material capable of forming magenta dye images of good heat and moisture resistance.
• magenta dye images are ordinarily unstable to heat and moisture, and when they are exposed to heat or moisture or are stored for a long period of time, the low density portions of the magenta dye images tend to fade. It is known that such a phenomenon occurs due to unreacted coupler remaining in the color photographic material, and, thus, the aforesaid tendency is particularly seen at low density image portions where a large amount of unreacted coupler remains (see, e.g., P. W. Vittum; Journal of the American Chemical Society; Vol. 72, 1533(1950)).
• a bispyrazolone prepared by the condensation of 3-acylamino-5- pyrazolone and an aldehyde is used as the magenta coupler.
• a bispyrazolone has the fault that it does not give a sufficient coupling density upon color development.
• the dye image formed by such a bispyrazolone is not very fast to heat and moisture.
• One object of this invention is, therefore, to provide a color photographic material capable of forming fast magenta images.
• non-diffusible in this specification has its well known meaning as it is used for color couplers in the field of color photography, i.e., it means that the coupler does not substantially move in the colloid layers of a photographic material in the presence of an aqueous alkaline processing solution.
• R represents an alkyl group
• most generally the alkyl group will have 1 to 32 carbon atoms, though this range is not limitative. It is most preferred that when R, is an alkyl group it have 8 to 18 carbon atoms, since an alkyl group with 8 or more carbon atoms acts as a ballasting group, while alkyl groups of 19 or more carbon atoms are not preferred from an industrial stand point, i.e., the compounds have an increased production cost, difficulty of synthesis, etc.
• R is an aryl group, it is monoaryl as exemplified in the following paragraphs.
• R represents a substituted phenyl group
• preferred substituents include halogen, cyano, nitro, alkyl of 1-18 carbon atoms, alkoxy of l-l8 carbon atoms, aryl, e.g., phenyl, tolyl, etc., aryloxy, e.g., phenoxy, etc., carbamoyl, sulphamoyl, sulphonamido or acyl.
• R examples include phenyl, 2- chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 2,6- dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 3,5-dibromophenyl, 2-cyanophenyl, 3-nitrophenyl, 4- methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-butylphenyl, 2-trifluoromethylphenyl, 2- ethoxyphenyl, 4-phenylphenyl, 4-phenoxyphenyl, N- methylbenzamidophenyl, N,N-diphenylcarbamoylphenyl, N,N-dibutylsulfamoylphenyl, N,N-diphenylsulfamoylphenyl, N-methylsulfonamidophenyl, Z-methyl- 5-nitrophenyl, 2-ch
• the couplers of the formula in which at least one orthoposition of the phenyl group represented-by R has been substituted by a halogen atom, an alkyl group having l-5 carbon atoms, or an alkoxyl group having 1-5 carbon atoms is particularly preferred.
• R R R R R R R and R H R each represents an alkyl group; R R and R each rep- 5 resents a hydrogen atom or an alkyl group; and n is an integer of 1-5.
• any alkyl group for the moi- R 5 eties R to R listed above will have from 1 to 18 car- -NHCO CH bon atoms, and for practical purposes are preferably I unsubstituted.
• ballast groups are hydrophobic groups usually containing 8 to 32 carbon atoms.
• the 3-ureido-5pyrazolor e couplers used in this in.- vention can be prepared according to the methods described in US. Pat. No. 3,558,319; and Japanese Patent Applications 100911/1970; 106716/1970, etc.
• the abovementioned 3-ureido-5-pyrazolone couplers can be used alone or as a combination of two or more couplers.
• the 3-ureido-5-pyrazolor e coupler may be used together with other two-equivalent or four-equivalent couplers.
• These couplers are sometimes called colorless couplers, colored couplers or DlR couplers, and specific examples of them include the couplers described in US. Pat. Nos. 2,455,170; 2,600;7,88; 2,908,573; 3,062,653; 3,148,062;
• the 3-ureido-5-pyrazolene couplers of the present invention are not particularly limited in proportions so long as the objects of the present invention are met. However, generally speaking, they will be used in an amount of from about to about 100 percent by weight, preferably 50 to 100 percent by weight, of the total amount of magenta color forming couplers used.
• Those color couplers are introduced into a hydrophilic colloid as is typically used for photographic materials according to any known method. For instance, they can be dispersed in a hydrophilic colloid using a high boiling point organic solvent such as dibutyl phthalate and tricresyl phosphate as described in U.S. Pat. No. 2,322,027 and/or a low-boiling point organic solvent such as ethyl acetate and tetrahydrofuran as described in U.S. Pat. Nos. 2,801,170; 2,801,171; and 2,946,360.
• a high boiling point organic solvent such as dibutyl phthalate and tricresyl phosphate as described in U.S. Pat. No. 2,322,027
• a low-boiling point organic solvent such as ethyl acetate and tetrahydrofuran as described in U.S. Pat. Nos. 2,801,170; 2,801,171; and 2,
• the aldehydes used together with the 3-ureido-5- pyrazolone coupler according to the present invention include compounds having an alkyl group, an aryl group, or a heterocyclic group bonded to the aldehyde group, i.e., aliphatic aldehydes, aromatic aldehydes or heterocyclic aldehydes can be used in the present invention.
• the aliphatic aldehydes preferably contain from 2 to 20 carbon atoms, most preferably 2 to 8 carbon atoms.
• aromatic aldehydes most preferred are those containing a formyl group attached to the phenyl or naphthyl ring, though aryl substituted with halogen, nitro, hydroxy, C -C alkyl, C,C alkoxy ally], carboxy, sulpho and the like are also useful.
• aldehydes benzaldehydes with or without the above substituents are preferred.
• Such compounds are acetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, pivalylaldehyde, heptaldehyde, laurin aldehyde, stearinaldehyde, succindialdehyde, crotonaldehyde, benzaldehyde, o-chlorobenzaldehyde, mchlorobenzaldehyde, p-chlorobenzaldehyde, pbromobenzaldehyde, p-nitrobenzaldehyde, p-
• aldehydes can be used alone or as a combination of two or more of such aldehydes.
• the addition amount of the aldehyde is usually about 0.05 to about mols, in particular about 0.1 mol to about 10 mols, per mol of the coupler.
• the aldehyde be added to a hydrophilic colloid when preparing the coupler dispersion by adding the abovedescribed coupler or couplers to the hydrophilic colloid together with the aforesaid high boiling point organic solvent and/or the low boiling point organic solvent.
• they can be added to a silver halide emulsion at the preparation of coating compositions together with the coupler dispersion, a hardening agent, a stabilizer, a wetting agent, etc.
• the amount of magenta forming coupler in accordance with the present invention is not limited so long as, of course, the color photographic material of the present invention meets the objects heretofore recited, that is, yields a magenta dye image of good heat and moisture resistance.
• the amount of magenta color forming coupler will be from about 0.05 to about 0.5 moles per mole of silver halide, most preferably, 0.07 to 0.2 moles per mole of silver halide.
• hydrophilic colloid(s) as are used in the color photographic art can be used as the hydrophilic colloid for the silver halide photographic emulsion layer of this invention.
• hydrophilic colloids are gelatin, albumin, gum arabic. agar agar, cellulose derivatives (such as alkyl esters of carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), and synthetic resins (such as polyvinyl alcohol, polyvinyl pyrrolidone, etc.).
• hydrophilic colloids are also preferably used as the binders for layers of the photographic material other than the silver halide emulsion layers, such as a protective layer, a filter layer, an intermediate layer, an antihalation layer, a subbing layer, a backing layer, etc.
• hydrophilic colloids used in various layers of the photographic material of this invention can be effectively hardened by hardening agents such as 1,4- dioxanes, aziridines, iso-oxazoles, active halogens, active vinyl compounds, etc. Typical examples of such hardening agents are described in U.S. Pat. Nos.
• any silver halide emulsion as is usually used in the field of photography such as a silver bromide emulsion, silver iodobromide emulsion, silver chloroiodobromide emulsion, silver chlorobromide emulsion and silver chloride emulsion can be used.
• the so-called converted halide type silver halide emulsions as described in, e.g., U.S. Pat. No. 3,622,318 and British Pat. No. 635,841 can be used.
• a preferred average gain 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. These values are not limitative, but provide a most superior element.
• the silver halide emulsions (used in the color photographic materials) of this invention can be chemically sensitized by active gelatin or a sulfur compound according to the process described in U.S. Pat. Nos. 1,574,944; 1,623,499 and 2,410,869. They can also be sensitized by a noble metal salt such as a palladium or a gold salt as described in U.S. Pat. Nos. 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. No. 2,487,850, or sensitized by a polyalkylene derivative.
• the silver halide emulsion of this invention can contain a stabilizer such as a mercury compound, mercaptotetrazole, thiazole, azaindene, etc.; a plasticizer such as glycerin, latex, etc.; and a wetting agent such as saponin, polyethylene glycol monolauryl ether, etc.
• a stabilizer such as a mercury compound, mercaptotetrazole, thiazole, azaindene, etc.
• a plasticizer such as glycerin, latex, etc.
• a wetting agent such as saponin, polyethylene glycol monolauryl ether, etc.
• the silver halide emulsion can contain an antistatic agent, an ultraviolet absorbent, a fluorescent whitening agent, dyes, etc.
• the silver halide emulsion containing the 3-ureido-5- pyrazolone and the aldehyde compound according to this invention is effectively used as a green-sensitive emulsion layer in an ordinary multi-layer color photographic material.
• the order of the photosensitive emulsion layers may be, from the support side, a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, or may be a blue-sensitive emulsion layer, red-sensitive emulsion layer and a green-sensitive emulsion layer.
• the color photographic material of this invention can have an antihalation layer, intermediate layer(s), filter layer, protective layer, etc.
• the support for the photographic materials of this invention on which the photosensitive silver halide emulsion layers are formed is preferably a cellulose ester film such as a cellulose nitrate film, a cellulose acetate film, etc.; a polyester film such as a polyethylene terephthalate film; a polyvinyl chloride film; a polystyrene film; a polycarbonate film; a baryta-coated paper; a resin-coated paper, and the like.
• This listing is, of course, not limitative.
• the color photographic material of this invention is imagewise exposed in an ordinary way and then processed according to usual color photographic processings.
• the main processing steps are a color development, a bleach and a fix and, if necessary, a washing step may be applied between each step.
• After fixing the color photographic material is washed and dried but it is desirable to process the color photographic material in a stabilization bath prior to drying.
• photographic processing temperatures typically range from about C or less to 60C or higher. Temperatures of about 30C or higher are suitable for high speed processing procedures. Processing times for each processing step can vary widely, depending on the processing temperature, but usually range from several seconds to several minutes or more.
• Useful color developers are aqueous alkaline solutions containing a color developing agent.
• a color developing agent all known primary aromatic amine dye-forming developing agents can be used.
• color developing agents are phenylenediamines such as N,N-diethyl p-phenylenediamine, N-ethylhydroxyethyl p-phenylenediamine, N-ethyl-N- hydroxyethyl-2-methyl p-phenylenediamine, N-ethyl- B-N-methane sulfoneamidoethyl-3-methyl-4- aminoaniline, N,N-diethyl-2-methyl-pphenylenediamine, and sulfates, hydrochlorides, sulfides, etc., thereof.
• the color developer used for developing the color photographic material of this invention may further contain ordinary additives as are used in this art such as a sulfite of an alkali metal, a carbonate, a bisulfite, a bromide, an iodide, benzyl alcohol, etc.
• the bleach solution can contain any known bleaching agent such as ferricyanide, bichromate, etc.
• the fix solution can contain any known fixing agent such as sodium thiosulfate, potassium thiocyanate, etc.
• the bleach step and the fix step can be conducted in one bath, and such a blix bath is described in, e.g., U.S. Pat. No. 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. No. 3,189,452; typical fix agents in Mason, Photographic Processing Chemistry, pages 187-188, Focal Press (1966); and typical blix solutions in German Pat. Nos. 866,605 and 966,410, in British Journal of Photography, pages 122123 and 126 (1966) and in U.S. Pat. No. 3,582,322. These references also discloses generally used proportions.
• the photographic material of this invention provides stable color images which are not faded if the photographic material is exposed to heat or moisture or stored for a long period of time.
• This merit is obtained by the combination of the 3-ureido-5-pyrazolonc and the aldehyde as mentioned above without using formulin, i.e., since the aldehydes of the present invention are limited to those having an aldehyde group bonded to a carbon atom, formaldehyde is excluded from the scope of the present invention. This is quite astonishing upon considering that if the aforesaid aldehyde is used together with 3-acylamino-5-pyrazolone, the stability of the color images cannot be improved.
• the aldehyde used in this invention does not have a harmful influence on the photographic properties, e.g., hindering the coupling of couplers and causing stain as in the case of using formalin or a compound releasing formalin.
• the aldehyde in this invention has the effect of preventing the formation of magenta development fog. Further, changes in sensitivity of the photosensitive emulsion of this invention during storage is prevented. This effect is further observed in the emulsion layers formed over or under the silver halide emulsion layer of this invention, and is a surprisingly effect.
• Coupler dispersion A B C D Coupler l g 100 g 100 g (earlier set out) Coupler A (known) 100 g Dibutyl phthalate 100 g 100 g I00 g 100 g Ethyl acetate 200 g 200 g 200 g 200 g 10% aqueous gelatin 1000 g 1000 g 1000 g 1000 g solution Aqueous solution of 50 g 50 g 50 g 50 g 5% sodium dodecylbenzene sulfonate Acetaldehyde 6 g Heptaldehyde 5 g Known coupler A: the condensation product of 1- phenyl-3-[3-(2-carboxymethyleicos-3-enamide)-benzamido]-5-pyrazolone and acetaldehyde described in U.S. Pat. No. 3,468,666.
• Sample D containing the known coupler gave insodium metaborate 25 g sufficient coupling density and gave unstable dye M- sodium sulfite 2 g ages hydroxylamine (sulfate) 2 g potassium bromide 0.5 g 6-nitrobenzimidazole (nitrate) 0.02 g sodium hydroxide 4 g
• EXAMPLE 2 benzyl alcohol l5.8 ml dNiethhylprltle glycol 20 ml
• a subbing layer was formed on a cellulose acetate -et y- -B-(methanesulfone- 8 g amidoelhyl) p phenylenediamine fllm support having an antlhalatlon layer contain ng water to make 1000 ml carbon black on the opposlte slde, and then a coating composition containing a silver iodobromide emulsion lron salt of ethylenedlaml
• Stabilizing bath a blue-sensitive layer.
• a gelatin intermediate layer was "F acid 10 2; formed on the blue-sensitive layer and a coating comzlnc sulfate 10 g Sodium member 20 g posltlon containing a gelatlno silver chlorobromlde water to make 1000 ml.
• the perintermediate layer was coated on the red-sensitive layer centage of dye remaining in the portions having image and then a coating composition containing 100 g of sildensities of 0.5 and 1.5 before the fading test were calver chlorobromide (containing 0.06 mol of silver) conculated by the following equation and are shown in taining 35 mol percent bromide and spectrally sensi- Table l. tized so that it had its sensitization maximum at about 555 mg, and 250 g ofa coupler dispersion prepared by Dye rema ng Pe ce tage X 100 dispersing the following components by means of a ho- A.
• the compositions of the processing solutions used in the steps were as follows:
• 2-amino-S-diethylaminotoluene hydrochloride (anhydrous) gg I a coupler dispersion prepared by dispersing a sensitizwater 0 ma e m a Colo, developer; mg dye having its sensitization maximum at about 545 Water 800 ml my. and the components shown below by means of a sodium hexametaphosphate 2 g anhydrous Sodium Sulfite 4 g homogenizer was coated in a coated silver amount of l X 10 mol/m 3 g sodium carbonate (monohydrate) 2.5 g potassium bromide 2 0 g water to make 1000 ml Blix solution:
• a color photographic material which provides magenta dye images of excellent heat and moisture resistance and reduced magenta development for comprising a support having thereon a silver halide photographic emulsion layer containing a 3-ureido-5- pyrazolone magenta coupler and a compound having an aldehyde group bonded to a carbon atom;
• magenta coupler is a compound represented by the formula wherein R, represents an alkyl group or an aryl group and R represents a phenyl group;
• aldehyde group is bonded to the carbon atom of an alkyl group, an aryl group or a furfural group, wherein said alkyl group contains from 2-20 carbon atoms and said aromatic group is a formylsubstituted phenyl or naphthyl ring.
• R is a C,C carbon atom alkyl group or a monoaryl group and R is a phenyl group.
• R is a C,,C,,, carbon atom alkyl group, a phenyl group or a tolyl group.
• R is a phenyl group substituted with a halogen atom, a C,C alkyl group or a C,C alkoxyl group.
• ballast group is a C -C hydrophobic group.
• tolualdehyde tolualdehyde, cinnamaldehyde, a-naphthaldehyde or furfural.
• R is a phenyl group selected from:
• R R R R R R and R each represent an alkyl group, and n is an integer of 1-5.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=12972341

Family Applications (1)

Country Status (4)

Cited By (2)

Families Citing this family (3)

Citations (5)

• 1972
  • 1972-05-31 JP JP5450072A patent/JPS5535696B2/ja not_active Expired
• 1973
  • 1973-05-30 DE DE19732327731 patent/DE2327731A1/de active Pending
  • 1973-05-31 GB GB2612673A patent/GB1397175A/en not_active Expired
  • 1973-05-31 US US365678A patent/US3861923A/en not_active Expired - Lifetime

Patent Citations (5)

Also Published As

Similar Documents