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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
• • 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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
  • G03C7/3005—Combinations of couplers and photographic additives
  • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
  • G03C7/3012—Combinations of couplers having the coupling site in pyrazolone rings and photographic additives

Definitions

• This invention relates to photography, and specifically to color photographic materials containing 2- equivalent 5-pyrazolone couplers and hydrazide oxidized color developer competitors.
• Color reversal silver halide photographic materials rely on coupler compounds to form dyes that make up the image recorded in such materials.
• a yellow dye-forming coupler will be associated with a blue-sensitive silver halide emulsion layer
• a magenta dye-forming coupler will be associated with a green-sensitive silver halide emulsion layer
• a cyan dye-forming coupler will be associated with a red-sensitive silver halide emulsion layer.
• color negative materials the material is exposed to light and processed with a color developer that imagewise forms a silver image and a dye image. The silver image is bleached and solubilized for removal, leaving only a negative color dye image.
• This image is then used to expose another color negative material to form a positive color dye image.
• the material is exposed and processed with a black-and-white developer to form a negative silver image in each layer.
• the silver is then bleached and solubilized for removal, leaving a positive imagewise pattern of unexposed silver halide.
• the material is then chemically fogged and processed in a color developer to form a positive silver and dye image.
• the silver is then bleached and solubilized for removal, leaving only the positive color dye image.
• 5-Pyrazolone coupler compounds are well-known as magenta dye-forming couplers. Such couplers are described in, for example, James, The Theory of the Photographic Process, MacMillan, 1977..
• a color photographic element that includes
• the photographic element of the invention provides magenta dye images in response to exposure with radiation.
• the element's response to exposure exhibits increased contrast compared to prior art 2- equivalent 5-pyrazolone coupler-containing photographic elements. Additionally, improvements in D-max are observed with 2-equivalent 5-pyrazolone couplers.
• R 1 substituents which are electron donating groups, include alkyl, which can be substituted or unsubstituted, straight or branched chain, having from 1 to 20 carbon atoms, preferably from 8 to 16 carbon atoms; alkoxy, which can be substituted or an unsubstituted, straight or branched chain, having from 1 to 20 carbon atoms, preferably from 8 to 16 carbon atoms; carboxy, carbonamido having the formula -NR 4 COR 5 ; sulfonamido having the -NR 4 S0 2 R 5 ; or amino having the formula -NR 4 R 5 where R 4 is hydrogen or alkyl having from 1 to 8 carbon atoms and R 5 is as defined for R 4 or is a benzyl or a phenyl group which may be substituted.
• R 2 substituents that are alkyl or alkoxy can be as defined for these same substituents in R 1 , or R 2 can be substituted or unsubstituted aryl or substituted or unsubstituted aryloxy having from 6 to 30 carbon atoms, such as phenyl, phenoxy, naphthyl or naphthoxy.
• R 2 represents phenyl or phenoxy it is preferred that the aryl ring have a hydrogen bonding substituent in a position ortho to the point of attachment of the carbonyl group to a hydrazide nitrogen atom.
• Preferred hydrogen bonding groups include hydroxy, primary or secondary amino groups of the formula -NR 4 R 5 , sulfonamido of the formula -NHS0 2 R 4 , carbonamido of the formula -NR 4 COR 5 and ureido of the formula -NHCONHR 4 where R 4 and R 5 can be hydrogen or alkyl of from 1 to 8 carbon atoms and R 5 is as defined for R 4 or a benzyl or phenyl group.
• R 2 alkyl groups can also be present as substituents on R 2 alkyl groups or on other positions of R 2 aryl groups.
• a polar group which can represent R 1 or R 2 can be a single group or a combination of groups which have a ⁇ constant which is more negative than -1.0.
• the ⁇ constant is defined by C. Hansch, A. Leo, S. Unger, K. Hwan Kim, D. Nikaitani and E. T. Lien, in JOURNAL OF ORGANIC CHEMISTRY, 11, 1973 (pp. 1207-1216).
• the R 1 or R 2 polar group or groups include, but are not limited to, -NHS0 2 CH 3 , -NHS0 2 aryl, -CH 2 0H, -NH 2 , -COOH, -CONH 2 , -NHCONH 2 , -NHCSNH 2 , -N + (R 5 ) 3 , -SO 3 -, -S0 2 - and These groups tend to increase the surfactant nature of the hydrazine during alkaline processing.
• alkyl, alkoxy, aryl, aryloxy, aralkyl and benzyl groups which are represented by one or more of R 1 , R 2 , R 3 , R 4 and R 5 can be substituted with halogen atoms, for example chlorine, or with haloalkyl groups, for example trifluoromethyl, or with
• 2-Equivalent 5-pyrazolone couplers as a class are well-known to one skilled in the art.
• the couplers may be polymeric or non-polymeric.
• Non-polymeric 2-equivalent 5-pyrazolone couplers useful in the practice of the invention include those according to the formula: wherein
• Examples of coupling-off groups include a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy, dodecyloxy, carboxypropyloxy), an aryloxy group (e.g., 4-chlorophenoxy group, a 4-methoxyphenoxy group), an acyloxy group (e.g., an acetoxy group, a tetradecanoyloxy group), an aliphatic or aromatic sulfonyloxy group (e.g., a methanesulfonyloxy group, a toluenesulfonyloxy group), an acylamino group (e.g., a dichloroacetylamino group, a trifluoroacetylamino group), an aliphatic or aromatic sulfonamido group (e.g., a methanesulfonamido group, a p
• the aliphatic, aromatic, or heterocyclic groups included in X and the groups shown by R 1 and R 2 may be substituted by a substituent such as, for example a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (e.g., a methyl group, a t-octyl group, a dodecyl group, a trifluoromethyl group, etc.), an alkenyl group (e.g., an allyl group, an octadecenyl group, etc.), an aryl group (e.g., a phenyl group, a p-tolyl group, a naphthyl group, etc.), an alkoxy group (e.g., a methoxy group, a benzyloxy group, a methoxyethoxy group, etc.), an aryloxy group (e.g.
• examples of the coupler having the releasable group through a carbon atom for X include a so-called bis type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone.
• R i , R 2 and X may be a divalent or a more polyvalent group to form an oligomer such as a dimer, etc., or may connect a polymeric main chain and a coupler skeleton to form a polymeric coupler, as shown below in formulas (III), (IV), and (V).
• Polymeric 2-equivalent 5-pyrazolone couplers useful in the practice of the invention include those according to the formulas: and
• R 4 represents an alkyl group, a substituted alkyl group (e.g., haloalkyl such as fluoroalkyl, cyanoalkyl and benzylalkyl), or a substituted or unsubstituted aryl group.
• a substituted alkyl group e.g., haloalkyl such as fluoroalkyl, cyanoalkyl and benzylalkyl
• R 4 represents an alkyl group, a substituted alkyl group (e.g., haloalkyl such as fluoroalkyl, cyanoalkyl and benzylalkyl), or a substituted or unsubstituted aryl group.
• substituents examples include an alkyl group (e.g., a methyl group and an ethyl group), an alkoxyl group (e.g., a methoxy group and an ethoxy group), an aryloxy group (e.g., a phenyloxy group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an acylamino group (e.g., an acetylamino group), a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbamoyl group and an ethylcarbamoyl group), a dialkylcarbamoyl group (e.g., a dimethylcarbamoyl group), an arylcarbamoyl group (e.g., a phenylcarbamoyl group), an alkylsulfonyl group (e.g.,
• R 4 is an aryl group
• substituents are a halogen atom, an alkyl group, an alkoxyl group, an alkoxycarbonyl group, and a cyano group.
• a particularly preferred substituent is a halogen atom.
• R 3 is a substituted or unsubstituted anilino group, a carbonamido group (e.g., an alkylcarbonamido group, a phenylcarbonamido group, an alkoxycarbonamido group and a phenyloxycarbonamido group), a ureido group (e.g., an alkylureido group and a phenylureido group), a sulfonamido group, an alkylamino group, a heterocyclic amino group, and preferably is a carbonamido group.
• a carbonamido group e.g., an alkylcarbonamido group, a phenylcarbonamido group, an alkoxycarbonamido group and a phenyloxycarbonamido group
• a ureido group e.g., an alkylureido group and a phenylureido group
• X' is a coupling-off group defined as above for X.
• Particularly preferred examples of the releasable group are nitrogen atom-containing releasable groups forming a heterocyclic ring such as an imidazolyl group and a pyrazolyl group.
• X" represents a divalent group, derived from X', having bonding sites to the pyrazolone ring and to in the formulas (VI) and (VII).
• the polymer coupler useful in the practice of the invention may be a homopolymer of a monomer coupler represented by formula (VI), or a copolymer of two or more of monomer couplers represented by formula (VI), or a copolymer of a monomer coupler of formula (VI) and one or more non-color-forming ethylenic monomer which does not couple with an oxidized product of an aromatic primary amine developing agent.
• a copolymer comprising two or more of the monmer couplers represented by formula (VI) together with one or more of a non-color-forming ethylenical monomers may be used.
• a copolymer of a monomer coupler of formula (VI) and a non-color-forming ethylenical monomer may be used.
• the ethylenical monomer not forming color on coupling with an oxidized product of an aromatic primary amine developing agent includes acrylic acid, a-chloroacrylic acid, a-alkylacrylic acid (e.g., methacrylic acid), and their ester or amide derivatives (e.g., acrylamide, methacrylamide, n-butylacrylamide, tert- butylacrylamide, diacetoneacrylamide, methylenebisacrylamide, methyl methacrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butylmethacrylate, and ,8-hydroxyl methacrylate), vinyl esters
• Particularly preferred examples are acrylic acid esters, methacrylic acid esters, and maleic acid esters.
• the above non-color forming ethylenically unsaturated monomers can be used as mixtures comprising two or more thereof.
• Typical examples are a combination of methyl acrylate and butyl acrylate, a combination of butyl acrylate and styrene, a combination of butyl methacrylate and methacrylic acid, and a combination of methyl acrylate and diacetone acrylamide.
• the type of the ethylenicaly unsaturated monomer to be copolymerized with the monomer coupler of the general formula (V) can be chosen appropriately so as to exert favorable influences on the physical and/or chemical properties of the resulting copolymer, such as solubility, compatibility with a binder (e.g., gelatin) of a photographic colloid composition, flexibility, and heat stability.
• a binder e.g., gelatin
• magenta polymer coupler as used herein can be conveniently handled in the form of a latex during the preparation of light-sensitive material.
• This latex can be prepared by two methods: one of the methods is such that an oleophilic polymer coupler as prepared by polymerization of the above monomer coupler is dissolved in an organic solvent and then dispersed or emulsified in an aqueous gelatin solution, and the other method is a direct emulsion polymerization method.
• the former method is described in U. S. Patent 3,451,820, and the latter method is described in U. S. Patents 4,080,211 and 3,370,952.
• the polymerization temperature is determined taking into consideration the molecular weight of the polymer formed, the type of the polymerization initiator, and so forth.
• the polymerization temperature can be between 0 and 100° C. Usually, the polymerization is carried out in range of from 30 to 100° C.
• the proportion of the color forming portion of the monomer of formula (V) in the copolymer coupler is usually from 5 to 80 wt %. In view of color reproductivity, color forming properties and stability, the proportion is preferably from 20 to 70 wt %. In this case, the molecular weight equivalent (number of grams of the polymer containing 1 mol of the monomer coupler) is preferably from 250 to 4,000 although it is not limited thereto.
• substituents for the groups can include, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfonylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a s
• polymeric 2-equivalent 5-pyrazolone couplers examples include:
• Color reversal photographic materials are well-known in the art, and include those that are processable in Kodak E-6@ processing (e.g., Kodak Ektachrome@ products, Fuji Fujichrome@ products). E-6@ processing is described in British Journal of Photography Annual, 1977, pp. 194-197.
• the support of the element of the invention can be any of a number of well-known supports for photographic elements. These include polymeric films such as cellulose esters (e.g., cellulose triacetate and diacetate) and polyesters of dibasic aromatic carboxylic acids with divalent alcohols (e.g., poly(ethylene terephthalate)), paper, and polymer-coated paper. Such supports are described in further detail in Research Disclosure, December, 1989, Item 308119 [hereinafter referred to as Research Disclosure I], Section XVII.
• the silver halide emulsion used in the practice of the invention can contain, for example, silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, or mixtures thereof.
• the emulsions can include coarse, medium, or fine silver halide grains bounded by 100, 111, or 110 crystal planes.
• Silver halide emulsions and their preparation are further described in Research Disclosure I, Section I. Also useful are tabular grain silver halide emulsions, as described in Research Disclosure, January, 1983, Item 22534 and U.S. Patent 4,425,426.
• the 2-equivalent 5-pyrazolone coupler (or mixtures of such couplers or mixtures with other magenta couplers) and the competitor of formula (I) (or mixtures of such competitors) used in the practice of the invention can be incorporated in hydrophilic layers of photographic materials by techniques well-known in the art.
• One common technique involves the use of high-boiling water-immiscible organic solvents and/or surfactants.
• Useful organic solvents include tricresyl phosphates, di-n-butyl phthalate, and others described in Research Disclosure I, Section XIV.
• Surfactants are well-known to one skilled in the art, and are described in Research Disclosure I, Section XI. Mixtures of solvents and surfactants may also be used.
• the silver halide described above can be sensitized to a particular wavelength range of radiation, such as the red, blue, or green portions of the visible spectrum, or to other wavelength ranges, such as ultraviolet, infrared, and the like.
• the silver halide emulsion associated with the 2-equivalent 5-pyrazolone coupler is spectrally sensitized to green light so as to complement the magenta color of the dye formed by the coupler during processing.
• Chemical sensitization of silver halide can be accomplished with chemical sensitizers such as gold compounds, iridium compounds, or other group VIII metal compounds.
• Spectral sensitization is accomplished with spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, styryls, or other known spectral sensitizers. Additional information on sensitization of silver halide is described in Research Disclosure I, Sections I-IV.
• the photographic element of the invention may be a full color element or monochromatic.
• Multicolor photographic elements according to the invention generally comprise a blue-sensitive silver halide layer having a yellow color-forming coupler associated therewith, a green-sensitive layer having a magenta color-forming coupler associated therewith, and a red-sensitive silver halide layer having a cyan color-forming coupler associated therewith.
• Color photographic elements and color-forming couplers are well-known in the art and are further described in Research Disclosure I, Section VII.
• the element of the invention can also include any of a number of other well-known additives and layers, as described in Research Disclosure I. These include, for example, optical brighteners, antifoggants, oxidized developer scavengers (which can be the same as or different than the competitor according to formula (I)), development accelerators, image stabilizers, light-absorbing materials such as filter layers or intergrain absorbers, light-scattering materials, gelatin hardeners, coating aids and various surfactants, overcoat layers, interlayers and barrier layers, antistatic layers, plasticizers and lubricants, matting agents, development inhibitor-releasing couplers, bleach accelerator-releasing couplers, and other additives and layers known in the art.
• optical brighteners for example, optical brighteners, antifoggants, oxidized developer scavengers (which can be the same as or different than the competitor according to formula (I)), development accelerators, image stabilizers, light-absorbing materials such as filter layers or intergrain absorbers, light-s
• the photographic elements of the invention when exposed, are processed to yield an image.
• Processing can be by any type of known photographic processing, as described in Research Disclosure I, Sections XIX-XXIV.
• a negative image can be developed by color development with a chromogenic developing agent followed by bleaching and fixing.
• a positive image can be developed by first developing with a non-chromogenic developer, then uniformly fogging the element, and then developing with a chromogenic developer, followed by bleaching and fixing.
• Bleaching and fixing can be performed with any of the materials known to be used for that purpose.
• Bleach baths generally comprise an aqueous solution of an oxidizing agent such as water soluble salts and complexes of iron (III) (e.g., potassium ferricyanide, ferric chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic acid), water-soluble persulfates (e.g., potassium, sodium, or ammonium persulfate), water-soluble dichromates (e.g., potassium, sodium, and lithium dichromate), and the like.
• an oxidizing agent such as water soluble salts and complexes of iron (III) (e.g., potassium ferricyanide, ferric chloride, ammonium or potassium salts of ferric ethylenediaminetetraacetic acid), water-soluble persulfates (e.g., potassium, sodium, or ammonium persulfate), water-soluble dichromates (e.g., potassium
• Fixing baths generally comprise an aqueous solution of compounds that form soluble salts with silver ions, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, and the like.
• Photographic elements were prepared by coating a cellulose triacetate film support with a photosensitive layer containing a silver bromoiodide emulsion at 0.83 g Ag/m 2 , gelatin at 1.56 g/m 2 , and one or two of the couplers identified below dispersed in one-half their total weight of tricresyl phosphate and coated at 1.13 mmoles/m 2 .
• the competitor was added to the coating, it was dispersed in an equivalent weight of di-n-butyl phthalate and was coated at 0.28 mmoles/m 2.
• the photosensitive layer was overcoated with a layer containing gelatin at 2.16 g/m 2 and bis-vinyl sulfonylmethyl ether at 1.5 weight percent based on total gelatin.

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• 1991
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